ACS Publications. Most Trusted. Most Cited. Most Read
My Activity
CONTENT TYPES

Electroactive Nanoporous Metal Oxides and Chalcogenides by Chemical Design

View Author Information
Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United States
Department of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AY, United Kingdom
§ Kathleen Lonsdale Materials Chemistry, Department of Chemistry, University College London, 20 Gordon Street, London, WC1H 0AJ, United Kingdom
Diamond Light Source Ltd., Diamond House, Harwell Science and Innovation Campus, Didcot, Oxfordshire OX11 0DE, United Kingdom
Department of Chemistry, University of Toronto, Toronto, Ontario M5S 3H6, Canada
# Department of Materials Science and Engineering, Yonsei University, Seoul 03722, South Korea
Department of Materials, Imperial College London, Exhibition Road, London SW7 2AZ, United Kingdom
Cite this: Chem. Mater. 2017, 29, 8, 3663–3670
Publication Date (Web):March 27, 2017
https://doi.org/10.1021/acs.chemmater.7b00464

Copyright © 2017 American Chemical Society. This publication is licensed under CC-BY.

  • Open Access

Article Views

2409

Altmetric

-

Citations

LEARN ABOUT THESE METRICS
PDF (4 MB)
Supporting Info (1)»

Abstract

The archetypal silica- and aluminosilicate-based zeolite-type materials are renowned for wide-ranging applications in heterogeneous catalysis, gas-separation and ion-exchange. Their compositional space can be expanded to include nanoporous metal chalcogenides, exemplified by germanium and tin sulfides and selenides. By comparison with the properties of bulk metal dichalcogenides and their 2D derivatives, these open-framework analogues may be viewed as three-dimensional semiconductors filled with nanometer voids. Applications exist in a range of molecule size and shape discriminating devices. However, what is the electronic structure of nanoporous metal chalcogenides? Herein, materials modeling is used to describe the properties of a homologous series of nanoporous metal chalcogenides denoted np-MX2, where M = Si, Ge, Sn, Pb, and X = O, S, Se, Te, with Sodalite, LTA and aluminum chromium phosphate-1 structure types. Depending on the choice of metal and anion their properties can be tuned from insulators to semiconductors to metals with additional modification achieved through doping, solid solutions, and inclusion (with fullerene, quantum dots, and hole transport materials). These systems form the basis of a new branch of semiconductor nanochemistry in three dimensions.

1 Introduction

ARTICLE SECTIONS
Jump To

The concept of reconstructing a bulk semiconductor through chemical synthesis into a semiconductor containing a periodic array of nanopores was introduced in 1992. (1) The vision was a new genre of semiconductor device with electronic, optoelectronic, and optical properties that were sensitive to the size and shape of molecules adsorbed within the nanopores. The archetypes of this class of zeolitic semiconductors (ZSs) were based on germanium and tin sulfide and selenide compositions. They were found to have open-framework structures, reminiscent of silica- and alumina-based zeolites, comprising tetrahedrally connected networks of tetrahedral metal chalcogenide building blocks. (2) Inspired by this knowledge, their potential as electronic sensors was explored; (3) however, information about their electronic structure, which is key to establishing their physical structure, property, function, and utility relations, remains largely unknown today.
The synthesis of ZSs is as challenging as it is important. In the first decade of this century, great efforts were expended to produce alternative zeolitic materials by replacing oxygen with chalcogens and substituting the ubiquitous Si and Al with alternate tetrahedral metal centers. (4-6) Further structural diversity—including the isolation of metastable and unstable structures—was realized by application of structure directing agents thereby expanding the structural library. (7) Structurally, the incorporation of germanium allowed a proliferation of new frameworks and the synthesis of ultraporous framework materials. (8, 9) Moreover, the highly polarizable nature of chalcogen atoms was found to result in enhanced gas absorption in these systems. (10, 11) Latterly, alternative synthetic routes, such as ionothermal synthesis and post-synthesis reduction, have reinvigorated the search for new framework structures and compositions. (12-15) The recent report of measured semiconducting behavior in a zeolite-analogue material, (16) as well as more exotic electronic phenomena such as anomalous band gap evolution in nanocrystalline topological insulators, (17) shows that this field offers great potential. One very recent study demonstrated the synthesis of open-frame ZSM-5 high tin sulfide and selenide zeolite analogues, (18) with surface areas and stabilities equivalent or superior to zeolites. The confluence of novel synthetic methods, early reports of semiconducting behavior, and advances in modern computational techniques have inspired us to address the electronic structure of these materials.
We report the electronic properties of nanoporous metal chalcogenides (np-MX2, where M = Si, Ge, Sn, Pb; X = O, S, Se, Te) exemplified by the sodalite (SOD), Linde Type A (LTA) and aluminum chromium phosphate-1 (ACO) structures and compare these properties with those of the bulk forms (MX2). The electronic structure is calculated from first-principles within Density Functional Theory (DFT), a predictive tool in contemporary materials design. (19, 20) We assess the nanoporous and bulk forms of the simplest metal chalcogenides, the corresponding metal oxides (np-MO2 and MO2) and mixed anion and cation solid solutions. The results allow insights into how the structure and composition of nanoporous metal chalcogenides determine their electrical and optical properties, and provide a robust platform for developing “inverse quantum dot” nanoporous semiconductors.

2 Structural Stability

ARTICLE SECTIONS
Jump To

Before we consider the electronic structure, it is pertinent to assess the stability of the phases. We emphasize that the formation of most porous solids is kinetically controlled, with nucleation and templating being key in the crystallization process. Nonetheless, the thermodynamic stability relative to known siliceous zeolites is an important comparison, which has been made before to assess the viability of hypothetic framework structures. (21)
First of all, all structures were found to be dynamically stable with no negativity frequency phonon modes at the center of the Brillouin zone. To address thermodynamic stability, we have calculated the total energies of the three framework types and compare them to the corresponding bulk crystal ground-state structures. The data is presented in Table S1. The pure silica forms of ACO, SOD, and LTA are known to exist (22, 23) and can be accessed through hydrothermal synthesis routes, employing structure directing agents (SDAs or templates) as required. We characterize the stability of the frameworks relative to the ground-state crystal structure of the same stoichiometry by calculating the energy difference per atom. For the ACO, SOD, and LTA frameworks of SiO2 the enthalpic cost associated with the formation of the porous solid is 0.55, 0.54, and 0.55 eV per formula unit, respectively.
The SiO2-ZMS-5 material was also included in our energetic assessment, as an industrially relevant material, and was found to be highly stable with a formation enthalpy cost of 0.004 eV per formula unit relative to SOD-SiO2. This stabilization is attributed to the reduction in acute M-O-M bonding angles. These angles are critical descriptors in the assessment of stability of larger metal and chalcogenide-containing structures, where more larger metal/chalcogenides favor more obtuse M-O-M angles. (24-26) ZSM-5 was not studied in all compositional arrangements because its large unit cell presented computational challenges for the heavier metal-chalcogenides. However, the electronic properties of the ZSM-5-SiO2 were similar to that of ACO, SOD, and LTA. The electronic properties of the np-MX2 materials are essentially unperturbed by structure-type; our computations on the smaller cell zeolites represent an upper limit in formation enthalpy.
The GeO2 frameworks display a similar stability with respect to the reference state than the SiO2 analogues with an enthalpic cost of 0.85 eV (SOD), 0.79 eV (LDA), and 0.84 eV (ACO), respectively. The ability of germanium to form the same mineral structures as silicon can be understood from their similar ionic radii, electronegativities, and valence shell characteristics. (27) Indeed, large numbers of germanates that are isostructural to natural silicates have been synthesized. Some differences exist between the Si–O–Si motif and the Ge–O–Ge motif, (25) for example, the Ge–O bond is longer and the germanate angle is smaller than the silicate species. (28) The difference in bond length is related to ionic radius, while the variation in bond angle can be understood in the context of the valence shell electron pair repulsion (VSEPR) model. (29) In line with VSEPR, there is a greater repulsion between nonbonded electrons than bonded, thus the two nonbonded pairs force a tighter angle in the bonding electrons in the germanate structure.
There is an increase in formation enthalpy for the nanoporous sulfides and selenides. As has been noted previously, the tilt angle joining the tetrahedral building blocks of zeolite frameworks is largely fixed at 109° in sulfide species, (30) meaning that the formation of these frameworks involves additional strain, as reflected in the energies of Si, Sn, and Ge sulfide and selenide species. The Pb chalcogenides and SiTe2 represent a deviation from this trend. In these cases, the increased bond-lengths and higher atomic polarizability may be responsible for an enhanced flexibility. For reference, the formation enthalpies for all materials examined here are comparable to the formation enthalpy of other metastable materials (e.g., MOF-5). (31)
It should be further noted that chalcogenide zeolitic frameworks are known, which consist of assemblages of nanoparticle building blocks of MX2 stoichiometry. (32-35) This is further suggested from our calculations; the one exception is the tellurides of which there are no reports in the solid-state with a stoichiometry of MTe2. Given the predicted accessibility of many of these species—and other more strained ring frameworks (36)—the existence of a plethora of experimentally realized analogues and the need for electronic insights to assist in the realization of their true potential, we now undertake a systematic exploration of the effects of chemical and structural modifications on the band-structure of these materials.

3 Electronic Structure

ARTICLE SECTIONS
Jump To

The electronic properties of many porous materials feature localization of the electronic density of states in real space and hence a lack of dispersion in the bands in reciprocal space. This is certainly true for other porous materials (e.g., metal–organic frameworks) in which many recent publications have shown flat electronic bands in reciprocal space (37-39) that can be modulated through chemical substitutions and inclusions. (40, 41) In the case of the porous metal oxides and chalcogenides presented here, the valence band is nondisperse (this is described by a large effective mass for hole transport: mh* > 1 me for np-SiO2), composed entirely of oxygen/chalcogen p-orbitals, independent of crystal morphology. These p-orbitals are orientated into the pores and thus do not form a continuous pathway in the framework of the structure for charge transport; similar obstacles to hole mobility are often encountered in amorphous oxides. (42)
Owing to the stoichiometry and IV oxidation state of the group 14 metals Si, Ge, Sn, and Pb, the lowest unoccupied states are a hybrid of unoccupied oxide/chalcogen and metal s-orbitals. The crystal orbitals are delocalized throughout the structure. As a result, np-MX2 materials demonstrate pronounced band dispersion (a parabolic effective mass of me* = 0.64 me for np-SiO2 in the SOD structure) comparable to other wide band gap semiconductors. (43)
The valence and conduction band edges are defined by the chalcogen and metal/chalcogen identity, respectively (Supporting Information, Figure S1). These bands can be aligned to the universal vacuum level: (44)Figure 1 illustrates that the work functions of np-MO2 semiconductors are relatively independent of metal and morphology. This results from the similarities between the oxygen crystal environment–at the vertices of tetrahedra of M(IV) cations–and reflects the fact that the electron energies at these sites are dominated by the Madelung potential. (45, 46) The electron affinity (EA) is related to the energy of the unoccupied metal center s-orbitals. The EA displays a clear trend to increase as we move to larger metals, a trend related to the relativistic effects of the nucleus on the electrons that scales with Z2. This observed increase in electron affinity may be attributed to a contraction in the s and p and expansion of the d and f orbitals of the metal, resulting in stabilization of the low lying unoccupied states.

Figure 1

Figure 1. Electronic band structures (DFT/HSE06), aligned to the vacuum level by the ionization potential (Φ), of MO2 (M = Si, Ge, Sn, Pb) in the zeolite-type structures shown on the left. Plotted following 0,0,0 to 1/2,1/2,1/2 in reciprocal space (where 0,0,0 = gamma and 1/2,1/2,1/2 = special point as described in the figure), SOD structured materials show the most significant dispersion in the conduction band (ca. 2 eV), followed by ACO (ca. 1.6 eV), and LTA (ca. 0.7 eV). The conduction band is composed of delocalized antibonding O s and M s-orbitals. The valence band is composed of localized O p-orbitals, resulting in flat bands, and the bulk potential is relatively insensitive to the cation identity.

To isolate the effect of the anion, the electronic structure of the SnX2 series was explored, Figure 2. The ionization potential (Φ) decreases with increase in anion size but only the oxide is predicted to have a band gap. Heavier np-MX2 compounds result in valence and conduction band crossing, thus forming a semimetal (a zero gap material) with a low electronic density of states at the Fermi level. This is true of all np-MX2 materials, with the exception of SOD-SiS2 that has a predicted band gap of 0.2 eV. Further details of band alignments for np-MX2 are provided in Table S1.

Figure 2

Figure 2. Electronic band structures (plotted from 0,0,0 to 1/2,1/2,1/2 in reciprocal space) for sodalite SnX2 (X = O, S, Se, Te) relative to the vacuum level. The oxide has a band gap, while the sulfide, selenide, and telluride are metallic and their work functions are defined by their Fermi levels (in the limit of T → 0 K).

Previous studies on nanostructured ZnO showed a large effect of the porosity of the material on the band gap. (47) Although the magnitude of the band gap of IV–VI np-MX2 materials is not as clearly modulated with morphology, we observe a similar tendency toward a wider band gap with increased porosity, with LTA displaying the largest gap in all cases. Moreover, conduction band dispersion is affected by nanoporosity, offering a route toward the engineering of electron transport properties. For instance, the conduction band effective mass me* = 0.74 me for LTA-SiO2 compared to me* = 0.64 me for SOD-SiO2.
Band engineering of solid-state semiconductors by creating solid solutions (compositional alloys) is a well-established practice. To consider the effects of forming ZS alloys we treat two possible isovalent substitution routes for the SOD SiO2 framework: (i) a single extrinsic inclusion of another metal at the Si site; (ii) a single extrinsic chalcogenide substitution at an oxygen site. The results are summarized in Figure 3 (higher chalcogenide concentrations and energetics are presented in the Figure S4 and the Supporting Information, respectively). In both the metal and the anion substitution cases, the band gaps are intermediate between the binary end-points, that is, following Vegard’s rule. (48)

Figure 3

Figure 3. Isovalent dopants introduce localized states in the electronic band structure of porous metal chalcogenides (DFT/HSE06), allowing for modular electronic band gaps and ionization potentials (Φ). For example, in SiO2-xSex (left-hand side), the low binding energy of the filled Se 4p orbitals introduces a state 2 eV above the valence of SiO2, while in Si1–xPbxO2 (right-hand side), the high binding energy of the unoccupied Pb 6s orbital introduces a state 3 eV below the conduction band of SiO2.

The different substitution types offer precision control over which electronic property is tuned. The ionization potential can be altered by anion substitution, electron affinity by metal mixing, and the band gap by either or both. In all cases the band engineering is achieved by introducing well-defined states in the gap of the host material. Doping on the chalcogen site leaves the intrinsic band structure essentially unaltered and the resultant midgap state is highly localized, as evidenced by the lack of dispersion in the upper valence band (Figure 3). Note that the Te-substituted chalcogen resulted in a framework with a stress beyond the ultimate tensile strength of the framework and could not be mechanically stabilized, although solid solutions with heavier chalcogen frameworks (e.g., MSe2-xTex) may be possible.
The metal substitution induced gap state shows a trend toward increased localization as we move further in chemical space from the original host species. The dispersion for the Ge defined conduction band is similar to that in purely siliceous SOD. The band dispersion in reciprocal decreases as we move down the column of the periodic table, until the flat, midgap state of Pb. The trend can be understood in terms of atomic orbital mixing and overlap in forming the crystal wave functions. As the metals become more chemically distinct the degree of mixing is reduced and the state defining the band edge participates to a lesser extent in the interconnected matrix of the framework. This observation has implications for charge transport in the material, as higher effective masses will reduce electron mobility and hence conductivity.

4 Semiconductor Applications

ARTICLE SECTIONS
Jump To

Thus far we have considered the properties of ZSs with respect to conventional solid-state semiconductors. However, the trends and properties that have been revealed are of interest in their own right, provoking the question: what is the nanoporous semiconductor advantage?
The answer lies in the void, with the availability of a continuous, ordered, porous, conducting network. These systems can be intimately mixed with materials possessing complementary electronic properties. This concept opens up a plethora of combinations and opportunities. To illustrate the potential for forming composite systems we initially consider a prototypical pore-filling material: fullerene, ubiquitous in organic electronics. In combination with ZSs, we demonstrate how it can find enhanced application. Figure 4 shows the upper valence electron density of LTA-SiO2 with a fullerene in the pore, (49) along with the associated electron energies, on the left-hand side the energy levels. The straddling type-I offset of the isolated materials is reproduced in the composite system. This type of junction is widely applied in quantum dots and wells to stabilize excitons and provide enhanced luminesce in the confined system. The arrangement means that both holes and electrons are blocked from leaving the fullerene, yet the fullerenes can still form an ordered array, afforded by the framework structure of the ZS. We note that during the preparation of this manuscript an exciting report of Ag nanoparticles contained within zeolitic-SiO2 was reported and demonstrated unusual quantum confinement effects, (50) substantiating this potential application.

Figure 4

Figure 4. Representations of (a) C60@LTA-SiO2 forming a type I semiconductor internal heterojunction, with strong quantum confinement which could provide enhanced exciton lifetimes and luminescence. The calculated offsets based on the isolated and composite systems are shown (blue bands corresponding to C60-centered bands). SOD-SnO2 pores (d = 10.7 Å) may be filled with small PbS quantum dots, where confinement effects can be exploited to change the nature of the band offsets. Here we show the broadening of the electronic gap in slightly larger PbS quantum dots and can project that the smaller dots will form the type-II semiconductor heterojunction. Loading ACO-GeO2 with the conductive polymer, polypyrrole (c), should form a type-III semiconductor heterojunction, which could lead to selective hole transport in the polypyrrole layer and electron injection into the GeO2 framework.

Type-II offsets or staggered band gaps alignment is perhaps the most desirable alignment regime for semiconductor devices, finding application for example in bipolar transistors, light emitting diodes, and photovoltaic devices. This type of offset allows for robust separation of charges (electrons and holes) between the two materials. To illustrate the possibility of utility of ZSs with other nanotechnologies we demonstrate the alignment of SOD-SnO2 with PbS quantum dots in Figure 4b. In this case the size of the quantum dot as well as the porosity and composition of the framework allows for fine-tuning of the alignments. One application is the synthesis of photovoltaic absorber layers with the high interfacial areas associated with bulk heterojunction solar cells but with a degree of order and regularity unobtainable in typical donor–acceptor composites. This in turn could lead to enhanced charge separation, carrier lifetimes, and ultimately device performance. For the compositions considered here the frameworks would be best suited to acting as n-type semiconductors in such an architecture, because of the greater dispersion and lower effective mass in the conduction band as opposed to the valence. Design rules for p-type frameworks could include the use of metal cations with lone-pair s-electrons constituting the valence band maximum, similar principles have been explored for establishing p-type transparent conductive oxides. (51)
Type-III offsets usually occur in materials with contrasting electronegativities, in this case the valence band of one material lies closer to the vacuum level than the conduction band of the other material, resulting in a spontaneous transfer of charge at the interface. Such architectures have been proposed for biomedical applications; however, these offsets are uncommon in traditional semiconductors (52, 53) as the change in electronegativity is generally accompanied by a large difference in crystal structure. Recent developments in epitaxial growth of nanowires have opened up new possibilities for defect-free type-III interfaces. (54, 55) The application of ZSs with semiconducting inclusion materials offers another route to the fabrication of this important class of semiconductor architectures. LTA-SiO2 with polypyrrole in the pore is depicted in Figure 4c. This case corresponds to a type-III offset, with the valence bands of the polypyrrole higher in energy than the conduction band of the ZS, due to the destabilizing effects of the lone pair on the nitrogen site.
Another potential application of the frameworks is as transparent conductors (TCs). Traditionally TCs have relied on taking a wide gap material (usually an oxide) and tuning the carrier levels to induce conductivity. Recently, however, Zunger and co-workers (56) demonstrated a new route to achieving TCs through the control of interband transitions in metallic conductors. The proposed type 2 intrinsic conductors are semimetals with large direct bandgaps and zero indirect bandgaps. The SnX2 series presented in Figure 2 demonstrate how this kind of band structure is achievable in porous chalcogenides. Through the choice of metal and anion the interband transitions can be tuned to be symmetry allowed or forbidden, suggesting the possible application of ZSs as transparent intrinsic conductors.
The applications outlined above represent a select few examples; the field is limited only by the imagination of its practitioners. We have demonstrated the thermodynamic feasibility of electroactive porous chalcogenide frameworks, and recent work in the field of infiltrated carbon nanotubes (57) and electro-activated MOFs (58) already demonstrates the wide array of novel technologies made possible by such strategies. The gauntlet is now thrown down to engineers to design and develop novel applications, to physicists to explore and explain the rich electronic structure, and to chemists to synthesize and realize these configurations.

5 Catalytic Applications

ARTICLE SECTIONS
Jump To

While the substitution of metallic heteroatoms into the microporous matrix of zeolites has resulted in a large number of novel catalytic systems, the isomorphic substitutions of the bridging oxygen atoms in these materials by other elements, such as S, Se, and Te, to produce microporous metal chalcogenides has seldom been explored and continues to be an exciting topic in the context of catalytic bond activation. (59) This lack of understanding exists despite our ability to, on the one hand, synthesize well-defined metal chalcogenide structures, and on the other hand, use such materials with open architectures as catalysts in a variety of photo- and electrochemical applications. (60)
An opportunity exists for the use of microporous metal chalcogenides to generate exotic catalytic environments that combine the confinement effects of microporous materials with the electronic properties generated by the metal-chalcogen motifs. Indeed, microporous environments can discriminate chemical pathways by allowing the diffusion of molecules with the correct shape and size. The pores and voids of these materials have molecular dimensions capable of stabilizing reactive intermediates and transitions states that mediate chemical reactivity by van der Waals interactions. This is reminiscent of the solvation effects prevalent within enzyme pockets and has analogous consequences for catalytic specificity. (61) The topochemical characteristics of the pores mediate enthalpy–entropy compromises that determine Gibbs free energies of the reactive adducts, thus extending the diversity of the microporous solid matrix well beyond simple size discrimination allowing the utilization of entropy as a design principle. (62) Microporous environments have been exploited to stabilize late transition metal clusters via encapsulation to generate bifunctional catalysts. (63) Notably, the porous materials described herein can be synthesized with tunable bandgaps, making them suitable as selective photoredox catalysts. Taken together, all these properties can be combined to address a variety of challenging transformations. For example, these catalysts are promising materials for the selective removal of endocrine disruptor compounds—water-soluble organic pollutants known for their ability to mimic hormones, leading to adverse health effects on aquatic organisms (64) and in the early stages of human life (65) even at exceedingly low (i.e., pg/L) concentrations—from wastewater streams via chemoselective photodegradation in the presence of other organic species. Interestingly, the decomposition of organic waste could lead to the production of fuels and electricity when using these materials in photofuel-cells. (66) Similar approaches could be implemented for the removal of air pollutants in vehicles and buildings. Further, the cooperative effects between the semiconducting framework with encapsulated redox-active clusters can be exploited for light-assisted bond activation in thermocatalysis (an example is shown in Figure S3), akin to the cooperative effect attained with localized surface plasmons to lower activation barriers and increase the selectivity by allowing the thermocatalytic production of sensitive compounds at lower temperatures. (67, 68)

6 Conclusion

ARTICLE SECTIONS
Jump To

From a predictive materials modeling investigation, we have shown that nanoporous oxides and chalcogenides exhibit an impressive diversity in their electronic behavior. Depending on the choice of metal or chalcogen, the band gaps can be tuned from the regime of wide band gap insulators to semiconductors, with metallicity observed for the heavier chalcogens. Perhaps these heavier chalcogenide materials could be interesting electrically conductive materials. These properties can be further tuned through doping and solid solutions, and their porosity can be exploited to construct a range of electronic offsets within the materials by using electroactive guests. The thermodynamic cost of forming the chalcogenide frameworks is similar to known nanoporous materials, and they should be amenable to the full range of established synthetic techniques including chemical templating. Furthermore, the diversity and chemical modularity provides unusual routes toward high surface area heterogeneous catalysts with compelling compositions for photo-, electro-, and thermal catalytic applications. Thus, this class of porous metal chalcogenides has the potential to bring semiconductor nanochemistry firmly into three dimensions.

Supporting Information

ARTICLE SECTIONS
Jump To

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.chemmater.7b00464.

  • Further details on the computational methods and a table of the calculated electronic and structural properties of each material (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.

Author Information

ARTICLE SECTIONS
Jump To

  • Corresponding Author
    • Aron Walsh - Department of Materials Science and Engineering, Yonsei University, Seoul 03722, South KoreaDepartment of Materials, Imperial College London, Exhibition Road, London SW7 2AZ, United KingdomOrcidhttp://orcid.org/0000-0001-5460-7033 Email: [email protected]
  • Authors
    • Christopher H. Hendon - Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United StatesDepartment of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AY, United KingdomOrcidhttp://orcid.org/0000-0002-7132-768X
    • Keith T. Butler - Department of Chemistry, University of Bath, Claverton Down, Bath, BA2 7AY, United Kingdom
    • Alex M. Ganose - Kathleen Lonsdale Materials Chemistry, Department of Chemistry, University College London, 20 Gordon Street, London, WC1H 0AJ, United KingdomDiamond Light Source Ltd., Diamond House, Harwell Science and Innovation Campus, Didcot, Oxfordshire OX11 0DE, United Kingdom
    • Yuriy Román-Leshkov - Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, United StatesOrcidhttp://orcid.org/0000-0002-0025-4233
    • David O. Scanlon - Kathleen Lonsdale Materials Chemistry, Department of Chemistry, University College London, 20 Gordon Street, London, WC1H 0AJ, United KingdomDiamond Light Source Ltd., Diamond House, Harwell Science and Innovation Campus, Didcot, Oxfordshire OX11 0DE, United KingdomOrcidhttp://orcid.org/0000-0001-9174-8601
    • Geoffrey A. Ozin - Department of Chemistry, University of Toronto, Toronto, Ontario M5S 3H6, Canada
  • Notes
    The authors declare no competing financial interest.

Acknowledgment

ARTICLE SECTIONS
Jump To

A.W., K.T.B., and C.H.H. are supported by the Royal Society, the EPSRC (Grant EP/M009580/1) and the ERC (Grant 277757). D.O.S. and A.W. acknowledge membership of the Materials Design Network. A.M.G. acknowledges Diamond Light Source for the cosponsorship of a studentship on the EPSRC Centre for Doctoral Training in Molecular Modelling and Materials Science (EP/L015862/1). GAO is a Government of Canada Research Chair in Materials Chemistry and Nanochemistry. He deeply appreciates the strong and sustained support of his research from the Natural Sciences and Engineering Research Council of Canada. This work benefitted from access to the ARCHER, through the UK High Performance Computing Consortium, which is funded by EPSRC Grant EP/L000202, and access to XSEDE Grant Number AC-1053575.

References

ARTICLE SECTIONS
Jump To

This article references 68 other publications.

  1. 1
    Ozin, G. A. Nanochemistry: Synthesis in Diminishing Dimensions Adv. Mater. 1992, 4, 612 649 DOI: 10.1002/adma.19920041003
  2. 2
    Han, C.; Sun, Q.; Li, Z.; Dou, S. X. Thermoelectric Enhancement of Different Kinds of Metal Chalcogenides Adv. Energy Mater. 2016, 6, 1600498 DOI: 10.1002/aenm.201600498
  3. 3
    Zheng, N.; Bu, X.; Wang, B.; Feng, P. Microporous and Photoluminescent Chalcogenide Zeolite Analogs Science 2002, 298, 2366 2369 DOI: 10.1126/science.1078663
  4. 4
    Trikalitis, P. N.; Rangan, K. K.; Bakas, T.; Kanatzidis, M. G. Varied Pore Organization in Mesostructured Semiconductors Based on the [SnSe4]4- Anion Nature 2001, 410, 671 675 DOI: 10.1038/35070533
  5. 5
    Bag, S.; Trikalitis, P. N.; Chupas, P. J.; Armatas, G. S.; Kanatzidis, M. G. Porous Semiconducting Gels and Aerogels from Chalcogenide Clusters Science 2007, 317, 490 493 DOI: 10.1126/science.1142535
  6. 6
    Feng, P.; Bu, X.; Zheng, N. The Interface Chemistry between Chalcogenide Clusters and Open Framework Chalcogenides Acc. Chem. Res. 2005, 38, 293 303 DOI: 10.1021/ar0401754
  7. 7
    Lewis, D. W.; Willock, D. J.; Catlow, C. R. A.; Thomas, J. M.; Hutchings, G. J. De Novo Design of Structure Directing Agents for the Synthesis of Microporous Solids Nature 1996, 382, 604 606 DOI: 10.1038/382604a0
  8. 8
    Jiang, J.; Jorda, J. L.; Diaz-Cabanas, M. J.; Yu, J.; Corma, A. The Synthesis of an Extra-Large-Pore Zeolite with Double Three-Ring Building Units and a Low Framework Density Angew. Chem., Int. Ed. 2010, 49, 4986 4988 DOI: 10.1002/anie.201001506
  9. 9
    Corma, A.; Díaz-Cabañas, M. J.; Martínez-Triguero, J.; Rey, F.; Rius, J. A Large-Cavity Zeolite with Wide Pore Windows and Potential as an Oil Refining Catalyst Nature 2002, 418, 514 517 DOI: 10.1038/nature00924
  10. 10
    Armatas, G. S.; Kanatzidis, M. G. Mesoporous Germanium-Rich Chalcogenido Frameworks with Highly Polarizable Surfaces and Relevance to Gas Separation Nat. Mater. 2009, 8, 217 222 DOI: 10.1038/nmat2381
  11. 11
    Bag, S.; Kanatzidis, M. G. Chalcogels: Porous Metal–Chalcogenide Networks from Main-Group Metal Ions. Effect of Surface Polarizability on Selectivity in Gas Separation J. Am. Chem. Soc. 2010, 132, 14951 14959 DOI: 10.1021/ja1059284
  12. 12
    Santner, S.; Dehnen, S. [M4Sn4Se17]10- Cluster Anions (M = Mn, Zn, Cd) in a Cs+ Environment and as Ternary Precursors for Ionothermal Treatment Inorg. Chem. 2015, 54, 1188 1190 DOI: 10.1021/ic5026087
  13. 13
    Lin, Y.; Dehnen, S. [BMIm]4[Sn9Se20]: Ionothermal Synthesis of a Selenidostannate with a 3D Open-Framework Structure Inorg. Chem. 2011, 50, 7913 7915 DOI: 10.1021/ic200697k
  14. 14
    Jiao, F.; Jumas, J. C.; Womes, M.; Chadwick, A. V.; Harrison, A.; Bruce, P. G. Synthesis of Ordered Mesoporous Fe3O4 and γ-Fe2O3 with Crystalline Walls Using Post-Template Reduction/Oxidation J. Am. Chem. Soc. 2006, 128, 12905 12909 DOI: 10.1021/ja063662i
  15. 15
    Hu, D.-D.; Lin, J.; Zhang, Q.; Lu, J.-N.; Wang, X.-Y.; Wang, Y.-W.; Bu, F.; Ding, L.-F.; Wang, L.; Wu, T. Multi-Step Host–Guest Energy Transfer Between Inorganic Chalcogenide-Based Semiconductor Zeolite Material and Organic Dye Molecules Chem. Mater. 2015, 27, 4099 4104 DOI: 10.1021/acs.chemmater.5b01158
  16. 16
    Lin, J.; Dong, Y.; Zhang, Q.; Hu, D.; Li, N.; Wang, L.; Liu, Y.; Wu, T. Interrupted Chalcogenide-Based Zeolite-Analog Semiconductor: Atomically Precise Doping for Tunable Electro-/Photoelectrochemical Properties Angew. Chem. 2015, 127, 5192 5196 DOI: 10.1002/ange.201500659
  17. 17
    Arachchige, I. U.; Kanatzidis, M. G. Anomalous Band Gap Evolution from Band Inversion in Pb1-xSnxTe Nanocrystals Nano Lett. 2009, 9, 1583 1587 DOI: 10.1021/nl8037757
  18. 18
    Lin, Q.; Bu, X.; Mao, C.; Zhao, X.; Sasan, K.; Feng, P. Mimicking High-Silica Zeolites: Highly Stable Germanium- and Tin-Rich Zeolite-Type Chalcogenides J. Am. Chem. Soc. 2015, 137, 6184 6187 DOI: 10.1021/jacs.5b03550
  19. 19
    Davies, D. W.; Butler, K. T.; Jackson, A. J.; Morris, A.; Frost, J. M.; Skelton, J. M.; Walsh, A. Computational Screening of All Stoichiometric Inorganic Materials Chem. 2016, 1, 617 627 DOI: 10.1016/j.chempr.2016.09.010
  20. 20
    Butler, K. T.; Frost, J. M.; Skelton, J. M.; Svane, K. L.; Walsh, A. Computational Materials Design of Crystalline Solids Chem. Soc. Rev. 2016, 45, 6138 6146 DOI: 10.1039/C5CS00841G
  21. 21
    Zwijnenburg, M. A.; Bromley, S. T.; Foster, M. D.; Bell, R. G.; Delgado-Friedrichs, O.; Jansen, J. C.; Maschmeyer, T. Toward Understanding the Thermodynamic Viability of Zeolites and Related Frameworks through a Simple Topological Model Chem. Mater. 2004, 16, 3809 3820 DOI: 10.1021/cm049256k
  22. 22
    Corma, A.; Rey, F.; Rius, J.; Sabater, M. J.; Valencia, S. Supramolecular Self-Assembled Molecules as Organic Directing Agent for Synthesis of Zeolites Nature 2004, 431, 287 290 DOI: 10.1038/nature02909
  23. 23
    Couves, J. W.; Jones, R. H.; Parker, S. C.; Tschaufeser, P.; Catlow, C. R. A. Experimental Verification of a Predicted Negative Thermal Expansivity of Crystalline Zeolites J. Phys.: Condens. Matter 1993, 5, L329 L332 DOI: 10.1088/0953-8984/5/27/001
  24. 24
    Foster, M. D.; Rivin, I.; Treacy, M. M. J.; Friedrichs, O. D. A Geometric Solution to the Largest-Free-Sphere Problem in Zeolite Frameworks Microporous Mesoporous Mater. 2006, 90, 32 38 DOI: 10.1016/j.micromeso.2005.08.025
  25. 25
    O’Keeffe, M.; Yaghi, O. M. Germanate Zeolites: Contrasting the Behavior of Germanate and Silicate Structures Built from Cubic T8O20 Units (T = Ge or Si) Chem. - Eur. J. 1999, 5, 2796 2801 DOI: 10.1002/(SICI)1521-3765(19991001)5:10<2796::AID-CHEM2796>3.0.CO;2-6
  26. 26
    Piccione, P. M.; Laberty, C.; Yang, S.; Camblor, M. A.; Navrotsky, A.; Davis, M. E. Thermochemistry of Pure-Silica Zeolites J. Phys. Chem. B 2000, 104, 10001 10011 DOI: 10.1021/jp002148a
  27. 27
    Goldschmidt, V. M. The Principles of Distribution of Chemical Elements in Minerals and Rocks J. Chem. Soc. 1937, 0, 655 673 DOI: 10.1039/JR9370000655
  28. 28
    Sastre, G.; Corma, A. Predicting Structural Feasibility of Silica and Germania Zeolites J. Phys. Chem. C 2010, 114, 1667 1673 DOI: 10.1021/jp909348s
  29. 29
    Gillespie, R. J. The Valence-Shell Electron-Pair Repulsion (VSEPR) Theory of Directed Valency J. Chem. Educ. 1963, 40, 295 DOI: 10.1021/ed040p295
  30. 30
    Li, H. Supertetrahedral Sulfide Crystals with Giant Cavities and Channels Science 1999, 283, 1145 1147 DOI: 10.1126/science.283.5405.1145
  31. 31
    Hughes, J. T.; Navrotsky, A. MOF-5: Enthalpy of Formation and Energy Landscape of Porous Materials J. Am. Chem. Soc. 2011, 133, 9184 9187 DOI: 10.1021/ja202132h
  32. 32
    Feng, P.; Bu, X.; Zheng, N. The Interface Chemistry between Chalcogenide Clusters and Open Framework Chalcogenides Acc. Chem. Res. 2005, 38, 293 303 DOI: 10.1021/ar0401754
  33. 33
    Mohanan, J. L.; Arachchige, I. U.; Brock, S. L. Porous Semiconductor Chalcogenide Aerogels Science 2005, 307, 397 400
  34. 34
    Li, H.; Eddaoudi, M.; Laine, A.; O’Keeffe, M.; Yaghi, O. M. Noninterpenetrating Indium Sulfide Supertetrahedral Cristobalite Framework J. Am. Chem. Soc. 1999, 121, 6096 6097 DOI: 10.1021/ja990410r
  35. 35
    Luc, W.; Jiao, F. Synthesis of Nanoporous Metals, Oxides, Carbides, and Sulfides: Beyond Nanocasting Acc. Chem. Res. 2016, 49, 1351 1358 DOI: 10.1021/acs.accounts.6b00109
  36. 36
    Zwijnenburg, M. A.; Corà, F.; Bell, R. G. Dramatic Differences between the Energy Landscapes of SiO2 and SiS2 Zeotype Materials J. Am. Chem. Soc. 2007, 129, 12588 12589 DOI: 10.1021/ja0727666
  37. 37
    Butler, K. T.; Hendon, C. H.; Walsh, A. Electronic Structure Modulation of Metal–Organic Frameworks for Hybrid Devices ACS Appl. Mater. Interfaces 2014, 6, 22044 22050 DOI: 10.1021/am507016r
  38. 38
    Sun, L.; Hendon, C. H.; Minier, M. A.; Walsh, A.; Dinca, M. Million-Fold Electrical Conductivity Enhancement in Fe2(DEBDC) versus Mn2(DEBDC) (E = S, O) J. Am. Chem. Soc. 2015, 137, 6164 6167 DOI: 10.1021/jacs.5b02897
  39. 39
    Hendon, C. H.; Walsh, A. Chemical Principles Underpinning the Performance of the Metal–organic Framework HKUST-1 Chem. Sci. 2015, 6, 3674 3683 DOI: 10.1039/C5SC01489A
  40. 40
    McDonald, T. M.; Mason, J. A.; Kong, X.; Bloch, E. D.; Gygi, D.; Dani, A.; Crocellà, V.; Giordanino, F.; Odoh, S. O.; Drisdell, W. S.; Vlaisavljevich, B.; Dzubak, A. L.; Poloni, R.; Schnell, S. K.; Planas, N.; Lee, K.; Pascal, T.; Wan, L. F.; Prendergast, D.; Neaton, J. B.; Smit, B.; Kortright, J. B.; Gagliardi, L.; Bordiga, S.; Reimer, J. A.; Long, J. R. Cooperative Insertion of CO2 in Diamine-Appended Metal-Organic Frameworks Nature 2015, 519, 303 308 DOI: 10.1038/nature14327
  41. 41
    Park, S. S.; Hontz, E. R.; Sun, L.; Hendon, C. H.; Walsh, A.; Van Voorhis, T.; Dinca, M. Cation-Dependent Intrinsic Electrical Conductivity in Isostructural Tetrathiafulvalene-Based Microporous Metal-Organic Frameworks J. Am. Chem. Soc. 2015, 137, 1774 1777 DOI: 10.1021/ja512437u
  42. 42
    Wahila, M. J.; Butler, K. T.; Lebens-Higgins, Z. W.; Hendon, C. H.; Nandur, A. S.; Treharne, R. E.; Quackenbush, N. F.; Sallis, S.; Mason, K.; Paik, H.; Schlom, D. G.; Woicik, J. C.; Guo, J.; Arena, D. A.; White, B. E.; Watson, G. W.; Walsh, A.; Piper, L. F. J. Lone-Pair Stabilization in Transparent Amorphous Tin Oxides: A Potential Route to P-Type Conduction Pathways Chem. Mater. 2016, 28, 4706 4713 DOI: 10.1021/acs.chemmater.6b01608
  43. 43
    Hinuma, Y.; Hatakeyama, T.; Kumagai, Y.; Burton, L. A.; Sato, H.; Muraba, Y.; Iimura, S.; Hiramatsu, H.; Tanaka, I.; Hosono, H.; Oba, F. Discovery of Earth-Abundant Nitride Semiconductors by Computational Screening and High-Pressure Synthesis Nat. Commun. 2016, 7, 11962 DOI: 10.1038/ncomms11962
  44. 44
    Butler, K. T.; Hendon, C. H.; Walsh, A. Electronic Chemical Potentials of Porous Metal-Organic Frameworks J. Am. Chem. Soc. 2014, 136, 2703 2706 DOI: 10.1021/ja4110073
  45. 45
    Born, M.; Huang, K. Dynamical Theory of Crystal Lattices; Clarendon Press, 1998.
  46. 46
    Sallis, S.; Butler, K. T.; Quackenbush, N. F.; Williams, D. S.; Junda, M.; Fischer, D. a.; Woicik, J. C.; Podraza, N. J.; White, B. E.; Walsh, A.; Piper, L. F. J. Origin of Deep Subgap States in Amorphous Indium Gallium Zinc Oxide: Chemically Disordered Coordination of Oxygen Appl. Phys. Lett. 2014, 104, 232108 DOI: 10.1063/1.4883257
  47. 47
    Zwijnenburg, M. A.; Bromley, S. T. Structure Direction in Zinc Oxide and Related Materials by Cation Substitution: An Analogy with Zeolites J. Mater. Chem. 2011, 21, 15255 15261 DOI: 10.1039/c1jm12383a
  48. 48
    Vegard, L. Die Konstitution Der Mischkristalle Und Die Raumfüllung Der Atome Eur. Phys. J. A 1921, 5, 17 26 DOI: 10.1007/BF01349680
  49. 49
    Hamilton, B. B.; Rimmer, J. S.; Anderson, M.; Leigh, D. White Light Emission from C60 Molecules Confined in Molecular Cage Materials Adv. Mater. 1993, 5, 583 585 DOI: 10.1002/adma.19930050717
  50. 50
    Fenwick, O.; Coutiño-Gonzalez, E.; Grandjean, D.; Baekelant, W.; Richard, F.; Bonacchi, S.; De Vos, D.; Lievens, P.; Roeffaers, M.; Hofkens, J.; Samorì, P. Tuning the Energetics and Tailoring the Optical Properties of Silver Clusters Confined in Zeolites Nat. Mater. 2016, 15, 1017 1022 DOI: 10.1038/nmat4652
  51. 51
    Hautier, G.; Miglio, A.; Ceder, G.; Rignanese, G.-M.; Gonze, X. Identification and Design Principles of Low Hole Effective Mass P-Type Transparent Conducting Oxides Nat. Commun. 2013, 4, 2292 DOI: 10.1038/ncomms3292
  52. 52
    Butler, K. T. Morphological Control of Band Offsets for Transparent Bipolar Heterojunctions: The Bädeker Diode Phys. Status Solidi A 2015, 212, 1461 1465 DOI: 10.1002/pssa.201532004
  53. 53
    Wahila, M. J.; Lebens-Higgins, Z. W.; Quackenbush, N. F.; Nishitani, J.; Walukiewicz, W.; Glans, P.-A.; Guo, J.-H.; Woicik, J. C.; Yu, K. M.; Piper, L. F. J. Evidence of Extreme Type-III Band Offset at Buried N -Type CdO/P-Type SnTe Interfaces Phys. Rev. B: Condens. Matter Mater. Phys. 2015, 91, 205307 DOI: 10.1103/PhysRevB.91.205307
  54. 54
    Pitanti, A.; Ercolani, D.; Sorba, L.; Roddaro, S.; Beltram, F.; Nasi, L.; Salviati, G.; Tredicucci, A. InAs/InP/InSb Nanowires as Low Capacitance N – N Heterojunction Diodes Phys. Rev. X 2011, 1, 11006 DOI: 10.1103/PhysRevX.1.011006
  55. 55
    Chen, C. Y.; Shik, A.; Pitanti, A.; Tredicucci, A.; Ercolani, D.; Sorba, L.; Beltram, F.; Ruda, H. E. Electron Beam Induced Current in InSb-InAs Nanowire Type-III Heterostructures Appl. Phys. Lett. 2012, 101, 63116 DOI: 10.1063/1.4745603
  56. 56
    Zhang, X.; Zhang, L.; Perkins, J. D.; Zunger, A. Intrinsic Transparent Conductors without Doping Phys. Rev. Lett. 2015, 115, 176602 DOI: 10.1103/PhysRevLett.115.176602
  57. 57
    Lim, H. E.; Miyata, Y.; Fujihara, M.; Okada, S.; Liu, Z.; Arifin; Sato, K.; Omachi, H.; Kitaura, R.; Irle, S.; Suenaga, K.; Shinohara, H. Fabrication and Optical Probing of Highly Extended, Ultrathin Graphene Nanoribbons in Carbon Nanotubes ACS Nano 2015, 9, 5034 5040 DOI: 10.1021/nn507408m
  58. 58
    Talin, A.; Centrone, A.; Ford, A. C.; Foster, M. E.; Stavila, V.; Haney, P.; Kinney, R. A.; Szalai, V.; El Gabaly, F.; Yoon, H. P.; Léonard, F.; Allendorf, M. D. Tunable Electrical Conductivity in Metal-Organic Framework Thin-Film Devices Science 2014, 343, 66 69 DOI: 10.1126/science.1246738
  59. 59
    Benz, S.; López-andarias, J.; Mareda, J.; Sakai, N.; Matile, S. Catalysis with Chalcogen Bonds Communications Angew. Chem., Int. Ed. 2017, 56, 812 815 DOI: 10.1002/anie.201611019
  60. 60
    Regulacio, M. D.; Han, M. Multinary I-III-VI2 and I2-II-IV-VI4 Semiconductor Nanostructures for Photocatalytic Applications Acc. Chem. Res. 2016, 49, 511 519 DOI: 10.1021/acs.accounts.5b00535
  61. 61
    Gounder, R.; Iglesia, E. The Roles of Entropy and Enthalpy in Stabilizing Catalysis Acc. Chem. Res. 2012, 45, 229 238 DOI: 10.1021/ar200138n
  62. 62
    Butler, K. T.; Walsh, A.; Cheetham, A. K.; Kieslich, G. Organised Chaos: Entropy in Hybrid Inorganic–Organic Systems and Other Materials Chem. Sci. 2016, 7, 6316 6324 DOI: 10.1039/C6SC02199A
  63. 63
    Na, K.; Choi, K. M.; Yaghi, O. M.; Somorjai, G. A. Metal Nanocrystals Embedded in Single Nanocrystals of MOFs Give Unusual Selectivity as Heterogeneous Catalysts Nano Lett. 2014, 14, 5979 5983 DOI: 10.1021/nl503007h
  64. 64
    Milla, S.; Depiereux, S.; Kestemont, P. The Effects of Estrogenic and Androgenic Endocrine Disruptors on the Immune System of Fish: A Review Ecotoxicology 2011, 20, 305 319 DOI: 10.1007/s10646-010-0588-7
  65. 65
    Colborn, T.; Saal, F. S.; Soto, A. M. Developmental Effects of Endocrine-Disrupting Chemicals in Wildlife and Humans Enviromental Heal. Perspect. 1993, 101, 378 384 DOI: 10.1289/ehp.93101378
  66. 66
    Viswanathan, B.; Subramanian, V.; Lee, J. S. Materials and Processes for Solar Fuel Production; Lockwood, D. J., Ed.; Springer, 2014.
  67. 67
    Linic, S.; Aslam, U.; Boerigter, C.; Morabito, M. Photochemical Transformations on Plasmonic Metal Nanoparticles Nat. Mater. 2015, 14, 567 576 DOI: 10.1038/nmat4281
  68. 68
    Boerigter, C.; Aslam, U.; Linic, S. Mechanism of Charge Transfer from Plasmonic Nanostructures to Chemically Attached ACS Nano 2016, 10, 6108 6115 DOI: 10.1021/acsnano.6b01846

Cited By

ARTICLE SECTIONS
Jump To

This article is cited by 8 publications.

  1. Tien Le, Bin Wang. First-Principles Study of Interaction between Molecules and Lewis Acid Zeolites Manipulated by Injection of Energized Charge Carriers. Industrial & Engineering Chemistry Research 2021, 60 (39) , 14124-14133. https://doi.org/10.1021/acs.iecr.1c02808
  2. Christopher H. Hendon, Adam J. Rieth, Maciej D. Korzyński, and Mircea Dincă . Grand Challenges and Future Opportunities for Metal–Organic Frameworks. ACS Central Science 2017, 3 (6) , 554-563. https://doi.org/10.1021/acscentsci.7b00197
  3. Thanh Duy Cam Ha, Heehyeon Lee, Ioannis Vamvasakis, Gerasimos S. Armatas, Youngtak Oh, Myung‐Gil Kim. Recent developments in porous metal chalcogenides for environmental remediation and sustainable energy. EcoMat 2023, 5 (12) https://doi.org/10.1002/eom2.12419
  4. Elindjeane Sheela Sowbakkiyavathi, Vignesh Murugadoss, Ramadasse Sittaramane, Ragupathy Dhanusuraman, Subramania Angaiah. Cobalt selenide decorated polyaniline composite nanofibers as a newer counter electrode for dye‐sensitized solar cell. Polymers for Advanced Technologies 2021, 32 (8) , 3137-3149. https://doi.org/10.1002/pat.5326
  5. Xin Shi, Hui Wang, Palanisamy Kannan, Jieting Ding, Shan Ji, Fusheng Liu, Hengjun Gai, Rongfang Wang. Rich-grain-boundary of Ni 3 Se 2 nanowire arrays as multifunctional electrode for electrochemical energy storage and conversion applications. Journal of Materials Chemistry A 2019, 7 (7) , 3344-3352. https://doi.org/10.1039/C8TA10912E
  6. Ji Sang Park, Sunghyun Kim, Zijuan Xie, Aron Walsh. Point defect engineering in thin-film solar cells. Nature Reviews Materials 2018, 3 (7) , 194-210. https://doi.org/10.1038/s41578-018-0026-7
  7. Gloria Tabacchi. Supramolecular Organization in Confined Nanospaces. ChemPhysChem 2018, 19 (11) , 1249-1297. https://doi.org/10.1002/cphc.201701090
  8. Daniel W. Davies, Keith T. Butler, Jonathan M. Skelton, Congwei Xie, Artem R. Oganov, Aron Walsh. Computer-aided design of metal chalcohalide semiconductors: from chemical composition to crystal structure. Chemical Science 2018, 9 (4) , 1022-1030. https://doi.org/10.1039/C7SC03961A
  • Abstract

    Figure 1

    Figure 1. Electronic band structures (DFT/HSE06), aligned to the vacuum level by the ionization potential (Φ), of MO2 (M = Si, Ge, Sn, Pb) in the zeolite-type structures shown on the left. Plotted following 0,0,0 to 1/2,1/2,1/2 in reciprocal space (where 0,0,0 = gamma and 1/2,1/2,1/2 = special point as described in the figure), SOD structured materials show the most significant dispersion in the conduction band (ca. 2 eV), followed by ACO (ca. 1.6 eV), and LTA (ca. 0.7 eV). The conduction band is composed of delocalized antibonding O s and M s-orbitals. The valence band is composed of localized O p-orbitals, resulting in flat bands, and the bulk potential is relatively insensitive to the cation identity.

    Figure 2

    Figure 2. Electronic band structures (plotted from 0,0,0 to 1/2,1/2,1/2 in reciprocal space) for sodalite SnX2 (X = O, S, Se, Te) relative to the vacuum level. The oxide has a band gap, while the sulfide, selenide, and telluride are metallic and their work functions are defined by their Fermi levels (in the limit of T → 0 K).

    Figure 3

    Figure 3. Isovalent dopants introduce localized states in the electronic band structure of porous metal chalcogenides (DFT/HSE06), allowing for modular electronic band gaps and ionization potentials (Φ). For example, in SiO2-xSex (left-hand side), the low binding energy of the filled Se 4p orbitals introduces a state 2 eV above the valence of SiO2, while in Si1–xPbxO2 (right-hand side), the high binding energy of the unoccupied Pb 6s orbital introduces a state 3 eV below the conduction band of SiO2.

    Figure 4

    Figure 4. Representations of (a) C60@LTA-SiO2 forming a type I semiconductor internal heterojunction, with strong quantum confinement which could provide enhanced exciton lifetimes and luminescence. The calculated offsets based on the isolated and composite systems are shown (blue bands corresponding to C60-centered bands). SOD-SnO2 pores (d = 10.7 Å) may be filled with small PbS quantum dots, where confinement effects can be exploited to change the nature of the band offsets. Here we show the broadening of the electronic gap in slightly larger PbS quantum dots and can project that the smaller dots will form the type-II semiconductor heterojunction. Loading ACO-GeO2 with the conductive polymer, polypyrrole (c), should form a type-III semiconductor heterojunction, which could lead to selective hole transport in the polypyrrole layer and electron injection into the GeO2 framework.

  • References

    ARTICLE SECTIONS
    Jump To

    This article references 68 other publications.

    1. 1
      Ozin, G. A. Nanochemistry: Synthesis in Diminishing Dimensions Adv. Mater. 1992, 4, 612 649 DOI: 10.1002/adma.19920041003
    2. 2
      Han, C.; Sun, Q.; Li, Z.; Dou, S. X. Thermoelectric Enhancement of Different Kinds of Metal Chalcogenides Adv. Energy Mater. 2016, 6, 1600498 DOI: 10.1002/aenm.201600498
    3. 3
      Zheng, N.; Bu, X.; Wang, B.; Feng, P. Microporous and Photoluminescent Chalcogenide Zeolite Analogs Science 2002, 298, 2366 2369 DOI: 10.1126/science.1078663
    4. 4
      Trikalitis, P. N.; Rangan, K. K.; Bakas, T.; Kanatzidis, M. G. Varied Pore Organization in Mesostructured Semiconductors Based on the [SnSe4]4- Anion Nature 2001, 410, 671 675 DOI: 10.1038/35070533
    5. 5
      Bag, S.; Trikalitis, P. N.; Chupas, P. J.; Armatas, G. S.; Kanatzidis, M. G. Porous Semiconducting Gels and Aerogels from Chalcogenide Clusters Science 2007, 317, 490 493 DOI: 10.1126/science.1142535
    6. 6
      Feng, P.; Bu, X.; Zheng, N. The Interface Chemistry between Chalcogenide Clusters and Open Framework Chalcogenides Acc. Chem. Res. 2005, 38, 293 303 DOI: 10.1021/ar0401754
    7. 7
      Lewis, D. W.; Willock, D. J.; Catlow, C. R. A.; Thomas, J. M.; Hutchings, G. J. De Novo Design of Structure Directing Agents for the Synthesis of Microporous Solids Nature 1996, 382, 604 606 DOI: 10.1038/382604a0
    8. 8
      Jiang, J.; Jorda, J. L.; Diaz-Cabanas, M. J.; Yu, J.; Corma, A. The Synthesis of an Extra-Large-Pore Zeolite with Double Three-Ring Building Units and a Low Framework Density Angew. Chem., Int. Ed. 2010, 49, 4986 4988 DOI: 10.1002/anie.201001506
    9. 9
      Corma, A.; Díaz-Cabañas, M. J.; Martínez-Triguero, J.; Rey, F.; Rius, J. A Large-Cavity Zeolite with Wide Pore Windows and Potential as an Oil Refining Catalyst Nature 2002, 418, 514 517 DOI: 10.1038/nature00924
    10. 10
      Armatas, G. S.; Kanatzidis, M. G. Mesoporous Germanium-Rich Chalcogenido Frameworks with Highly Polarizable Surfaces and Relevance to Gas Separation Nat. Mater. 2009, 8, 217 222 DOI: 10.1038/nmat2381
    11. 11
      Bag, S.; Kanatzidis, M. G. Chalcogels: Porous Metal–Chalcogenide Networks from Main-Group Metal Ions. Effect of Surface Polarizability on Selectivity in Gas Separation J. Am. Chem. Soc. 2010, 132, 14951 14959 DOI: 10.1021/ja1059284
    12. 12
      Santner, S.; Dehnen, S. [M4Sn4Se17]10- Cluster Anions (M = Mn, Zn, Cd) in a Cs+ Environment and as Ternary Precursors for Ionothermal Treatment Inorg. Chem. 2015, 54, 1188 1190 DOI: 10.1021/ic5026087
    13. 13
      Lin, Y.; Dehnen, S. [BMIm]4[Sn9Se20]: Ionothermal Synthesis of a Selenidostannate with a 3D Open-Framework Structure Inorg. Chem. 2011, 50, 7913 7915 DOI: 10.1021/ic200697k
    14. 14
      Jiao, F.; Jumas, J. C.; Womes, M.; Chadwick, A. V.; Harrison, A.; Bruce, P. G. Synthesis of Ordered Mesoporous Fe3O4 and γ-Fe2O3 with Crystalline Walls Using Post-Template Reduction/Oxidation J. Am. Chem. Soc. 2006, 128, 12905 12909 DOI: 10.1021/ja063662i
    15. 15
      Hu, D.-D.; Lin, J.; Zhang, Q.; Lu, J.-N.; Wang, X.-Y.; Wang, Y.-W.; Bu, F.; Ding, L.-F.; Wang, L.; Wu, T. Multi-Step Host–Guest Energy Transfer Between Inorganic Chalcogenide-Based Semiconductor Zeolite Material and Organic Dye Molecules Chem. Mater. 2015, 27, 4099 4104 DOI: 10.1021/acs.chemmater.5b01158
    16. 16
      Lin, J.; Dong, Y.; Zhang, Q.; Hu, D.; Li, N.; Wang, L.; Liu, Y.; Wu, T. Interrupted Chalcogenide-Based Zeolite-Analog Semiconductor: Atomically Precise Doping for Tunable Electro-/Photoelectrochemical Properties Angew. Chem. 2015, 127, 5192 5196 DOI: 10.1002/ange.201500659
    17. 17
      Arachchige, I. U.; Kanatzidis, M. G. Anomalous Band Gap Evolution from Band Inversion in Pb1-xSnxTe Nanocrystals Nano Lett. 2009, 9, 1583 1587 DOI: 10.1021/nl8037757
    18. 18
      Lin, Q.; Bu, X.; Mao, C.; Zhao, X.; Sasan, K.; Feng, P. Mimicking High-Silica Zeolites: Highly Stable Germanium- and Tin-Rich Zeolite-Type Chalcogenides J. Am. Chem. Soc. 2015, 137, 6184 6187 DOI: 10.1021/jacs.5b03550
    19. 19
      Davies, D. W.; Butler, K. T.; Jackson, A. J.; Morris, A.; Frost, J. M.; Skelton, J. M.; Walsh, A. Computational Screening of All Stoichiometric Inorganic Materials Chem. 2016, 1, 617 627 DOI: 10.1016/j.chempr.2016.09.010
    20. 20
      Butler, K. T.; Frost, J. M.; Skelton, J. M.; Svane, K. L.; Walsh, A. Computational Materials Design of Crystalline Solids Chem. Soc. Rev. 2016, 45, 6138 6146 DOI: 10.1039/C5CS00841G
    21. 21
      Zwijnenburg, M. A.; Bromley, S. T.; Foster, M. D.; Bell, R. G.; Delgado-Friedrichs, O.; Jansen, J. C.; Maschmeyer, T. Toward Understanding the Thermodynamic Viability of Zeolites and Related Frameworks through a Simple Topological Model Chem. Mater. 2004, 16, 3809 3820 DOI: 10.1021/cm049256k
    22. 22
      Corma, A.; Rey, F.; Rius, J.; Sabater, M. J.; Valencia, S. Supramolecular Self-Assembled Molecules as Organic Directing Agent for Synthesis of Zeolites Nature 2004, 431, 287 290 DOI: 10.1038/nature02909
    23. 23
      Couves, J. W.; Jones, R. H.; Parker, S. C.; Tschaufeser, P.; Catlow, C. R. A. Experimental Verification of a Predicted Negative Thermal Expansivity of Crystalline Zeolites J. Phys.: Condens. Matter 1993, 5, L329 L332 DOI: 10.1088/0953-8984/5/27/001
    24. 24
      Foster, M. D.; Rivin, I.; Treacy, M. M. J.; Friedrichs, O. D. A Geometric Solution to the Largest-Free-Sphere Problem in Zeolite Frameworks Microporous Mesoporous Mater. 2006, 90, 32 38 DOI: 10.1016/j.micromeso.2005.08.025
    25. 25
      O’Keeffe, M.; Yaghi, O. M. Germanate Zeolites: Contrasting the Behavior of Germanate and Silicate Structures Built from Cubic T8O20 Units (T = Ge or Si) Chem. - Eur. J. 1999, 5, 2796 2801 DOI: 10.1002/(SICI)1521-3765(19991001)5:10<2796::AID-CHEM2796>3.0.CO;2-6
    26. 26
      Piccione, P. M.; Laberty, C.; Yang, S.; Camblor, M. A.; Navrotsky, A.; Davis, M. E. Thermochemistry of Pure-Silica Zeolites J. Phys. Chem. B 2000, 104, 10001 10011 DOI: 10.1021/jp002148a
    27. 27
      Goldschmidt, V. M. The Principles of Distribution of Chemical Elements in Minerals and Rocks J. Chem. Soc. 1937, 0, 655 673 DOI: 10.1039/JR9370000655
    28. 28
      Sastre, G.; Corma, A. Predicting Structural Feasibility of Silica and Germania Zeolites J. Phys. Chem. C 2010, 114, 1667 1673 DOI: 10.1021/jp909348s
    29. 29
      Gillespie, R. J. The Valence-Shell Electron-Pair Repulsion (VSEPR) Theory of Directed Valency J. Chem. Educ. 1963, 40, 295 DOI: 10.1021/ed040p295
    30. 30
      Li, H. Supertetrahedral Sulfide Crystals with Giant Cavities and Channels Science 1999, 283, 1145 1147 DOI: 10.1126/science.283.5405.1145
    31. 31
      Hughes, J. T.; Navrotsky, A. MOF-5: Enthalpy of Formation and Energy Landscape of Porous Materials J. Am. Chem. Soc. 2011, 133, 9184 9187 DOI: 10.1021/ja202132h
    32. 32
      Feng, P.; Bu, X.; Zheng, N. The Interface Chemistry between Chalcogenide Clusters and Open Framework Chalcogenides Acc. Chem. Res. 2005, 38, 293 303 DOI: 10.1021/ar0401754
    33. 33
      Mohanan, J. L.; Arachchige, I. U.; Brock, S. L. Porous Semiconductor Chalcogenide Aerogels Science 2005, 307, 397 400
    34. 34
      Li, H.; Eddaoudi, M.; Laine, A.; O’Keeffe, M.; Yaghi, O. M. Noninterpenetrating Indium Sulfide Supertetrahedral Cristobalite Framework J. Am. Chem. Soc. 1999, 121, 6096 6097 DOI: 10.1021/ja990410r
    35. 35
      Luc, W.; Jiao, F. Synthesis of Nanoporous Metals, Oxides, Carbides, and Sulfides: Beyond Nanocasting Acc. Chem. Res. 2016, 49, 1351 1358 DOI: 10.1021/acs.accounts.6b00109
    36. 36
      Zwijnenburg, M. A.; Corà, F.; Bell, R. G. Dramatic Differences between the Energy Landscapes of SiO2 and SiS2 Zeotype Materials J. Am. Chem. Soc. 2007, 129, 12588 12589 DOI: 10.1021/ja0727666
    37. 37
      Butler, K. T.; Hendon, C. H.; Walsh, A. Electronic Structure Modulation of Metal–Organic Frameworks for Hybrid Devices ACS Appl. Mater. Interfaces 2014, 6, 22044 22050 DOI: 10.1021/am507016r
    38. 38
      Sun, L.; Hendon, C. H.; Minier, M. A.; Walsh, A.; Dinca, M. Million-Fold Electrical Conductivity Enhancement in Fe2(DEBDC) versus Mn2(DEBDC) (E = S, O) J. Am. Chem. Soc. 2015, 137, 6164 6167 DOI: 10.1021/jacs.5b02897
    39. 39
      Hendon, C. H.; Walsh, A. Chemical Principles Underpinning the Performance of the Metal–organic Framework HKUST-1 Chem. Sci. 2015, 6, 3674 3683 DOI: 10.1039/C5SC01489A
    40. 40
      McDonald, T. M.; Mason, J. A.; Kong, X.; Bloch, E. D.; Gygi, D.; Dani, A.; Crocellà, V.; Giordanino, F.; Odoh, S. O.; Drisdell, W. S.; Vlaisavljevich, B.; Dzubak, A. L.; Poloni, R.; Schnell, S. K.; Planas, N.; Lee, K.; Pascal, T.; Wan, L. F.; Prendergast, D.; Neaton, J. B.; Smit, B.; Kortright, J. B.; Gagliardi, L.; Bordiga, S.; Reimer, J. A.; Long, J. R. Cooperative Insertion of CO2 in Diamine-Appended Metal-Organic Frameworks Nature 2015, 519, 303 308 DOI: 10.1038/nature14327
    41. 41
      Park, S. S.; Hontz, E. R.; Sun, L.; Hendon, C. H.; Walsh, A.; Van Voorhis, T.; Dinca, M. Cation-Dependent Intrinsic Electrical Conductivity in Isostructural Tetrathiafulvalene-Based Microporous Metal-Organic Frameworks J. Am. Chem. Soc. 2015, 137, 1774 1777 DOI: 10.1021/ja512437u
    42. 42
      Wahila, M. J.; Butler, K. T.; Lebens-Higgins, Z. W.; Hendon, C. H.; Nandur, A. S.; Treharne, R. E.; Quackenbush, N. F.; Sallis, S.; Mason, K.; Paik, H.; Schlom, D. G.; Woicik, J. C.; Guo, J.; Arena, D. A.; White, B. E.; Watson, G. W.; Walsh, A.; Piper, L. F. J. Lone-Pair Stabilization in Transparent Amorphous Tin Oxides: A Potential Route to P-Type Conduction Pathways Chem. Mater. 2016, 28, 4706 4713 DOI: 10.1021/acs.chemmater.6b01608
    43. 43
      Hinuma, Y.; Hatakeyama, T.; Kumagai, Y.; Burton, L. A.; Sato, H.; Muraba, Y.; Iimura, S.; Hiramatsu, H.; Tanaka, I.; Hosono, H.; Oba, F. Discovery of Earth-Abundant Nitride Semiconductors by Computational Screening and High-Pressure Synthesis Nat. Commun. 2016, 7, 11962 DOI: 10.1038/ncomms11962
    44. 44
      Butler, K. T.; Hendon, C. H.; Walsh, A. Electronic Chemical Potentials of Porous Metal-Organic Frameworks J. Am. Chem. Soc. 2014, 136, 2703 2706 DOI: 10.1021/ja4110073
    45. 45
      Born, M.; Huang, K. Dynamical Theory of Crystal Lattices; Clarendon Press, 1998.
    46. 46
      Sallis, S.; Butler, K. T.; Quackenbush, N. F.; Williams, D. S.; Junda, M.; Fischer, D. a.; Woicik, J. C.; Podraza, N. J.; White, B. E.; Walsh, A.; Piper, L. F. J. Origin of Deep Subgap States in Amorphous Indium Gallium Zinc Oxide: Chemically Disordered Coordination of Oxygen Appl. Phys. Lett. 2014, 104, 232108 DOI: 10.1063/1.4883257
    47. 47
      Zwijnenburg, M. A.; Bromley, S. T. Structure Direction in Zinc Oxide and Related Materials by Cation Substitution: An Analogy with Zeolites J. Mater. Chem. 2011, 21, 15255 15261 DOI: 10.1039/c1jm12383a
    48. 48
      Vegard, L. Die Konstitution Der Mischkristalle Und Die Raumfüllung Der Atome Eur. Phys. J. A 1921, 5, 17 26 DOI: 10.1007/BF01349680
    49. 49
      Hamilton, B. B.; Rimmer, J. S.; Anderson, M.; Leigh, D. White Light Emission from C60 Molecules Confined in Molecular Cage Materials Adv. Mater. 1993, 5, 583 585 DOI: 10.1002/adma.19930050717
    50. 50
      Fenwick, O.; Coutiño-Gonzalez, E.; Grandjean, D.; Baekelant, W.; Richard, F.; Bonacchi, S.; De Vos, D.; Lievens, P.; Roeffaers, M.; Hofkens, J.; Samorì, P. Tuning the Energetics and Tailoring the Optical Properties of Silver Clusters Confined in Zeolites Nat. Mater. 2016, 15, 1017 1022 DOI: 10.1038/nmat4652
    51. 51
      Hautier, G.; Miglio, A.; Ceder, G.; Rignanese, G.-M.; Gonze, X. Identification and Design Principles of Low Hole Effective Mass P-Type Transparent Conducting Oxides Nat. Commun. 2013, 4, 2292 DOI: 10.1038/ncomms3292
    52. 52
      Butler, K. T. Morphological Control of Band Offsets for Transparent Bipolar Heterojunctions: The Bädeker Diode Phys. Status Solidi A 2015, 212, 1461 1465 DOI: 10.1002/pssa.201532004
    53. 53
      Wahila, M. J.; Lebens-Higgins, Z. W.; Quackenbush, N. F.; Nishitani, J.; Walukiewicz, W.; Glans, P.-A.; Guo, J.-H.; Woicik, J. C.; Yu, K. M.; Piper, L. F. J. Evidence of Extreme Type-III Band Offset at Buried N -Type CdO/P-Type SnTe Interfaces Phys. Rev. B: Condens. Matter Mater. Phys. 2015, 91, 205307 DOI: 10.1103/PhysRevB.91.205307
    54. 54
      Pitanti, A.; Ercolani, D.; Sorba, L.; Roddaro, S.; Beltram, F.; Nasi, L.; Salviati, G.; Tredicucci, A. InAs/InP/InSb Nanowires as Low Capacitance N – N Heterojunction Diodes Phys. Rev. X 2011, 1, 11006 DOI: 10.1103/PhysRevX.1.011006
    55. 55
      Chen, C. Y.; Shik, A.; Pitanti, A.; Tredicucci, A.; Ercolani, D.; Sorba, L.; Beltram, F.; Ruda, H. E. Electron Beam Induced Current in InSb-InAs Nanowire Type-III Heterostructures Appl. Phys. Lett. 2012, 101, 63116 DOI: 10.1063/1.4745603
    56. 56
      Zhang, X.; Zhang, L.; Perkins, J. D.; Zunger, A. Intrinsic Transparent Conductors without Doping Phys. Rev. Lett. 2015, 115, 176602 DOI: 10.1103/PhysRevLett.115.176602
    57. 57
      Lim, H. E.; Miyata, Y.; Fujihara, M.; Okada, S.; Liu, Z.; Arifin; Sato, K.; Omachi, H.; Kitaura, R.; Irle, S.; Suenaga, K.; Shinohara, H. Fabrication and Optical Probing of Highly Extended, Ultrathin Graphene Nanoribbons in Carbon Nanotubes ACS Nano 2015, 9, 5034 5040 DOI: 10.1021/nn507408m
    58. 58
      Talin, A.; Centrone, A.; Ford, A. C.; Foster, M. E.; Stavila, V.; Haney, P.; Kinney, R. A.; Szalai, V.; El Gabaly, F.; Yoon, H. P.; Léonard, F.; Allendorf, M. D. Tunable Electrical Conductivity in Metal-Organic Framework Thin-Film Devices Science 2014, 343, 66 69 DOI: 10.1126/science.1246738
    59. 59
      Benz, S.; López-andarias, J.; Mareda, J.; Sakai, N.; Matile, S. Catalysis with Chalcogen Bonds Communications Angew. Chem., Int. Ed. 2017, 56, 812 815 DOI: 10.1002/anie.201611019
    60. 60
      Regulacio, M. D.; Han, M. Multinary I-III-VI2 and I2-II-IV-VI4 Semiconductor Nanostructures for Photocatalytic Applications Acc. Chem. Res. 2016, 49, 511 519 DOI: 10.1021/acs.accounts.5b00535
    61. 61
      Gounder, R.; Iglesia, E. The Roles of Entropy and Enthalpy in Stabilizing Catalysis Acc. Chem. Res. 2012, 45, 229 238 DOI: 10.1021/ar200138n
    62. 62
      Butler, K. T.; Walsh, A.; Cheetham, A. K.; Kieslich, G. Organised Chaos: Entropy in Hybrid Inorganic–Organic Systems and Other Materials Chem. Sci. 2016, 7, 6316 6324 DOI: 10.1039/C6SC02199A
    63. 63
      Na, K.; Choi, K. M.; Yaghi, O. M.; Somorjai, G. A. Metal Nanocrystals Embedded in Single Nanocrystals of MOFs Give Unusual Selectivity as Heterogeneous Catalysts Nano Lett. 2014, 14, 5979 5983 DOI: 10.1021/nl503007h
    64. 64
      Milla, S.; Depiereux, S.; Kestemont, P. The Effects of Estrogenic and Androgenic Endocrine Disruptors on the Immune System of Fish: A Review Ecotoxicology 2011, 20, 305 319 DOI: 10.1007/s10646-010-0588-7
    65. 65
      Colborn, T.; Saal, F. S.; Soto, A. M. Developmental Effects of Endocrine-Disrupting Chemicals in Wildlife and Humans Enviromental Heal. Perspect. 1993, 101, 378 384 DOI: 10.1289/ehp.93101378
    66. 66
      Viswanathan, B.; Subramanian, V.; Lee, J. S. Materials and Processes for Solar Fuel Production; Lockwood, D. J., Ed.; Springer, 2014.
    67. 67
      Linic, S.; Aslam, U.; Boerigter, C.; Morabito, M. Photochemical Transformations on Plasmonic Metal Nanoparticles Nat. Mater. 2015, 14, 567 576 DOI: 10.1038/nmat4281
    68. 68
      Boerigter, C.; Aslam, U.; Linic, S. Mechanism of Charge Transfer from Plasmonic Nanostructures to Chemically Attached ACS Nano 2016, 10, 6108 6115 DOI: 10.1021/acsnano.6b01846
  • Supporting Information

    Supporting Information

    ARTICLE SECTIONS
    Jump To

    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.chemmater.7b00464.

    • Further details on the computational methods and a table of the calculated electronic and structural properties of each material (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.

Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

Pair your accounts.

Export articles to Mendeley

Get article recommendations from ACS based on references in your Mendeley library.

You’ve supercharged your research process with ACS and Mendeley!

STEP 1:
Click to create an ACS ID

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

MENDELEY PAIRING EXPIRED
Your Mendeley pairing has expired. Please reconnect