Fullerenes Enhance Self-Assembly and Electron Injection of Photosystem I in Biophotovoltaic DevicesClick to copy article linkArticle link copied!
- Nahid TorabiNahid TorabiStratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The NetherlandsZernike Institute for Advanced Materials, Nijenborgh 4, 9747 AG Groningen, The NetherlandsDepartment of Materials Engineering, Isfahan University of Technology, Isfahan 84156-83111, IranMore by Nahid Torabi
- Xinkai QiuXinkai QiuStratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The NetherlandsZernike Institute for Advanced Materials, Nijenborgh 4, 9747 AG Groningen, The NetherlandsMore by Xinkai Qiu
- Manuel López-OrtizManuel López-OrtizIBEC—Institut de Bioenginyeria de Catalunya, The Barcelona Institute of Science and Technology, Baldiri Reixac 15-21, Barcelona 08028, SpainNetwork Biomedical Research Center in Biomaterials, Bioengineering and Nanomedicine (CIBER-BBN), Madrid 28029, SpainMore by Manuel López-Ortiz
- Mark LoznikMark LoznikInstitute of Technical and Macromolecular Chemistry, RWTH Aachen University, Worringerweg 2, 52074 Aachen, GermanyDWI-Leibniz Institute for Interactive Materials, Forckenbeckstr. 50, 52056 Aachen, GermanyMore by Mark Loznik
- Andreas HerrmannAndreas HerrmannZernike Institute for Advanced Materials, Nijenborgh 4, 9747 AG Groningen, The NetherlandsInstitute of Technical and Macromolecular Chemistry, RWTH Aachen University, Worringerweg 2, 52074 Aachen, GermanyDWI-Leibniz Institute for Interactive Materials, Forckenbeckstr. 50, 52056 Aachen, GermanyMore by Andreas Herrmann
- Ahmad KermanpurAhmad KermanpurDepartment of Materials Engineering, Isfahan University of Technology, Isfahan 84156-83111, IranMore by Ahmad Kermanpur
- Ali AshrafiAli AshrafiDepartment of Materials Engineering, Isfahan University of Technology, Isfahan 84156-83111, IranMore by Ali Ashrafi
- Ryan C. Chiechi*Ryan C. Chiechi*Email: [email protected]Stratingh Institute for Chemistry, University of Groningen, Nijenborgh 4, 9747 AG Groningen, The NetherlandsZernike Institute for Advanced Materials, Nijenborgh 4, 9747 AG Groningen, The NetherlandsMore by Ryan C. Chiechi
Abstract
This paper describes the fabrication of microfluidic devices with a focus on controlling the orientation of photosystem I (PSI) complexes, which directly affects the performance of biophotovoltaic devices by maximizing the efficiency of the extraction of electron/hole pairs from the complexes. The surface chemistry of the electrode on which the complexes assemble plays a critical role in their orientation. We compared the degree of orientation on self-assembled monolayers of phenyl-C61-butyric acid and a custom peptide on nanostructured gold electrodes. Biophotovoltaic devices fabricated with the C61 fulleroid exhibit significantly improved performance and reproducibility compared to those utilizing the peptide, yielding a 1.6-fold increase in efficiency. In addition, the C61-based devices were more stable under continuous illumination. Our findings show that fulleroids, which are well-known acceptor materials in organic photovoltaic devices, facilitate the extraction of electrons from PSI complexes without sacrificing control over the orientation of the complexes, highlighting this combination of traditional organic semiconductors with biomolecules as a viable approach to coopting natural photosynthetic systems for use in solar cells.
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Introduction
Experimental Section
Photosystem I Preparation and Purification
Fabrication of Soft Devices
IQAc Peptide Design
Fabrication of BPV Devices Based on the Bilayer of PCBA/PSI
Fabrication of BPV Devices Based on the Monolayer of IQAc-PSI
Photocurrent Measurements
Results and Discussion
Device Design
Device Performance
VOC (V) | JSC (μA/cm2) | FF | Pmax (μW/cm2) | η (%) | |
---|---|---|---|---|---|
PCBA/PSI | 0.59 | 126.02 | 0.31 | 22.07 | 0.0043 |
IQAc-PSI | 0.51 | 111.94 | 0.25 | 12.02 | 0.0027 |
VOC (V) | JSC (μA/cm2) | FF | |
---|---|---|---|
PCBA/PSI | |||
day 1 | 0.58 | 115.78 | 0.294 |
day 2 | 0.58 | 113.78 | 0.254 |
day 4 | 0.57 | 108.27 | 0.236 |
day 7 | 0.56 | 88.77 | 0.197 |
day 8 | 0.58 | 126.02 | 0.300 |
day 9 | 0.57 | 121.53 | 0.292 |
day 12 | 0.56 | 100.60 | 0.241 |
day 15 | 0.56 | 93.63 | 0.186 |
IQAc-PSI | |||
day 1 | 0.50 | 90.43 | 0.220 |
day 2 | 0.49 | 81.74 | 0.208 |
day 4 | 0.48 | 81.47 | 0.192 |
day 7 | 0.47 | 57.66 | 0.175 |
day 8 | 0.49 | 101.94 | 0.225 |
day 9 | 0.48 | 99.52 | 0.218 |
day 12 | 0.47 | 92.13 | 0.202 |
day 15 | 0.47 | 71.21 | 0.195 |
Fresh PSI was introduced after day 7.
Conclusions
Supporting Information
The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.langmuir.1c01542.
Atomic force microscopy (AFM) images of PCBA/PSI and IQAc-PSI, multiday current density, and output power measurements of PCBA/PSI and IQAc-PSI PV devices; comparative photochronoamperometric measurements of PCBA/PSI devices, stability of BPV devices under continuous illumination, UV–vis absorbance spectra of PCBA/PSI devices, longevity study of PCBA/PSI and IQAc-PSI BPV devices in the dark and under illumination; and control measurements (PDF)
Terms & Conditions
Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html.
Acknowledgments
N.T. acknowledges the Zernike Institute of Advanced Materials. N.T. acknowledges financial support from the Ministry of Science, Research, and Technology of Iran (MSRT). We thank Pau Gorostiza Langa and Ricardo Zamora Brito at the Institute for Bioengineering of Catalonia (IBEC) for their cooperation during the preparation of IQAc peptides.
References
This article references 67 other publications.
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- 5Brettel, K.; Leibl, W. Electron Transfer in Photosystem I. Biochim. Biophys. Acta, Bioenerg. 2001, 1507, 100– 114, DOI: 10.1016/S0005-2728(01)00202-XGoogle Scholar5https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3MXnvFCktbY%253D&md5=54853ac113aab68bf53d1d9495a8a7a7Electron transfer in photosystem IBrettel, Klaus; Leibl, WinfriedBiochimica et Biophysica Acta, Bioenergetics (2001), 1507 (1-3), 100-114CODEN: BBBEB4; ISSN:0005-2728. (Elsevier B.V.)A review. This mini-review focuses on recent exptl. results and questions, which came up since the last more comprehensive reviews on the subject. We include a brief discussion of the different techniques used for time-resolved studies of electron transfer in photosystem I (PS I) and relate the kinetic results to new structural data of the PS I reaction center.
- 6Nelson, N.; Ben-Shem, A. The Complex Architecture of Oxygenic Photosynthesis. Nat. Rev. Mol. Cell Biol. 2004, 5, 971– 982, DOI: 10.1038/nrm1525Google Scholar6https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2cXhtVarsbzP&md5=861031c7898c616cda294676edac6607The complex architecture of oxygenic photosynthesisNelson, Nathan; Ben-Shem, AdamNature Reviews Molecular Cell Biology (2004), 5 (12), 971-982CODEN: NRMCBP; ISSN:1471-0072. (Nature Publishing Group)A review. Oxygenic photosynthesis is the principal producer of both oxygen and org. matter on earth. The primary step in this process, i.e., the conversion of sunlight into chem. energy, is driven by four multisubunit membrane-protein complexes that are known as photosystem I, photosystem II, cytochrome b6f and F-ATPase. Structural insights into these complexes have provided a framework for the exploration not only of energy and electron transfer, but also of the evolutionary forces that shaped the photosynthetic app.
- 7Nelson, N.; Yocum, C. F. Structure And Function Of Photosystems I And Ii. Annu. Rev. Plant Biol. 2006, 57, 521– 565, DOI: 10.1146/annurev.arplant.57.032905.105350Google Scholar7https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28XosVKht7w%253D&md5=b6e2c2856d90824f9855afe39ac78adbStructure and function of photosystems I and IINelson, Nathan; Yocum, Charles F.Annual Review of Plant Biology (2006), 57 (), 521-565CODEN: ARPBDW ISSN:. (Annual Reviews Inc.)A review. Oxygenic photosynthesis, the principal converter of sunlight into chem. energy on earth, is catalyzed by four multi-subunit membrane-protein complexes: photosystem I (PSI), photosystem II (PSII), the cytochrome b6f complex, and F-ATPase. PSI generates the most neg. redox potential in nature and largely dets. the global amt. of enthalpy in living systems. PSII generates an oxidant whose redox potential is high enough to enable it to oxidize H2O, a substrate so abundant that it assures a practically unlimited electron source for life on earth. During the last century, the sophisticated techniques of spectroscopy, mol. genetics, and biochem. were used to reveal the structure and function of the two photosystems. The new structures of PSI and PSII from cyanobacteria, algae, and plants has shed light not only on the architecture and mechanism of action of these intricate membrane complexes, but also on the evolutionary forces that shaped oxygenic photosynthesis.
- 8El-Mohsnawy, E.; Kopczak, M. J.; Schlodder, E.; Nowaczyk, M.; Meyer, H. E.; Warscheid, B.; Karapetyan, N. V.; Rögner, M. Structure and Function of Intact Photosystem 1 Monomers From the Cyanobacterium Thermosynechococcus elongatus. Biochemistry 2010, 49, 4740– 4751, DOI: 10.1021/bi901807pGoogle Scholar8https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXmtlCrt78%253D&md5=1103363c3a1f714f07e1179bb7708a03Structure and Function of Intact Photosystem 1 Monomers from the Cyanobacterium Thermosynechococcus elongatusEl-Mohsnawy, Eithar; Kopczak, Marta J.; Schlodder, Eberhard; Nowaczyk, Marc; Meyer, Helmut E.; Warscheid, Bettina; Karapetyan, Navassard V.; Roegner, MatthiasBiochemistry (2010), 49 (23), 4740-4751CODEN: BICHAW; ISSN:0006-2960. (American Chemical Society)Until now, the functional and structural characterization of monomeric photosystem 1 (PS1) complexes from Thermosynechococcus elongatus has been hampered by the lack of a fully intact PS1 prepn.; for this reason, the three-dimensional crystal structure at 2.5 Å resoln. was detd. with the trimeric PS1 complex. Here, the possibility of isolating from this cyanobacterium the intact monomeric PS1 complex which preserves all subunits and the photochem. activity of the isolated trimeric complex is shown. Moreover, the equil. between these complexes in the thylakoid membrane can be shifted by a high-salt treatment in favor of monomeric PS1 which can be quant. extd. below the phase transition temp. Both monomers and trimers exhibit identical post-translational modifications of their subunits and the same reaction centers but differ in the long-wavelength antenna chlorophylls. Their chlorophyll/P700 ratio (108 for the monomer and 112 for the trimer) is slightly higher than in the crystal structure, confirming mild prepn. conditions. Interaction of antenna chlorophylls of the monomers within the trimer leads to a larger amt. of long-wavelength chlorophylls, resulting in a higher photochem. activity of the trimers under red or far-red illumination. The dynamic equil. between monomers and trimers in the thylakoid membrane may indicate a transient monomer population in the course of biogenesis and could also be the basis for short-term adaptation of the cell to changing environmental conditions.
- 9Gordiichuk, P. I.; Wetzelaer, G.-J. A. H.; Rimmerman, D.; Gruszka, A.; de Vries, J. W.; Saller, M.; Gautier, D. A.; Catarci, S.; Pesce, D.; Richter, S.; Blom, P. W. M.; Herrmann, A. Solid-State Biophotovoltaic Cells Containing Photosystem I. Adv. Mater. 2014, 26, 4863– 4869, DOI: 10.1002/adma.201401135Google Scholar9https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXos1CjtL0%253D&md5=2ca7ed4b6f064ba7a6480e00fc62f364Solid-state biophotovoltaic cells containing Photosystem IGordiichuk, Pavlo I.; Wetzelaer, Gert-Jan A. H.; Rimmerman, Dolev; Gruszka, Agnieszka; Willem de Vries, Jan X.; Saller, Manfred; Gautier, Daniel A.; Catarci, Stefano; Pesce, Diego; Richter, Shachar; Blom, Paul W. M.; Herrmann, AndreasAdvanced Materials (Weinheim, Germany) (2014), 26 (28), 4863-4869CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)Processes occurring during photosynthesis, such as dynamic self-repair, light harvesting and quantum effects can be integrated into man-made photovoltaic devices. One of the most frequently used photoactive building blocks for that purpose is the multiprotein complex photosystem I (PSI). Biophotovoltaic devices similar to DSSCs were fabricated by self-assembly of PSI on 3D nanostructured semiconductor electrodes using a liq. electrolyte as redox mediator. Here, we introduce the implementation of PSI in org. electronic devices that combine the ease of processing of org. semiconductors with the biophotovoltaic activity of PSI.
- 10Gizzie, E. A.; Niezgoda, J. S.; Robinson, M. T.; Harris, A. G.; Jennings, G. K.; Rosenthal, S. J.; Cliffel, D. E. Photosystem I-Polyaniline/TiO2 Solid-State Solar Cells: Simple Devices for Biohybrid Solar Energy Conversion. Energy Environ. Sci. 2015, 8, 3572– 3576, DOI: 10.1039/C5EE03008KGoogle Scholar10https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhslKlu7zF&md5=68fc1fd014604ab64e98f33aeea837b2Photosystem I-polyaniline/TiO2 solid-state solar cells: simple devices for biohybrid solar energy conversionGizzie, Evan A.; Scott Niezgoda, J.; Robinson, Maxwell T.; Harris, Andrew G.; Kane Jennings, G.; Rosenthal, Sandra J.; Cliffel, David E.Energy & Environmental Science (2015), 8 (12), 3572-3576CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)Novel Photosystem I (PSI) based solid-state solar cells were prepd. by directly electropolymg. polyaniline (PAni) in the presence of solubilized PSI on a TiO2 anode. These devices feature a unique bio-derived, photoactive composite layer for efficient charge sepn. and charge transfer from protein to electrode. This work introduces a new artificial photosynthesis platform for scalable and sustainable solar energy conversion.
- 11Beam, J. C.; LeBlanc, G.; Gizzie, E. A.; Ivanov, B. L.; Needell, D. R.; Shearer, M. J.; Jennings, G. K.; Lukehart, C. M.; Cliffel, D. E. Construction of a Semiconductor-Biological Interface for Solar Energy Conversion: P-Doped Silicon/Photosystem I/Zinc Oxide. Langmuir 2015, 31, 10002– 10007, DOI: 10.1021/acs.langmuir.5b02334Google Scholar11https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhsVWnt7vN&md5=778629b0d4513362da375db30f6af127Construction of a Semiconductor-Biological Interface for Solar Energy Conversion: p-Doped Silicon/Photosystem I/Zinc OxideBeam, Jeremiah C.; LeBlanc, Gabriel; Gizzie, Evan A.; Ivanov, Borislav L.; Needell, David R.; Shearer, Melinda J.; Jennings, G. Kane; Lukehart, Charles M.; Cliffel, David E.Langmuir (2015), 31 (36), 10002-10007CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)The interface between photoactive biol. materials with two distinct semiconducting electrodes is challenging both to develop and analyze. Building off of our previous work using films of photosystem I (PSI) on p-doped silicon, we have deposited a cryst. zinc oxide (ZnO) anode using confined-plume chem. deposition (CPCD). We demonstrate the ability of CPCD to deposit cryst. ZnO without damage to the PSI biomaterial. Using electrochem. techniques, we were able to probe this complex semiconductor-biol. interface. Finally, as a proof of concept, a solid-state photovoltaic device consisting of p-doped silicon, PSI, ZnO, and ITO was constructed and evaluated.
- 12Das, R.; Kiley, P. J.; Segal, M.; Norville, J.; Yu, A. A.; Wang, L.; Trammell, S. A.; Reddick, L. E.; Kumar, R.; Stellacci, F.; Lebedev, N.; Schnur, J.; Bruce, B. D.; Zhang, S.; Baldo, M. Integration of Photosynthetic Protein Molecular Complexes in Solid-State Electronic Devices. Nano Lett. 2004, 4, 1079– 1083, DOI: 10.1021/nl049579fGoogle Scholar12https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2cXktValsLc%253D&md5=19670ae6c5c5c6a2b2f59da6b38f4b17Integration of Photosynthetic Protein Molecular Complexes in Solid-State Electronic DevicesDas, Rupa; Kiley, Patrick J.; Segal, Michael; Norville, Julie; Yu, A. Amy; Wang, Leyu; Trammell, Scott A.; Reddick, L. Evan; Kumar, Rajay; Stellacci, Francesco; Lebedev, Nikolai; Schnur, Joel; Bruce, Barry D.; Zhang, Shuguang; Baldo, MarcNano Letters (2004), 4 (6), 1079-1083CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)Plants and photosynthetic bacteria contain protein-mol. complexes that harvest photons with nearly optimum quantum yield and an expected power conversion efficiency exceeding 20%. In this work, we demonstrate the integration of elec. active photosynthetic protein-mol. complexes in solid-state devices, realizing photodetectors and photovoltaic cells with internal quantum efficiencies of approx. 12%. Electronic integration of devices is achieved by self-assembling an oriented monolayer of photosynthetic complexes, stabilizing them with surfactant peptides, and then coating them with a protective org. semiconductor.
- 13Ciornii, D.; Riedel, M.; Stieger, K. R.; Feifel, S. C.; Hejazi, M.; Lokstein, H.; Zouni, A.; Lisdat, F. Bioelectronic Circuit on a 3D Electrode Architecture: Enzymatic Catalysis Interconnected With Photosystem I. J. Am. Chem. Soc. 2017, 139, 16478– 16481, DOI: 10.1021/jacs.7b10161Google Scholar13https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhslGnu77O&md5=1101e3a8e40811274e87b4ceda75dd28Bioelectronic Circuit on a 3D Electrode Architecture: Enzymatic Catalysis Interconnected with Photosystem ICiornii, Dmitri; Riedel, Marc; Stieger, Kai R.; Feifel, Sven C.; Hejazi, Mahdi; Lokstein, Heiko; Zouni, Athina; Lisdat, FredJournal of the American Chemical Society (2017), 139 (46), 16478-16481CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Artificial light-driven signal chains are particularly important for the development of systems converting light into a current, into chems. or for light-induced sensing. Here, we report on the construction of an all-protein, light-triggered, catalytic circuit based on photosystem I, cytochrome c (cyt c) and human sulfite oxidase (hSOX). The defined assembly of all components using a modular design results in an artificial biohybrid electrode architecture, combining the photophys. features of PSI with the biocatalytic properties of hSOX for advanced light-controlled bioelectronics. The working principle is based on a competitive switch between electron supply from the electrode or by enzymic substrate conversion.
- 14Passantino, J. M.; Wolfe, K. D.; Simon, K. T.; Cliffel, D. E.; Jennings, G. K. Photosystem I Enhances the Efficiency of a Natural, Gel-Based Dye-Sensitized Solar Cell. ACS Appl. Bio Mater. 2020, 3, 4465– 4473, DOI: 10.1021/acsabm.0c00446Google Scholar14https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhtVaqs7%252FF&md5=c05ce99e63af1f6cc0dc60fe61134da6Photosystem I Enhances the Efficiency of a Natural, Gel-Based Dye-Sensitized Solar CellPassantino, Joshua M.; Wolfe, Kody D.; Simon, Keiann T.; Cliffel, David E.; Jennings, G. KaneACS Applied Bio Materials (2020), 3 (7), 4465-4473CODEN: AABMCB; ISSN:2576-6422. (American Chemical Society)The photosystem I (PSI) protein complex is known to enhance bioelectrode performance for many liq.-based photoelectrochem. cells. A hydrogel as electrolyte media allows for simpler fabrication of more robust and practical solar cells in comparison to liq.-based devices. This paper reports a natural, gel-based dye-sensitized solar cell that integrates PSI to improve device efficiency. TiO2-coated FTO slides, dyed by blackberry anthocyanin, act as a photoanode, while a film of PSI deposited onto copper comprises the photocathode. Ascorbic acid (AscH) and 2,6-dichlorophenolindophenol (DCPIP) are the redox mediator couple inside an agarose hydrogel, enabling PSI to produce excess oxidized species near the cathode to improve device performance. A comparison of performance at low pH and neutral pH was performed to test the pH-dependent properties of the AscH/DCPIP couple. Devices at neutral pH performed better than those at lower pH. The PSI film enhanced photovoltage by 75 mV to a total photovoltage of 0.45 V per device and provided a mediator concn.-dependent photocurrent enhancement over non-PSI devices, reaching an instantaneous power conversion efficiency of 0.30% compared to 0.18% without PSI, a 1.67-fold increase. At steady state, power conversion efficiencies for devices with and without PSI were 0.042 and 0.028%, resp.
- 15Qiu, X.; Ocampo, O. C.; de Vries, H. W.; van Putten, M.; Loznik, M.; Herrmann, A.; Chiechi, R. C. Self-Regenerating Soft Biophotovoltaic Devices. ACS Appl. Mater. Interfaces 2018, 10, 37625– 37633, DOI: 10.1021/acsami.8b11115Google Scholar15https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhvVKlurvO&md5=a9327ea3e2adb1c8ef286d1386da8a2dSelf-Regenerating Soft Biophotovoltaic DevicesQiu, Xinkai; Castaneda Ocampo, Olga; de Vries, Hendrik W.; van Putten, Maikel; Loznik, Mark; Herrmann, Andreas; Chiechi, Ryan C.ACS Applied Materials & Interfaces (2018), 10 (43), 37625-37633CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)This paper describes the fabrication of soft, stretchable biophotovoltaic devices that generate photocurrent from photosystem I (PSI) complexes that are self-assembled onto Au electrodes with a preferred orientation. Charge is collected by the direct injection of electrons into the Au electrode and the transport of holes through a redox couple to liq. eutectic gallium-indium (EGaIn) (alloy) electrodes that are confined to microfluidic pseudochannels by arrays of posts. The pseudochannels are defined in a single fabrication step that leverages the non-Newtonian rheol. of EGaIn. This strategy is extended to the fabrication of reticulated electrodes that are inherently stretchable. A simple shadow evapn. technique is used to increase the surface area of the Au electrodes by a factor of approx. 106 compared to planar electrodes. The power conversion efficiency of the biophotovoltaic devices decreases over time, presumably as the PSI complexes denature and/or detach from the Au electrodes. However, by circulating a soln. of active PSI complexes the devices self-regenerate by mass action/self-assembly. These devices leverage simple fabrication techniques to produce complex function and prove that photovoltaic devices comprising PSI can retain the ability to regenerate, one of the most important functions of photosynthetic organisms.
- 16Wolfe, K. D.; Dervishogullari, D.; Stachurski, C. D.; Passantino, J. M.; Jennings, G. K.; Cliffel, D. E. Photosystem I Multilayers Within Porous Indium Tin Oxide Cathodes Enhance Mediated Electron Transfer. ChemElectroChem 2020, 7, 596– 603, DOI: 10.1002/celc.201901628Google Scholar16https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXitlGhsbrM&md5=56202e4e1f090f3abc5b509c6aa10892Photosystem I Multilayers within Porous Indium Tin Oxide Cathodes Enhance Mediated Electron TransferWolfe, Kody D.; Dervishogullari, Dilek; Stachurski, Christopher D.; Passantino, Joshua M.; Kane Jennings, G.; Cliffel, David E.ChemElectroChem (2020), 7 (3), 596-603CODEN: CHEMRA; ISSN:2196-0216. (Wiley-VCH Verlag GmbH & Co. KGaA)Understanding and improving charge transfer pathways between extd. Photosystem I (PSI) protein complexes and electrodes is necessary for the development of low-cost PSI-based devices for energy conversion. We incorporated PSI multilayers within porous indium tin oxide (ITO) electrodes and obsd. a greater mediated photocurrent in comparison to multilayers on planar ITO. First, the mediated electron transfer (MET) pathway in the presence of 2,6-dichlorophenolindophenol (DCPIP) and ascorbate (AscH) was studied via photochronoamperometry on planar ITO. ITO nanoparticles were then used to fabricate two porous electrode morphologies; mesoporous (20-100 nm pores) and macroporous (5μm pores). PSI multilayers within macroporous ITO cathodes produced 42±5μA cm-2 of photocurrent, three times the photocurrent produced by mesoporous ITO. Addnl., macroporous cathodes are able to utilize twice as much active surface area, when compared to mesoporous cathodes. Our findings show that MET within PSI multilayers is greater in 5μm macropores than mesoporous ITO due to both an increase in electrode surface area and the location of PSI complexes within the pores. Improving MET in PSI-based bioelectrodes has applications including improving the total charge transfer achieved in PSI-based photoelectrochem. cells or even incorporation in bio-photocatalytic cells.
- 17Ciesielski, P. N.; Hijazi, F. M.; Scott, A. M.; Faulkner, C. J.; Beard, L.; Emmett, K.; Rosenthal, S. J.; Cliffel, D.; Jennings, G. K. Photosystem I-Based biohybrid photoelectrochemical cells. Bioresour. Technol. 2010, 101, 3047– 3053, DOI: 10.1016/j.biortech.2009.12.045Google Scholar17https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXhtVantrg%253D&md5=9e8050e1f7147619d3395b9aa0072acfPhotosystem I- based biohybrid photoelectrochemical cellsCiesielski, Peter N.; Hijazi, Frederick M.; Scott, Amanda M.; Faulkner, Christopher J.; Beard, Lisa; Emmett, Kevin; Rosenthal, Sandra J.; Cliffel, David; Kane Jennings, G.Bioresource Technology (2010), 101 (9), 3047-3053CODEN: BIRTEB; ISSN:0960-8524. (Elsevier Ltd.)Photosynthesis is the process by which Nature coordinates a tandem of protein complexes of impressive complexity that function to harness staggering amts. of solar energy on a global scale. Advances in biochem. and nanotechnol. have provided tools to isolate and manipulate the individual components of this process, thus opening a door to a new class of highly functional and vastly abundant biol. resources. Here we show how one of these components, Photosystem I (PSI), is incorporated into an electrochem. system to yield a stand-alone biohybrid photoelectrochem. cell that converts light energy into elec. energy. The cells make use of a dense multilayer of PSI complexes assembled on the surface of the cathode to produce a photocatalytic effect that generates photocurrent densities of ∼2 μA/cm2 at moderate light intensities. We describe the relationship between the current and voltage prodn. of the cells and the photoinduced interactions of PSI complexes with electrochem. mediators, and show that the performance of the present device is limited by diffusional transport of the electrochem. mediators through the electrolyte. These biohybrid devices display remarkable stability, as they remain active in ambient conditions for at least 280 days. Even at bench-scale prodn., the materials required to fabricate the cells described in this manuscript cost ∼10 cents per cm2 of active electrode area.
- 18Tschörtner, J.; Lai, B.; Krömer, J. O. Biophotovoltaics: Green Power Generation From Sunlight and Water. Front. Microbiol. 2019, 10, 866 DOI: 10.3389/fmicb.2019.00866Google Scholar18https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BB3M7otlemsA%253D%253D&md5=36cf44fed74aed94e6e870f7ee5c031fBiophotovoltaics: Green Power Generation From Sunlight and WaterTschortner Jenny; Lai Bin; Kromer Jens OFrontiers in microbiology (2019), 10 (), 866 ISSN:1664-302X.Biophotovoltaics is a relatively new discipline in microbial fuel cell research. The basic idea is the conversion of light energy into electrical energy using photosynthetic microorganisms. The microbes will use their photosynthetic apparatus and the incoming light to split the water molecule. The generated protons and electrons are harvested using a bioelectrochemical system. The key challenge is the extraction of electrons from the microbial electron transport chains into a solid-state anode. On the cathode, a corresponding electrochemical counter reaction will consume the protons and electrons, e.g., through the oxygen reduction to water, or hydrogen formation. In this review, we are aiming to summarize the current state of the art and point out some limitations. We put a specific emphasis on cyanobacteria, as these microbes are considered future workhorses for photobiotechnology and are currently the most widely applied microbes in biophotovoltaics research. Current progress in biophotovoltaics is limited by very low current outputs of the devices while a lack of comparability and standardization of the experimental set-up hinders a systematic optimization of the systems. Nevertheless, the fundamental questions of redox homeostasis in photoautotrophs and the potential to directly harvest light energy from a highly efficient photosystem, rather than through oxidation of inefficiently produced biomass are highly relevant aspects of biophotovoltaics.
- 19Sokol, K. P.; Mersch, D.; Hartmann, V.; Zhang, J. Z.; Nowaczyk, M. M.; Rögner, M.; Ruff, A.; Schuhmann, W.; Plumeré, N.; Reisner, E. Rational Wiring of Photosystem II to Hierarchical Indium Tin Oxide Electrodes Using Redox Polymers. Energy Environ. Sci. 2016, 9, 3698– 3709, DOI: 10.1039/C6EE01363EGoogle Scholar19https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhtFSntr%252FF&md5=19daa1e0f16d1b093fdcba607a154fd1Rational wiring of photosystem II to hierarchical indium tin oxide electrodes using redox polymersSokol, Katarzyna P.; Mersch, Dirk; Hartmann, Volker; Zhang, Jenny Z.; Nowaczyk, Marc M.; Rogner, Matthias; Ruff, Adrian; Schuhmann, Wolfgang; Plumere, Nicolas; Reisner, ErwinEnergy & Environmental Science (2016), 9 (12), 3698-3709CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)A benchmark Photosystem II (PSII)-electrode system that combines the efficient wiring afforded by redox-active polymers with the high loading provided by hierarchically-structured inverse opal indium tin oxide (IO-ITO) electrodes was reported. Compared to flat electrodes, the hierarchical IO-ITO electrodes enabled up to an approx. 50-fold increase in the immobilization of an Os complex-modified and a phenothiazine-modified polymer. When the Os complex-modified polymer is co-adsorbed with PSII on the hierarchical electrodes, photocurrent densities of up to ∼410μA cm-2 at 0.5 V vs. SHE were obsd. in the absence of diffusional mediators, demonstrating a substantially improved wiring of PSII to the IO-ITO electrode with the redox polymer. The high photocurrent d. allowed for the quantification of O2 evolution, and a Faradaic efficiency of 85 ± 9% was measured. As such, we have demonstrated a high performing and fully integrated host-guest system with excellent electronic wiring and loading capacity. This assembly strategy may form the basis of all-integrated electrode designs for a wide range of biol. and synthetic catalysts.
- 20Takekuma, Y.; Ikeda, N.; Kawakami, K.; Kamiya, N.; Nango, M.; Nagata, M. Photocurrent Generation by a Photosystem I-NiO Photocathode for a P-Type Biophotovoltaic Tandem Cell. RSC Adv. 2020, 10, 15734– 15739, DOI: 10.1039/D0RA01793KGoogle Scholar20https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXnsFSrt74%253D&md5=7af29c8b5f726082b7b6fdc3cd18acbfPhotocurrent generation by a photosystem I-NiO photocathode for a p-type biophotovoltaic tandem cellTakekuma, Yuya; Ikeda, Nobuhiro; Kawakami, Keisuke; Kamiya, Nobuo; Nango, Mamoru; Nagata, MorioRSC Advances (2020), 10 (27), 15734-15739CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)Photosynthesis is a process used by algae and plants to convert light energy into chem. energy. Due to their uniquely natural and environmentally friendly nature, photosynthetic proteins have attracted attention for use in a variety of artificial applications. Among the various types, biophotovoltaics based on dye-sensitized solar cells have been demonstrated in many studies. Although most related works have used n-type semiconductors, a p-type semiconductor is also a significant potential component for tandem cells. In this work, we used mesoporous NiO as a p-type semiconductor substrate for Photosystem I (PSI) and demonstrated a p-type PSI-biophotovoltaic and tandem cell based on dye-sensitized solar cells. Under visible light illumination, the PSI-adsorbed NiO electrode generated a cathodic photocurrent. The p-type biophotovoltaic cell using the PSI-adsorbed NiO electrode generated electricity, and the IPCE spectrum was consistent with the absorption spectrum of PSI. These results indicate that the PSI-adsorbed NiO electrode acts as a photocathode. Moreover, a tandem cell consisting of the PSI-NiO photocathode and a PSI-TiO2 photoanode showed a high open-circuit voltage of over 0.7 V under illumination to the TiO2 side. Thus, the tandem strategy can be utilized for biophotovoltaics, and the use of other biomaterials that match the solar spectrum will lead to further progress in photovoltaic performance.
- 21Takeuchi, R.; Suzuki, A.; Sakai, K.; Kitazumi, Y.; Shirai, O.; Kano, K. Construction of Photo-Driven Bioanodes Using Thylakoid Membranes and Multi-Walled Carbon Nanotubes. Bioelectrochemistry 2018, 122, 158– 163, DOI: 10.1016/j.bioelechem.2018.04.001Google Scholar21https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXntlSht7Y%253D&md5=00463d46342ea4662f259478b016262eConstruction of photo-driven bioanodes using thylakoid membranes and multi-walled carbon nanotubesTakeuchi, Ryosuke; Suzuki, Arato; Sakai, Kento; Kitazumi, Yuki; Shirai, Osamu; Kano, KenjiBioelectrochemistry (2018), 122 (), 158-163CODEN: BIOEFK; ISSN:1567-5394. (Elsevier B.V.)A photo-driven bioanode was constructed using the thylakoid membrane from spinach, carbon nanotubes, and an artificial mediator. By considering a linear free-energy relationship in the electron transfer from the thylakoid membrane to the mediators, and the oxygen resistance of the reduced mediators, 1,2-naphthoquinone was selected as the most suitable mediator for the photo-driven bioanode. Water-dispersed multi-walled carbon nanotubes served as scaffolds to hold the thylakoid membrane on a porous electrode. The constructed photo-driven bioanode exhibited a photocurrent d. of over 100 μA cm-2 at a photon flux d. of 1500 μmol m-2 s-1.
- 22Pankratov, D.; Zhao, J.; Nur, M. A.; Shen, F.; Leech, D.; Chi, Q.; Pankratova, G.; Gorton, L. The Influence of Surface Composition of Carbon Nanotubes on the Photobioelectrochemical Activity of Thylakoid Bioanodes Mediated by Osmium-Complex Modified Redox Polymer. Electrochim. Acta 2019, 310, 20– 25, DOI: 10.1016/j.electacta.2019.04.097Google Scholar22https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXosVSltbk%253D&md5=5d9395e92ef715c2b79468266833dc80The influence of surface composition of carbon nanotubes on the photobioelectrochemical activity of thylakoid bioanodes mediated by osmium-complex modified redox polymerPankratov, Dmitry; Zhao, Jianming; Nur, Mohammed Ahmed; Shen, Fei; Leech, Donal; Chi, Qijin; Pankratova, Galina; Gorton, LoElectrochimica Acta (2019), 310 (), 20-25CODEN: ELCAAV; ISSN:0013-4686. (Elsevier Ltd.)A combination of photosynthetic biocatalysts with high surface area conductive materials mediated by an Os-complex modified redox polymer (OsRP) holds promising features for the development of sustainable green systems for solar energy conversion. The authors performed a comparative study of two types of C nanotubes (CNTs) synthesized by pyrolysis of polymeric precursors. Both CNTs were of similar morphol., but had a different surface C/O ratio. The CNTs were used as a support for immobilization of thylakoid membranes, electrochem. wired through the OsRP. The photobioanodes based on the CNTs with a higher C/O ratio exhibit a higher max. photocurrent d. of 97.1 ± 8.3μA cm-2 at a light intensity of 400 W m-2 with reduced charge transfer resistance, but had lower operational stability. The authors' results demonstrate the significance of studying of electrochem. communication between the photosynthetic component, the redox mediator and the support nanomaterial and may offer new opportunities for designing and optimization of mediated bioelectrochem. systems.
- 23Feifel, S. C.; Stieger, K. R.; Hejazi, M.; Wang, X.; Ilbert, M.; Zouni, A.; Lojou, E.; Lisdat, F. Dihemic C4-Type Cytochrome Acting as a Surrogate Electron Conduit: Artificially Interconnecting a Photosystem I Supercomplex With Electrodes. Electrochem. Commun. 2018, 91, 49– 53, DOI: 10.1016/j.elecom.2018.05.006Google Scholar23https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXpt1Grurs%253D&md5=ec66fe8f8cea36b34ca061106819f57dDihemic c4-type cytochrome acting as a surrogate electron conduit: Artificially interconnecting a photosystem I supercomplex with electrodesFeifel, Sven C.; Stieger, Kai R.; Hejazi, Mahdi; Wang, Xie; Ilbert, Marianne; Zouni, Athina; Lojou, Elisabeth; Lisdat, FredElectrochemistry Communications (2018), 91 (), 49-53CODEN: ECCMF9; ISSN:1388-2481. (Elsevier B.V.)Connection of photosystem I (PSI) with electrodes has been shown to create artificial photosynthetic systems that hold promise for the synthesis of solar fuels. The high quantum yields of PSI require efficient electron transfer from the electrode to the reaction center of PSI in order to restock the light-induced holes, a task which in nature is performed by small redox proteins. Here, we have investigated the potential "wiring" properties of a dihemic c-type cytochrome (cyt c4), in order to efficiently connect PSI with electrodes. Cyt c4 has shown direct electron transfer (DET) with both hemes in elec. communication with two different electrode materials (ITO and Au) and on the basis of cyt c4-multilayer electrodes "self-exchange" properties can also be deduced. Investigation of cyt c4 in combination with PSI within an inverse opal ITO electrode has shown the dihemic protein to be a valuable mol. electron conduit, able to interconnect the photoenzymic reaction with the 3D electrode. The properties have been compared with those of electrodes based on monohemic cyt c derived from horse heart.
- 24Stieger, K. R.; Feifel, S. C.; Lokstein, H.; Hejazi, M.; Zouni, A.; Lisdat, F. Biohybrid Architectures for Efficient Light-to-Current Conversion Based on Photosystem I Within Scalable 3D Mesoporous Electrodes. J. Mater. Chem. A 2016, 4, 17009– 17017, DOI: 10.1039/C6TA07141DGoogle Scholar24https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28Xhs1SjsrzP&md5=bbbf8b48b5bdcc25f409edd081fdbd3eBiohybrid architectures for efficient light-to-current conversion based on photosystem I within scalable 3D mesoporous electrodesStieger, K. R.; Feifel, S. C.; Lokstein, H.; Hejazi, M.; Zouni, A.; Lisdat, F.Journal of Materials Chemistry A: Materials for Energy and Sustainability (2016), 4 (43), 17009-17017CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)The combination of advanced materials and defined surface design with complex proteins from natural photosynthesis is currently one of the major topics in the development of biohybrid systems and biophotovoltaic devices. In this study transparent mesoporous indium tin oxide (μITO) electrodes have been used in combination with the trimeric supercomplex photosystem I (PSI) from Thermosynechococcus elongatus and the small redox protein cytochrome c (cyt c) from horse heart to fabricate advanced and efficient photobiocathodes. The prepn. of the μITO via spin coating allows easy scalability and ensures a defined increase in the electrochem. active surface area with accessibility for both proteins. Using these 3D electrodes up to 40 μm thickness, the immobilization of cyt c and PSI with full monolayer coverage and their elec. communication to the electrode can be achieved. Significant improvement can be made when the heterogeneous electron transfer rate const. of cyt c with the electrode is increased by an appropriate surface treatment. The photocurrent follows linearly the thickness of the μITO and current densities of up to 150 μA/cm2 can be obtained without indications of a limitation. The internal quantum efficiency is detd. to be 39% which demonstrates that the wiring of PSI via cyt c can be advantageously used in a system with high protein loading and efficient electron pathways inside 3D transparent conducting oxides.
- 25Ciornii, D.; Kölsch, A.; Zouni, A.; Lisdat, F. A Precursor-Approach in Constructing 3D ITO Electrodes for the Improved Performance of Photosystem I-Cyt C Photobioelectrodes. Nanoscale 2019, 11, 15862– 15870, DOI: 10.1039/C9NR04344FGoogle Scholar25https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhtlGrsLzP&md5=6489c1d9447e871ca7804714e93dcf9dA precursor-approach in constructing 3D ITO electrodes for the improved performance of photosystem I-cyt c photobioelectrodesCiornii, Dmitri; Koelsch, Adrian; Zouni, Athina; Lisdat, FredNanoscale (2019), 11 (34), 15862-15870CODEN: NANOHL; ISSN:2040-3372. (Royal Society of Chemistry)In recent years the use of photoelectrodes based on conductive metal oxides has become very popular in the field of photovoltaics. The application of 3D electrodes holds great promise since they can integrate large amts. of photoactive proteins. In this study photosystem I (PSI) from the thermophilic cyanobacterium Thermosynechococcus elongatus was immobilized on 3D ITO electrodes and elec. wired via the redox protein cytochrome c (cyt c). The main goal, however, was the investigation of construction parameters of such electrodes for achieving a high performance. For this, ITO electrodes were constructed from liq. precursors resulting in improved transmission compared to previous nanoparticle-based prepn. protocols. First, the doping level of Sn was varied for establishing suitable conditions for a fast cyt c electrochem. on such 3D electrodes. In a second step the pore diam. was varied in order to elucidate optimal conditions. Third, the scalability of the template-based prepn. was studied from 3 to 15 layers during spin coating and the subsequent baking step. In the thickness range from 3 to 17 μm no limitation in the protein immobilization and also in the photocurrent generation was found. Consequently, a photocurrent of about 270 μA cm-2 and a turnover no. (Te) of 30 e- s-1 at PSI were achieved. Because of the high current flow the withdrawal of electrons at the stromal side of PSI becomes clearly rate limiting. Here improved transport conditions and alternative electron acceptors were studied to overcome this limitation.
- 26Stieger, K. R.; Feifel, S. C.; Lokstein, H.; Lisdat, F. Advanced Unidirectional Photocurrent Generation via Cytochrome C as Reaction Partner for Directed Assembly of Photosystem I. Phys. Chem. Chem. Phys. 2014, 16, 15667– 15674, DOI: 10.1039/C4CP00935EGoogle Scholar26https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhtVCis7vI&md5=a98d058ac69140163341466e72f692b7Advanced unidirectional photocurrent generation via cytochrome c as reaction partner for directed assembly of photosystem IStieger, Kai R.; Feifel, Sven C.; Lokstein, Heiko; Lisdat, FredPhysical Chemistry Chemical Physics (2014), 16 (29), 15667-15674CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)Conversion of light into an elec. current based on biohybrid systems mimicking natural photosynthesis is becoming increasingly popular. Photosystem I (PSI) is particularly useful in such photo-bioelectrochem. devices. Herein, we report on a novel biomimetic approach for an effective assembly of photosystem I with the electron transfer carrier cytochrome c (cyt c), deposited on a thiol-modified gold-surface. Atomic force microscopy and surface plasmon resonance measurements have been used for characterization of the assembly process. Photoelectrochem. expts. demonstrate a cyt c mediated generation of an enhanced unidirectional cathodic photocurrent. Here, cyt c can act as a template for the assembly of an oriented and dense layer of PSI and as wiring agent to direct the electrons from the electrode towards the photosynthetic reaction center of PSI. Furthermore, three-dimensional protein architectures have been formed via the layer-by-layer deposition technique resulting in a successive increase in photocurrent densities. An intermittent cyt c layer is essential for an efficient connection of PSI layers with the electrode and for an improvement of photocurrent densities.
- 27Szalkowski, M.; Olmos, J. D. J.; Buczyńska, D.; Maćkowski, S.; Kowalska, D.; Kargul, J. Plasmon-Induced Absorption of Blind Chlorophylls in Photosynthetic Proteins Assembled on Silver Nanowires. Nanoscale 2017, 9, 10475– 10486, DOI: 10.1039/C7NR03866FGoogle Scholar27https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhtV2qt7%252FI&md5=233ee6126bc853fabc2720248293bc08Plasmon-induced absorption of blind chlorophylls in photosynthetic proteins assembled on silver nanowiresSzalkowski, Marcin; Janna Olmos, Julian David; Buczynska, Dorota; Mackowski, Sebastian; Kowalska, Dorota; Kargul, JoannaNanoscale (2017), 9 (29), 10475-10486CODEN: NANOHL; ISSN:2040-3372. (Royal Society of Chemistry)We demonstrate that controlled assembly of eukaryotic photosystem I with its assocd. light harvesting antenna complex (PSI-LHCI) on plasmonically active silver nanowires (AgNWs) substantially improves the optical functionality of such a novel biohybrid nanostructure. By comparing fluorescence intensities measured for PSI-LHCI complex randomly oriented on AgNWs and the results obtained for the PSI-LHCI/cytochrome c553 (cyt c553) bioconjugate with AgNWs we conclude that the specific binding of photosynthetic complexes with defined uniform orientation yields selective excitation of a pool of chlorophyll (Chl) mols. that are otherwise almost non-absorbing. This is remarkable, as this study shows for the first time that plasmonic excitations in metallic nanostructures can not only be used to enhance native absorption of photosynthetic pigments, but also - by employing cyt c553 as the conjugation cofactor - to activate the specific Chl pools as the absorbing sites only when the uniform and well-defined orientation of PSI-LHCI with respect to plasmonic nanostructures is achieved. As absorption of PSI alone is comparatively low, our approach lends itself as an innovative approach to outperform the reported-to-date biohybrid devices with respect to solar energy conversion.
- 28Gordiichuk, P.; Pesce, D.; Ocampo, O. E. C.; Marcozzi, A.; Wetzelaer, G.-J. A. H.; Paul, A.; Loznik, M.; Gloukhikh, E.; Richter, S.; Chiechi, R. C.; Herrmann, A. Orientation and Incorporation of Photosystem I in Bioelectronics Devices Enabled by Phage Display. Adv. Sci. 2017, 4, 1600393 DOI: 10.1002/advs.201600393Google Scholar28https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BC1cnhsFehtg%253D%253D&md5=ac726426219ea715a84d650868b10fc9Orientation and Incorporation of Photosystem I in Bioelectronics Devices Enabled by Phage DisplayGordiichuk Pavlo; Pesce Diego; Marcozzi Alessio; Wetzelaer Gert-Jan A H; Paul Avishek; Loznik Mark; Herrmann Andreas; Ocampo Olga E Castaneda; Chiechi Ryan C; Gloukhikh Ekaterina; Richter ShacharAdvanced science (Weinheim, Baden-Wurttemberg, Germany) (2017), 4 (5), 1600393 ISSN:2198-3844.Interfacing proteins with electrode surfaces is important for the field of bioelectronics. Here, a general concept based on phage display is presented to evolve small peptide binders for immobilizing and orienting large protein complexes on semiconducting substrates. Employing this method, photosystem I is incorporated into solid-state biophotovoltaic cells.
- 29Castañeda Ocampo, O. E.; Gordiichuk, P.; Catarci, S.; Gautier, D. A.; Herrmann, A.; Chiechi, R. C. Mechanism of Orientation-Dependent Asymmetric Charge Transport in Tunneling Junctions Comprising Photosystem I. J. Am. Chem. Soc. 2015, 137, 8419– 8427, DOI: 10.1021/jacs.5b01241Google Scholar29https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhtVansLzP&md5=703c9c1be3e0c71bca1efc07de0bf0ccMechanism of Orientation-Dependent Asymmetric Charge Transport in Tunneling Junctions Comprising Photosystem ICastaneda Ocampo, Olga E.; Gordiichuk, Pavlo; Catarci, Stefano; Gautier, Daniel A.; Herrmann, Andreas; Chiechi, Ryan C.Journal of the American Chemical Society (2015), 137 (26), 8419-8427CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Recently, photoactive proteins have gained a lot of attention due to their incorporation into bioinspired (photo)electrochem. and solar cells. This paper describes the measurement of the asymmetry of current transport of self-assembled monolayers (SAMs) of the entire photosystem I (PSI) protein complex (not the isolated reaction center, RCI), on two different "director SAMs" supported by ultraflat Au substrates. The director SAMs induce the preferential orientation of PSI, which manifest as asymmetry in tunneling charge-transport. We measured the oriented SAMs of PSI using eutectic Ga-In (EGaIn), a large-area technique, and conducting probe at. force microscopy (CP-AFM), a single-complex technique, and detd. that the transport properties are comparable. By varying the temps. at which the measurements were performed, we found that there is no measurable dependence of the current on temp. from ±0.1 to ±1.0 V bias, and thus, we suggest tunneling as the mechanism for transport; there are no thermally activated (e.g., hopping) processes. Therefore, it is likely that relaxation in the electron transport chain is not responsible for the asymmetry in the conductance of SAMs of PSI complexes in these junctions, which we ascribe instead to the presence of a large, net dipole moment present in PSI.
- 30Gunther, D.; LeBlanc, G.; Prasai, D.; Zhang, J. R.; Cliffel, D. E.; Bolotin, K. I.; Jennings, G. K. Photosystem I on Graphene as a Highly Transparent, Photoactive Electrode. Langmuir 2013, 29, 4177– 4180, DOI: 10.1021/la305020cGoogle Scholar30https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXktF2mtbc%253D&md5=9de728bb1d5bcf5f93da74f7baf05911Photosystem I on Graphene as a Highly Transparent, Photoactive ElectrodeGunther, Darlene; LeBlanc, Gabriel; Prasai, Dhiraj; Zhang, Jamie R.; Cliffel, David E.; Bolotin, Kirill I.; Jennings, G. KaneLangmuir (2013), 29 (13), 4177-4180CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)We report the fabrication of a hybrid light-harvesting electrode consisting of photosystem I (PSI) proteins extd. from spinach and adsorbed as a monolayer onto elec. contacted, large-area graphene. The transparency of graphene supports the choice of an opaque mediator at elevated concns. For example, we report a photocurrent of 550 nA/cm2 from a monolayer of PSI on graphene in the presence of 20 mM methylene blue, which yields an opaque blue soln. The PSI-modified graphene electrode has a total thickness of less than 10 nm and demonstrates photoactivity that is an order of magnitude larger than that for unmodified graphene, establishing the feasibility of conjoining these nanomaterials as potential constructs in next-generation photovoltaic devices.
- 31Manocchi, A. K.; Baker, D. R.; Pendley, S. S.; Nguyen, K.; Hurley, M. M.; Bruce, B. D.; Sumner, J. J.; Lundgren, C. A. Photocurrent Generation From Surface Assembled Photosystem I on Alkanethiol Modified Electrodes. Langmuir 2013, 29, 2412– 2419, DOI: 10.1021/la304477uGoogle Scholar31https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhvVynur0%253D&md5=669eafadcfda7f831a4c8e0a462f73dcPhotocurrent generation from surface assembled photosystem I on alkanethiol modified electrodesManocchi, Amy K.; Baker, David R.; Pendley, Scott S.; Nguyen, Khoa; Hurley, Margaret M.; Bruce, Barry D.; Sumner, James J.; Lundgren, Cynthia A.Langmuir (2013), 29 (7), 2412-2419CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)Photosystem I (PSI) is a key component of oxygenic photosynthetic electron transport because of its light-induced electron transfer to the sol. electron acceptor ferredoxin. This work demonstrates the incorporation of surface assembled cyanobacterial trimeric PSI complexes into a biohybrid system for light-driven current generation. Specifically, this work demonstrates the improved assembly of PSI via electrophoretic deposition, with controllable surface assembled PSI d., on different self-assembled alkanethiol monolayers. Using artificial electron donors and acceptors (Os(bpy)2Cl2 and Me viologen) we demonstrate photocurrent generation from a single PSI layer, which remains photoactive for at least three hours of intermittent illumination. Photoelectrochem. comparison of the biohybrid systems assembled from different alkanethiols (hexanethiol, aminohexanethiol, mercaptohexanol, and mercaptohexanoic acid) reveals that the PSI generated photocurrent is enhanced by almost 5 times on neg. charged SAM surfaces as compared to pos. charged surfaces. These results are discussed in light of how PSI is oriented upon electrodeposition on a SAM.
- 32Badura, A.; Kothe, T.; Schuhmann, W.; Rögner, M. Wiring Photosynthetic Enzymes to Electrodes. Energy Environ. Sci. 2011, 4, 3263, DOI: 10.1039/c1ee01285aGoogle Scholar32https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXht1Cqs7jF&md5=878fdd7d7c689e1110c78db776258354Wiring photosynthetic enzymes to electrodesBadura, Adrian; Kothe, Tim; Schuhmann, Wolfgang; Roegner, MatthiasEnergy & Environmental Science (2011), 4 (9), 3263-3274CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)A review. The efficient electron transfer between redox enzymes and electrode surfaces can be obtained by wiring redox enzymes using, for instance, polymer-bound redox relays as has been demonstrated as a basis for the design of amperometric biosensors, logic gates or sensor arrays and more general as a central aspect of "bioelectrochem.". Related devices allow exploiting the unique catalytic properties of enzymes, among which photosynthetic enzymes are esp. attractive due to the possibility to trigger the redox reactions upon irradn. with light. Photocatalytic properties such as the light-driven water splitting by photosystem 2 make them unique candidates for the development of semiartificial devices which convert light energy into stable chem. product, like hydrogen. This review summarizes recent concepts for the integration of photosystem 1 and photosystem 2 into bioelectrochem. devices with special focus on strategies for the design of electron transfer pathways between redox enzymes and conductive supports.
- 33Pachoumi, O.; Bakulin, A. A.; Sadhanala, A.; Sirringhaus, H.; Friend, R. H.; Vaynzof, Y. Improved Performance of ZnO/Polymer Hybrid Photovoltaic Devices by Combining Metal Oxide Doping and Interfacial Modification. J. Phys. Chem. C 2014, 118, 18945– 18950, DOI: 10.1021/jp506266fGoogle Scholar33https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXht1Sqsb%252FJ&md5=73d602ba597e489f75c6ae4f2749224fImproved Performance of ZnO/Polymer Hybrid Photovoltaic Devices by Combining Metal Oxide Doping and Interfacial ModificationPachoumi, Olympia; Bakulin, Artem A.; Sadhanala, Aditya; Sirringhaus, Henning; Friend, Richard H.; Vaynzof, YanaJournal of Physical Chemistry C (2014), 118 (33), 18945-18950CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)Photoinduced charge sepn. at hybrid org.-inorg. interfaces is poorly understood and challenging to control. Charge sepn. is investigated at a model system of ZnO/poly(3-hexylthiophene) (P3HT) and employ Sr doping of ZnO and phenyl-C61-butyric acid (PCBA) self-assembled modification to study and enhance the charge sepn. efficiency. Ti was found that doping alone lowers the efficiency of charge sepn. due to the introduction of defect states at the oxide surface. However, with the combination of doping and mol. modification, charge sepn. efficiency is significantly enhanced due to the passivation of interfacial traps and improved modifier coverage. This demonstrates a complex noncumulative effect of doping and surface modification and shows that with the correct choice of metal oxide dopant and org. modifier, a poorly performing hybrid interface can be turned into an efficient one.
- 34Lee, E. J.; Heo, S. W.; Han, Y. W.; Moon, D. K. An Organic-inorganic Hybrid Interlayer for Improved Electron Extraction in Inverted Polymer Solar Cells. J. Mater. Chem. C 2016, 4, 2463– 2469, DOI: 10.1039/C5TC03754AGoogle Scholar34https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XlsVSksg%253D%253D&md5=f836d3e8a73f5dbe14d2004188ff2d68An organic-inorganic hybrid interlayer for improved electron extraction in inverted polymer solar cellsLee, Eui Jin; Heo, Soo Won; Han, Yong Woon; Moon, Doo KyungJournal of Materials Chemistry C: Materials for Optical and Electronic Devices (2016), 4 (13), 2463-2469CODEN: JMCCCX; ISSN:2050-7534. (Royal Society of Chemistry)We fabricated inverted polymer solar cells (PSCs) using an org.-inorg. hybrid interlayer for electron extn. The surface energy and surface defects of an org.-inorg. ZnO-PFN hybrid film, which was prepd. by dissolving the conjugated polymer electrolyte poly[(9,9-bis(3'-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctyl-fluorene)] (PFN) in a ZnO soln., were reduced, compared to ZnO film. By introducing the ZnO-PFN electron extn. layer, the interfacial contact between the active and electron extn. layers was improved and the series resistance of the PSC device was decreased. As a result, electron extn. from the active layer to the electrode was enhanced. The highest power conversion efficiency (PCE) of the inverted PSCs was 9.2%. Also, the ZnO-PFN-based inverted PSCs showed improved long-term stability compared to ZnO-based devices. The ZnO-PFN interlayer aimed to overcome the drawbacks of the conventional hydrophilic surface of ZnO, based on the properties of the conjugated polymer (PFN) without the need for addnl. processes. It was therefore simple to fabricate the inverted PSCs, making the devices com. viable.
- 35Thu, C. Role of the Metal-Oxide Work Function on Photocurrent Generation in Hybrid Solar Cells. Sci. Rep. 2018, 8, 3559 DOI: 10.1038/s41598-018-21721-2Google Scholar35https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BC1MrkvVOhtw%253D%253D&md5=1842ee7f3709658f9c60eb85da1a8d18Role of the Metal-Oxide Work Function on Photocurrent Generation in Hybrid Solar CellsThu Chawloon; Ehrenreich Philipp; Wong Ka Kan; Zimmermann Eugen; Wang Wei; Fakharuddin Azhar; Putnik Martin; Kalb Julian; Pfadler Thomas; Schmidt-Mende Lukas; Dorman James; Drivas Charalampos; Kennou Stella; Koutsoubelitis Aimilios; Palilis Leonidas C; Vasilopoulou MariaScientific reports (2018), 8 (1), 3559 ISSN:.ZnO is a widely used metal-oxide semiconductor for photovoltaic application. In solar cell heterostructures they not only serve as a charge selective contact, but also act as electron acceptor. Although ZnO offers a suitable interface for exciton dissociation, charge separation efficiencies have stayed rather poor and conceptual differences to organic acceptors are rarely investigated. In this work, we employ Sn doping to ZnO nanowires in order to understand the role of defect and surface states in the charge separation process. Upon doping we are able to modify the metal-oxide work function and we show its direct correlation with the charge separation efficiency. For this purpose, we use the polymer poly(3-hexylthiophene) as donor and the squaraine dye SQ2 as interlayer. Interestingly, neither mobilities nor defects are prime performance limiting factor, but rather the density of available states around the conduction band is of crucial importance for hybrid interfaces. This work highlights crucial aspects to improve the charge generation process of metal-oxide based solar cells and reveals new strategies to improve the power conversion efficiency of hybrid solar cells.
- 36Aryal, U. K.; Arivunithi, V. M.; Reddy, S. S.; Kim, J.; Gal, Y.-S.; Jin, S.-H. Efficient Dual Cathode Interfacial Layer for High Performance Organic and Perovskite Solar Cells. Org. Electron. 2018, 63, 222– 230, DOI: 10.1016/j.orgel.2018.09.034Google Scholar36https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhvVegsrbF&md5=b5e5cbf20306ceab76f0bac5a3aae69fEfficient dual cathode interfacial layer for high performance organic and perovskite solar cellsAryal, Um Kanta; Arivunithi, Veera Murugan; Reddy, Saripally Sudhaker; Kim, Junyoung; Gal, Yeong-Soon; Jin, Sung-HoOrganic Electronics (2018), 63 (), 222-230CODEN: OERLAU; ISSN:1566-1199. (Elsevier B.V.)Cathode interfacial layer (CIL), phenylquinoline-based, 10-ethyl-3,7-bis(4-phenylquinolin-2-yl)-10H-phenothiazine (PTDPQ) was employed between the ZnO and photoactive layer, poly[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl] thieno[3,4-b]-thiophenediyl] (PTB7):[6,6]-Ph C71-butyric acid Me ester (PC71BM) for the inverted org. solar cells (IOSCs) and between LiF and PTB7:PC71BM for conventional org. solar cells (COSCs). It was also incorporated as interfacial layer in perovskite solar cells (PSCs). For the ZnO/PTDPQ bilayer, the power conversion efficiency (PCE) enhanced to 8.69%, which is about 15% improvement than that of the control IOSCs ref. device. For the PTDPQ/LiF bilayer, it was achieved to 8.06%, and after insertion of PTDPQ as interfacial layer for PSCs, av. PCE enhanced to 16.45% from that of 15.28% ref. device. Hereinafter, PTDPQ as CIL enhances the solar cells device performance. It is analyzed that the charge recombination is suppressed and facilitates charge extn. due to the incorporation of the dual CIL as accordance with obsd. improvement of the solar cell parameters. The devices with dual CIL showed the higher electron mobility which matches with the higher fill factor and improved c.d. The dual CIL exhibited excellent impact on enhancing the photovoltaic properties of OSCs and PSCs along with long-term stability.
- 37Alshanableh, A.; Tan, S. T.; Yap, C. C.; Lee, H. B.; Oleiwi, H. F.; Hong, K. J.; Jumali, M. H. H.; Yahaya, M. Surface Engineering of ZnO Nanorod for Inverted Organic Solar Cell. Mater. Sci. Eng., B 2018, 238–239, 136– 141, DOI: 10.1016/j.mseb.2018.12.024Google Scholar37https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXotFer&md5=4e9c163ac271747f0eabdd4ec5350f7aSurface engineering of ZnO nanorod for inverted organic solar cellAlshanableh, Abdelelah; Tan, Sin Tee; Yap, Chi Chin; Lee, Hock Beng; Oleiwi, Hind Fadhil; Hong, Kai Jeat; Jumali, Mohd. Hafizuddin Hj.; Yahaya, MuhammadMaterials Science & Engineering, B: Advanced Functional Solid-State Materials (2018), 238-239 (), 136-141CODEN: MSBTEK; ISSN:0921-5107. (Elsevier B.V.)Crystallinity and band offset alignment of inorg. electron acceptor play a vital role in enhancing the device performance of inverted org. solar cell (IOSC). In this report, homogenous and vertically-aligned chem. treated ZnO nanorods (ZNR) were successfully grown on fluorine-doped tin oxide (FTO) substrate via a fully-soln. method. It was found that the morphol. of ZnO was fine-tuned from truncated surface to tubular structure under both of the anionic (KOH) and protonic (HCl) treatment. An extraordinary defect quenching phenomenon and hyperchromic energy band edge shift were obsd. in 0.1 M KOH-treated ZNR proven by the highest (002) peak detection and the lowest defect d. Compared with the pristine sample, the 0.1 M KOH-treated ZNR device showed a remarkable improvement in power conversion efficiency (PCE) up to 0.32%, signifying the effectiveness of anodic treatment. The robust correlation between the dependency of chem. treated ZNR and the device performance was established. This work elucidates a feasible method towards efficient IOSC devices development.
- 38Hummelen, J. C.; Knight, B. W.; LePeq, F.; Wudl, F.; Yao, J.; Wilkins, C. L. Preparation and Characterization of Fulleroid and Methanofullerene Derivatives. J. Org. Chem. 1995, 60, 532– 538, DOI: 10.1021/jo00108a012Google Scholar38https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2MXjtlOhtrY%253D&md5=d273aa4dee90ae3622b0d24d838d41d3Preparation and Characterization of Fulleroid and Methanofullerene DerivativesHummelen, Jan C.; Knight, Brian W.; LePeq, F.; Wudl, Fred; Yao, Jie; Wilkins, Charles L.Journal of Organic Chemistry (1995), 60 (3), 532-8CODEN: JOCEAH; ISSN:0022-3263. (American Chemical Society)We describe the synthesis and complete characterization of sol. derivs. of C60 for applications to physics and biol. The goal of the strategy was to have a "modular" approach in order to be able to easily vary a functional group attached indirectly to the cluster. The functionality could be hydrophilic (e.g., histamide) or hydrophobic (e.g., cholestanoxy). The former was prepd. for biol. studies and the latter for photophys. studies toward improvement of photoinduced electron transfer efficiencies in the fabrication of photodetectors and photodiodes. An important intermediate, a carboxylic acid, was found to be recalcitrant to characterization by the usual mass spectroscopic and elemental anal. techniques. This problem was solved by the use of MALDI-MS. The carboxylic acid was easily converted to the key intermediate acid chloride, which in turn was convertible to a large variety of derivs. Both isomeric forms ([5,6], fulleroid and [6,6], methanofullerene) of the C61 clusters were prepd. The fulleroid formation could have given rise to a 50:50 mixt. of phenyl-over-former pentagon phenyl-over-former hexagon isomers but, remarkably, afforded a 95:5 mixt. of these isomers, resp. The fulleroid and methanofullerene gave different cyclic voltammograms, with the former being reduced at 34 mV more pos. potential than the latter.
- 39Ortiz, M. L.; Zamora, R. A.; Giannotti, M. I.; Hu, C.; Croce, R.; Gorostiza, P. Distance and Potential Dependence of Charge Transport Through the P700 Reaction Center of Photosystem I. ChemRxiv 2021, DOI: 10.26434/chemrxiv.14556048Google ScholarThere is no corresponding record for this reference.
- 40Qiu, X.; Ivasyshyn, V.; Qiu, L.; Enache, M.; Dong, J.; Rousseva, S.; Portale, G.; Stöhr, M.; Hummelen, J. C.; Chiechi, R. C. Thiol-Free Self-Assembled Oligoethylene Glycols Enable Robust Air-Stable Molecular Electronics. Nat. Mater. 2020, 19, 330– 337, DOI: 10.1038/s41563-019-0587-xGoogle Scholar40https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXivFKhu7s%253D&md5=7be85fccbe6c04386651e776832efa08Thiol-free self-assembled oligoethylene glycols enable robust air-stable molecular electronicsQiu, Xinkai; Ivasyshyn, Viktor; Qiu, Li; Enache, Mihaela; Dong, Jingjin; Rousseva, Sylvia; Portale, Giuseppe; Stohr, Meike; Hummelen, Jan C.; Chiechi, Ryan C.Nature Materials (2020), 19 (3), 330-337CODEN: NMAACR; ISSN:1476-1122. (Nature Research)Self-assembled monolayers (SAMs) are widely used to engineer the surface properties of metals. The relatively simple and versatile chem. of metal-thiolate bonds makes thiolate SAMs the preferred option in a range of applications, yet fragility and a tendency to oxidize in air limit their long-term use. Here, we report the formation of thiol-free self-assembled mono- and bilayers of glycol ethers, which bind to the surface of coinage metals through the spontaneous chemisorption of glycol ether-functionalized fullerenes. As-prepd. assemblies are bilayers presenting fullerene cages at both the substrate and ambient interface. Subsequent exposure to functionalized glycol ethers displaces the topmost layer of glycol ether-functionalized fullerenes, and the resulting assemblies expose functional groups to the ambient interface. These layers exhibit the key properties of thiolate SAMs, yet they are stable to ambient conditions for several weeks, as shown by the performance of tunnelling junctions formed from SAMs of alkyl-functionalized glycol ethers. Glycol ether-functionalized spiropyrans incorporated into mixed monolayers lead to reversible, light-driven conductance switching. Self-assemblies of glycol ethers are drop-in replacements for thiolate SAMs that retain all of their useful properties while avoiding the drawbacks of metal-thiolate bonds.
- 41Vaynzof, Y.; Kabra, D.; Zhao, L.; Ho, P. K. H.; Wee, A. T.-S.; Friend, R. H. Improved Photoinduced Charge Carriers Separation in Organic-Inorganic Hybrid Photovoltaic Devices. Appl. Phys. Lett. 2010, 97, 033309 DOI: 10.1063/1.3464973Google Scholar41https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXptFKjs7Y%253D&md5=04a2df49c4241d355701c823b3b01e71Improved photoinduced charge carriers separation in organic-inorganic hybrid photovoltaic devicesVaynzof, Yana; Kabra, Dinesh; Zhao, Lihong; Ho, Peter K. H.; Wee, Andrew T.-S.; Friend, Richard H.Applied Physics Letters (2010), 97 (3), 033309/1-033309/3CODEN: APPLAB; ISSN:0003-6951. (American Institute of Physics)We demonstrate enhanced performance of a hybrid photovoltaic device, where poly3-hexylthiophene (P3HT) is used as active material and a soln.-processed thin flat film of ZnO-modified by a self-assembled monolayer (SAM) of phenyl-C61-butyric acid (PCBA) is used as electron extg. electrode. UV photoemission spectroscopy measurements reveal an increase in the substrate work function from 3.6 to 4.1 eV upon PCBA SAM deposition due to an interfacial dipole pointing away from the ZnO. External quantum efficiency (EQE) of the SAM modified devices reached 9%, greatly improved over the 3% EQE of the unmodified devices. This corresponds to full charge sepn. of all photoexcitations generated in the P3HT within an exciton diffusion range from the interface. (c) 2010 American Institute of Physics.
- 42Vaynzof, Y.; Bakulin, A. A.; Gélinas, S.; Friend, R. H. Direct Observation of Photoinduced Bound Charge-Pair States at an Organic-Inorganic Semiconductor Interface. Phys. Rev. Lett. 2012, 108, 246605 DOI: 10.1103/PhysRevLett.108.246605Google Scholar42https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XhtVamt77M&md5=6dab33a72a665864e44bcb86ff7fc59dDirect observation of photoinduced bound charge-pair states at an organic-inorganic semiconductor interfaceVaynzof, Yana; Bakulin, Artem A.; Gelinas, Simon; Friend, Richard H.Physical Review Letters (2012), 108 (24), 246605/1-246605/5CODEN: PRLTAO; ISSN:0031-9007. (American Physical Society)It is generally considered that photoinduced charge transfer at the org.-inorg. interfaces in hybrid photovoltaic devices immediately results in a pair of free charge carriers. We extend a novel interface-selective ultrafast "optical pump-push photocurrent probe" technique to study hybrid photovoltaic systems and observe bound electron-hole pair states at the org.-inorg. interface formed between electron-accepting zinc oxide and electron-donating conjugated polymers. We est. that ∼50% of photogenerated charges stay bound and later recombine, thus hindering the photovoltaic performance of polymer/ZnO cells. We further demonstrate that interface modification with a fullerene deriv. decreases the fraction of bound charges to ∼25%, which substantially improves the device efficiency.
- 43Lee, I.; Lee, J. W.; Greenbaum, E. Biomolecular Electronics: Vectorial Arrays of Photosynthetic Reaction Centers. Phys. Rev. Lett. 1997, 79, 3294– 3297, DOI: 10.1103/PhysRevLett.79.3294Google Scholar43https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2sXmvV2rt70%253D&md5=4d9c2307afc49d3cdb36872c7fd0287eBiomolecular Electronics: Vectorial Arrays of Photosynthetic Reaction CentersLee, Ida; Lee, James W.; Greenbaum, EliasPhysical Review Letters (1997), 79 (17), 3294-3297CODEN: PRLTAO; ISSN:0031-9007. (American Physical Society)Two-dimensional vectorial arrays of functional Photosystem I reaction centers have been prepd. on atomically flat derivatized gold surfaces. The nature and extent of orientation were controlled by chem. modification of the surface deriv. For mercaptoacetic acid, 83 of the electron transport vectors were parallel to the surface, whereas with 2-mercaptoethanol 70 were oriented perpendicularly in the "up" position and only 2 were in the "down" position. No preferential orientation was obsd. with 2-dimethylaminoethanethiol.
- 44Faulkner, C. J.; Lees, S.; Ciesielski, P. N.; Cliffel, D. E.; Jennings, G. K. Rapid Assembly of Photosystem I Monolayers on Gold Electrodes. Langmuir 2008, 24, 8409– 8412, DOI: 10.1021/la800670bGoogle Scholar44https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXos1ahtr8%253D&md5=8a4e1f81b64db8fc401089debdf8c6cfRapid Assembly of Photosystem I Monolayers on Gold ElectrodesFaulkner, Christopher J.; Lees, Susan; Ciesielski, Peter N.; Cliffel, David E.; Jennings, G. KaneLangmuir (2008), 24 (16), 8409-8412CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)Photosystem I (PSI) has drawn widespread interest for use in biomimetically inspired energy conversion devices upon extg. it from plants or cyanobacteria and assembling it at surfaces. Here, we demonstrate that a critically dense monolayer of spinach-derived PSI must be formed on an electrode surface to achieve optimal photocurrents, and we introduce a new method for prepg. these dense PSI monolayers that reduces the time required for assembly by ∼80-fold in comparison to that for adsorption from soln. This method consists of applying a vacuum above the aq. PSI soln. during assembly to conc. PSI and ppt. it into a thick layer onto the surface of various self-assembled monolayers or directly onto the electrode surface. Rinsing with water yields a dense monolayer of PSI that draws ∼100 nA/cm of light-induced current from the gold electrode in the presence of appropriate mediators.
- 45Rippka, R.; Stanier, R. Y.; Deruelles, J.; Herdman, M.; Waterbury, J. B. Generic Assignments, Strain Histories and Properties of Pure Cultures of Cyanobacteria. Microbiology 1979, 111, 1– 61, DOI: 10.1099/00221287-111-1-1Google ScholarThere is no corresponding record for this reference.
- 46Mukherjee, D.; May, M.; Vaughn, M.; Bruce, B. D.; Khomami, B. Controlling the Morphology of Photosystem I Assembly on Thiol-Activated Au Substrates. Langmuir 2010, 26, 16048– 16054, DOI: 10.1021/la102832xGoogle Scholar46https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXhtFKlu7bN&md5=a3ae7031c54effac2215ebe5d7c20de3Controlling the Morphology of Photosystem I Assembly on Thiol-Activated Au SubstratesMukherjee, Dibyendu; May, Mark; Vaughn, Michael; Bruce, Barry D.; Khomami, BaminLangmuir (2010), 26 (20), 16048-16054CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)Morphol. variations of Photosystem I (PS I) assembly on hydroxyl-terminated alkanethiolate self-assembled monolayer (SAM)/Au substrates with various deposition techniques is presented. Our studies indicate that deposition conditions such as PS I concn. and driving force play a central role in detg. organization of immobilized PS I on thiol-activated Au surfaces. Specifically, at. force microscopy (AFM) and ellipsometry analyses indicate that gravity-driven deposition from concd. PS I solns. results in a large no. of columnar PS I aggregates, which assemble perpendicular to the Au surface. PS I deposition yields much more uniform layers when deposited at lower concns., suggesting preassembly of the aggregate formation in the soln. phase. Moreover, in elec.-field assisted deposition at high field strengths, columnar self-assembly is largely prevented, thereby allowing a uniform, monolayer-like deposition even at very high PS I concns. In situ dynamic light scattering (DLS) studies of soln.-phase aggregation dynamics of PS I suspensions in both the presence and absence of an applied elec. field support these observations and clearly demonstrate that the externally imposed elec. field effectively fragments large PS I aggregates in the soln. phase, thereby permitting a uniform deposition of PS I trimers on SAM/Au substrates.
- 47So, J.; Dickey, M. Inherently Aligned Microfluidic Electrodes Composed of Liquid Metal. Lab Chip 2011, 11, 905– 911, DOI: 10.1039/c0lc00501kGoogle Scholar47https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXitVWguro%253D&md5=015e5539a6ce123df27e51ac3a4d9963Inherently aligned microfluidic electrodes composed of liquid metalSo, Ju-Hee; Dickey, Michael D.Lab on a Chip (2011), 11 (5), 905-911CODEN: LCAHAM; ISSN:1473-0197. (Royal Society of Chemistry)This paper describes the fabrication and characterization of microelectrodes that are inherently aligned with microfluidic channels and in direct contact with the fluid in the channels. Injecting low m.p. alloys, such as eutectic gallium indium (EGaIn), into microchannels at room temp. (or just above room temp.) offers a simple way to fabricate microelectrodes. The channels that define the shape and position of the microelectrodes are fabricated simultaneously with other microfluidic channels (i.e., those used to manipulate fluids) in a single step; consequently, all of the components are inherently aligned. In contrast, conventional techniques require multiple fabrication steps and registration (i.e., alignment of the electrodes with the microfluidic channels), which are tech. challenging. The distinguishing characteristic of this work is that the electrodes are in direct contact with the fluid in the microfluidic channel, which is useful for a no. of applications such as electrophoresis. Periodic posts between the microelectrodes and the microfluidic channel prevent the liq. metal from entering the microfluidic channel during injection. A thin oxide skin that forms rapidly and spontaneously on the surface of the metal stabilizes mech. the otherwise low viscosity, high surface tension fluid within the channel. Moreover, the injected electrodes vertically span the sidewalls of the channel, which allows for the application of uniform elec. field lines throughout the height of the channel and perpendicular to the direction of flow. The electrodes are mech. stable over operating conditions commonly used in microfluidic applications; the mech. stability depends on the magnitude of the applied bias, the nature of the bias (d.c. vs. a.c.), and the cond. of the solns. in the microfluidic channel. Electrodes formed using alloys with m.ps. above room temp. ensure mech. stability over all of the conditions explored. As a demonstration of their utility, the fluidic electrodes are used for electrohydrodynamic mixing, which requires extremely high elec. fields (∼105 V m-1).
- 48Dickey, M.; Weiss, E.; Smythe, E.; Chiechi, R.; Capasso, F.; Whitesides, G. Fabrication of Arrays of Metal and Metal Oxide Nanotubes by Shadow Evaporation. ACS Nano 2008, 2, 800– 808, DOI: 10.1021/nn800036rGoogle Scholar48https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXjs1Gjt7g%253D&md5=f1877a0ea92cfe41ca508f4debfd282eFabrication of Arrays of Metal and Metal Oxide Nanotubes by Shadow EvaporationDickey, Michael D.; Weiss, Emily A.; Smythe, Elizabeth J.; Chiechi, Ryan C.; Capasso, Federico; Whitesides, George M.ACS Nano (2008), 2 (4), 800-808CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)This paper describes a simple technique for fabricating uniform arrays of metal and metal oxide nanotubes with controlled heights and diams. The technique involves depositing material onto an anodized aluminum oxide (AAO) membrane template using a collimated electron beam evapn. source. The evapg. material enters the porous openings of the AAO membrane and deposits onto the walls of the pores. The membrane is tilted with respect to the column of evapg. material, so the shadows cast by the openings of the pores onto the inside walls of the pores define the geometry of the tubes. Rotation of the membrane during evapn. ensures uniform deposition inside the pores. After evapn., dissoln. of the AAO in base easily removes the template to yield an array of nanotubes connected by a thin backing of the same metal or metal oxide. The diam. of the pores dictates the diam. of the tubes, and the incident angle of evapn. dets. the height of the tubes. Tubes up to ∼1.5 μm in height and 20-200 nm in diam. were fabricated. This method is adaptable to any material that can be vapor-deposited, including indium-tin oxide (ITO), a conductive, transparent material that is useful for many optoelectronic applications. An array of gold nanotubes produced by this technique served as a substrate for surface-enhanced Raman spectroscopy: the Raman signal (per mol.) from a monolayer of benzenethiolate was a factor of ∼5 × 105 greater than that obtained using bulk liq. benzenethiol.
- 49Petrova, A.; Mamedov, M.; Ivanov, B.; Semenov, A.; Kozuleva, M. Effect of Artificial Redox Mediators on the Photoinduced Oxygen Reduction by Photosystem I Complexes. Photosynth. Res. 2018, 137, 421– 429, DOI: 10.1007/s11120-018-0514-zGoogle Scholar49https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXpsFyhsb4%253D&md5=b035bd051506a6b479457382c4984729Effect of artificial redox mediators on the photoinduced oxygen reduction by photosystem I complexesPetrova, Anastasia; Mamedov, Mahir; Ivanov, Boris; Semenov, Alexey; Kozuleva, MarinaPhotosynthesis Research (2018), 137 (3), 421-429CODEN: PHRSDI; ISSN:0166-8595. (Springer)The peculiarities of interaction of cyanobacterial photosystem I with redox mediators 2,6-dichlorophenolindophenol (DCPIP) and N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD) were investigated. The higher donor efficiency of the reduced DCPIP form was demonstrated. The oxidized form of DCPIP was shown to be an efficient electron acceptor for terminal iron-sulfur cluster of photosystem I. Likewise Me viologen, after one-electron redn., DCPIP transfers an electron to the mol. oxygen. These results were discussed in terms of influence of these interactions on photosystem I reactions with the mol. oxygen and natural electron acceptors.
- 50Santiago, A. R. P.; Fernandez-Delgado, O.; Gomez, A.; Ahsan, M. A.; Echegoyen, L. Fullerenes as Key Components for Low-Dimensional (Photo)electrocatalytic Nanohybrid Materials. Angew. Chem., Int. Ed. 2021, 133, 124– 143, DOI: 10.1002/ange.202009449Google ScholarThere is no corresponding record for this reference.
- 51Pan, Y.; Liu, X.; Zhang, W.; Liu, Z.; Zeng, G.; Shao, B.; Liang, Q.; He, Q.; Yuan, X.; Huang, D.; Chen, M. Advances in photocatalysis based on fullerene C60 and its derivatives: Properties, mechanism, synthesis, and applications. Appl. Catal., B 2020, 265, 118579 DOI: 10.1016/j.apcatb.2019.118579Google Scholar51https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXps1Ggsg%253D%253D&md5=75b21ab17dd3c4144e1a9257d975a07dAdvances in photocatalysis based on fullerene C60 and its derivatives: properties, mechanism, synthesis, and applicationsPan, Yuan; Liu, Xiaojuan; Zhang, Wei; Liu, Zhifeng; Zeng, Guangming; Shao, Binbin; Liang, Qinghua; He, Qingyun; Yuan, Xingzhong; Huang, Danlian; Chen, MingApplied Catalysis, B: Environmental (2020), 265 (), 118579CODEN: ACBEE3; ISSN:0926-3373. (Elsevier B.V.)A review. Fullerenes possess high chem. stability, large sp. surface area, good elec. cond. and unique three-dimensional structure. In this paper, we provide a general overview of the latest research results of fullerene-based photocatalysts. Firstly, the current status of semiconductor materials and fullerenes in photocatalytic applications are briefly introduced. Secondly, introduced action mechanisms of photocatalysts modified by fullerene C60 and its derivs., including basic structure, exclusive properties and its effect in photocatalysis and material prepn. process. Thirdly, factors affecting material effectiveness and the synthesis strategy of composite photocatalyst modified by fullerene are introduced. Meanwhile, the application advances of the photocatalysts are introduced, including in the degrdn. of pollutants, org. synthesis, hydrogen prodn., antibacterial and disinfection in water. Finally, the development trends of fullerenes and their derivs. in photocatalysis are also summarized, including theor. calcns., the morphol. structure control, stable derivs. and increase the selectivity, and new other types of fullerene materials.
- 52Blom, P.; Mihailetchi, V.; Koster, L.; Markov, D. Device Physics of Polymer:Fullerene Bulk Heterojunction Solar Cells. Adv. Mater. 2007, 19, 1551– 1566, DOI: 10.1002/adma.200601093Google Scholar52https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2sXnsVagsL4%253D&md5=6b0fb9c0d385111ca70c49679eccad55Device physics of polymer:fullerene bulk heterojunction solar cellsBlom, Paul W. M.; Mihailetchi, Valentin D.; Koster, L. Jan Anton; Markov, Denis E.Advanced Materials (Weinheim, Germany) (2007), 19 (12), 1551-1566CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)A review of processes and limitations that govern device operation of polymer:fullerene bulk heterojunction solar cells, with respect to the charge-carrier transport and photogeneration mechanism. The transport of electrons/holes in the blend is a crucial parameter and must be controlled (e.g., by controlling the nanoscale morphol.) and enhanced in order to allow fabrication of thicker films to maximize the absorption, without significant recombination losses. Concomitantly, a balanced transport of electrons and holes in the blend is needed to suppress the build-up of the space charge that will significantly reduce the power conversion efficiency. Dissocn. of electron-hole pairs at the donor/acceptor interface is an important process that limits the charge generation efficiency under normal operation condition. Based on these findings, there is a compromise between charge generation (light absorption) and open-circuit voltage when attempting to reduce the bandgap of the polymer (or fullerene). Therefore, an increase in open-circuit voltage of polymer:fullerene solar cells, for example by raising the LUMO level of the fullerene, will benefit cell performance as both fill factor and short-circuit current increase simultaneously.
- 53Li, S.; Lei, M.; Lv, M.; Watkins, S. E.; Tan, Z.; Zhu, J.; Hou, J.; Chen, X.; Li, Y. [6, 6]-Phenyl-C61-Butyric Acid Dimethylamino Ester as a Cathode Buffer Layer for High-Performance Polymer Solar Cells. Adv. Energy Mater. 2013, 3, 1569– 1574, DOI: 10.1002/aenm.201300425Google Scholar53https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhvV2itbrI&md5=b66a11b89684116042cdb0aa25a4c5bb[6,6]-Phenyl-C61-Butyric Acid Dimethylamino Ester as a Cathode Buffer Layer for High-Performance Polymer Solar CellsLi, Shusheng; Lei, Ming; Lv, Menglan; Watkins, Scott E.; Tan, Zhan'ao; Zhu, Jin; Hou, Jianhui; Chen, Xiwen; Li, YongfangAdvanced Energy Materials (2013), 3 (12), 1569-1574CODEN: ADEMBC; ISSN:1614-6840. (Wiley-Blackwell)This paper discusses the [6,6]-phenyl-C61-butyric acid dimethylamino ester as cathode buffer layer for high-performance polymer solar cells. Fullerene derivs. could be ideal cathode buffer layer materials in considering their n-type semiconductor character, higher electron mobility, and the good energy level matching with the fullerene acceptors (such as [6,6]-phenyl-C61-butyric acid Me ester (PCBM)) used in the active layer of the PSCs were discussed.
- 54Tel-Vered, R.; Willner, I. Photo-Bioelectrochemical Cells for Energy Conversion, Sensing, and Optoelectronic Applications. ChemElectroChem 2014, 1, 1778– 1797, DOI: 10.1002/celc.201402133Google Scholar54https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhvVylsbfF&md5=47a6e29da1eaabc6cb1886f07dc37e5aPhoto-bioelectrochemical Cells for Energy Conversion, Sensing, and Optoelectronic ApplicationsTel-Vered, Ran; Willner, ItamarChemElectroChem (2014), 1 (11), 1778-1797CODEN: CHEMRA; ISSN:2196-0216. (Wiley-VCH Verlag GmbH & Co. KGaA)The native photosynthetic reaction centers photosystem I (PSI) and photosystem II (PSII) act as functional nanostructures for the assembly of photo-biofuel cells. By elec. wiring of PSI and/or PSII with electrodes, the conversion of light energy into elec. power has been demonstrated. Different methodologies to elec. contact the photosystems with the electrodes have been developed, including the reconstitution of the photosystems on relay units, the application of redox-active polymers as charge-transport matrixes, and the use of metallic nanoparticles or nanoclusters as electron-transfer relays. Elec. contact of the photosystems with the electrodes facilitates charge sepn. of the redox intermediates generated upon illumination of the assemblies, thus retarding destructive back electron-transfer reactions and enhancing the conversion of light energy into elec. power. Recent advances to fabricate elec. wired PSI and/or PSII electrodes are surveyed, and different approaches to assemble photo-bioelectrochem. cells are discussed. The limitations and future perspectives of the systems will also be presented.
- 55Tsarev, S.; Dubinina, T. S.; Luchkin, S. Y.; Zhidkov, I. S.; Kurmaev, E. Z.; Stevenson, K. J.; Troshin, P. A. Phenyl-C61-butyric Acid as an Interface Passivation Layer for Highly Efficient and Stable Perovskite Solar Cells. J. Phys. Chem. C 2020, 124, 1872– 1877, DOI: 10.1021/acs.jpcc.9b10709Google Scholar55https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXpvFI%253D&md5=85fb3a694907c4f99716cfa01559d185Phenyl-C61-butyric Acid as an Interface Passivation Layer for Highly Efficient and Stable Perovskite Solar CellsTsarev, Sergey; Dubinina, Tatiana S.; Luchkin, Sergey Yu.; Zhidkov, Ivan S.; Kurmaev, Ernst Z.; Stevenson, Keith J.; Troshin, Pavel A.Journal of Physical Chemistry C (2020), 124 (3), 1872-1877CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)Here, phenyl-C61-butyric acid (PCBA) is presented as a generic passivation coating for metal oxide electron transport layers used in planar n-i-p configuration of perovskite solar cells. PCBA shows better adhesion to Sn and Zn oxides due to strong acid-base interactions as compared to the conventionally used phenyl-C61-butyric acid Me ether (PCBM). Therefore, depositing a compact PCBA passivation coating can be achieved in a much more economical way using 100 times less concd. precursor soln. PCBA coating delivers higher power conversion efficiencies (up to 20.3%) as compared to the pristine oxide layers with or without PCBM coating. Finally, the fabricated solar cells using PCBA coating are more stable in comparison with the ref. cells with conventional PCBM passivation and preserved ∼70% of the initial efficiency after 1500 h of continuous 30 mW/cm2 white light illumination at 50°.
- 56Mishra, A.; Bäuerle, P. Small Molecule Organic Semiconductors on the Move: Promises for Future Solar Energy Technology. Angew. Chem., Int. Ed. 2012, 51, 2020– 2067, DOI: 10.1002/anie.201102326Google Scholar56https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38Xitlygs7g%253D&md5=3bd032ed84f6c2a11c7f6d8efb770901Small Molecule Organic Semiconductors on the Move: Promises for Future Solar Energy TechnologyMishra, Amaresh; Baeuerle, PeterAngewandte Chemie, International Edition (2012), 51 (9), 2020-2067CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)A review. This article, written from an org. chemist's point of view, provides an up-to-date overview of org. solar cells based on small mols. or oligomers as absorbers and describes devices that incorporate planar-heterojunctions and bulk heterojunctions between a donor (p-type semiconductor) and an acceptor (n-type semiconductor) material. The article pays particular attention to the design and development of mol. materials and their performance in corresponding devices. In recent years, a substantial amt. of both, academic and industrial research, has been directed towards org. solar cells, in an effort to develop new materials and to improve their tunability, processability, power conversion efficiency, and stability. On the eve of commercialization of org. solar cells, this review provides an overview of efficiencies attained with small mols./oligomers in org. solar cells and summarizes materials and device concepts developed over the last decade. Approaches to enhancing the efficiency of org. solar cells are analyzed.
- 57Nelson, J. Polymer:fullerene bulk heterojunction solar cells. Mater. Today 2011, 14, 462– 470, DOI: 10.1016/S1369-7021(11)70210-3Google Scholar57https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXht1CqurfJ&md5=9fa4d2f695ac9261d624b7ed5a5d23e7Polymer:fullerene bulk heterojunction solar cellsNelson, JennyMaterials Today (Oxford, United Kingdom) (2011), 14 (10), 462-470CODEN: MTOUAN; ISSN:1369-7021. (Elsevier Ltd.)A review. The efficiency of solar cells made from a conjugated polymer blended with a fullerene deriv. has risen from around 1 % to over 9 % in the last ten years, making org. photovoltaic technol. a viable contender for commercialization. The efficiency increases have resulted from the development of new materials with lower optical gaps, new polymer:fullerene combinations with higher charge sepd. state energies, and new approaches to control the blend microstructure, all driven by a qual. understanding of the principles governing org. solar cell operation. In parallel, a device physics framework has been developed that enables the rational design of device structures and materials for improved org. photovoltaic devices. We review developments in both materials science and device physics for org. photovoltaics.
- 58Nakanishi, W.; Minami, K.; Shrestha, L. K.; Ji, Q.; Hill, J. P.; Ariga, K. Bioactive nanocarbon assemblies: Nanoarchitectonics and applications. Nano Today 2014, 9, 378– 394, DOI: 10.1016/j.nantod.2014.05.002Google Scholar58https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhtVanurvF&md5=09e65b89b9e27c5f8dcd8e46ce278b71Bioactive nanocarbon assemblies: Nanoarchitectonics and applicationsNakanishi, Waka; Minami, Kosuke; Shrestha, Lok Kumar; Ji, Qingmin; Hill, Jonathan P.; Ariga, KatsuhikoNano Today (2014), 9 (3), 378-394CODEN: NTAOCG; ISSN:1748-0132. (Elsevier Ltd.)A review. Graphene, carbon nanotubes, and fullerene are representative nanocarbons which have zero, one, or two dimensional structures, resp. These nanocarbons can be used as building blocks for construction of higher dimensional or complex materials by nanoarchitectonics; a technol. used to control nanoscale structures and spaces. By combination with other materials and/or devices, nanoarchitectures of nanocarbons can be formed into structures of different dimensions and properties for biol. applications. In this review, biol. applications, esp. cell growth, sensing, and control using nanoarchitectures of nanocarbons are summarized.
- 59Yan, J.; Saunders, B. R. Third-generation solar cells: a review and comparison of polymer: fullerene, hybrid polymer and perovskite solar cells. RSC Adv. 2014, 4, 43286– 43314, DOI: 10.1039/C4RA07064JGoogle Scholar59https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhsVaksLnI&md5=f530f372f95b219d27535c41923d47f9Third-generation solar cells: a review and comparison of polymer:fullerene, hybrid polymer and perovskite solar cellsYan, Junfeng; Saunders, Brian R.RSC Advances (2014), 4 (82), 43286-43314CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)A review. The need for large scale low carbon solar electricity prodn. has become increasingly urgent for reasons of energy security and climate change mitigation. Third-generation solar cells (SCs) are soln. processed SCs based on semiconducting org. macromols., inorg. nanoparticles or hybrids. This review considers and compares three types of promising 3rd-generation SCs: polymer:fullerene, hybrid polymer and perovskite SCs. The review considers work reported since an earlier review and highlights the great progress that has been made in each area. We consider the operation principles for each SC type and also review the state-of-the-art devices. The polymer:fullerene and hybrid polymer SC open circuit voltages are compared to values predicted from the well-known Scharber equation and similarities and differences discussed. The perovskite SCs are also considered and their remarkable rate of power conversion efficiency performance increase is discussed. The review considers the requirements for large-scale deployment in the contexts of semiconducting polymer and hole transport matrix synthesis and materials selection. It is concluded that the 3rd-generation SC technologies discussed here are well placed for major contribution to large scale energy prodn. (This has already been partially demonstrated for polymer:fullerene SCs.) Looking further ahead we propose that several of the 3rd-generation SCs considered here have excellent potential to provide the low cost large-scale deployment needed to meet the terawatt challenge for solar electricity generation.
- 60Shi, X.-Q.; Hove, M. A. V.; Zhang, R.-Q. Survey of Structural and Electronic Properties of C60 on Close-Packed Metal Surfaces. J. Mater. Sci. 2012, 47, 7341– 7355, DOI: 10.1007/s10853-012-6361-yGoogle Scholar60https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XjtlSmtrw%253D&md5=cc42578f06ead6410e32c30ab2137517Survey of structural and electronic properties of C60 on close-packed metal surfacesShi, Xing-Qiang; Van Hove, Michel A.; Zhang, Rui-QinJournal of Materials Science (2012), 47 (21), 7341-7355CODEN: JMTSAS; ISSN:0022-2461. (Springer)A review. The adsorption of buckminsterfullerene (C60) on metal surfaces has been investigated extensively for its unique geometric and electronic properties. The two-dimensional systems formed on surfaces allow studying in detail the interplay between bonding and electronic structures. Recent studies reveal that C60 adsorption induces reconstruction of even the less-reactive close-packed metal surfaces. First-principles computations enable access to this important issue by providing not only detailed at. structure but also electronic properties of the substrate-adsorbate interaction, which can be compared with various exptl. techniques to det. and understand the interface structures. This review discusses in detail the ordered phases of C60 monolayers on metal surfaces and the surface reconstruction induced by C60 adsorption, with an emphasis on the different types of reconstruction resulting on close-packed metal surfaces. We show that the symmetry matching between C60 mols. and metal surfaces dets. the local adsorption configurations, while the size matching between C60 mols. and the metal surface lattice dets. the supercell sizes and shapes; importantly and uniquely for C60, the no. of surface metal atoms within one supercell dets. the different types of reconstruction that can occur. The at. structure at the mol.-metal interface is of crucial importance for the monolayer's electronic and transport properties: these will also be discussed for the well-defined adsorption structures, esp. from the perspective of tuning the electronic structure via C60-metal interface reconstruction and via relative inter-C60 orientations.
- 61Cho, N.-K.; Na, H.-J.; Yoo, J.; Kim, Y. S. Long-term stability in γ-CsPbI3 perovskite via an ultraviolet-curable polymer network. Commun. Mater. 2021, 2, 30 DOI: 10.1038/s43246-021-00134-1Google ScholarThere is no corresponding record for this reference.
- 62Suresh, L.; Vaghasiya, J. V.; Nandakumar, D. K.; Wu, T.; Jones, M. R.; Tan, S. C. High-Performance UV Enhancer Molecules Coupled with Photosynthetic Proteins for Ultra-Low-Intensity UV Detection. Chem 2019, 5, 1847– 1860, DOI: 10.1016/j.chempr.2019.04.017Google Scholar62https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhsVGrtLnO&md5=4aefff589dac1b94ceb57961c9365e51High-Performance UV Enhancer Molecules Coupled with Photosynthetic Proteins for Ultra-Low-Intensity UV DetectionSuresh, Lakshmi; Vaghasiya, Jayraj V.; Nandakumar, Dilip Krishna; Wu, Tingfeng; Jones, Michael R.; Tan, Swee ChingChem (2019), 5 (7), 1847-1860CODEN: CHEMVE; ISSN:2451-9294. (Cell Press)Dual attributes of UV-photo-responsive org.-ionic conductors are exploited in bio-photoelectrochem. cells based on photosynthetic RC-LH1 proteins from Rhodobacter sphaeroides. These UV enhancer mols. (UVEM) can generate small photocurrents in the absence of protein and are also effective electrolytes for photocurrent generation by RC-LH1 complexes in response to near-IR excitation. Mixing RC-LH1 and UVEM components strongly enhanced UV photocurrents relative to those obtained with protein or UVEM alone, an effect that is attributed to energy transfer from the hetero-anthracene chromophore of the UVEM to the carotenoids of the RC-LH1 complex. RC-LH1/UVEM bio-photoelectrochem. cells were superior to conventional RC-LH1 cells in terms of UV external quantum efficiency, photo-response sensitivity, and photocurrent rise-decay times. These bio-photodetectors could detect weak UV radiation with intensities as low as 2μW/cm2. This combination of photosynthetic proteins with dual-function electrolytes is the first attempt to construct fully functional bio-photoelectrochem. UV photodetector based on natural components.
- 63Long, S. P.; Humphries, S.; Falkowski, P. G. Photoinhibition of Photosynthesis in Nature. Annu. Rev. Plant Physiol. Plant Mol. Biol. 1994, 45, 633– 662, DOI: 10.1146/annurev.pp.45.060194.003221Google Scholar63https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2cXlt12rsLg%253D&md5=cdd440abee71cf2efb92cba109c07d99Photoinhibition of photosynthesis in natureLong, S. P.; Humphries, S.; Falkowski, P. G.Annual Review of Plant Physiology and Plant Molecular Biology (1994), 45 (), 633-62CODEN: ARPBEX; ISSN:1040-2519.A review with 142 refs., discussing photosystem II inactivation, avoidance of PS II damage, photoinhibition in the filed and open ocean, terrestrial vegetation, phytoplankton, significance to prodn., and photoinhibition and plant distributions.
- 64Allahverdiyeva, Y.; Aro, E.-M. Photosynthesis; Springer: Netherlands, 2011; pp 275– 297.Google ScholarThere is no corresponding record for this reference.
- 65Paul, N.; Suresh, L.; Vaghasiya, J. V.; Yang, L.; Zhang, Y.; Nandakumar, D. K.; Jones, M. R.; Tan, S. C. Self-powered all weather sensory systems powered by Rhodobacter sphaeroides protein solar cells. Biosens. Bioelectron. 2020, 165, 112423 DOI: 10.1016/j.bios.2020.112423Google Scholar65https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhsVCksbbL&md5=68b60a6ae03e527ee5ff7bae51563fe6Self-powered all weather sensory systems powered by Rhodobacter sphaeroides protein solar cellsPaul, Nikita; Suresh, Lakshmi; Vaghasiya, Jayraj V.; Yang, Lin; Zhang, Yaoxin; Nandakumar, Dilip Krishna; Jones, Michael R.; Tan, Swee ChingBiosensors & Bioelectronics (2020), 165 (), 112423CODEN: BBIOE4; ISSN:0956-5663. (Elsevier B.V.)Natural photosynthetic proteins can convert solar energy into elec. energy with close to 100% quantum efficiency, and there is increasing interest in their use for sustainable photoelectrochem. devices. The primary processes of photosynthesis remain operational and efficient down to extremely low temps., and natural photosystems exhibit a variety of self-healing mechanisms. Herein we demonstrate the use of an amphiphilic triblock copolymer, Pluronic F127, to fabricate a self-healing photosynthetic protein photoelectrochem. cell that operates optimally at sub-zero temps. A concn. of 30% (wt./wt.) Pluronic F127 depressed the f.p. of an electrolyte comprising 50 mM ubiquinone-0 in aq. buffer such that optimal device solar energy conversion was seen at -12°C rather than at room temp. Multiple bending cycles caused a marked deterioration of the photocurrent response to around a third of initial levels due to damage to the gel phase of the electrolyte, but this could be restored to ~ 95% by simply cooling and rewarming the device. This self-recoverability of the electrolyte extended the operational life of the protein cell through a process that increased its photoelectrochem. output during the repair. Utility of the cells as components of a touch sensor operational across a wide temp. range, including freezing conditions, is demonstrated.
- 66Liu, J.; Friebe, V. M.; Frese, R. N.; Jones, M. R. Polychromatic solar energy conversion in pigment-protein chimeras that unite the two kingdoms of (bacterio)chlorophyll-based photosynthesis. Nat. Commun. 2020, 11, 1542 DOI: 10.1038/s41467-020-15321-wGoogle Scholar66https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXlvFGnsLg%253D&md5=ee3b293e4d1ac27bf9c2f600476d123ePolychromatic solar energy conversion in pigment-protein chimeras that unite the two kingdoms of (bacterio)chlorophyll-based photosynthesisLiu, Juntai; Friebe, Vincent M.; Frese, Raoul N.; Jones, Michael R.Nature Communications (2020), 11 (1), 1542CODEN: NCAOBW; ISSN:2041-1723. (Nature Research)Natural photosynthesis can be divided between the chlorophyll-contg. plants, algae and cyanobacteria that make up the oxygenic phototrophs and a diversity of bacteriochlorophyll-contg. bacteria that make up the anoxygenic phototrophs. Photosynthetic light harvesting and reaction center proteins from both kingdoms have been exploited for solar energy conversion, solar fuel synthesis and sensing technologies, but the energy harvesting abilities of these devices are limited by each protein's individual palette of pigments. In this work we demonstrate a range of genetically-encoded, self-assembling photosystems in which recombinant plant light harvesting complexes are covalently locked with reaction centers from a purple photosynthetic bacterium, producing macromol. chimeras that display mechanisms of polychromatic solar energy harvesting and conversion. Our findings illustrate the power of a synthetic biol. approach in which bottom-up construction of photosystems using naturally diverse but mechanistically complementary components can be achieved in a predictable fashion through the encoding of adaptable, plug-and-play covalent interfaces.
- 67Molamohammadi, S.; Jalili, Y. S.; Riazi, G. Photosystem I application in biohybrid polymer solar cells. AIP Adv. 2018, 8, 095319 DOI: 10.1063/1.5030777Google Scholar67https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhvVSisb%252FN&md5=bfcc21784a42f9c6bdbf721e984658d7Photosystem I application in biohybrid polymer solar cellsMolamohammadi, Shahriar; Seyed Jalili, Yousef; Riazi, GholamhosseinAIP Advances (2018), 8 (9), 095319/1-095319/8CODEN: AAIDBI; ISSN:2158-3226. (American Institute of Physics)The use of Bio-photonic systems has attracted a lot of attention recently specially in the field of solar energy conversion and photovoltaic materials the use of photosynthetic organs of plants is very promising. The energy conversion in the process of photosynthesis is close to 100% and it's environmental compatibly are the main reasons for why photosynthesis has attracted the attention of energy system designers and researchers. The way of solar energy conversion in photosynthesis indicates a great potential as a fount of renewable energy. Use of the photosynthetic components in photosensors and photovoltaic devices solitarily, has disadvantages such as low extd. current compared to other kinds of photovoltaic materials. Accordingly, for more useful and better application, these photosynthetic components could be used as the optimizer of the other species of photovoltaic materials and solar cells. photosystem1 protein complex, which is the main member of photosynthetic components has max. absorption spectrum wavelength at 430nm and 665nm. Therefore, it can be an appropriate complement for polymeric solar cells with their absorption spectrum at the green wavelength region. In this paper we have used the photosystem1 protein complex in the inverted polymer solar cell with structure of ITO/P3HT:ICBA/PS1/Al and pos. results have been obsd. So that the polymer solar cells efficiency was enhanced from 4.3% to 4.53%. (c) 2018 American Institute of Physics.
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- 1Scharber, M.; Mühlbacher, D.; Koppe, M.; Denk, P.; Waldauf, C.; Heeger, A.; Brabec, C. Design Rules for Donors in Bulk-Heterojunction Solar Cells—Towards 10 % Energy-Conversion Efficiency. Adv. Mater. 2006, 18, 789– 794, DOI: 10.1002/adma.2005017171https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28XjsV2isrw%253D&md5=2b4b2b73db6b35d7f375c2ffd65e66c0Design rules for donors in bulk-heterojunction solar cells-towards 10 % energy-conversion efficiencyScharber, Markus C.; Muehlbacher, David; Koppe, Markus; Denk, Patrick; Waldauf, Christoph; Heeger, Alan J.; Brabec, Christoph J.Advanced Materials (Weinheim, Germany) (2006), 18 (6), 789-794CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)Solar cells were fabricated from a variety of com. available compds. and were studied. For bulk-heterojunction photovoltaic cells fabricated from conjugated polymers and a fullerene deriv., the relation between the open-circuit voltage (Voc) and the oxidn. potential for different conjugated polymers is studied. A linear relation between Voc and the oxidn. potential is found (see figure). Based on this relation, the energy-conversion efficiency of a bulk-heterojunction solar cell is derived as a function of the bandgap and the energy levels of the conjugated polymer.
- 2Clarke, T. M.; Durrant, J. R. Charge Photogeneration in Organic Solar Cells. Chem. Rev. 2010, 110, 6736– 6767, DOI: 10.1021/cr900271s2https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXjs1yksg%253D%253D&md5=64230a8447194c23ff34167436a83745Charge Photogeneration in Organic Solar CellsClarke, Tracey M.; Durrant, James R.Chemical Reviews (Washington, DC, United States) (2010), 110 (11), 6736-6767CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)A review. Org. solar cells utilizing π-conjugated polymers have attracted interest in the academic and com. communities. These polymers are promising in terms of their electronic properties, low cost, versatility of functionalization, thin film flexibility, and ease of processing. These factors indicate that org. solar cells, although currently having relatively low power conversion efficiencies of 5 to 7%, compared to inorg. solar cells, they can compete effectively with alternative solar cell technologies. The efficiency of org. solar cells need further improvement.
- 3Grätzel, M. Materials for Sustainable Energy; Co-Published with Macmillan Publishers Ltd.: U.K., 2010; pp 26– 32.There is no corresponding record for this reference.
- 4Nguyen, K.; Bruce, B. D. Growing Green Electricity: Progress and Strategies for Use of Photosystem I for Sustainable Photovoltaic Energy Conversion. Biochim. Biophys. Acta, Bioenerg. 2014, 1837, 1553– 1566, DOI: 10.1016/j.bbabio.2013.12.0134https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhvFGktrY%253D&md5=e52883e42b53520558ab28ffdc8e6f5cGrowing green electricity: Progress and strategies for use of Photosystem I for sustainable photovoltaic energy conversionNguyen, Khoa; Bruce, Barry D.Biochimica et Biophysica Acta, Bioenergetics (2014), 1837 (9), 1553-1566CODEN: BBBEB4; ISSN:0005-2728. (Elsevier B. V.)Oxygenic photosynthesis is driven via sequential action of Photosystem II (PSII) and (PSI)reaction centers via the Z-scheme. Both of these pigment-membrane protein complexes are found in cyanobacteria, algae, and plants. Unlike PSII, PSI is remarkably stable and does not undergo limiting photo-damage. This stability, as well as other fundamental structural differences, makes PSI the most attractive reaction centers for applied photosynthetic applications. These applied applications exploit the efficient light harvesting and high quantum yield of PSI where the isolated PSI particles are redeployed providing electrons directly as a photocurrent or, via a coupled catalyst to yield H2. Recent advances in mol. genetics, synthetic biol., and nanotechnol. have merged to allow PSI to be integrated into a myriad of biohybrid devices. In photocurrent producing devices, PSI has been immobilized onto various electrode substrates with a continuously evolving toolkit of strategies and novel reagents. However, these innovative yet highly variable designs make it difficult to identify the rate-limiting steps and/or components that function as bottlenecks in PSI-biohybrid devices. In this study we aim to highlight these recent advances with a focus on identifying the similarities and differences in electrode surfaces, immobilization/orientation strategies, and artificial redox mediators. Collectively this work has been able to maintain an annual increase in photocurrent d. (A cm- 2) of ∼ 10-fold over the past decade. The potential drawbacks and attractive features of some of these schemes are also discussed with their feasibility on a large-scale. As an environmentally benign and renewable resource, PSI may provide a new sustainable source of bioenergy. This article is part of a Special Issue entitled: Photosynthesis Research for Sustainability: Keys to Produce Clean Energy.
- 5Brettel, K.; Leibl, W. Electron Transfer in Photosystem I. Biochim. Biophys. Acta, Bioenerg. 2001, 1507, 100– 114, DOI: 10.1016/S0005-2728(01)00202-X5https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD3MXnvFCktbY%253D&md5=54853ac113aab68bf53d1d9495a8a7a7Electron transfer in photosystem IBrettel, Klaus; Leibl, WinfriedBiochimica et Biophysica Acta, Bioenergetics (2001), 1507 (1-3), 100-114CODEN: BBBEB4; ISSN:0005-2728. (Elsevier B.V.)A review. This mini-review focuses on recent exptl. results and questions, which came up since the last more comprehensive reviews on the subject. We include a brief discussion of the different techniques used for time-resolved studies of electron transfer in photosystem I (PS I) and relate the kinetic results to new structural data of the PS I reaction center.
- 6Nelson, N.; Ben-Shem, A. The Complex Architecture of Oxygenic Photosynthesis. Nat. Rev. Mol. Cell Biol. 2004, 5, 971– 982, DOI: 10.1038/nrm15256https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2cXhtVarsbzP&md5=861031c7898c616cda294676edac6607The complex architecture of oxygenic photosynthesisNelson, Nathan; Ben-Shem, AdamNature Reviews Molecular Cell Biology (2004), 5 (12), 971-982CODEN: NRMCBP; ISSN:1471-0072. (Nature Publishing Group)A review. Oxygenic photosynthesis is the principal producer of both oxygen and org. matter on earth. The primary step in this process, i.e., the conversion of sunlight into chem. energy, is driven by four multisubunit membrane-protein complexes that are known as photosystem I, photosystem II, cytochrome b6f and F-ATPase. Structural insights into these complexes have provided a framework for the exploration not only of energy and electron transfer, but also of the evolutionary forces that shaped the photosynthetic app.
- 7Nelson, N.; Yocum, C. F. Structure And Function Of Photosystems I And Ii. Annu. Rev. Plant Biol. 2006, 57, 521– 565, DOI: 10.1146/annurev.arplant.57.032905.1053507https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD28XosVKht7w%253D&md5=b6e2c2856d90824f9855afe39ac78adbStructure and function of photosystems I and IINelson, Nathan; Yocum, Charles F.Annual Review of Plant Biology (2006), 57 (), 521-565CODEN: ARPBDW ISSN:. (Annual Reviews Inc.)A review. Oxygenic photosynthesis, the principal converter of sunlight into chem. energy on earth, is catalyzed by four multi-subunit membrane-protein complexes: photosystem I (PSI), photosystem II (PSII), the cytochrome b6f complex, and F-ATPase. PSI generates the most neg. redox potential in nature and largely dets. the global amt. of enthalpy in living systems. PSII generates an oxidant whose redox potential is high enough to enable it to oxidize H2O, a substrate so abundant that it assures a practically unlimited electron source for life on earth. During the last century, the sophisticated techniques of spectroscopy, mol. genetics, and biochem. were used to reveal the structure and function of the two photosystems. The new structures of PSI and PSII from cyanobacteria, algae, and plants has shed light not only on the architecture and mechanism of action of these intricate membrane complexes, but also on the evolutionary forces that shaped oxygenic photosynthesis.
- 8El-Mohsnawy, E.; Kopczak, M. J.; Schlodder, E.; Nowaczyk, M.; Meyer, H. E.; Warscheid, B.; Karapetyan, N. V.; Rögner, M. Structure and Function of Intact Photosystem 1 Monomers From the Cyanobacterium Thermosynechococcus elongatus. Biochemistry 2010, 49, 4740– 4751, DOI: 10.1021/bi901807p8https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXmtlCrt78%253D&md5=1103363c3a1f714f07e1179bb7708a03Structure and Function of Intact Photosystem 1 Monomers from the Cyanobacterium Thermosynechococcus elongatusEl-Mohsnawy, Eithar; Kopczak, Marta J.; Schlodder, Eberhard; Nowaczyk, Marc; Meyer, Helmut E.; Warscheid, Bettina; Karapetyan, Navassard V.; Roegner, MatthiasBiochemistry (2010), 49 (23), 4740-4751CODEN: BICHAW; ISSN:0006-2960. (American Chemical Society)Until now, the functional and structural characterization of monomeric photosystem 1 (PS1) complexes from Thermosynechococcus elongatus has been hampered by the lack of a fully intact PS1 prepn.; for this reason, the three-dimensional crystal structure at 2.5 Å resoln. was detd. with the trimeric PS1 complex. Here, the possibility of isolating from this cyanobacterium the intact monomeric PS1 complex which preserves all subunits and the photochem. activity of the isolated trimeric complex is shown. Moreover, the equil. between these complexes in the thylakoid membrane can be shifted by a high-salt treatment in favor of monomeric PS1 which can be quant. extd. below the phase transition temp. Both monomers and trimers exhibit identical post-translational modifications of their subunits and the same reaction centers but differ in the long-wavelength antenna chlorophylls. Their chlorophyll/P700 ratio (108 for the monomer and 112 for the trimer) is slightly higher than in the crystal structure, confirming mild prepn. conditions. Interaction of antenna chlorophylls of the monomers within the trimer leads to a larger amt. of long-wavelength chlorophylls, resulting in a higher photochem. activity of the trimers under red or far-red illumination. The dynamic equil. between monomers and trimers in the thylakoid membrane may indicate a transient monomer population in the course of biogenesis and could also be the basis for short-term adaptation of the cell to changing environmental conditions.
- 9Gordiichuk, P. I.; Wetzelaer, G.-J. A. H.; Rimmerman, D.; Gruszka, A.; de Vries, J. W.; Saller, M.; Gautier, D. A.; Catarci, S.; Pesce, D.; Richter, S.; Blom, P. W. M.; Herrmann, A. Solid-State Biophotovoltaic Cells Containing Photosystem I. Adv. Mater. 2014, 26, 4863– 4869, DOI: 10.1002/adma.2014011359https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXos1CjtL0%253D&md5=2ca7ed4b6f064ba7a6480e00fc62f364Solid-state biophotovoltaic cells containing Photosystem IGordiichuk, Pavlo I.; Wetzelaer, Gert-Jan A. H.; Rimmerman, Dolev; Gruszka, Agnieszka; Willem de Vries, Jan X.; Saller, Manfred; Gautier, Daniel A.; Catarci, Stefano; Pesce, Diego; Richter, Shachar; Blom, Paul W. M.; Herrmann, AndreasAdvanced Materials (Weinheim, Germany) (2014), 26 (28), 4863-4869CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)Processes occurring during photosynthesis, such as dynamic self-repair, light harvesting and quantum effects can be integrated into man-made photovoltaic devices. One of the most frequently used photoactive building blocks for that purpose is the multiprotein complex photosystem I (PSI). Biophotovoltaic devices similar to DSSCs were fabricated by self-assembly of PSI on 3D nanostructured semiconductor electrodes using a liq. electrolyte as redox mediator. Here, we introduce the implementation of PSI in org. electronic devices that combine the ease of processing of org. semiconductors with the biophotovoltaic activity of PSI.
- 10Gizzie, E. A.; Niezgoda, J. S.; Robinson, M. T.; Harris, A. G.; Jennings, G. K.; Rosenthal, S. J.; Cliffel, D. E. Photosystem I-Polyaniline/TiO2 Solid-State Solar Cells: Simple Devices for Biohybrid Solar Energy Conversion. Energy Environ. Sci. 2015, 8, 3572– 3576, DOI: 10.1039/C5EE03008K10https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhslKlu7zF&md5=68fc1fd014604ab64e98f33aeea837b2Photosystem I-polyaniline/TiO2 solid-state solar cells: simple devices for biohybrid solar energy conversionGizzie, Evan A.; Scott Niezgoda, J.; Robinson, Maxwell T.; Harris, Andrew G.; Kane Jennings, G.; Rosenthal, Sandra J.; Cliffel, David E.Energy & Environmental Science (2015), 8 (12), 3572-3576CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)Novel Photosystem I (PSI) based solid-state solar cells were prepd. by directly electropolymg. polyaniline (PAni) in the presence of solubilized PSI on a TiO2 anode. These devices feature a unique bio-derived, photoactive composite layer for efficient charge sepn. and charge transfer from protein to electrode. This work introduces a new artificial photosynthesis platform for scalable and sustainable solar energy conversion.
- 11Beam, J. C.; LeBlanc, G.; Gizzie, E. A.; Ivanov, B. L.; Needell, D. R.; Shearer, M. J.; Jennings, G. K.; Lukehart, C. M.; Cliffel, D. E. Construction of a Semiconductor-Biological Interface for Solar Energy Conversion: P-Doped Silicon/Photosystem I/Zinc Oxide. Langmuir 2015, 31, 10002– 10007, DOI: 10.1021/acs.langmuir.5b0233411https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhsVWnt7vN&md5=778629b0d4513362da375db30f6af127Construction of a Semiconductor-Biological Interface for Solar Energy Conversion: p-Doped Silicon/Photosystem I/Zinc OxideBeam, Jeremiah C.; LeBlanc, Gabriel; Gizzie, Evan A.; Ivanov, Borislav L.; Needell, David R.; Shearer, Melinda J.; Jennings, G. Kane; Lukehart, Charles M.; Cliffel, David E.Langmuir (2015), 31 (36), 10002-10007CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)The interface between photoactive biol. materials with two distinct semiconducting electrodes is challenging both to develop and analyze. Building off of our previous work using films of photosystem I (PSI) on p-doped silicon, we have deposited a cryst. zinc oxide (ZnO) anode using confined-plume chem. deposition (CPCD). We demonstrate the ability of CPCD to deposit cryst. ZnO without damage to the PSI biomaterial. Using electrochem. techniques, we were able to probe this complex semiconductor-biol. interface. Finally, as a proof of concept, a solid-state photovoltaic device consisting of p-doped silicon, PSI, ZnO, and ITO was constructed and evaluated.
- 12Das, R.; Kiley, P. J.; Segal, M.; Norville, J.; Yu, A. A.; Wang, L.; Trammell, S. A.; Reddick, L. E.; Kumar, R.; Stellacci, F.; Lebedev, N.; Schnur, J.; Bruce, B. D.; Zhang, S.; Baldo, M. Integration of Photosynthetic Protein Molecular Complexes in Solid-State Electronic Devices. Nano Lett. 2004, 4, 1079– 1083, DOI: 10.1021/nl049579f12https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2cXktValsLc%253D&md5=19670ae6c5c5c6a2b2f59da6b38f4b17Integration of Photosynthetic Protein Molecular Complexes in Solid-State Electronic DevicesDas, Rupa; Kiley, Patrick J.; Segal, Michael; Norville, Julie; Yu, A. Amy; Wang, Leyu; Trammell, Scott A.; Reddick, L. Evan; Kumar, Rajay; Stellacci, Francesco; Lebedev, Nikolai; Schnur, Joel; Bruce, Barry D.; Zhang, Shuguang; Baldo, MarcNano Letters (2004), 4 (6), 1079-1083CODEN: NALEFD; ISSN:1530-6984. (American Chemical Society)Plants and photosynthetic bacteria contain protein-mol. complexes that harvest photons with nearly optimum quantum yield and an expected power conversion efficiency exceeding 20%. In this work, we demonstrate the integration of elec. active photosynthetic protein-mol. complexes in solid-state devices, realizing photodetectors and photovoltaic cells with internal quantum efficiencies of approx. 12%. Electronic integration of devices is achieved by self-assembling an oriented monolayer of photosynthetic complexes, stabilizing them with surfactant peptides, and then coating them with a protective org. semiconductor.
- 13Ciornii, D.; Riedel, M.; Stieger, K. R.; Feifel, S. C.; Hejazi, M.; Lokstein, H.; Zouni, A.; Lisdat, F. Bioelectronic Circuit on a 3D Electrode Architecture: Enzymatic Catalysis Interconnected With Photosystem I. J. Am. Chem. Soc. 2017, 139, 16478– 16481, DOI: 10.1021/jacs.7b1016113https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhslGnu77O&md5=1101e3a8e40811274e87b4ceda75dd28Bioelectronic Circuit on a 3D Electrode Architecture: Enzymatic Catalysis Interconnected with Photosystem ICiornii, Dmitri; Riedel, Marc; Stieger, Kai R.; Feifel, Sven C.; Hejazi, Mahdi; Lokstein, Heiko; Zouni, Athina; Lisdat, FredJournal of the American Chemical Society (2017), 139 (46), 16478-16481CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Artificial light-driven signal chains are particularly important for the development of systems converting light into a current, into chems. or for light-induced sensing. Here, we report on the construction of an all-protein, light-triggered, catalytic circuit based on photosystem I, cytochrome c (cyt c) and human sulfite oxidase (hSOX). The defined assembly of all components using a modular design results in an artificial biohybrid electrode architecture, combining the photophys. features of PSI with the biocatalytic properties of hSOX for advanced light-controlled bioelectronics. The working principle is based on a competitive switch between electron supply from the electrode or by enzymic substrate conversion.
- 14Passantino, J. M.; Wolfe, K. D.; Simon, K. T.; Cliffel, D. E.; Jennings, G. K. Photosystem I Enhances the Efficiency of a Natural, Gel-Based Dye-Sensitized Solar Cell. ACS Appl. Bio Mater. 2020, 3, 4465– 4473, DOI: 10.1021/acsabm.0c0044614https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhtVaqs7%252FF&md5=c05ce99e63af1f6cc0dc60fe61134da6Photosystem I Enhances the Efficiency of a Natural, Gel-Based Dye-Sensitized Solar CellPassantino, Joshua M.; Wolfe, Kody D.; Simon, Keiann T.; Cliffel, David E.; Jennings, G. KaneACS Applied Bio Materials (2020), 3 (7), 4465-4473CODEN: AABMCB; ISSN:2576-6422. (American Chemical Society)The photosystem I (PSI) protein complex is known to enhance bioelectrode performance for many liq.-based photoelectrochem. cells. A hydrogel as electrolyte media allows for simpler fabrication of more robust and practical solar cells in comparison to liq.-based devices. This paper reports a natural, gel-based dye-sensitized solar cell that integrates PSI to improve device efficiency. TiO2-coated FTO slides, dyed by blackberry anthocyanin, act as a photoanode, while a film of PSI deposited onto copper comprises the photocathode. Ascorbic acid (AscH) and 2,6-dichlorophenolindophenol (DCPIP) are the redox mediator couple inside an agarose hydrogel, enabling PSI to produce excess oxidized species near the cathode to improve device performance. A comparison of performance at low pH and neutral pH was performed to test the pH-dependent properties of the AscH/DCPIP couple. Devices at neutral pH performed better than those at lower pH. The PSI film enhanced photovoltage by 75 mV to a total photovoltage of 0.45 V per device and provided a mediator concn.-dependent photocurrent enhancement over non-PSI devices, reaching an instantaneous power conversion efficiency of 0.30% compared to 0.18% without PSI, a 1.67-fold increase. At steady state, power conversion efficiencies for devices with and without PSI were 0.042 and 0.028%, resp.
- 15Qiu, X.; Ocampo, O. C.; de Vries, H. W.; van Putten, M.; Loznik, M.; Herrmann, A.; Chiechi, R. C. Self-Regenerating Soft Biophotovoltaic Devices. ACS Appl. Mater. Interfaces 2018, 10, 37625– 37633, DOI: 10.1021/acsami.8b1111515https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhvVKlurvO&md5=a9327ea3e2adb1c8ef286d1386da8a2dSelf-Regenerating Soft Biophotovoltaic DevicesQiu, Xinkai; Castaneda Ocampo, Olga; de Vries, Hendrik W.; van Putten, Maikel; Loznik, Mark; Herrmann, Andreas; Chiechi, Ryan C.ACS Applied Materials & Interfaces (2018), 10 (43), 37625-37633CODEN: AAMICK; ISSN:1944-8244. (American Chemical Society)This paper describes the fabrication of soft, stretchable biophotovoltaic devices that generate photocurrent from photosystem I (PSI) complexes that are self-assembled onto Au electrodes with a preferred orientation. Charge is collected by the direct injection of electrons into the Au electrode and the transport of holes through a redox couple to liq. eutectic gallium-indium (EGaIn) (alloy) electrodes that are confined to microfluidic pseudochannels by arrays of posts. The pseudochannels are defined in a single fabrication step that leverages the non-Newtonian rheol. of EGaIn. This strategy is extended to the fabrication of reticulated electrodes that are inherently stretchable. A simple shadow evapn. technique is used to increase the surface area of the Au electrodes by a factor of approx. 106 compared to planar electrodes. The power conversion efficiency of the biophotovoltaic devices decreases over time, presumably as the PSI complexes denature and/or detach from the Au electrodes. However, by circulating a soln. of active PSI complexes the devices self-regenerate by mass action/self-assembly. These devices leverage simple fabrication techniques to produce complex function and prove that photovoltaic devices comprising PSI can retain the ability to regenerate, one of the most important functions of photosynthetic organisms.
- 16Wolfe, K. D.; Dervishogullari, D.; Stachurski, C. D.; Passantino, J. M.; Jennings, G. K.; Cliffel, D. E. Photosystem I Multilayers Within Porous Indium Tin Oxide Cathodes Enhance Mediated Electron Transfer. ChemElectroChem 2020, 7, 596– 603, DOI: 10.1002/celc.20190162816https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXitlGhsbrM&md5=56202e4e1f090f3abc5b509c6aa10892Photosystem I Multilayers within Porous Indium Tin Oxide Cathodes Enhance Mediated Electron TransferWolfe, Kody D.; Dervishogullari, Dilek; Stachurski, Christopher D.; Passantino, Joshua M.; Kane Jennings, G.; Cliffel, David E.ChemElectroChem (2020), 7 (3), 596-603CODEN: CHEMRA; ISSN:2196-0216. (Wiley-VCH Verlag GmbH & Co. KGaA)Understanding and improving charge transfer pathways between extd. Photosystem I (PSI) protein complexes and electrodes is necessary for the development of low-cost PSI-based devices for energy conversion. We incorporated PSI multilayers within porous indium tin oxide (ITO) electrodes and obsd. a greater mediated photocurrent in comparison to multilayers on planar ITO. First, the mediated electron transfer (MET) pathway in the presence of 2,6-dichlorophenolindophenol (DCPIP) and ascorbate (AscH) was studied via photochronoamperometry on planar ITO. ITO nanoparticles were then used to fabricate two porous electrode morphologies; mesoporous (20-100 nm pores) and macroporous (5μm pores). PSI multilayers within macroporous ITO cathodes produced 42±5μA cm-2 of photocurrent, three times the photocurrent produced by mesoporous ITO. Addnl., macroporous cathodes are able to utilize twice as much active surface area, when compared to mesoporous cathodes. Our findings show that MET within PSI multilayers is greater in 5μm macropores than mesoporous ITO due to both an increase in electrode surface area and the location of PSI complexes within the pores. Improving MET in PSI-based bioelectrodes has applications including improving the total charge transfer achieved in PSI-based photoelectrochem. cells or even incorporation in bio-photocatalytic cells.
- 17Ciesielski, P. N.; Hijazi, F. M.; Scott, A. M.; Faulkner, C. J.; Beard, L.; Emmett, K.; Rosenthal, S. J.; Cliffel, D.; Jennings, G. K. Photosystem I-Based biohybrid photoelectrochemical cells. Bioresour. Technol. 2010, 101, 3047– 3053, DOI: 10.1016/j.biortech.2009.12.04517https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXhtVantrg%253D&md5=9e8050e1f7147619d3395b9aa0072acfPhotosystem I- based biohybrid photoelectrochemical cellsCiesielski, Peter N.; Hijazi, Frederick M.; Scott, Amanda M.; Faulkner, Christopher J.; Beard, Lisa; Emmett, Kevin; Rosenthal, Sandra J.; Cliffel, David; Kane Jennings, G.Bioresource Technology (2010), 101 (9), 3047-3053CODEN: BIRTEB; ISSN:0960-8524. (Elsevier Ltd.)Photosynthesis is the process by which Nature coordinates a tandem of protein complexes of impressive complexity that function to harness staggering amts. of solar energy on a global scale. Advances in biochem. and nanotechnol. have provided tools to isolate and manipulate the individual components of this process, thus opening a door to a new class of highly functional and vastly abundant biol. resources. Here we show how one of these components, Photosystem I (PSI), is incorporated into an electrochem. system to yield a stand-alone biohybrid photoelectrochem. cell that converts light energy into elec. energy. The cells make use of a dense multilayer of PSI complexes assembled on the surface of the cathode to produce a photocatalytic effect that generates photocurrent densities of ∼2 μA/cm2 at moderate light intensities. We describe the relationship between the current and voltage prodn. of the cells and the photoinduced interactions of PSI complexes with electrochem. mediators, and show that the performance of the present device is limited by diffusional transport of the electrochem. mediators through the electrolyte. These biohybrid devices display remarkable stability, as they remain active in ambient conditions for at least 280 days. Even at bench-scale prodn., the materials required to fabricate the cells described in this manuscript cost ∼10 cents per cm2 of active electrode area.
- 18Tschörtner, J.; Lai, B.; Krömer, J. O. Biophotovoltaics: Green Power Generation From Sunlight and Water. Front. Microbiol. 2019, 10, 866 DOI: 10.3389/fmicb.2019.0086618https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BB3M7otlemsA%253D%253D&md5=36cf44fed74aed94e6e870f7ee5c031fBiophotovoltaics: Green Power Generation From Sunlight and WaterTschortner Jenny; Lai Bin; Kromer Jens OFrontiers in microbiology (2019), 10 (), 866 ISSN:1664-302X.Biophotovoltaics is a relatively new discipline in microbial fuel cell research. The basic idea is the conversion of light energy into electrical energy using photosynthetic microorganisms. The microbes will use their photosynthetic apparatus and the incoming light to split the water molecule. The generated protons and electrons are harvested using a bioelectrochemical system. The key challenge is the extraction of electrons from the microbial electron transport chains into a solid-state anode. On the cathode, a corresponding electrochemical counter reaction will consume the protons and electrons, e.g., through the oxygen reduction to water, or hydrogen formation. In this review, we are aiming to summarize the current state of the art and point out some limitations. We put a specific emphasis on cyanobacteria, as these microbes are considered future workhorses for photobiotechnology and are currently the most widely applied microbes in biophotovoltaics research. Current progress in biophotovoltaics is limited by very low current outputs of the devices while a lack of comparability and standardization of the experimental set-up hinders a systematic optimization of the systems. Nevertheless, the fundamental questions of redox homeostasis in photoautotrophs and the potential to directly harvest light energy from a highly efficient photosystem, rather than through oxidation of inefficiently produced biomass are highly relevant aspects of biophotovoltaics.
- 19Sokol, K. P.; Mersch, D.; Hartmann, V.; Zhang, J. Z.; Nowaczyk, M. M.; Rögner, M.; Ruff, A.; Schuhmann, W.; Plumeré, N.; Reisner, E. Rational Wiring of Photosystem II to Hierarchical Indium Tin Oxide Electrodes Using Redox Polymers. Energy Environ. Sci. 2016, 9, 3698– 3709, DOI: 10.1039/C6EE01363E19https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XhtFSntr%252FF&md5=19daa1e0f16d1b093fdcba607a154fd1Rational wiring of photosystem II to hierarchical indium tin oxide electrodes using redox polymersSokol, Katarzyna P.; Mersch, Dirk; Hartmann, Volker; Zhang, Jenny Z.; Nowaczyk, Marc M.; Rogner, Matthias; Ruff, Adrian; Schuhmann, Wolfgang; Plumere, Nicolas; Reisner, ErwinEnergy & Environmental Science (2016), 9 (12), 3698-3709CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)A benchmark Photosystem II (PSII)-electrode system that combines the efficient wiring afforded by redox-active polymers with the high loading provided by hierarchically-structured inverse opal indium tin oxide (IO-ITO) electrodes was reported. Compared to flat electrodes, the hierarchical IO-ITO electrodes enabled up to an approx. 50-fold increase in the immobilization of an Os complex-modified and a phenothiazine-modified polymer. When the Os complex-modified polymer is co-adsorbed with PSII on the hierarchical electrodes, photocurrent densities of up to ∼410μA cm-2 at 0.5 V vs. SHE were obsd. in the absence of diffusional mediators, demonstrating a substantially improved wiring of PSII to the IO-ITO electrode with the redox polymer. The high photocurrent d. allowed for the quantification of O2 evolution, and a Faradaic efficiency of 85 ± 9% was measured. As such, we have demonstrated a high performing and fully integrated host-guest system with excellent electronic wiring and loading capacity. This assembly strategy may form the basis of all-integrated electrode designs for a wide range of biol. and synthetic catalysts.
- 20Takekuma, Y.; Ikeda, N.; Kawakami, K.; Kamiya, N.; Nango, M.; Nagata, M. Photocurrent Generation by a Photosystem I-NiO Photocathode for a P-Type Biophotovoltaic Tandem Cell. RSC Adv. 2020, 10, 15734– 15739, DOI: 10.1039/D0RA01793K20https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXnsFSrt74%253D&md5=7af29c8b5f726082b7b6fdc3cd18acbfPhotocurrent generation by a photosystem I-NiO photocathode for a p-type biophotovoltaic tandem cellTakekuma, Yuya; Ikeda, Nobuhiro; Kawakami, Keisuke; Kamiya, Nobuo; Nango, Mamoru; Nagata, MorioRSC Advances (2020), 10 (27), 15734-15739CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)Photosynthesis is a process used by algae and plants to convert light energy into chem. energy. Due to their uniquely natural and environmentally friendly nature, photosynthetic proteins have attracted attention for use in a variety of artificial applications. Among the various types, biophotovoltaics based on dye-sensitized solar cells have been demonstrated in many studies. Although most related works have used n-type semiconductors, a p-type semiconductor is also a significant potential component for tandem cells. In this work, we used mesoporous NiO as a p-type semiconductor substrate for Photosystem I (PSI) and demonstrated a p-type PSI-biophotovoltaic and tandem cell based on dye-sensitized solar cells. Under visible light illumination, the PSI-adsorbed NiO electrode generated a cathodic photocurrent. The p-type biophotovoltaic cell using the PSI-adsorbed NiO electrode generated electricity, and the IPCE spectrum was consistent with the absorption spectrum of PSI. These results indicate that the PSI-adsorbed NiO electrode acts as a photocathode. Moreover, a tandem cell consisting of the PSI-NiO photocathode and a PSI-TiO2 photoanode showed a high open-circuit voltage of over 0.7 V under illumination to the TiO2 side. Thus, the tandem strategy can be utilized for biophotovoltaics, and the use of other biomaterials that match the solar spectrum will lead to further progress in photovoltaic performance.
- 21Takeuchi, R.; Suzuki, A.; Sakai, K.; Kitazumi, Y.; Shirai, O.; Kano, K. Construction of Photo-Driven Bioanodes Using Thylakoid Membranes and Multi-Walled Carbon Nanotubes. Bioelectrochemistry 2018, 122, 158– 163, DOI: 10.1016/j.bioelechem.2018.04.00121https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXntlSht7Y%253D&md5=00463d46342ea4662f259478b016262eConstruction of photo-driven bioanodes using thylakoid membranes and multi-walled carbon nanotubesTakeuchi, Ryosuke; Suzuki, Arato; Sakai, Kento; Kitazumi, Yuki; Shirai, Osamu; Kano, KenjiBioelectrochemistry (2018), 122 (), 158-163CODEN: BIOEFK; ISSN:1567-5394. (Elsevier B.V.)A photo-driven bioanode was constructed using the thylakoid membrane from spinach, carbon nanotubes, and an artificial mediator. By considering a linear free-energy relationship in the electron transfer from the thylakoid membrane to the mediators, and the oxygen resistance of the reduced mediators, 1,2-naphthoquinone was selected as the most suitable mediator for the photo-driven bioanode. Water-dispersed multi-walled carbon nanotubes served as scaffolds to hold the thylakoid membrane on a porous electrode. The constructed photo-driven bioanode exhibited a photocurrent d. of over 100 μA cm-2 at a photon flux d. of 1500 μmol m-2 s-1.
- 22Pankratov, D.; Zhao, J.; Nur, M. A.; Shen, F.; Leech, D.; Chi, Q.; Pankratova, G.; Gorton, L. The Influence of Surface Composition of Carbon Nanotubes on the Photobioelectrochemical Activity of Thylakoid Bioanodes Mediated by Osmium-Complex Modified Redox Polymer. Electrochim. Acta 2019, 310, 20– 25, DOI: 10.1016/j.electacta.2019.04.09722https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXosVSltbk%253D&md5=5d9395e92ef715c2b79468266833dc80The influence of surface composition of carbon nanotubes on the photobioelectrochemical activity of thylakoid bioanodes mediated by osmium-complex modified redox polymerPankratov, Dmitry; Zhao, Jianming; Nur, Mohammed Ahmed; Shen, Fei; Leech, Donal; Chi, Qijin; Pankratova, Galina; Gorton, LoElectrochimica Acta (2019), 310 (), 20-25CODEN: ELCAAV; ISSN:0013-4686. (Elsevier Ltd.)A combination of photosynthetic biocatalysts with high surface area conductive materials mediated by an Os-complex modified redox polymer (OsRP) holds promising features for the development of sustainable green systems for solar energy conversion. The authors performed a comparative study of two types of C nanotubes (CNTs) synthesized by pyrolysis of polymeric precursors. Both CNTs were of similar morphol., but had a different surface C/O ratio. The CNTs were used as a support for immobilization of thylakoid membranes, electrochem. wired through the OsRP. The photobioanodes based on the CNTs with a higher C/O ratio exhibit a higher max. photocurrent d. of 97.1 ± 8.3μA cm-2 at a light intensity of 400 W m-2 with reduced charge transfer resistance, but had lower operational stability. The authors' results demonstrate the significance of studying of electrochem. communication between the photosynthetic component, the redox mediator and the support nanomaterial and may offer new opportunities for designing and optimization of mediated bioelectrochem. systems.
- 23Feifel, S. C.; Stieger, K. R.; Hejazi, M.; Wang, X.; Ilbert, M.; Zouni, A.; Lojou, E.; Lisdat, F. Dihemic C4-Type Cytochrome Acting as a Surrogate Electron Conduit: Artificially Interconnecting a Photosystem I Supercomplex With Electrodes. Electrochem. Commun. 2018, 91, 49– 53, DOI: 10.1016/j.elecom.2018.05.00623https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXpt1Grurs%253D&md5=ec66fe8f8cea36b34ca061106819f57dDihemic c4-type cytochrome acting as a surrogate electron conduit: Artificially interconnecting a photosystem I supercomplex with electrodesFeifel, Sven C.; Stieger, Kai R.; Hejazi, Mahdi; Wang, Xie; Ilbert, Marianne; Zouni, Athina; Lojou, Elisabeth; Lisdat, FredElectrochemistry Communications (2018), 91 (), 49-53CODEN: ECCMF9; ISSN:1388-2481. (Elsevier B.V.)Connection of photosystem I (PSI) with electrodes has been shown to create artificial photosynthetic systems that hold promise for the synthesis of solar fuels. The high quantum yields of PSI require efficient electron transfer from the electrode to the reaction center of PSI in order to restock the light-induced holes, a task which in nature is performed by small redox proteins. Here, we have investigated the potential "wiring" properties of a dihemic c-type cytochrome (cyt c4), in order to efficiently connect PSI with electrodes. Cyt c4 has shown direct electron transfer (DET) with both hemes in elec. communication with two different electrode materials (ITO and Au) and on the basis of cyt c4-multilayer electrodes "self-exchange" properties can also be deduced. Investigation of cyt c4 in combination with PSI within an inverse opal ITO electrode has shown the dihemic protein to be a valuable mol. electron conduit, able to interconnect the photoenzymic reaction with the 3D electrode. The properties have been compared with those of electrodes based on monohemic cyt c derived from horse heart.
- 24Stieger, K. R.; Feifel, S. C.; Lokstein, H.; Hejazi, M.; Zouni, A.; Lisdat, F. Biohybrid Architectures for Efficient Light-to-Current Conversion Based on Photosystem I Within Scalable 3D Mesoporous Electrodes. J. Mater. Chem. A 2016, 4, 17009– 17017, DOI: 10.1039/C6TA07141D24https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28Xhs1SjsrzP&md5=bbbf8b48b5bdcc25f409edd081fdbd3eBiohybrid architectures for efficient light-to-current conversion based on photosystem I within scalable 3D mesoporous electrodesStieger, K. R.; Feifel, S. C.; Lokstein, H.; Hejazi, M.; Zouni, A.; Lisdat, F.Journal of Materials Chemistry A: Materials for Energy and Sustainability (2016), 4 (43), 17009-17017CODEN: JMCAET; ISSN:2050-7496. (Royal Society of Chemistry)The combination of advanced materials and defined surface design with complex proteins from natural photosynthesis is currently one of the major topics in the development of biohybrid systems and biophotovoltaic devices. In this study transparent mesoporous indium tin oxide (μITO) electrodes have been used in combination with the trimeric supercomplex photosystem I (PSI) from Thermosynechococcus elongatus and the small redox protein cytochrome c (cyt c) from horse heart to fabricate advanced and efficient photobiocathodes. The prepn. of the μITO via spin coating allows easy scalability and ensures a defined increase in the electrochem. active surface area with accessibility for both proteins. Using these 3D electrodes up to 40 μm thickness, the immobilization of cyt c and PSI with full monolayer coverage and their elec. communication to the electrode can be achieved. Significant improvement can be made when the heterogeneous electron transfer rate const. of cyt c with the electrode is increased by an appropriate surface treatment. The photocurrent follows linearly the thickness of the μITO and current densities of up to 150 μA/cm2 can be obtained without indications of a limitation. The internal quantum efficiency is detd. to be 39% which demonstrates that the wiring of PSI via cyt c can be advantageously used in a system with high protein loading and efficient electron pathways inside 3D transparent conducting oxides.
- 25Ciornii, D.; Kölsch, A.; Zouni, A.; Lisdat, F. A Precursor-Approach in Constructing 3D ITO Electrodes for the Improved Performance of Photosystem I-Cyt C Photobioelectrodes. Nanoscale 2019, 11, 15862– 15870, DOI: 10.1039/C9NR04344F25https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhtlGrsLzP&md5=6489c1d9447e871ca7804714e93dcf9dA precursor-approach in constructing 3D ITO electrodes for the improved performance of photosystem I-cyt c photobioelectrodesCiornii, Dmitri; Koelsch, Adrian; Zouni, Athina; Lisdat, FredNanoscale (2019), 11 (34), 15862-15870CODEN: NANOHL; ISSN:2040-3372. (Royal Society of Chemistry)In recent years the use of photoelectrodes based on conductive metal oxides has become very popular in the field of photovoltaics. The application of 3D electrodes holds great promise since they can integrate large amts. of photoactive proteins. In this study photosystem I (PSI) from the thermophilic cyanobacterium Thermosynechococcus elongatus was immobilized on 3D ITO electrodes and elec. wired via the redox protein cytochrome c (cyt c). The main goal, however, was the investigation of construction parameters of such electrodes for achieving a high performance. For this, ITO electrodes were constructed from liq. precursors resulting in improved transmission compared to previous nanoparticle-based prepn. protocols. First, the doping level of Sn was varied for establishing suitable conditions for a fast cyt c electrochem. on such 3D electrodes. In a second step the pore diam. was varied in order to elucidate optimal conditions. Third, the scalability of the template-based prepn. was studied from 3 to 15 layers during spin coating and the subsequent baking step. In the thickness range from 3 to 17 μm no limitation in the protein immobilization and also in the photocurrent generation was found. Consequently, a photocurrent of about 270 μA cm-2 and a turnover no. (Te) of 30 e- s-1 at PSI were achieved. Because of the high current flow the withdrawal of electrons at the stromal side of PSI becomes clearly rate limiting. Here improved transport conditions and alternative electron acceptors were studied to overcome this limitation.
- 26Stieger, K. R.; Feifel, S. C.; Lokstein, H.; Lisdat, F. Advanced Unidirectional Photocurrent Generation via Cytochrome C as Reaction Partner for Directed Assembly of Photosystem I. Phys. Chem. Chem. Phys. 2014, 16, 15667– 15674, DOI: 10.1039/C4CP00935E26https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhtVCis7vI&md5=a98d058ac69140163341466e72f692b7Advanced unidirectional photocurrent generation via cytochrome c as reaction partner for directed assembly of photosystem IStieger, Kai R.; Feifel, Sven C.; Lokstein, Heiko; Lisdat, FredPhysical Chemistry Chemical Physics (2014), 16 (29), 15667-15674CODEN: PPCPFQ; ISSN:1463-9076. (Royal Society of Chemistry)Conversion of light into an elec. current based on biohybrid systems mimicking natural photosynthesis is becoming increasingly popular. Photosystem I (PSI) is particularly useful in such photo-bioelectrochem. devices. Herein, we report on a novel biomimetic approach for an effective assembly of photosystem I with the electron transfer carrier cytochrome c (cyt c), deposited on a thiol-modified gold-surface. Atomic force microscopy and surface plasmon resonance measurements have been used for characterization of the assembly process. Photoelectrochem. expts. demonstrate a cyt c mediated generation of an enhanced unidirectional cathodic photocurrent. Here, cyt c can act as a template for the assembly of an oriented and dense layer of PSI and as wiring agent to direct the electrons from the electrode towards the photosynthetic reaction center of PSI. Furthermore, three-dimensional protein architectures have been formed via the layer-by-layer deposition technique resulting in a successive increase in photocurrent densities. An intermittent cyt c layer is essential for an efficient connection of PSI layers with the electrode and for an improvement of photocurrent densities.
- 27Szalkowski, M.; Olmos, J. D. J.; Buczyńska, D.; Maćkowski, S.; Kowalska, D.; Kargul, J. Plasmon-Induced Absorption of Blind Chlorophylls in Photosynthetic Proteins Assembled on Silver Nanowires. Nanoscale 2017, 9, 10475– 10486, DOI: 10.1039/C7NR03866F27https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2sXhtV2qt7%252FI&md5=233ee6126bc853fabc2720248293bc08Plasmon-induced absorption of blind chlorophylls in photosynthetic proteins assembled on silver nanowiresSzalkowski, Marcin; Janna Olmos, Julian David; Buczynska, Dorota; Mackowski, Sebastian; Kowalska, Dorota; Kargul, JoannaNanoscale (2017), 9 (29), 10475-10486CODEN: NANOHL; ISSN:2040-3372. (Royal Society of Chemistry)We demonstrate that controlled assembly of eukaryotic photosystem I with its assocd. light harvesting antenna complex (PSI-LHCI) on plasmonically active silver nanowires (AgNWs) substantially improves the optical functionality of such a novel biohybrid nanostructure. By comparing fluorescence intensities measured for PSI-LHCI complex randomly oriented on AgNWs and the results obtained for the PSI-LHCI/cytochrome c553 (cyt c553) bioconjugate with AgNWs we conclude that the specific binding of photosynthetic complexes with defined uniform orientation yields selective excitation of a pool of chlorophyll (Chl) mols. that are otherwise almost non-absorbing. This is remarkable, as this study shows for the first time that plasmonic excitations in metallic nanostructures can not only be used to enhance native absorption of photosynthetic pigments, but also - by employing cyt c553 as the conjugation cofactor - to activate the specific Chl pools as the absorbing sites only when the uniform and well-defined orientation of PSI-LHCI with respect to plasmonic nanostructures is achieved. As absorption of PSI alone is comparatively low, our approach lends itself as an innovative approach to outperform the reported-to-date biohybrid devices with respect to solar energy conversion.
- 28Gordiichuk, P.; Pesce, D.; Ocampo, O. E. C.; Marcozzi, A.; Wetzelaer, G.-J. A. H.; Paul, A.; Loznik, M.; Gloukhikh, E.; Richter, S.; Chiechi, R. C.; Herrmann, A. Orientation and Incorporation of Photosystem I in Bioelectronics Devices Enabled by Phage Display. Adv. Sci. 2017, 4, 1600393 DOI: 10.1002/advs.20160039328https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BC1cnhsFehtg%253D%253D&md5=ac726426219ea715a84d650868b10fc9Orientation and Incorporation of Photosystem I in Bioelectronics Devices Enabled by Phage DisplayGordiichuk Pavlo; Pesce Diego; Marcozzi Alessio; Wetzelaer Gert-Jan A H; Paul Avishek; Loznik Mark; Herrmann Andreas; Ocampo Olga E Castaneda; Chiechi Ryan C; Gloukhikh Ekaterina; Richter ShacharAdvanced science (Weinheim, Baden-Wurttemberg, Germany) (2017), 4 (5), 1600393 ISSN:2198-3844.Interfacing proteins with electrode surfaces is important for the field of bioelectronics. Here, a general concept based on phage display is presented to evolve small peptide binders for immobilizing and orienting large protein complexes on semiconducting substrates. Employing this method, photosystem I is incorporated into solid-state biophotovoltaic cells.
- 29Castañeda Ocampo, O. E.; Gordiichuk, P.; Catarci, S.; Gautier, D. A.; Herrmann, A.; Chiechi, R. C. Mechanism of Orientation-Dependent Asymmetric Charge Transport in Tunneling Junctions Comprising Photosystem I. J. Am. Chem. Soc. 2015, 137, 8419– 8427, DOI: 10.1021/jacs.5b0124129https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2MXhtVansLzP&md5=703c9c1be3e0c71bca1efc07de0bf0ccMechanism of Orientation-Dependent Asymmetric Charge Transport in Tunneling Junctions Comprising Photosystem ICastaneda Ocampo, Olga E.; Gordiichuk, Pavlo; Catarci, Stefano; Gautier, Daniel A.; Herrmann, Andreas; Chiechi, Ryan C.Journal of the American Chemical Society (2015), 137 (26), 8419-8427CODEN: JACSAT; ISSN:0002-7863. (American Chemical Society)Recently, photoactive proteins have gained a lot of attention due to their incorporation into bioinspired (photo)electrochem. and solar cells. This paper describes the measurement of the asymmetry of current transport of self-assembled monolayers (SAMs) of the entire photosystem I (PSI) protein complex (not the isolated reaction center, RCI), on two different "director SAMs" supported by ultraflat Au substrates. The director SAMs induce the preferential orientation of PSI, which manifest as asymmetry in tunneling charge-transport. We measured the oriented SAMs of PSI using eutectic Ga-In (EGaIn), a large-area technique, and conducting probe at. force microscopy (CP-AFM), a single-complex technique, and detd. that the transport properties are comparable. By varying the temps. at which the measurements were performed, we found that there is no measurable dependence of the current on temp. from ±0.1 to ±1.0 V bias, and thus, we suggest tunneling as the mechanism for transport; there are no thermally activated (e.g., hopping) processes. Therefore, it is likely that relaxation in the electron transport chain is not responsible for the asymmetry in the conductance of SAMs of PSI complexes in these junctions, which we ascribe instead to the presence of a large, net dipole moment present in PSI.
- 30Gunther, D.; LeBlanc, G.; Prasai, D.; Zhang, J. R.; Cliffel, D. E.; Bolotin, K. I.; Jennings, G. K. Photosystem I on Graphene as a Highly Transparent, Photoactive Electrode. Langmuir 2013, 29, 4177– 4180, DOI: 10.1021/la305020c30https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXktF2mtbc%253D&md5=9de728bb1d5bcf5f93da74f7baf05911Photosystem I on Graphene as a Highly Transparent, Photoactive ElectrodeGunther, Darlene; LeBlanc, Gabriel; Prasai, Dhiraj; Zhang, Jamie R.; Cliffel, David E.; Bolotin, Kirill I.; Jennings, G. KaneLangmuir (2013), 29 (13), 4177-4180CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)We report the fabrication of a hybrid light-harvesting electrode consisting of photosystem I (PSI) proteins extd. from spinach and adsorbed as a monolayer onto elec. contacted, large-area graphene. The transparency of graphene supports the choice of an opaque mediator at elevated concns. For example, we report a photocurrent of 550 nA/cm2 from a monolayer of PSI on graphene in the presence of 20 mM methylene blue, which yields an opaque blue soln. The PSI-modified graphene electrode has a total thickness of less than 10 nm and demonstrates photoactivity that is an order of magnitude larger than that for unmodified graphene, establishing the feasibility of conjoining these nanomaterials as potential constructs in next-generation photovoltaic devices.
- 31Manocchi, A. K.; Baker, D. R.; Pendley, S. S.; Nguyen, K.; Hurley, M. M.; Bruce, B. D.; Sumner, J. J.; Lundgren, C. A. Photocurrent Generation From Surface Assembled Photosystem I on Alkanethiol Modified Electrodes. Langmuir 2013, 29, 2412– 2419, DOI: 10.1021/la304477u31https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhvVynur0%253D&md5=669eafadcfda7f831a4c8e0a462f73dcPhotocurrent generation from surface assembled photosystem I on alkanethiol modified electrodesManocchi, Amy K.; Baker, David R.; Pendley, Scott S.; Nguyen, Khoa; Hurley, Margaret M.; Bruce, Barry D.; Sumner, James J.; Lundgren, Cynthia A.Langmuir (2013), 29 (7), 2412-2419CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)Photosystem I (PSI) is a key component of oxygenic photosynthetic electron transport because of its light-induced electron transfer to the sol. electron acceptor ferredoxin. This work demonstrates the incorporation of surface assembled cyanobacterial trimeric PSI complexes into a biohybrid system for light-driven current generation. Specifically, this work demonstrates the improved assembly of PSI via electrophoretic deposition, with controllable surface assembled PSI d., on different self-assembled alkanethiol monolayers. Using artificial electron donors and acceptors (Os(bpy)2Cl2 and Me viologen) we demonstrate photocurrent generation from a single PSI layer, which remains photoactive for at least three hours of intermittent illumination. Photoelectrochem. comparison of the biohybrid systems assembled from different alkanethiols (hexanethiol, aminohexanethiol, mercaptohexanol, and mercaptohexanoic acid) reveals that the PSI generated photocurrent is enhanced by almost 5 times on neg. charged SAM surfaces as compared to pos. charged surfaces. These results are discussed in light of how PSI is oriented upon electrodeposition on a SAM.
- 32Badura, A.; Kothe, T.; Schuhmann, W.; Rögner, M. Wiring Photosynthetic Enzymes to Electrodes. Energy Environ. Sci. 2011, 4, 3263, DOI: 10.1039/c1ee01285a32https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXht1Cqs7jF&md5=878fdd7d7c689e1110c78db776258354Wiring photosynthetic enzymes to electrodesBadura, Adrian; Kothe, Tim; Schuhmann, Wolfgang; Roegner, MatthiasEnergy & Environmental Science (2011), 4 (9), 3263-3274CODEN: EESNBY; ISSN:1754-5706. (Royal Society of Chemistry)A review. The efficient electron transfer between redox enzymes and electrode surfaces can be obtained by wiring redox enzymes using, for instance, polymer-bound redox relays as has been demonstrated as a basis for the design of amperometric biosensors, logic gates or sensor arrays and more general as a central aspect of "bioelectrochem.". Related devices allow exploiting the unique catalytic properties of enzymes, among which photosynthetic enzymes are esp. attractive due to the possibility to trigger the redox reactions upon irradn. with light. Photocatalytic properties such as the light-driven water splitting by photosystem 2 make them unique candidates for the development of semiartificial devices which convert light energy into stable chem. product, like hydrogen. This review summarizes recent concepts for the integration of photosystem 1 and photosystem 2 into bioelectrochem. devices with special focus on strategies for the design of electron transfer pathways between redox enzymes and conductive supports.
- 33Pachoumi, O.; Bakulin, A. A.; Sadhanala, A.; Sirringhaus, H.; Friend, R. H.; Vaynzof, Y. Improved Performance of ZnO/Polymer Hybrid Photovoltaic Devices by Combining Metal Oxide Doping and Interfacial Modification. J. Phys. Chem. C 2014, 118, 18945– 18950, DOI: 10.1021/jp506266f33https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXht1Sqsb%252FJ&md5=73d602ba597e489f75c6ae4f2749224fImproved Performance of ZnO/Polymer Hybrid Photovoltaic Devices by Combining Metal Oxide Doping and Interfacial ModificationPachoumi, Olympia; Bakulin, Artem A.; Sadhanala, Aditya; Sirringhaus, Henning; Friend, Richard H.; Vaynzof, YanaJournal of Physical Chemistry C (2014), 118 (33), 18945-18950CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)Photoinduced charge sepn. at hybrid org.-inorg. interfaces is poorly understood and challenging to control. Charge sepn. is investigated at a model system of ZnO/poly(3-hexylthiophene) (P3HT) and employ Sr doping of ZnO and phenyl-C61-butyric acid (PCBA) self-assembled modification to study and enhance the charge sepn. efficiency. Ti was found that doping alone lowers the efficiency of charge sepn. due to the introduction of defect states at the oxide surface. However, with the combination of doping and mol. modification, charge sepn. efficiency is significantly enhanced due to the passivation of interfacial traps and improved modifier coverage. This demonstrates a complex noncumulative effect of doping and surface modification and shows that with the correct choice of metal oxide dopant and org. modifier, a poorly performing hybrid interface can be turned into an efficient one.
- 34Lee, E. J.; Heo, S. W.; Han, Y. W.; Moon, D. K. An Organic-inorganic Hybrid Interlayer for Improved Electron Extraction in Inverted Polymer Solar Cells. J. Mater. Chem. C 2016, 4, 2463– 2469, DOI: 10.1039/C5TC03754A34https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC28XlsVSksg%253D%253D&md5=f836d3e8a73f5dbe14d2004188ff2d68An organic-inorganic hybrid interlayer for improved electron extraction in inverted polymer solar cellsLee, Eui Jin; Heo, Soo Won; Han, Yong Woon; Moon, Doo KyungJournal of Materials Chemistry C: Materials for Optical and Electronic Devices (2016), 4 (13), 2463-2469CODEN: JMCCCX; ISSN:2050-7534. (Royal Society of Chemistry)We fabricated inverted polymer solar cells (PSCs) using an org.-inorg. hybrid interlayer for electron extn. The surface energy and surface defects of an org.-inorg. ZnO-PFN hybrid film, which was prepd. by dissolving the conjugated polymer electrolyte poly[(9,9-bis(3'-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctyl-fluorene)] (PFN) in a ZnO soln., were reduced, compared to ZnO film. By introducing the ZnO-PFN electron extn. layer, the interfacial contact between the active and electron extn. layers was improved and the series resistance of the PSC device was decreased. As a result, electron extn. from the active layer to the electrode was enhanced. The highest power conversion efficiency (PCE) of the inverted PSCs was 9.2%. Also, the ZnO-PFN-based inverted PSCs showed improved long-term stability compared to ZnO-based devices. The ZnO-PFN interlayer aimed to overcome the drawbacks of the conventional hydrophilic surface of ZnO, based on the properties of the conjugated polymer (PFN) without the need for addnl. processes. It was therefore simple to fabricate the inverted PSCs, making the devices com. viable.
- 35Thu, C. Role of the Metal-Oxide Work Function on Photocurrent Generation in Hybrid Solar Cells. Sci. Rep. 2018, 8, 3559 DOI: 10.1038/s41598-018-21721-235https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A280%3ADC%252BC1MrkvVOhtw%253D%253D&md5=1842ee7f3709658f9c60eb85da1a8d18Role of the Metal-Oxide Work Function on Photocurrent Generation in Hybrid Solar CellsThu Chawloon; Ehrenreich Philipp; Wong Ka Kan; Zimmermann Eugen; Wang Wei; Fakharuddin Azhar; Putnik Martin; Kalb Julian; Pfadler Thomas; Schmidt-Mende Lukas; Dorman James; Drivas Charalampos; Kennou Stella; Koutsoubelitis Aimilios; Palilis Leonidas C; Vasilopoulou MariaScientific reports (2018), 8 (1), 3559 ISSN:.ZnO is a widely used metal-oxide semiconductor for photovoltaic application. In solar cell heterostructures they not only serve as a charge selective contact, but also act as electron acceptor. Although ZnO offers a suitable interface for exciton dissociation, charge separation efficiencies have stayed rather poor and conceptual differences to organic acceptors are rarely investigated. In this work, we employ Sn doping to ZnO nanowires in order to understand the role of defect and surface states in the charge separation process. Upon doping we are able to modify the metal-oxide work function and we show its direct correlation with the charge separation efficiency. For this purpose, we use the polymer poly(3-hexylthiophene) as donor and the squaraine dye SQ2 as interlayer. Interestingly, neither mobilities nor defects are prime performance limiting factor, but rather the density of available states around the conduction band is of crucial importance for hybrid interfaces. This work highlights crucial aspects to improve the charge generation process of metal-oxide based solar cells and reveals new strategies to improve the power conversion efficiency of hybrid solar cells.
- 36Aryal, U. K.; Arivunithi, V. M.; Reddy, S. S.; Kim, J.; Gal, Y.-S.; Jin, S.-H. Efficient Dual Cathode Interfacial Layer for High Performance Organic and Perovskite Solar Cells. Org. Electron. 2018, 63, 222– 230, DOI: 10.1016/j.orgel.2018.09.03436https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhvVegsrbF&md5=b5e5cbf20306ceab76f0bac5a3aae69fEfficient dual cathode interfacial layer for high performance organic and perovskite solar cellsAryal, Um Kanta; Arivunithi, Veera Murugan; Reddy, Saripally Sudhaker; Kim, Junyoung; Gal, Yeong-Soon; Jin, Sung-HoOrganic Electronics (2018), 63 (), 222-230CODEN: OERLAU; ISSN:1566-1199. (Elsevier B.V.)Cathode interfacial layer (CIL), phenylquinoline-based, 10-ethyl-3,7-bis(4-phenylquinolin-2-yl)-10H-phenothiazine (PTDPQ) was employed between the ZnO and photoactive layer, poly[4,8-bis[(2-ethylhexyl)oxy]benzo[1,2-b:4,5-b']dithiophene-2,6-diyl][3-fluoro-2-[(2-ethylhexyl)carbonyl] thieno[3,4-b]-thiophenediyl] (PTB7):[6,6]-Ph C71-butyric acid Me ester (PC71BM) for the inverted org. solar cells (IOSCs) and between LiF and PTB7:PC71BM for conventional org. solar cells (COSCs). It was also incorporated as interfacial layer in perovskite solar cells (PSCs). For the ZnO/PTDPQ bilayer, the power conversion efficiency (PCE) enhanced to 8.69%, which is about 15% improvement than that of the control IOSCs ref. device. For the PTDPQ/LiF bilayer, it was achieved to 8.06%, and after insertion of PTDPQ as interfacial layer for PSCs, av. PCE enhanced to 16.45% from that of 15.28% ref. device. Hereinafter, PTDPQ as CIL enhances the solar cells device performance. It is analyzed that the charge recombination is suppressed and facilitates charge extn. due to the incorporation of the dual CIL as accordance with obsd. improvement of the solar cell parameters. The devices with dual CIL showed the higher electron mobility which matches with the higher fill factor and improved c.d. The dual CIL exhibited excellent impact on enhancing the photovoltaic properties of OSCs and PSCs along with long-term stability.
- 37Alshanableh, A.; Tan, S. T.; Yap, C. C.; Lee, H. B.; Oleiwi, H. F.; Hong, K. J.; Jumali, M. H. H.; Yahaya, M. Surface Engineering of ZnO Nanorod for Inverted Organic Solar Cell. Mater. Sci. Eng., B 2018, 238–239, 136– 141, DOI: 10.1016/j.mseb.2018.12.02437https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXotFer&md5=4e9c163ac271747f0eabdd4ec5350f7aSurface engineering of ZnO nanorod for inverted organic solar cellAlshanableh, Abdelelah; Tan, Sin Tee; Yap, Chi Chin; Lee, Hock Beng; Oleiwi, Hind Fadhil; Hong, Kai Jeat; Jumali, Mohd. Hafizuddin Hj.; Yahaya, MuhammadMaterials Science & Engineering, B: Advanced Functional Solid-State Materials (2018), 238-239 (), 136-141CODEN: MSBTEK; ISSN:0921-5107. (Elsevier B.V.)Crystallinity and band offset alignment of inorg. electron acceptor play a vital role in enhancing the device performance of inverted org. solar cell (IOSC). In this report, homogenous and vertically-aligned chem. treated ZnO nanorods (ZNR) were successfully grown on fluorine-doped tin oxide (FTO) substrate via a fully-soln. method. It was found that the morphol. of ZnO was fine-tuned from truncated surface to tubular structure under both of the anionic (KOH) and protonic (HCl) treatment. An extraordinary defect quenching phenomenon and hyperchromic energy band edge shift were obsd. in 0.1 M KOH-treated ZNR proven by the highest (002) peak detection and the lowest defect d. Compared with the pristine sample, the 0.1 M KOH-treated ZNR device showed a remarkable improvement in power conversion efficiency (PCE) up to 0.32%, signifying the effectiveness of anodic treatment. The robust correlation between the dependency of chem. treated ZNR and the device performance was established. This work elucidates a feasible method towards efficient IOSC devices development.
- 38Hummelen, J. C.; Knight, B. W.; LePeq, F.; Wudl, F.; Yao, J.; Wilkins, C. L. Preparation and Characterization of Fulleroid and Methanofullerene Derivatives. J. Org. Chem. 1995, 60, 532– 538, DOI: 10.1021/jo00108a01238https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2MXjtlOhtrY%253D&md5=d273aa4dee90ae3622b0d24d838d41d3Preparation and Characterization of Fulleroid and Methanofullerene DerivativesHummelen, Jan C.; Knight, Brian W.; LePeq, F.; Wudl, Fred; Yao, Jie; Wilkins, Charles L.Journal of Organic Chemistry (1995), 60 (3), 532-8CODEN: JOCEAH; ISSN:0022-3263. (American Chemical Society)We describe the synthesis and complete characterization of sol. derivs. of C60 for applications to physics and biol. The goal of the strategy was to have a "modular" approach in order to be able to easily vary a functional group attached indirectly to the cluster. The functionality could be hydrophilic (e.g., histamide) or hydrophobic (e.g., cholestanoxy). The former was prepd. for biol. studies and the latter for photophys. studies toward improvement of photoinduced electron transfer efficiencies in the fabrication of photodetectors and photodiodes. An important intermediate, a carboxylic acid, was found to be recalcitrant to characterization by the usual mass spectroscopic and elemental anal. techniques. This problem was solved by the use of MALDI-MS. The carboxylic acid was easily converted to the key intermediate acid chloride, which in turn was convertible to a large variety of derivs. Both isomeric forms ([5,6], fulleroid and [6,6], methanofullerene) of the C61 clusters were prepd. The fulleroid formation could have given rise to a 50:50 mixt. of phenyl-over-former pentagon phenyl-over-former hexagon isomers but, remarkably, afforded a 95:5 mixt. of these isomers, resp. The fulleroid and methanofullerene gave different cyclic voltammograms, with the former being reduced at 34 mV more pos. potential than the latter.
- 39Ortiz, M. L.; Zamora, R. A.; Giannotti, M. I.; Hu, C.; Croce, R.; Gorostiza, P. Distance and Potential Dependence of Charge Transport Through the P700 Reaction Center of Photosystem I. ChemRxiv 2021, DOI: 10.26434/chemrxiv.14556048There is no corresponding record for this reference.
- 40Qiu, X.; Ivasyshyn, V.; Qiu, L.; Enache, M.; Dong, J.; Rousseva, S.; Portale, G.; Stöhr, M.; Hummelen, J. C.; Chiechi, R. C. Thiol-Free Self-Assembled Oligoethylene Glycols Enable Robust Air-Stable Molecular Electronics. Nat. Mater. 2020, 19, 330– 337, DOI: 10.1038/s41563-019-0587-x40https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXivFKhu7s%253D&md5=7be85fccbe6c04386651e776832efa08Thiol-free self-assembled oligoethylene glycols enable robust air-stable molecular electronicsQiu, Xinkai; Ivasyshyn, Viktor; Qiu, Li; Enache, Mihaela; Dong, Jingjin; Rousseva, Sylvia; Portale, Giuseppe; Stohr, Meike; Hummelen, Jan C.; Chiechi, Ryan C.Nature Materials (2020), 19 (3), 330-337CODEN: NMAACR; ISSN:1476-1122. (Nature Research)Self-assembled monolayers (SAMs) are widely used to engineer the surface properties of metals. The relatively simple and versatile chem. of metal-thiolate bonds makes thiolate SAMs the preferred option in a range of applications, yet fragility and a tendency to oxidize in air limit their long-term use. Here, we report the formation of thiol-free self-assembled mono- and bilayers of glycol ethers, which bind to the surface of coinage metals through the spontaneous chemisorption of glycol ether-functionalized fullerenes. As-prepd. assemblies are bilayers presenting fullerene cages at both the substrate and ambient interface. Subsequent exposure to functionalized glycol ethers displaces the topmost layer of glycol ether-functionalized fullerenes, and the resulting assemblies expose functional groups to the ambient interface. These layers exhibit the key properties of thiolate SAMs, yet they are stable to ambient conditions for several weeks, as shown by the performance of tunnelling junctions formed from SAMs of alkyl-functionalized glycol ethers. Glycol ether-functionalized spiropyrans incorporated into mixed monolayers lead to reversible, light-driven conductance switching. Self-assemblies of glycol ethers are drop-in replacements for thiolate SAMs that retain all of their useful properties while avoiding the drawbacks of metal-thiolate bonds.
- 41Vaynzof, Y.; Kabra, D.; Zhao, L.; Ho, P. K. H.; Wee, A. T.-S.; Friend, R. H. Improved Photoinduced Charge Carriers Separation in Organic-Inorganic Hybrid Photovoltaic Devices. Appl. Phys. Lett. 2010, 97, 033309 DOI: 10.1063/1.346497341https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXptFKjs7Y%253D&md5=04a2df49c4241d355701c823b3b01e71Improved photoinduced charge carriers separation in organic-inorganic hybrid photovoltaic devicesVaynzof, Yana; Kabra, Dinesh; Zhao, Lihong; Ho, Peter K. H.; Wee, Andrew T.-S.; Friend, Richard H.Applied Physics Letters (2010), 97 (3), 033309/1-033309/3CODEN: APPLAB; ISSN:0003-6951. (American Institute of Physics)We demonstrate enhanced performance of a hybrid photovoltaic device, where poly3-hexylthiophene (P3HT) is used as active material and a soln.-processed thin flat film of ZnO-modified by a self-assembled monolayer (SAM) of phenyl-C61-butyric acid (PCBA) is used as electron extg. electrode. UV photoemission spectroscopy measurements reveal an increase in the substrate work function from 3.6 to 4.1 eV upon PCBA SAM deposition due to an interfacial dipole pointing away from the ZnO. External quantum efficiency (EQE) of the SAM modified devices reached 9%, greatly improved over the 3% EQE of the unmodified devices. This corresponds to full charge sepn. of all photoexcitations generated in the P3HT within an exciton diffusion range from the interface. (c) 2010 American Institute of Physics.
- 42Vaynzof, Y.; Bakulin, A. A.; Gélinas, S.; Friend, R. H. Direct Observation of Photoinduced Bound Charge-Pair States at an Organic-Inorganic Semiconductor Interface. Phys. Rev. Lett. 2012, 108, 246605 DOI: 10.1103/PhysRevLett.108.24660542https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XhtVamt77M&md5=6dab33a72a665864e44bcb86ff7fc59dDirect observation of photoinduced bound charge-pair states at an organic-inorganic semiconductor interfaceVaynzof, Yana; Bakulin, Artem A.; Gelinas, Simon; Friend, Richard H.Physical Review Letters (2012), 108 (24), 246605/1-246605/5CODEN: PRLTAO; ISSN:0031-9007. (American Physical Society)It is generally considered that photoinduced charge transfer at the org.-inorg. interfaces in hybrid photovoltaic devices immediately results in a pair of free charge carriers. We extend a novel interface-selective ultrafast "optical pump-push photocurrent probe" technique to study hybrid photovoltaic systems and observe bound electron-hole pair states at the org.-inorg. interface formed between electron-accepting zinc oxide and electron-donating conjugated polymers. We est. that ∼50% of photogenerated charges stay bound and later recombine, thus hindering the photovoltaic performance of polymer/ZnO cells. We further demonstrate that interface modification with a fullerene deriv. decreases the fraction of bound charges to ∼25%, which substantially improves the device efficiency.
- 43Lee, I.; Lee, J. W.; Greenbaum, E. Biomolecular Electronics: Vectorial Arrays of Photosynthetic Reaction Centers. Phys. Rev. Lett. 1997, 79, 3294– 3297, DOI: 10.1103/PhysRevLett.79.329443https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2sXmvV2rt70%253D&md5=4d9c2307afc49d3cdb36872c7fd0287eBiomolecular Electronics: Vectorial Arrays of Photosynthetic Reaction CentersLee, Ida; Lee, James W.; Greenbaum, EliasPhysical Review Letters (1997), 79 (17), 3294-3297CODEN: PRLTAO; ISSN:0031-9007. (American Physical Society)Two-dimensional vectorial arrays of functional Photosystem I reaction centers have been prepd. on atomically flat derivatized gold surfaces. The nature and extent of orientation were controlled by chem. modification of the surface deriv. For mercaptoacetic acid, 83 of the electron transport vectors were parallel to the surface, whereas with 2-mercaptoethanol 70 were oriented perpendicularly in the "up" position and only 2 were in the "down" position. No preferential orientation was obsd. with 2-dimethylaminoethanethiol.
- 44Faulkner, C. J.; Lees, S.; Ciesielski, P. N.; Cliffel, D. E.; Jennings, G. K. Rapid Assembly of Photosystem I Monolayers on Gold Electrodes. Langmuir 2008, 24, 8409– 8412, DOI: 10.1021/la800670b44https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXos1ahtr8%253D&md5=8a4e1f81b64db8fc401089debdf8c6cfRapid Assembly of Photosystem I Monolayers on Gold ElectrodesFaulkner, Christopher J.; Lees, Susan; Ciesielski, Peter N.; Cliffel, David E.; Jennings, G. KaneLangmuir (2008), 24 (16), 8409-8412CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)Photosystem I (PSI) has drawn widespread interest for use in biomimetically inspired energy conversion devices upon extg. it from plants or cyanobacteria and assembling it at surfaces. Here, we demonstrate that a critically dense monolayer of spinach-derived PSI must be formed on an electrode surface to achieve optimal photocurrents, and we introduce a new method for prepg. these dense PSI monolayers that reduces the time required for assembly by ∼80-fold in comparison to that for adsorption from soln. This method consists of applying a vacuum above the aq. PSI soln. during assembly to conc. PSI and ppt. it into a thick layer onto the surface of various self-assembled monolayers or directly onto the electrode surface. Rinsing with water yields a dense monolayer of PSI that draws ∼100 nA/cm of light-induced current from the gold electrode in the presence of appropriate mediators.
- 45Rippka, R.; Stanier, R. Y.; Deruelles, J.; Herdman, M.; Waterbury, J. B. Generic Assignments, Strain Histories and Properties of Pure Cultures of Cyanobacteria. Microbiology 1979, 111, 1– 61, DOI: 10.1099/00221287-111-1-1There is no corresponding record for this reference.
- 46Mukherjee, D.; May, M.; Vaughn, M.; Bruce, B. D.; Khomami, B. Controlling the Morphology of Photosystem I Assembly on Thiol-Activated Au Substrates. Langmuir 2010, 26, 16048– 16054, DOI: 10.1021/la102832x46https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3cXhtFKlu7bN&md5=a3ae7031c54effac2215ebe5d7c20de3Controlling the Morphology of Photosystem I Assembly on Thiol-Activated Au SubstratesMukherjee, Dibyendu; May, Mark; Vaughn, Michael; Bruce, Barry D.; Khomami, BaminLangmuir (2010), 26 (20), 16048-16054CODEN: LANGD5; ISSN:0743-7463. (American Chemical Society)Morphol. variations of Photosystem I (PS I) assembly on hydroxyl-terminated alkanethiolate self-assembled monolayer (SAM)/Au substrates with various deposition techniques is presented. Our studies indicate that deposition conditions such as PS I concn. and driving force play a central role in detg. organization of immobilized PS I on thiol-activated Au surfaces. Specifically, at. force microscopy (AFM) and ellipsometry analyses indicate that gravity-driven deposition from concd. PS I solns. results in a large no. of columnar PS I aggregates, which assemble perpendicular to the Au surface. PS I deposition yields much more uniform layers when deposited at lower concns., suggesting preassembly of the aggregate formation in the soln. phase. Moreover, in elec.-field assisted deposition at high field strengths, columnar self-assembly is largely prevented, thereby allowing a uniform, monolayer-like deposition even at very high PS I concns. In situ dynamic light scattering (DLS) studies of soln.-phase aggregation dynamics of PS I suspensions in both the presence and absence of an applied elec. field support these observations and clearly demonstrate that the externally imposed elec. field effectively fragments large PS I aggregates in the soln. phase, thereby permitting a uniform deposition of PS I trimers on SAM/Au substrates.
- 47So, J.; Dickey, M. Inherently Aligned Microfluidic Electrodes Composed of Liquid Metal. Lab Chip 2011, 11, 905– 911, DOI: 10.1039/c0lc00501k47https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXitVWguro%253D&md5=015e5539a6ce123df27e51ac3a4d9963Inherently aligned microfluidic electrodes composed of liquid metalSo, Ju-Hee; Dickey, Michael D.Lab on a Chip (2011), 11 (5), 905-911CODEN: LCAHAM; ISSN:1473-0197. (Royal Society of Chemistry)This paper describes the fabrication and characterization of microelectrodes that are inherently aligned with microfluidic channels and in direct contact with the fluid in the channels. Injecting low m.p. alloys, such as eutectic gallium indium (EGaIn), into microchannels at room temp. (or just above room temp.) offers a simple way to fabricate microelectrodes. The channels that define the shape and position of the microelectrodes are fabricated simultaneously with other microfluidic channels (i.e., those used to manipulate fluids) in a single step; consequently, all of the components are inherently aligned. In contrast, conventional techniques require multiple fabrication steps and registration (i.e., alignment of the electrodes with the microfluidic channels), which are tech. challenging. The distinguishing characteristic of this work is that the electrodes are in direct contact with the fluid in the microfluidic channel, which is useful for a no. of applications such as electrophoresis. Periodic posts between the microelectrodes and the microfluidic channel prevent the liq. metal from entering the microfluidic channel during injection. A thin oxide skin that forms rapidly and spontaneously on the surface of the metal stabilizes mech. the otherwise low viscosity, high surface tension fluid within the channel. Moreover, the injected electrodes vertically span the sidewalls of the channel, which allows for the application of uniform elec. field lines throughout the height of the channel and perpendicular to the direction of flow. The electrodes are mech. stable over operating conditions commonly used in microfluidic applications; the mech. stability depends on the magnitude of the applied bias, the nature of the bias (d.c. vs. a.c.), and the cond. of the solns. in the microfluidic channel. Electrodes formed using alloys with m.ps. above room temp. ensure mech. stability over all of the conditions explored. As a demonstration of their utility, the fluidic electrodes are used for electrohydrodynamic mixing, which requires extremely high elec. fields (∼105 V m-1).
- 48Dickey, M.; Weiss, E.; Smythe, E.; Chiechi, R.; Capasso, F.; Whitesides, G. Fabrication of Arrays of Metal and Metal Oxide Nanotubes by Shadow Evaporation. ACS Nano 2008, 2, 800– 808, DOI: 10.1021/nn800036r48https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD1cXjs1Gjt7g%253D&md5=f1877a0ea92cfe41ca508f4debfd282eFabrication of Arrays of Metal and Metal Oxide Nanotubes by Shadow EvaporationDickey, Michael D.; Weiss, Emily A.; Smythe, Elizabeth J.; Chiechi, Ryan C.; Capasso, Federico; Whitesides, George M.ACS Nano (2008), 2 (4), 800-808CODEN: ANCAC3; ISSN:1936-0851. (American Chemical Society)This paper describes a simple technique for fabricating uniform arrays of metal and metal oxide nanotubes with controlled heights and diams. The technique involves depositing material onto an anodized aluminum oxide (AAO) membrane template using a collimated electron beam evapn. source. The evapg. material enters the porous openings of the AAO membrane and deposits onto the walls of the pores. The membrane is tilted with respect to the column of evapg. material, so the shadows cast by the openings of the pores onto the inside walls of the pores define the geometry of the tubes. Rotation of the membrane during evapn. ensures uniform deposition inside the pores. After evapn., dissoln. of the AAO in base easily removes the template to yield an array of nanotubes connected by a thin backing of the same metal or metal oxide. The diam. of the pores dictates the diam. of the tubes, and the incident angle of evapn. dets. the height of the tubes. Tubes up to ∼1.5 μm in height and 20-200 nm in diam. were fabricated. This method is adaptable to any material that can be vapor-deposited, including indium-tin oxide (ITO), a conductive, transparent material that is useful for many optoelectronic applications. An array of gold nanotubes produced by this technique served as a substrate for surface-enhanced Raman spectroscopy: the Raman signal (per mol.) from a monolayer of benzenethiolate was a factor of ∼5 × 105 greater than that obtained using bulk liq. benzenethiol.
- 49Petrova, A.; Mamedov, M.; Ivanov, B.; Semenov, A.; Kozuleva, M. Effect of Artificial Redox Mediators on the Photoinduced Oxygen Reduction by Photosystem I Complexes. Photosynth. Res. 2018, 137, 421– 429, DOI: 10.1007/s11120-018-0514-z49https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXpsFyhsb4%253D&md5=b035bd051506a6b479457382c4984729Effect of artificial redox mediators on the photoinduced oxygen reduction by photosystem I complexesPetrova, Anastasia; Mamedov, Mahir; Ivanov, Boris; Semenov, Alexey; Kozuleva, MarinaPhotosynthesis Research (2018), 137 (3), 421-429CODEN: PHRSDI; ISSN:0166-8595. (Springer)The peculiarities of interaction of cyanobacterial photosystem I with redox mediators 2,6-dichlorophenolindophenol (DCPIP) and N,N,N',N'-tetramethyl-p-phenylenediamine (TMPD) were investigated. The higher donor efficiency of the reduced DCPIP form was demonstrated. The oxidized form of DCPIP was shown to be an efficient electron acceptor for terminal iron-sulfur cluster of photosystem I. Likewise Me viologen, after one-electron redn., DCPIP transfers an electron to the mol. oxygen. These results were discussed in terms of influence of these interactions on photosystem I reactions with the mol. oxygen and natural electron acceptors.
- 50Santiago, A. R. P.; Fernandez-Delgado, O.; Gomez, A.; Ahsan, M. A.; Echegoyen, L. Fullerenes as Key Components for Low-Dimensional (Photo)electrocatalytic Nanohybrid Materials. Angew. Chem., Int. Ed. 2021, 133, 124– 143, DOI: 10.1002/ange.202009449There is no corresponding record for this reference.
- 51Pan, Y.; Liu, X.; Zhang, W.; Liu, Z.; Zeng, G.; Shao, B.; Liang, Q.; He, Q.; Yuan, X.; Huang, D.; Chen, M. Advances in photocatalysis based on fullerene C60 and its derivatives: Properties, mechanism, synthesis, and applications. Appl. Catal., B 2020, 265, 118579 DOI: 10.1016/j.apcatb.2019.11857951https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXps1Ggsg%253D%253D&md5=75b21ab17dd3c4144e1a9257d975a07dAdvances in photocatalysis based on fullerene C60 and its derivatives: properties, mechanism, synthesis, and applicationsPan, Yuan; Liu, Xiaojuan; Zhang, Wei; Liu, Zhifeng; Zeng, Guangming; Shao, Binbin; Liang, Qinghua; He, Qingyun; Yuan, Xingzhong; Huang, Danlian; Chen, MingApplied Catalysis, B: Environmental (2020), 265 (), 118579CODEN: ACBEE3; ISSN:0926-3373. (Elsevier B.V.)A review. Fullerenes possess high chem. stability, large sp. surface area, good elec. cond. and unique three-dimensional structure. In this paper, we provide a general overview of the latest research results of fullerene-based photocatalysts. Firstly, the current status of semiconductor materials and fullerenes in photocatalytic applications are briefly introduced. Secondly, introduced action mechanisms of photocatalysts modified by fullerene C60 and its derivs., including basic structure, exclusive properties and its effect in photocatalysis and material prepn. process. Thirdly, factors affecting material effectiveness and the synthesis strategy of composite photocatalyst modified by fullerene are introduced. Meanwhile, the application advances of the photocatalysts are introduced, including in the degrdn. of pollutants, org. synthesis, hydrogen prodn., antibacterial and disinfection in water. Finally, the development trends of fullerenes and their derivs. in photocatalysis are also summarized, including theor. calcns., the morphol. structure control, stable derivs. and increase the selectivity, and new other types of fullerene materials.
- 52Blom, P.; Mihailetchi, V.; Koster, L.; Markov, D. Device Physics of Polymer:Fullerene Bulk Heterojunction Solar Cells. Adv. Mater. 2007, 19, 1551– 1566, DOI: 10.1002/adma.20060109352https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BD2sXnsVagsL4%253D&md5=6b0fb9c0d385111ca70c49679eccad55Device physics of polymer:fullerene bulk heterojunction solar cellsBlom, Paul W. M.; Mihailetchi, Valentin D.; Koster, L. Jan Anton; Markov, Denis E.Advanced Materials (Weinheim, Germany) (2007), 19 (12), 1551-1566CODEN: ADVMEW; ISSN:0935-9648. (Wiley-VCH Verlag GmbH & Co. KGaA)A review of processes and limitations that govern device operation of polymer:fullerene bulk heterojunction solar cells, with respect to the charge-carrier transport and photogeneration mechanism. The transport of electrons/holes in the blend is a crucial parameter and must be controlled (e.g., by controlling the nanoscale morphol.) and enhanced in order to allow fabrication of thicker films to maximize the absorption, without significant recombination losses. Concomitantly, a balanced transport of electrons and holes in the blend is needed to suppress the build-up of the space charge that will significantly reduce the power conversion efficiency. Dissocn. of electron-hole pairs at the donor/acceptor interface is an important process that limits the charge generation efficiency under normal operation condition. Based on these findings, there is a compromise between charge generation (light absorption) and open-circuit voltage when attempting to reduce the bandgap of the polymer (or fullerene). Therefore, an increase in open-circuit voltage of polymer:fullerene solar cells, for example by raising the LUMO level of the fullerene, will benefit cell performance as both fill factor and short-circuit current increase simultaneously.
- 53Li, S.; Lei, M.; Lv, M.; Watkins, S. E.; Tan, Z.; Zhu, J.; Hou, J.; Chen, X.; Li, Y. [6, 6]-Phenyl-C61-Butyric Acid Dimethylamino Ester as a Cathode Buffer Layer for High-Performance Polymer Solar Cells. Adv. Energy Mater. 2013, 3, 1569– 1574, DOI: 10.1002/aenm.20130042553https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3sXhvV2itbrI&md5=b66a11b89684116042cdb0aa25a4c5bb[6,6]-Phenyl-C61-Butyric Acid Dimethylamino Ester as a Cathode Buffer Layer for High-Performance Polymer Solar CellsLi, Shusheng; Lei, Ming; Lv, Menglan; Watkins, Scott E.; Tan, Zhan'ao; Zhu, Jin; Hou, Jianhui; Chen, Xiwen; Li, YongfangAdvanced Energy Materials (2013), 3 (12), 1569-1574CODEN: ADEMBC; ISSN:1614-6840. (Wiley-Blackwell)This paper discusses the [6,6]-phenyl-C61-butyric acid dimethylamino ester as cathode buffer layer for high-performance polymer solar cells. Fullerene derivs. could be ideal cathode buffer layer materials in considering their n-type semiconductor character, higher electron mobility, and the good energy level matching with the fullerene acceptors (such as [6,6]-phenyl-C61-butyric acid Me ester (PCBM)) used in the active layer of the PSCs were discussed.
- 54Tel-Vered, R.; Willner, I. Photo-Bioelectrochemical Cells for Energy Conversion, Sensing, and Optoelectronic Applications. ChemElectroChem 2014, 1, 1778– 1797, DOI: 10.1002/celc.20140213354https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhvVylsbfF&md5=47a6e29da1eaabc6cb1886f07dc37e5aPhoto-bioelectrochemical Cells for Energy Conversion, Sensing, and Optoelectronic ApplicationsTel-Vered, Ran; Willner, ItamarChemElectroChem (2014), 1 (11), 1778-1797CODEN: CHEMRA; ISSN:2196-0216. (Wiley-VCH Verlag GmbH & Co. KGaA)The native photosynthetic reaction centers photosystem I (PSI) and photosystem II (PSII) act as functional nanostructures for the assembly of photo-biofuel cells. By elec. wiring of PSI and/or PSII with electrodes, the conversion of light energy into elec. power has been demonstrated. Different methodologies to elec. contact the photosystems with the electrodes have been developed, including the reconstitution of the photosystems on relay units, the application of redox-active polymers as charge-transport matrixes, and the use of metallic nanoparticles or nanoclusters as electron-transfer relays. Elec. contact of the photosystems with the electrodes facilitates charge sepn. of the redox intermediates generated upon illumination of the assemblies, thus retarding destructive back electron-transfer reactions and enhancing the conversion of light energy into elec. power. Recent advances to fabricate elec. wired PSI and/or PSII electrodes are surveyed, and different approaches to assemble photo-bioelectrochem. cells are discussed. The limitations and future perspectives of the systems will also be presented.
- 55Tsarev, S.; Dubinina, T. S.; Luchkin, S. Y.; Zhidkov, I. S.; Kurmaev, E. Z.; Stevenson, K. J.; Troshin, P. A. Phenyl-C61-butyric Acid as an Interface Passivation Layer for Highly Efficient and Stable Perovskite Solar Cells. J. Phys. Chem. C 2020, 124, 1872– 1877, DOI: 10.1021/acs.jpcc.9b1070955https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXpvFI%253D&md5=85fb3a694907c4f99716cfa01559d185Phenyl-C61-butyric Acid as an Interface Passivation Layer for Highly Efficient and Stable Perovskite Solar CellsTsarev, Sergey; Dubinina, Tatiana S.; Luchkin, Sergey Yu.; Zhidkov, Ivan S.; Kurmaev, Ernst Z.; Stevenson, Keith J.; Troshin, Pavel A.Journal of Physical Chemistry C (2020), 124 (3), 1872-1877CODEN: JPCCCK; ISSN:1932-7447. (American Chemical Society)Here, phenyl-C61-butyric acid (PCBA) is presented as a generic passivation coating for metal oxide electron transport layers used in planar n-i-p configuration of perovskite solar cells. PCBA shows better adhesion to Sn and Zn oxides due to strong acid-base interactions as compared to the conventionally used phenyl-C61-butyric acid Me ether (PCBM). Therefore, depositing a compact PCBA passivation coating can be achieved in a much more economical way using 100 times less concd. precursor soln. PCBA coating delivers higher power conversion efficiencies (up to 20.3%) as compared to the pristine oxide layers with or without PCBM coating. Finally, the fabricated solar cells using PCBA coating are more stable in comparison with the ref. cells with conventional PCBM passivation and preserved ∼70% of the initial efficiency after 1500 h of continuous 30 mW/cm2 white light illumination at 50°.
- 56Mishra, A.; Bäuerle, P. Small Molecule Organic Semiconductors on the Move: Promises for Future Solar Energy Technology. Angew. Chem., Int. Ed. 2012, 51, 2020– 2067, DOI: 10.1002/anie.20110232656https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38Xitlygs7g%253D&md5=3bd032ed84f6c2a11c7f6d8efb770901Small Molecule Organic Semiconductors on the Move: Promises for Future Solar Energy TechnologyMishra, Amaresh; Baeuerle, PeterAngewandte Chemie, International Edition (2012), 51 (9), 2020-2067CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)A review. This article, written from an org. chemist's point of view, provides an up-to-date overview of org. solar cells based on small mols. or oligomers as absorbers and describes devices that incorporate planar-heterojunctions and bulk heterojunctions between a donor (p-type semiconductor) and an acceptor (n-type semiconductor) material. The article pays particular attention to the design and development of mol. materials and their performance in corresponding devices. In recent years, a substantial amt. of both, academic and industrial research, has been directed towards org. solar cells, in an effort to develop new materials and to improve their tunability, processability, power conversion efficiency, and stability. On the eve of commercialization of org. solar cells, this review provides an overview of efficiencies attained with small mols./oligomers in org. solar cells and summarizes materials and device concepts developed over the last decade. Approaches to enhancing the efficiency of org. solar cells are analyzed.
- 57Nelson, J. Polymer:fullerene bulk heterojunction solar cells. Mater. Today 2011, 14, 462– 470, DOI: 10.1016/S1369-7021(11)70210-357https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC3MXht1CqurfJ&md5=9fa4d2f695ac9261d624b7ed5a5d23e7Polymer:fullerene bulk heterojunction solar cellsNelson, JennyMaterials Today (Oxford, United Kingdom) (2011), 14 (10), 462-470CODEN: MTOUAN; ISSN:1369-7021. (Elsevier Ltd.)A review. The efficiency of solar cells made from a conjugated polymer blended with a fullerene deriv. has risen from around 1 % to over 9 % in the last ten years, making org. photovoltaic technol. a viable contender for commercialization. The efficiency increases have resulted from the development of new materials with lower optical gaps, new polymer:fullerene combinations with higher charge sepd. state energies, and new approaches to control the blend microstructure, all driven by a qual. understanding of the principles governing org. solar cell operation. In parallel, a device physics framework has been developed that enables the rational design of device structures and materials for improved org. photovoltaic devices. We review developments in both materials science and device physics for org. photovoltaics.
- 58Nakanishi, W.; Minami, K.; Shrestha, L. K.; Ji, Q.; Hill, J. P.; Ariga, K. Bioactive nanocarbon assemblies: Nanoarchitectonics and applications. Nano Today 2014, 9, 378– 394, DOI: 10.1016/j.nantod.2014.05.00258https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhtVanurvF&md5=09e65b89b9e27c5f8dcd8e46ce278b71Bioactive nanocarbon assemblies: Nanoarchitectonics and applicationsNakanishi, Waka; Minami, Kosuke; Shrestha, Lok Kumar; Ji, Qingmin; Hill, Jonathan P.; Ariga, KatsuhikoNano Today (2014), 9 (3), 378-394CODEN: NTAOCG; ISSN:1748-0132. (Elsevier Ltd.)A review. Graphene, carbon nanotubes, and fullerene are representative nanocarbons which have zero, one, or two dimensional structures, resp. These nanocarbons can be used as building blocks for construction of higher dimensional or complex materials by nanoarchitectonics; a technol. used to control nanoscale structures and spaces. By combination with other materials and/or devices, nanoarchitectures of nanocarbons can be formed into structures of different dimensions and properties for biol. applications. In this review, biol. applications, esp. cell growth, sensing, and control using nanoarchitectures of nanocarbons are summarized.
- 59Yan, J.; Saunders, B. R. Third-generation solar cells: a review and comparison of polymer: fullerene, hybrid polymer and perovskite solar cells. RSC Adv. 2014, 4, 43286– 43314, DOI: 10.1039/C4RA07064J59https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC2cXhsVaksLnI&md5=f530f372f95b219d27535c41923d47f9Third-generation solar cells: a review and comparison of polymer:fullerene, hybrid polymer and perovskite solar cellsYan, Junfeng; Saunders, Brian R.RSC Advances (2014), 4 (82), 43286-43314CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)A review. The need for large scale low carbon solar electricity prodn. has become increasingly urgent for reasons of energy security and climate change mitigation. Third-generation solar cells (SCs) are soln. processed SCs based on semiconducting org. macromols., inorg. nanoparticles or hybrids. This review considers and compares three types of promising 3rd-generation SCs: polymer:fullerene, hybrid polymer and perovskite SCs. The review considers work reported since an earlier review and highlights the great progress that has been made in each area. We consider the operation principles for each SC type and also review the state-of-the-art devices. The polymer:fullerene and hybrid polymer SC open circuit voltages are compared to values predicted from the well-known Scharber equation and similarities and differences discussed. The perovskite SCs are also considered and their remarkable rate of power conversion efficiency performance increase is discussed. The review considers the requirements for large-scale deployment in the contexts of semiconducting polymer and hole transport matrix synthesis and materials selection. It is concluded that the 3rd-generation SC technologies discussed here are well placed for major contribution to large scale energy prodn. (This has already been partially demonstrated for polymer:fullerene SCs.) Looking further ahead we propose that several of the 3rd-generation SCs considered here have excellent potential to provide the low cost large-scale deployment needed to meet the terawatt challenge for solar electricity generation.
- 60Shi, X.-Q.; Hove, M. A. V.; Zhang, R.-Q. Survey of Structural and Electronic Properties of C60 on Close-Packed Metal Surfaces. J. Mater. Sci. 2012, 47, 7341– 7355, DOI: 10.1007/s10853-012-6361-y60https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC38XjtlSmtrw%253D&md5=cc42578f06ead6410e32c30ab2137517Survey of structural and electronic properties of C60 on close-packed metal surfacesShi, Xing-Qiang; Van Hove, Michel A.; Zhang, Rui-QinJournal of Materials Science (2012), 47 (21), 7341-7355CODEN: JMTSAS; ISSN:0022-2461. (Springer)A review. The adsorption of buckminsterfullerene (C60) on metal surfaces has been investigated extensively for its unique geometric and electronic properties. The two-dimensional systems formed on surfaces allow studying in detail the interplay between bonding and electronic structures. Recent studies reveal that C60 adsorption induces reconstruction of even the less-reactive close-packed metal surfaces. First-principles computations enable access to this important issue by providing not only detailed at. structure but also electronic properties of the substrate-adsorbate interaction, which can be compared with various exptl. techniques to det. and understand the interface structures. This review discusses in detail the ordered phases of C60 monolayers on metal surfaces and the surface reconstruction induced by C60 adsorption, with an emphasis on the different types of reconstruction resulting on close-packed metal surfaces. We show that the symmetry matching between C60 mols. and metal surfaces dets. the local adsorption configurations, while the size matching between C60 mols. and the metal surface lattice dets. the supercell sizes and shapes; importantly and uniquely for C60, the no. of surface metal atoms within one supercell dets. the different types of reconstruction that can occur. The at. structure at the mol.-metal interface is of crucial importance for the monolayer's electronic and transport properties: these will also be discussed for the well-defined adsorption structures, esp. from the perspective of tuning the electronic structure via C60-metal interface reconstruction and via relative inter-C60 orientations.
- 61Cho, N.-K.; Na, H.-J.; Yoo, J.; Kim, Y. S. Long-term stability in γ-CsPbI3 perovskite via an ultraviolet-curable polymer network. Commun. Mater. 2021, 2, 30 DOI: 10.1038/s43246-021-00134-1There is no corresponding record for this reference.
- 62Suresh, L.; Vaghasiya, J. V.; Nandakumar, D. K.; Wu, T.; Jones, M. R.; Tan, S. C. High-Performance UV Enhancer Molecules Coupled with Photosynthetic Proteins for Ultra-Low-Intensity UV Detection. Chem 2019, 5, 1847– 1860, DOI: 10.1016/j.chempr.2019.04.01762https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1MXhsVGrtLnO&md5=4aefff589dac1b94ceb57961c9365e51High-Performance UV Enhancer Molecules Coupled with Photosynthetic Proteins for Ultra-Low-Intensity UV DetectionSuresh, Lakshmi; Vaghasiya, Jayraj V.; Nandakumar, Dilip Krishna; Wu, Tingfeng; Jones, Michael R.; Tan, Swee ChingChem (2019), 5 (7), 1847-1860CODEN: CHEMVE; ISSN:2451-9294. (Cell Press)Dual attributes of UV-photo-responsive org.-ionic conductors are exploited in bio-photoelectrochem. cells based on photosynthetic RC-LH1 proteins from Rhodobacter sphaeroides. These UV enhancer mols. (UVEM) can generate small photocurrents in the absence of protein and are also effective electrolytes for photocurrent generation by RC-LH1 complexes in response to near-IR excitation. Mixing RC-LH1 and UVEM components strongly enhanced UV photocurrents relative to those obtained with protein or UVEM alone, an effect that is attributed to energy transfer from the hetero-anthracene chromophore of the UVEM to the carotenoids of the RC-LH1 complex. RC-LH1/UVEM bio-photoelectrochem. cells were superior to conventional RC-LH1 cells in terms of UV external quantum efficiency, photo-response sensitivity, and photocurrent rise-decay times. These bio-photodetectors could detect weak UV radiation with intensities as low as 2μW/cm2. This combination of photosynthetic proteins with dual-function electrolytes is the first attempt to construct fully functional bio-photoelectrochem. UV photodetector based on natural components.
- 63Long, S. P.; Humphries, S.; Falkowski, P. G. Photoinhibition of Photosynthesis in Nature. Annu. Rev. Plant Physiol. Plant Mol. Biol. 1994, 45, 633– 662, DOI: 10.1146/annurev.pp.45.060194.00322163https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADyaK2cXlt12rsLg%253D&md5=cdd440abee71cf2efb92cba109c07d99Photoinhibition of photosynthesis in natureLong, S. P.; Humphries, S.; Falkowski, P. G.Annual Review of Plant Physiology and Plant Molecular Biology (1994), 45 (), 633-62CODEN: ARPBEX; ISSN:1040-2519.A review with 142 refs., discussing photosystem II inactivation, avoidance of PS II damage, photoinhibition in the filed and open ocean, terrestrial vegetation, phytoplankton, significance to prodn., and photoinhibition and plant distributions.
- 64Allahverdiyeva, Y.; Aro, E.-M. Photosynthesis; Springer: Netherlands, 2011; pp 275– 297.There is no corresponding record for this reference.
- 65Paul, N.; Suresh, L.; Vaghasiya, J. V.; Yang, L.; Zhang, Y.; Nandakumar, D. K.; Jones, M. R.; Tan, S. C. Self-powered all weather sensory systems powered by Rhodobacter sphaeroides protein solar cells. Biosens. Bioelectron. 2020, 165, 112423 DOI: 10.1016/j.bios.2020.11242365https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXhsVCksbbL&md5=68b60a6ae03e527ee5ff7bae51563fe6Self-powered all weather sensory systems powered by Rhodobacter sphaeroides protein solar cellsPaul, Nikita; Suresh, Lakshmi; Vaghasiya, Jayraj V.; Yang, Lin; Zhang, Yaoxin; Nandakumar, Dilip Krishna; Jones, Michael R.; Tan, Swee ChingBiosensors & Bioelectronics (2020), 165 (), 112423CODEN: BBIOE4; ISSN:0956-5663. (Elsevier B.V.)Natural photosynthetic proteins can convert solar energy into elec. energy with close to 100% quantum efficiency, and there is increasing interest in their use for sustainable photoelectrochem. devices. The primary processes of photosynthesis remain operational and efficient down to extremely low temps., and natural photosystems exhibit a variety of self-healing mechanisms. Herein we demonstrate the use of an amphiphilic triblock copolymer, Pluronic F127, to fabricate a self-healing photosynthetic protein photoelectrochem. cell that operates optimally at sub-zero temps. A concn. of 30% (wt./wt.) Pluronic F127 depressed the f.p. of an electrolyte comprising 50 mM ubiquinone-0 in aq. buffer such that optimal device solar energy conversion was seen at -12°C rather than at room temp. Multiple bending cycles caused a marked deterioration of the photocurrent response to around a third of initial levels due to damage to the gel phase of the electrolyte, but this could be restored to ~ 95% by simply cooling and rewarming the device. This self-recoverability of the electrolyte extended the operational life of the protein cell through a process that increased its photoelectrochem. output during the repair. Utility of the cells as components of a touch sensor operational across a wide temp. range, including freezing conditions, is demonstrated.
- 66Liu, J.; Friebe, V. M.; Frese, R. N.; Jones, M. R. Polychromatic solar energy conversion in pigment-protein chimeras that unite the two kingdoms of (bacterio)chlorophyll-based photosynthesis. Nat. Commun. 2020, 11, 1542 DOI: 10.1038/s41467-020-15321-w66https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BB3cXlvFGnsLg%253D&md5=ee3b293e4d1ac27bf9c2f600476d123ePolychromatic solar energy conversion in pigment-protein chimeras that unite the two kingdoms of (bacterio)chlorophyll-based photosynthesisLiu, Juntai; Friebe, Vincent M.; Frese, Raoul N.; Jones, Michael R.Nature Communications (2020), 11 (1), 1542CODEN: NCAOBW; ISSN:2041-1723. (Nature Research)Natural photosynthesis can be divided between the chlorophyll-contg. plants, algae and cyanobacteria that make up the oxygenic phototrophs and a diversity of bacteriochlorophyll-contg. bacteria that make up the anoxygenic phototrophs. Photosynthetic light harvesting and reaction center proteins from both kingdoms have been exploited for solar energy conversion, solar fuel synthesis and sensing technologies, but the energy harvesting abilities of these devices are limited by each protein's individual palette of pigments. In this work we demonstrate a range of genetically-encoded, self-assembling photosystems in which recombinant plant light harvesting complexes are covalently locked with reaction centers from a purple photosynthetic bacterium, producing macromol. chimeras that display mechanisms of polychromatic solar energy harvesting and conversion. Our findings illustrate the power of a synthetic biol. approach in which bottom-up construction of photosystems using naturally diverse but mechanistically complementary components can be achieved in a predictable fashion through the encoding of adaptable, plug-and-play covalent interfaces.
- 67Molamohammadi, S.; Jalili, Y. S.; Riazi, G. Photosystem I application in biohybrid polymer solar cells. AIP Adv. 2018, 8, 095319 DOI: 10.1063/1.503077767https://chemport.cas.org/services/resolver?origin=ACS&resolution=options&coi=1%3ACAS%3A528%3ADC%252BC1cXhvVSisb%252FN&md5=bfcc21784a42f9c6bdbf721e984658d7Photosystem I application in biohybrid polymer solar cellsMolamohammadi, Shahriar; Seyed Jalili, Yousef; Riazi, GholamhosseinAIP Advances (2018), 8 (9), 095319/1-095319/8CODEN: AAIDBI; ISSN:2158-3226. (American Institute of Physics)The use of Bio-photonic systems has attracted a lot of attention recently specially in the field of solar energy conversion and photovoltaic materials the use of photosynthetic organs of plants is very promising. The energy conversion in the process of photosynthesis is close to 100% and it's environmental compatibly are the main reasons for why photosynthesis has attracted the attention of energy system designers and researchers. The way of solar energy conversion in photosynthesis indicates a great potential as a fount of renewable energy. Use of the photosynthetic components in photosensors and photovoltaic devices solitarily, has disadvantages such as low extd. current compared to other kinds of photovoltaic materials. Accordingly, for more useful and better application, these photosynthetic components could be used as the optimizer of the other species of photovoltaic materials and solar cells. photosystem1 protein complex, which is the main member of photosynthetic components has max. absorption spectrum wavelength at 430nm and 665nm. Therefore, it can be an appropriate complement for polymeric solar cells with their absorption spectrum at the green wavelength region. In this paper we have used the photosystem1 protein complex in the inverted polymer solar cell with structure of ITO/P3HT:ICBA/PS1/Al and pos. results have been obsd. So that the polymer solar cells efficiency was enhanced from 4.3% to 4.53%. (c) 2018 American Institute of Physics.
Supporting Information
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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.langmuir.1c01542.
Atomic force microscopy (AFM) images of PCBA/PSI and IQAc-PSI, multiday current density, and output power measurements of PCBA/PSI and IQAc-PSI PV devices; comparative photochronoamperometric measurements of PCBA/PSI devices, stability of BPV devices under continuous illumination, UV–vis absorbance spectra of PCBA/PSI devices, longevity study of PCBA/PSI and IQAc-PSI BPV devices in the dark and under illumination; and control measurements (PDF)
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