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Engineering the Optical Response of the Titanium-MIL-125 Metal–Organic Framework through Ligand Functionalization
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† Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, U.K.
‡ Laboratoire de Chimie des Processus Biologiques, Collège de France, CNRS FRE 3488, 11 Place Marcelin Berthelot, 75005 Paris, France
§ UPMC Univ Paris 06, UMR 7574, Chimie de la Matière Condensée de Paris, Collège de France, 11 Place Marcelin Berthelot, 75231 Paris Cedex 05, France
[email protected]; [email protected]; [email protected]
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Cite this: J. Am. Chem. Soc. 2013, 135, 30, 10942–10945
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https://doi.org/10.1021/ja405350u
Published July 10, 2013

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Abstract

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Herein we discuss band gap modification of MIL-125, a TiO2/1,4-benzenedicarboxylate (bdc) metal–organic framework (MOF). Through a combination of synthesis and computation, we elucidated the electronic structure of MIL-125 with aminated linkers. The band gap decrease observed when the monoaminated bdc-NH2 linker was used arises from donation of the N 2p electrons to the aromatic linking unit, resulting in a red-shifted band above the valence-band edge of MIL-125. We further explored in silico MIL-125 with the diaminated linker bdc-(NH2)2 and other functional groups (−OH, −CH3, −Cl) as alternative substitutions to control the optical response. The bdc-(NH2)2 linking unit was predicted to lower the band gap of MIL-125 to 1.28 eV, and this was confirmed through the targeted synthesis of the bdc-(NH2)2-based MIL-125. This study illustrates the possibility of tuning the optical response of MOFs through rational functionalization of the linking unit, and the strength of combined synthetic/computational approaches for targeting functionalized hybrid materials.

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Metal–organic frameworks (MOFs) are a class of structures composed of organic and inorganic building blocks. These highly ordered and porous networks are of interest for their applications in gas storage, catalysis, and photoelectrics. (1-10) In particular, MOFs have the ability to behave as semiconductors when exposed to light, (11, 12) making them unique platforms for light harvesting and photoinduced catalysis. (13) A subfield of research has thus emerged with the aim of tuning the optical response of MOFs by modifying the inorganic unit or the organic linker (length, chemical functionalization) through synthetic (14, 15) or computational screening. (16-22) In this context, the highly porous titanium-based MOF MIL-125 (MIL = Materials of Institut Lavoisier) (Figure 1) is an interesting candidate. (23) This material, which contains cyclic octamers of TiO2 octahedra, is photochromic, which is related to the reduction of Ti(IV) to Ti(III) under UV irradiation. (24)

Figure 1

Figure 1. (left) [001] and (right) [010] orientations of MIL-125. Ti, O, C, and H are depicted in blue, red, black, and beige, respectively.

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When synthesized with the 1,4-benzenedicarboxylate (bdc) linker, MIL-125 has an optical band gap in the UV region (ca. 3.6 eV/345 nm; see Figure 3a) and is an active photocatalyst for the oxidation of alcohols to aldehydes. (23) MIL-125-NH2 made with the monoaminated bdc-NH2 linker (25) was reported to be a photocatalyst with visible-light-induced activity for CO2 reduction (26) and H2 production. (27) The bdc-NH2 linker was shown to be responsible for the extra absorption band in the visible region, indicative of a band gap reduction (to ca. 2.6 eV/475 nm). (25-28) García and co-workers further confirmed the ability of MIL-125-NH2 to undergo photoinduced charge separation. (29) A similar band gap reduction and red shift were reported for Zr-UiO-66 upon synthesis with bdc-NH2, emphasizing the electronic role of the −NH2 group in determining the optical response in MOFs. (30) Coincidently, aminated linkers are becoming particularly popular in porous MOF synthesis, as polar −NH2 groups are expected to enhance CO2 capture, yield selective gas adsorption, (31-35) and enable postsynthetic modifications. (36-38)

These recent findings make it necessary to develop strategies to control the band gap of MIL-125. Here we performed a combined experimental and computational study to elucidate the band structure of MIL-125 and the impact of functional groups on the bdc linker, exploring the observed red shift in MIL-125-NH2. We then computationally predicted the beneficial impact of using the diaminated bdc-(NH2)2 linker, which was confirmed by a targeted synthesis. We finally explored in silico other potential bdc linkers (Figure 2) as candidates for optical control in MIL-125.

Figure 2

Figure 2. Neutral linking molecules explored in this study: (left) monosubstituted linkers bdc-R; (right) diaminated linker bdc-(NH2)2.

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Amines are ring-activating substituents; as an initial study, we investigated the change in the band gap in response to increasing the concentration of monoaminated bdc-NH2. MIL-125 (Figure 3a) and three aminated MIL-125 analogues (Figure 3b–d) were synthesized under solvothermal conditions by varying the ratio of bdc and bdc-NH2 linkers (i.e., 10%, 50%, and 100% bdc-NH2, equating to ∼1, 6, and 12 bdc-NH2 linkers per unit cell). Figure 3 presents scanning electron microscopy (SEM) images of these four samples and their accompanying UV spectra and powder colors. It is apparent that the absorption onset (ca. 475 nm) is similar for all of the monoaminated samples. The samples also demonstrated similar band gaps of ∼2.6 eV [Table S2 in the Supporting Information (SI)], but the molar extinction coefficient notably increased in proportion with the bdc-NH2 content. This feature was reflected in the physical crystal appearance: the yellow color increased in intensity. This characteristic absorption pattern suggests that a single −NH2 motif is responsible for the reduced band gap of the monoaminated series of MIL-125 analogues.

Figure 3

Figure 3. SEM images of (a) MIL-125, (b) 10%-MIL-125-NH2, (c) 50%-MIL-125-NH2, (d) 100%-MIL-125-NH2, and (e) 10%-MIL-125-(NH2)2/90%-MIL-125-NH2, with their respective UV spectra and powder colors. All of the monoaminated systems show the same absorption onset.

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Electronic structure calculations on the same series of monoaminated MIL-125-NH2 solids were performed using density functional theory (DFT) as described in the SI. Figure 4a,b depicts the valence band (VB) and conduction band (CB) orbitals, respectively, for standard MIL-125. The upper VB is composed of bdc aromatic 2p orbitals. Introducing a single bdc-NH2 linker per unit cell (i.e., to give 10%-MIL-125-NH2) breaks the original I4/mmm symmetry and splits the VB into a high-energy occupied state (depicted in blue in Figure 4c). The other aromatic bands are also split within 0.3 eV of each other and contribute to the VB-1,2...12. Because of the strong electron-donating characteristics of aromatic amines, the modified VB is 1.2 eV above that of MIL-125 (depicted with the blue arrow in Figure 4c), resulting in the lower band gap. This localized electronic modification results in a flat band in k space, which emphasizes the absence of long-range chemical interactions.

Figure 4

Figure 4. (a, b) Frontier electron density of unsubstituted MIL-125: (a) the valence band is composed of the bdc C 2p orbitals (shown on the right), making these favorable for linker-based band gap modifications; (b) the conduction band is composed of O 2p orbitals and Ti 3d orbitals (shown on the right), suggesting that modifications of the aromatic bdc units are unlikely to affect the CB. Isovalue = 0.001 e·Å–3. (c) PBEsol band structures for synthetic MIL-125 (black), 10%-MIL-125-NH2 (blue), 10%-MIL-125-(NH2)2/90%-MIL-125-NH2 (orange) and the theoretical 10%-MIL-125-(NH2)2 (green). The orange bands, which have been truncated to improve the clarity of the band structures, maintain flat characteristics. The enlarged section emphasizes the VB-1...12 of the 11 nondegenerate monoamine bands. The energies are adjusted such that the highest occupied non-amine band is at 0 eV. The changes in the occupied VBs are depicted by the arrows. PBEsol is a qualitative approach; band structures could not be computed at the HSE06 level of theory because of the system size. (d) HSE06-calculated VB and CB energies of MIL-125-NH2 models containing increasing numbers of bdc-NH2 linkers [i.e. 0 (MIL-125) to 12 (100%-MIL-125-NH2)] per unit cell. The degree of amination does not affect the band gap.

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Further calculations were carried out by systematically increasing the amine content from 1 to 12 bdc-NH2 linkers per unit cell (Figure 4d). It is apparent that the VB is modified upon amination of the linker while the lower CB is unchanged. Thus, a single −NH2 group electronically saturates MIL-125. The band structure of 10%-MIL-125-NH2 (blue in Figure 4c) depicts a localized noninteracting state, which was observed for all of the monoaminated systems independent of the bdc-NH2 content.

The amine functional motif plays a crucial role in the band structure of MIL-125. We therefore considered the plausible extension of further increasing the electron density of the aromatic motifs through polyamination of the bdc linker. Selecting diaminated bdc-(NH2)2 (Figure 2 right) as a potentially interesting linker, we constructed a 10%-MIL-125-(NH2)2 model as a mixture of 10% bdc-(NH2)2 and 90% bdc and computed its band structure (shown in green in Figure 4c). This model may be compared to its monoaminated analogue (shown in blue in Figure 4c). Our calculations predicted that 10%-MIL-125-(NH2)2 would exhibit a larger red shift due to the increase in aromatic electronic density, with a resultant band gap of 1.28 eV. This presents a further band gap decrease of 1.1 eV relative to the 10%-monoaminated analogue.

We subsequently targeted the synthesis of a diaminated MIL-125 derivative, which was successfully achieved with a mixture of 10% bdc-(NH2)2 and 90% bdc-NH2 (Figure 3e). This compound differs from the 10%-MIL-125-(NH2)2 model described in the previous paragraph by the presence of bdc-NH2 instead of bdc. We did not isolate the 10%-MIL-125-(NH2)2, but our compound should act electronically in a similar fashion, since the amine motifs are indeed noninteracting and produce highly localized electronic bands. Optical measurements (Figure 3e) revealed a further band gap decrease of 1.1 eV for this solid relative to the monoaminated samples to give an optical band gap of 1.3 eV, shifting the absorption onset to the red/IR region. This is in striking agreement with the above computational prediction. To approximate the blended solid, we further computed the electronic structure of a mixed 10%-MIL-125-(NH2)2/90%-MIL-125-NH2 model (shown in Figure 4c in orange). In both the experimental spectrum and the band structure calculations we observed the presence of the monoamine motifs. The multiple orange bands in the 1–1.5 eV region are the result of the inequivalent monoamines. Our computational approach predicted a band gap of 1.55 eV (orange in Figure 5). The difference between the experimental (1.3 eV) and computed (1.55 eV) band gaps is attributed to the challenge of describing this partially disordered system computationally, including using lattice constants fixed at the equilibrium values of the parent MIL-125 structure.

Figure 5

Figure 5. HSE06-predicted band gaps of MIL-125 (black) and its analogues containing functionalized bdc linkers. Substitutions of ca. 10% (i.e., one functionalized linker per unit cell) were made, unless otherwise stated. Control of the band gap was achieved by varying the substituent.

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Finally, we extended the computational exploration to three potential MIL-125 analogues. Amines are one of the stronger electron-donating substituents; weaker electron-donating substituents should reduce the band gap to a lesser extent. (39, 40) The introduction of 10% bdc-R (R = −OH, −CH3, −Cl; Figure 2 left) per unit cell resulted in flexible band gap control between 3.5 and 2.4 eV (Figure 5). The weakest electron-donating group, −CH3, moderately decreases the band gap to 3.5 eV. Aromatic halides are more chemically complex and may be either weakly electron-donating or -withdrawing. In MIL-125, −Cl acts as a weak electron donor with a predicted band gap similar to that for the −CH3 group. The −OH group is more electron-donating than −CH3 and −Cl, which is reflected by the predicted band gap of 2.8 eV for the 10%-MIL-125-OH model. The −Br and −CF3 substituents were also computed. Our results suggest that −Br motifs produce band gap control similar to −Cl, but the crystal could not be stabilized above eight substitutions per unit cell. The −CF3 group is strongly electron-withdrawing, potentially lowering a CB+n band into the band gap. It was found that the inclusion of −CF3 resulted in destabilization of the Ti–O bond, and a single substitution produced an unstable crystal. Thus, −NH2, −OH, −CH3, and −Cl are the most promising and favorable substitutions.

In conclusion, we have elucidated the specific role of the −NH2 group of the monoaminated bdc-NH2 linker in lowering the optical band gap of the titanium-containing MIL-125-NH2 (ca. 2.6 eV). We confirmed that electronic modifications of the aromatic motifs are localized and directly control the optical properties through modification of the valence band. DFT calculations showed that the optical response of MIL-125 may be tailored toward absorption in the visible region through rational selection of substituents of the aromatic bdc linker. The diaminated bdc-(NH2)2 linker was expected to demonstrate the most significant red shift. This prediction was confirmed by the synthesis of 10%-MIL-125-(NH2)2/90%-MIL-125-NH2 (1.3 eV/950 nm). From the experimental perspective, we have described the synthesis of a MIL-125 derivative with mixed aminated linkers. This methodology can be further extended to the large range of aromatic linkers used in MOF synthesis, which should enable accurate and predictable band gap control in tailored frameworks. For example, the Zn–bdc-based IRMOF-1 (14, 41) has an electronic structure comparable to that of MIL-125 (3.57 eV), (39) thus posing potential for similar control of its band gap through the modifications proposed here.

Supporting Information

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Synthetic procedures; PXRD, N2 sorption, and optical band gap data; and computational details. This material is available free of charge via the Internet at http://pubs.acs.org.

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Author Information

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  • Corresponding Authors
    • Laurence Rozes - UPMC Univ Paris 06, UMR 7574, Chimie de la Matière Condensée de Paris, Collège de France, 11 Place Marcelin Berthelot, 75231 Paris Cedex 05, France
    • Caroline Mellot-Draznieks - Laboratoire de Chimie des Processus Biologiques, Collège de France, CNRS FRE 3488, 11 Place Marcelin Berthelot, 75005 Paris, France
    • Aron Walsh - Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, U.K.
  • Authors
    • Christopher H. Hendon - Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, U.K.
    • Davide Tiana - Department of Chemistry, University of Bath, Claverton Down, Bath BA2 7AY, U.K.
    • Marc Fontecave - Laboratoire de Chimie des Processus Biologiques, Collège de France, CNRS FRE 3488, 11 Place Marcelin Berthelot, 75005 Paris, France
    • Clément Sanchez - UPMC Univ Paris 06, UMR 7574, Chimie de la Matière Condensée de Paris, Collège de France, 11 Place Marcelin Berthelot, 75231 Paris Cedex 05, France
    • Loïc D’arras - UPMC Univ Paris 06, UMR 7574, Chimie de la Matière Condensée de Paris, Collège de France, 11 Place Marcelin Berthelot, 75231 Paris Cedex 05, France
    • Capucine Sassoye - UPMC Univ Paris 06, UMR 7574, Chimie de la Matière Condensée de Paris, Collège de France, 11 Place Marcelin Berthelot, 75231 Paris Cedex 05, France
  • Notes
    The authors declare no competing financial interest.

Acknowledgment

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A.W. was supported a Royal Society University Research Fellowship, while C.H.H. and D.T. were funded under an ERC Starting Grant. The work benefited from the University of Bath’s High Performance Computing Facility and access to the HECToR supercomputer through membership of the U.K.’s HPC Materials Chemistry Consortium, which is funded by the EPSRC (Grant EP/F067496).

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  • Abstract

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    Figure 1

    Figure 1. (left) [001] and (right) [010] orientations of MIL-125. Ti, O, C, and H are depicted in blue, red, black, and beige, respectively.

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    Figure 2

    Figure 2. Neutral linking molecules explored in this study: (left) monosubstituted linkers bdc-R; (right) diaminated linker bdc-(NH2)2.

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    Figure 3

    Figure 3. SEM images of (a) MIL-125, (b) 10%-MIL-125-NH2, (c) 50%-MIL-125-NH2, (d) 100%-MIL-125-NH2, and (e) 10%-MIL-125-(NH2)2/90%-MIL-125-NH2, with their respective UV spectra and powder colors. All of the monoaminated systems show the same absorption onset.

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    Figure 4

    Figure 4. (a, b) Frontier electron density of unsubstituted MIL-125: (a) the valence band is composed of the bdc C 2p orbitals (shown on the right), making these favorable for linker-based band gap modifications; (b) the conduction band is composed of O 2p orbitals and Ti 3d orbitals (shown on the right), suggesting that modifications of the aromatic bdc units are unlikely to affect the CB. Isovalue = 0.001 e·Å–3. (c) PBEsol band structures for synthetic MIL-125 (black), 10%-MIL-125-NH2 (blue), 10%-MIL-125-(NH2)2/90%-MIL-125-NH2 (orange) and the theoretical 10%-MIL-125-(NH2)2 (green). The orange bands, which have been truncated to improve the clarity of the band structures, maintain flat characteristics. The enlarged section emphasizes the VB-1...12 of the 11 nondegenerate monoamine bands. The energies are adjusted such that the highest occupied non-amine band is at 0 eV. The changes in the occupied VBs are depicted by the arrows. PBEsol is a qualitative approach; band structures could not be computed at the HSE06 level of theory because of the system size. (d) HSE06-calculated VB and CB energies of MIL-125-NH2 models containing increasing numbers of bdc-NH2 linkers [i.e. 0 (MIL-125) to 12 (100%-MIL-125-NH2)] per unit cell. The degree of amination does not affect the band gap.

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    Figure 5

    Figure 5. HSE06-predicted band gaps of MIL-125 (black) and its analogues containing functionalized bdc linkers. Substitutions of ca. 10% (i.e., one functionalized linker per unit cell) were made, unless otherwise stated. Control of the band gap was achieved by varying the substituent.

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      Martin, Richard Luis; Haranczyk, Maciej
      Chemical Science (2013), 4 (4), 1781-1785CODEN: CSHCCN; ISSN:2041-6520. (Royal Society of Chemistry)
      Metal-org. frameworks (MOFs) have enjoyed considerable interest due to their high internal surface areas as well as tunable pore geometry and chem. However, design of optimal MOFs is a great challenge due to the significant no. of possible structures. In this work, the authors present a strategy to rapidly explore the frontiers of these high surface area materials. Org. ligands are abstracted by geometrical (alchem.) building blocks, and an optimization of their defining geometrical parameters is performed to identify shapes of ligands which maximize gravimetric surface area of the resulting MOFs. A strength of this approach is that the space of ligands to be explored can be rigorously bounded, allowing discovery of the optimum ligand shape within any criteria, conforming to synthetic requirements or arbitrary exploratory limits. By modifying these bounds, one can project to what extent achievable surface area increases when moving beyond the present limits of org. synthesis. Projecting optimal ligand shapes onto real chem. species, the authors achieve blueprints for MOFs of various topologies that are predicted to achieve up to 70% higher surface area than the current benchmark materials.
    4. 4

      Thematic issue on MOFs:

      Chem. Rev. 2012, 112, 673– 1268.
      4
      Introduction to Metal-Organic Frameworks
      Zhou, Hong-Cai; Long, Jeffrey R.; Yaghi, Omar M.
      Chemical Reviews (Washington, DC, United States) (2012), 112 (2), 673-674CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
      A review is presented on prepn., structure and application of Metal-Org. Frameworks.
    5. 5
      Li, J.-R.; Kuppler, R. J.; Zhou, H.-C. Chem. Soc. Rev. 2009, 38, 1477
      5
      Selective gas adsorption and separation in metal-organic frameworks
      Li, Jian-Rong; Kuppler, Ryan J.; Zhou, Hong-Cai
      Chemical Society Reviews (2009), 38 (5), 1477-1504CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
      A review. Adsorptive sepn. is very important in industry. Generally, the process uses porous solid materials such as zeolites, activated carbons, or silica gels as adsorbents. With an ever increasing need for a more efficient, energy-saving, and environmentally benign procedure for gas sepn., adsorbents with tailored structures and tunable surface properties must be found. Metal-org. frameworks (MOFs), constructed by metal-contg. nodes connected by org. bridges, are such a new type of porous materials. They are promising candidates as adsorbents for gas sepns. due to their large surface areas, adjustable pore sizes and controllable properties, as well as acceptable thermal stability. This crit. review starts with a brief introduction to gas sepn. and purifn. based on selective adsorption, followed by a review of gas selective adsorption in rigid and flexible MOFs. Based on possible mechanisms, selective adsorptions obsd. in MOFs are classified, and primary relationships between adsorption properties and framework features are analyzed. As a specific example of tailor-made MOFs, mesh-adjustable mol. sieves are emphasized and the underlying working mechanism elucidated. In addn. to the exptl. aspect, theor. investigations from adsorption equil. to diffusion dynamics via mol. simulations are also briefly reviewed. Furthermore, gas sepns. in MOFs, including the mol. sieving effect, kinetic sepn., the quantum sieving effect for H2/D2 sepn., and MOF-based membranes are also summarized (227 refs.).
    6. 6
      Allendorf, M. D.; Schwartzberg, A.; Stavila, V.; Talin, A. A. Chem.—Eur. J. 2011, 17, 11372
      6
      A Roadmap to Implementing Metal-Organic Frameworks in Electronic Devices: Challenges and Critical Directions
      Allendorf, Mark D.; Schwartzberg, Adam; Stavila, Vitalie; Talin, A. Alec
      Chemistry - A European Journal (2011), 17 (41), 11372-11388CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)
      A review. Metal-org. frameworks (MOFs) and related material classes are attracting considerable attention for applications such as gas storage, sepns., and catalysis. In contrast, research focused on potential uses in electronic devices is in its infancy. Several sensing concepts in which the tailorable chem. of MOFs was used to enhance sensitivity or provide chem. specificity were demonstrated, but in only a few cases are MOFs an integral part of an actual device. The synthesis of a few elec. conducting MOFs and their known structural flexibility suggest that MOF-based electronic devices exploiting these properties could be constructed. It is clear, however, that new fabrication methods are required to take advantage of the unique properties of MOFs and extend their use to the realms of electronic circuitry. In this Concepts article, the authors describe the basic functional elements needed to fabricate electronic devices and summarize the current state of relevant MOF research, and then review recent work in which MOFs serve as active components in electronic devices. Finally, the authors propose a high-level roadmap for device-related MOF research, the objective of which is to stimulate thinking within the MOF community concerning the development these materials for applications including sensing, photonics, and microelectronics. This is a review with 93 refs.
    7. 7
      Farrusseng, D.; Aguado, S.; Pinel, C. Angew. Chem., Int. Ed. 2009, 48, 7502
      7
      Metal-Organic Frameworks: Opportunities for Catalysis
      Farrusseng, David; Aguado, Sonia; Pinel, Catherine
      Angewandte Chemie, International Edition (2009), 48 (41), 7502-7513CODEN: ACIEF5; ISSN:1433-7851. (Wiley-VCH Verlag GmbH & Co. KGaA)
      A review; the role of metal-org. frameworks (MOFs) in the field of catalysis is discussed, and special focus is placed on their assets and limits in light of current challenges in catalysis and green chem. Their structural and dynamic features are presented in terms of catalytic functions along with how MOFs can be designed to bridge the gap between zeolites and enzymes. The contributions of MOFs to the field of catalysis are comprehensively reviewed and a list of catalytic candidates is given. The subject is presented from a multidisciplinary point of view covering solid-state chem., materials science, and catalysis.
    8. 8
      Ma, L.; Abney, C.; Lin, W. Chem. Soc. Rev. 2009, 38, 1248
      8
      Enantioselective catalysis with homochiral metal-organic frameworks
      Ma, Liqing; Abney, Carter; Lin, Wenbin
      Chemical Society Reviews (2009), 38 (5), 1248-1256CODEN: CSRVBR; ISSN:0306-0012. (Royal Society of Chemistry)
      This tutorial review presents recent developments of homochiral metal-org. frameworks (MOFs) for enantioselective catalysis. Following a brief introduction of the basic concepts and potential virtues of MOFs in catalysis, three distinct strategies that have been utilized to synthesize homochiral MOFs were summarized. Framework stability and accessibility of the open channels to reagents were then addressed. Some recent successful examples of catalytically active homochiral MOFs based on three approaches, namely, homochiral MOFs with achiral catalytic sites, incorporation of asym. catalysts directly into the framework, and post-synthetic modification of homochiral MOFs were finally surveyed. Although still in their infancy, homochiral MOFs have clearly demonstrated their utility in heterogeneous asym. catalysis, and a bright future is foreseen for the development of practically useful homochiral MOFs in the prodn. of optically pure org. mols.
    9. 9
      Corma, A.; García, H.; Llabrés i Xamena, F. X. Chem. Rev. 2010, 110, 4606
      9
      Engineering Metal Organic Frameworks for Heterogeneous Catalysis
      Corma, A.; Garcia, H.; Llabres i Xamena, F. X.
      Chemical Reviews (Washington, DC, United States) (2010), 110 (8), 4606-4655CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
      A review, including the design of MOFs for catalysis and evaluation of its potential as catalyst as well as catalysis by MOFs with active metal sites, with reactive functional groups, and MOFs as host matrixes or nanometric reaction cavities.
    10. 10
      Banerjee, R.; Phan, A.; Wang, B.; Knobler, C.; Furukawa, H.; O’Keeffe, M.; Yaghi, O. M. Science 2008, 319, 939
      10
      High-Throughput Synthesis of Zeolitic Imidazolate Frameworks and Application to CO2 Capture
      Banerjee, Rahul; Phan, Anh; Wang, Bo; Knobler, Carolyn; Furukawa, Hiroyasu; O'Keeffe, Michael; Yaghi, Omar M.
      Science (Washington, DC, United States) (2008), 319 (5865), 939-943CODEN: SCIEAS; ISSN:0036-8075. (American Association for the Advancement of Science)
      A high-throughput protocol was developed for the synthesis of zeolitic imidazolate frameworks (ZIFs). Twenty-five different ZIF crystals were synthesized from only 9600 microreactions of either Zn(II)/Co(II) and imidazolate/imidazolate-type linkers. All of the ZIF structures have tetrahedral frameworks: 10 of which have two different links (heterolinks), 16 of which are previously unobserved compns. and structures, and 5 of which have topologies as yet unobserved in zeolites. Members of a selection of these ZIFs (termed ZIF-68, ZIF-69, and ZIF-70) have high thermal stability (up to 390°) and chem. stability in refluxing org. and aq. media. Their frameworks have high porosity (with surface areas up to 1970 square meters per g), and they exhibit unusual selectivity for CO2 capture from CO2/CO mixts. and extraordinary capacity for storing CO2: 1 L of ZIF-69 can hold ∼83 L of CO2 at 273 K under ambient pressure.
    11. 11
      Alvaro, M.; Carbonell, E.; Ferrer, B.; Llabrés i Xamena, F. X.; García, H. Chem.—Eur. J. 2007, 13, 5106
      11
      Semiconductor behavior of a metal-organic framework (MOF)
      Alvaro, Mercedes; Carbonell, Esther; Ferrer, Belen; Llabres i Xamena, Francese X.; Garcia, Hermenegildo
      Chemistry - A European Journal (2007), 13 (18), 5106-5112CODEN: CEUJED; ISSN:0947-6539. (Wiley-VCH Verlag GmbH & Co. KGaA)
      Upon light excitation MOF-5 behaves as a semiconductor and undergoes charge sepn. (electrons and holes) decaying in the microsecond time scale. The actual conduction band energy value is 0.2 V vs. normal H electrode with a band gap of 3.4 eV. Photoinduced electron transfer processes to viologen generates the corresponding viologen radical cation, while holes of MOF-5 oxidizes N,N,N',N'-tetramethyl-p-phenylenediamine. One application studied for MOF-5 as a semiconductor was the shape-selective photocatalyzed degrdn. of phenol in aq. solns.
    12. 12
      Silva, C. G.; Corma, A.; García, H. J. Mater. Chem. 2010, 20, 3141
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    13. 13
      Wang, J.-L.; Wang, C.; Lin, W. ACS Catal. 2012, 2, 2630
      13
      Metal-Organic Frameworks for Light Harvesting and Photocatalysis
      Wang, Jin-Liang; Wang, Cheng; Lin, Wenbin
      ACS Catalysis (2012), 2 (12), 2630-2640CODEN: ACCACS; ISSN:2155-5435. (American Chemical Society)
      A review. Metal-org. frameworks (MOFs), a new class of cryst. mol. solids built from linking org. ligands with metal or metal-cluster connecting points, have recently emerged as a versatile platform for developing single-site solid catalysts. MOFs have been used to drive a range of reactions, including Lewis acid/base catalyzed reactions, redox reactions, asym. reactions, and photocatalysis. MOF catalysts are easily sepd. from the reaction mixts. for reuse, and yet their mol. nature introduces unprecedented chem. diversity and tunability to drive a large scope of catalytic reactions. This Perspective aims to summarize recent progress on light harvesting and photocatalysis with MOFs. The charge-sepd. excited states of the chromophoric building blocks created upon photon excitation can migrate over long distances to be harvested as redox equiv. at the MOF/liq. interfaces via electron transfer reactions or can directly activate the substrates that have diffused into the MOF channels for photocatalytic reactions. MOF-catalyzed and photodriven proton redn., CO2 redn., and org. transformations will be discussed in this Perspective.
    14. 14
      Gascon, J.; Hernández-Alonso, M. D.; Almeida, A. R.; van Klink, G. P. M.; Kapteijn, F.; Mul, G. ChemSusChem 2008, 1, 981
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    15. 15
      Lin, C.-K.; Zhao, D.; Gao, W.-Y.; Yang, Z.; Ye, J.; Xu, T.; Ge, Q.; Ma, S.; Liu, D.-J. Inorg. Chem. 2012, 51, 9039
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    16. 16
      Fuentes-Cabrera, M.; Nicholson, D. M.; Sumpter, B. G.; Widom, M. J. Chem. Phys. 2005, 123124713
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    17. 17
      Choi, J. H.; Choi, Y. J.; Lee, J. W.; Shin, W. H.; Kang, J. K. Phys. Chem. Chem. Phys. 2009, 11, 628
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    18. 18
      Kuc, A.; Enyashin, A.; Seifert, G. J. Phys. Chem. B 2007, 111, 8179
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    19. 19
      Yang, L.-M.; Ravindran, P.; Vajeeston, P.; Tilset, M. RSC Adv. 2012, 2, 1618
      19
      Ab initio investigations on the crystal structure, formation enthalpy, electronic structure, chemical bonding, and optical properties of experimentally synthesized isoreticular metal-organic framework-10 and its analogues: M-IRMOF-10 (M = Zn, Cd, Be, Mg, Ca, Sr and Ba)
      Yang, Li-Ming; Ravindran, Ponniah; Vajeeston, Ponniah; Tilset, Mats
      RSC Advances (2012), 2 (4), 1618-1631CODEN: RSCACL; ISSN:2046-2069. (Royal Society of Chemistry)
      The equil. solid-state structure, electronic structure, formation enthalpy, chem. bonding, and optical properties of IRMOF-10 and its alk. earth metal analogs M-IRMOF-10 (M = Cd, Be, Mg, Ca, Sr, Ba) have been investigated with d. functional calcns. The unit cell vol. and at. positions were fully optimized with the GGA functional. This supplements the incomplete exptl. structural parameters available for Zn-IRMOF-10. The calcd. bulk moduli decrease monotonically from Zn to Cd, and from Be to Ba, and indicate that Zn-IRMOF-10 and its analogs are relatively soft materials. The estd. bandgap values are in the range 2.9 to 3.0 eV, indicating nonmetallic character. Importantly, the bandgaps within the M-IRMOF-10 series (contg. a rather long 4,4'-biphenyldicarboxylate linker) are smaller than those within the M-IRMOF-1 series (shorter benzene dicarboxylate linker). The optical properties (dielec. function .vepsiln.(ω), refractive index n(ω), absorption coeff. α(ω), optical cond. σ(ω), reflectivity R(ω), and electron energy-loss spectrum L(ω)) of the M-IRMOF-10 series were computed. The observation of very small reflectivities over a wide energy range suggests possible uses in hybrid solar cell applications. The main characteristics of the optical properties are similar for the whole series although differences are seen in the details. An anal. of chem. bonding in the M-IRMOF-10 series reveals as might be anticipated that M-O bonds are largely ionic whereas C-O, C-H and C-C exhibit mainly covalent interactions. The BOP values of M-O decrease through the series when going from Zn to Cd, and from Be to Ba, i.e. the ionicity increases and the covalency decreases for the M-O bonds.
    20. 20
      Yang, L.-M.; Ravindran, P.; Vajeeston, P.; Tilset, M. J. Mater. Chem. 2012, 22, 16324
      There is no corresponding record for this reference.
    21. 21
      Choi, J. H.; Jeon, H. J.; Choi, K. M.; Kang, J. K. J. Mater. Chem. 2012, 22, 10144
      There is no corresponding record for this reference.
    22. 22
      Hendon, C. H.; Tiana, D.; Vaid, T. P.; Walsh, A. J. Mater. Chem. C 2013, 1, 95
      22
      Thermodynamic and electronic properties of tunable II-VI and IV-VI semiconductor based metal-organic frameworks from computational chemistry
      Hendon, Christopher H.; Tiana, Davide; Vaid, Thomas P.; Walsh, Aron
      Journal of Materials Chemistry C: Materials for Optical and Electronic Devices (2013), 1 (1), 95-100CODEN: JMCCCX; ISSN:2050-7534. (Royal Society of Chemistry)
      Optoelec. control of metal-org. frameworks would open up a new area of applications for hybrid materials. This article reports the calcd. thermodn. and electronic properties of a family of M3(C6X6) metal-org. frameworks (M = Mg, Ca, Zn, Cd, Hg, Ge, Sn, Pb; X = O, S, Se, Te). Herein, we present a systematic approach for studying families of hybrid compds., and describe extended tunability of their electronic and enthalpic properties through compositional control. It was shown that the formation enthalpy is dictated by the stability of the ligand, and the band gap is tunable depending on both metal and chalcogenide selection. Five compds. were found to be candidate semiconductors as they combine thermodn. stability with band gaps in the visible range of the electromagnetic spectrum.
    23. 23
      Dan-Hardi, M.; Serre, C.; Frot, T.; Rozes, L.; Maurin, G.; Sanchez, C.; Férey, G. J. Am. Chem. Soc. 2009, 131, 10857
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    24. 24
      Walsh, A.; Catlow, C. R. A. ChemPhysChem 2010, 11, 2341
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    25. 25
      Zlotea, C.; Phanon, D.; Mazaj, M.; Heurtaux, D.; Guillerm, V.; Serre, C.; Horcajada, P.; Devic, T.; Magnier, E.; Cuevas, F.; Férey, G.; Llewellyn, P. L.; Latroche, M. Dalton Trans. 2011, 40, 4879
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    26. 26
      Fu, Y.; Sun, D.; Chen, Y.; Huang, R.; Ding, Z.; Fu, X.; Li, Z. Angew. Chem. Int. Ed. 2012, 51, 3364– 3367
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    27. 27
      Horiuchi, Y.; Toyao, T.; Saito, M.; Mochizuki, K.; Iwata, M.; Higashimura, H.; Anpo, M.; Matsuoka, M. J. Phys. Chem. C 2012, 116, 20848
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    28. 28
      Kim, S.-N.; Kim, J.; Kim, H.-Y.; Cho, H.-Y.; Ahn, W.-S. Catal. Today 2013, 204, 85
      28
      Adsorption/catalytic properties of MIL-125 and NH2-MIL-125
      Kim, Se-Na; Kim, Jun; Kim, Hee-Young; Cho, Hye-Young; Ahn, Wha-Seung
      Catalysis Today (2013), 204 (), 85-93CODEN: CATTEA; ISSN:0920-5861. (Elsevier B.V.)
      A Ti-incorporated metal org. framework structure, MIL-125, and its amine-functionalized form, NH2-MIL-125, were synthesized via a solvothermal route aided by microwave heating. The samples were characterized by XRD, SEM, TGA, EA, UV-vis spectroscopy, and N2 adsorption-desorption measurements. MIL-125 was unstable in aq. soln., but NH2-MIL-125 was stable both in water and in heptane; its hydrophilic property was further confirmed by water vapor adsorption. NH2-MIL-125 showed moderate CO2 adsorption capacity (136 mg g-1) but excellent selectivity over N2 (>27:1) at 298 K with a low heat of adsorption surpassing the performance of MIL-125. Four consecutive CO2 adsorption-desorption cycles over NH2-MIL-125 showed completely reversible adsorbent regeneration at 298 K under a helium flow for a total duration of 550 min. Catalytic properties of the materials were evaluated by cycloaddn. of epichlorohydrin and oxidative desulfurization of dibenzothiophene. Finally, batch mode liq.-phase competitive sepn. of isoprene from 2-Me butane was conducted, revealing high selectivity of isoprene against 2-Me butane (ca. 7.8 and 9.7) over MIL-125 and NH2-MIL-125, resp.
    29. 29
      de Miguel, M.; Ragon, F.; Devic, T.; Serre, C.; Horcajada, P.; García, H. ChemPhysChem 2012, 13, 3651
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      Long, J.; Wang, S.; Ding, Z.; Wang, S.; Zhou, Y.; Huang, L.; Wang, X. Chem. Commun. 2012, 48, 11656
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      Devic, T.; Horcajada, P.; Serre, C.; Salles, F.; Maurin, G.; Moulin, B.; Heurtaux, D.; Clet, G.; Vimont, A.; Grenéche, J.-M.; Le Ouay, B.; Moreau, F.; Magnier, E.; Filinchuk, Y.; Marrot, J.; Lavalley, J.-C.; Daturi, M.; Férey, G. J. Am. Chem. Soc. 2010, 132, 1127
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      Torrisi, A.; Bell, R. G.; Mellot-Draznieks, C. Cryst. Growth Des. 2010, 10, 2839
      33
      Functionalized MOFs for Enhanced CO2 Capture
      Torrisi, Antonio; Bell, Robert G.; Mellot-Draznieks, Caroline
      Crystal Growth & Design (2010), 10 (7), 2839-2841CODEN: CGDEFU; ISSN:1528-7483. (American Chemical Society)
      Based on computational studies, we propose new metal-org. framework materials, in which the bridging ligands have been functionalized by different substituents, with the aim of improving the CO2 adsorption capacity of the material. The materials are based on the large-pore form of MIL-53(Al3+), with the following functional groups: OH-, COOH-, NH2-, and CH3-. For each form, adsorption heats and isotherms were simulated using the Grand Canonical Monte Carlo method which were found to be consistent with DFT calcns. The study illustrates the enormous impact of the functional groups in enhancing CO2 capture in the pressure range 0.01-0.5 bar and at room temp. It also provides important insights into the structural factors which play a key role in the CO2 adsorption process in the functionalized MOFs. We propose the material (OH)2-MIL-53(Al3+) as an optimal candidate for improved CO2 capture at low pressures.
    34. 34
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      Cohen, S. M. Chem. Rev. 2012, 112, 970
      38
      Postsynthetic Methods for the Functionalization of Metal-Organic Frameworks
      Cohen, Seth M.
      Chemical Reviews (Washington, DC, United States) (2012), 112 (2), 970-1000CODEN: CHREAY; ISSN:0009-2665. (American Chemical Society)
      A review. The development of postsynthetic methods is discussed for the chem. modification and functionalization of metal-org. frameworks and related coordination polymers. Emphasis is placed on the chem. approaches that result in the covalent modification of the org. linkers within the metal-org. frameworks.
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  • Supporting Information

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    Synthetic procedures; PXRD, N2 sorption, and optical band gap data; and computational details. This material is available free of charge via the Internet at http://pubs.acs.org.


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