Amine-functionalized zirconium metal–organic framework as efficient visible-light photocatalyst for aerobic organic transformations

Long, Jinlin; Wang, Sibo; Ding, Zhengxin; Wang, Shuchao; Zhou, Yangen; Huang, Ling; Wang, Xuxu

doi:10.1039/c2cc34620f

Cited by 422 publications

(238 citation statements)

References 22 publications

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“…24,25 The small downeld feature at g ¼ 2.01 is associated with the spatially conned amino-groups in the MOF. 26,41 The EPR spectrum of Co@MOF in the dark (Fig. 8C), with a broad signal around g z 4, is similar to that of high-spin CoBr 2 in CH 3 CN, indicating the presence of residual high-spin Co II impurities (Fig.…”

Section: Mechanistic Aspects Of Hydrogen Evolution Catalysed By Co@momentioning

confidence: 99%

Co@NH₂-MIL-125(Ti): cobaloxime-derived metal–organic framework-based composite for light-driven H₂ production

Nasalevich

Becker

Ramos‐Fernández

et al. 2015

Energy Environ. Sci.

382

258

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Co@NH2-MIL-125(Ti): Cobaloxime-derived Metal-Organic Framework-based Composite for Light-driven H2 Production Nasalevich, M.A.; Becker, R.; Ramos-Fernandez, E.V.; Castellanos, S.; Veber, S.L.; Fedin, M.V.; Kapteijn, F.; Reek, J.N.H.; van der Vlugt, J.I.; Gascon, J. Disclaimer/Complaints regulationsIf you believe that digital publication of certain material infringes any of your rights or (privacy) interests, please let the Library know, stating your reasons. In case of a legitimate complaint, the Library will make the material inaccessible and/or remove it from the website. Please Ask the Library: http://uba.uva.nl/en/contact, or a letter to: Library of the University of Amsterdam, Secretariat, Singel 425, 1012 WP Amsterdam, The Netherlands. You will be contacted as soon as possible. We present a synthetic strategy for the efficient encapsulation of a derivative of a well-defined cobaloxime proton reduction catalyst within a photoresponsive metal-organic framework (NH 2 -MIL-125(Ti)). The resulting hybrid system Co@MOF is demonstrated to be a robust heterogeneous composite material. Furthermore, Co@MOF is an efficient and fully recyclable noble metal-free catalyst system for lightdriven hydrogen evolution from water under visible light illumination. Broader contextThe development of new strategies for the efficient valorization of solar light is one the most important challenges we face nowadays. Among the different possibilities, dihidrogen molecule is considered as one of the possible future energy carriers allowing for CO 2 -free energy cycle. Although the photocatalytic water splitting was the rst photocatalytic reaction to be discovered, no photocatalytic systems for this reaction have been industrially applied. This is both due to the fact that most discovered catalysts rely on the use of noble metals and to the low activities achieved so far by alternative catalysts. The application in this eld of materials such as metal-organic frameworks (MOFs) can be a game changer in this research eld. MOFs have been proven to be photoactive and their optical properties can be easily tuned towards visible light operation. The current challenge lies in the development of more appropriate active sites for the desired photocatalytic cycle. In this manuscript, we report a new strategy to achieve this goal. By introducing a derivative of the well-known molecular Co-based electrocatalyst Co-dioxime-diimine into the pores of a photo-active NH 2 -MIL-125(Ti) following a 'Ship-in-a-bottle' strategy, we were able to synthesize a highly active photocatalyst composite free of noble metals, and fully recyclable. Because of the novelty and the implications of this work, we feel that it might appeal to the interdisciplinary readership of energy and environmental science. The journal has previously been an important forum for the research topics touched upon in this paper (new earth abundant materials and their application in (photo) catalysis and hydrogen evolution from water under visible light illumination). We would be glad t...

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Section: Mechanistic Aspects Of Hydrogen Evolution Catalysed By Co@momentioning

confidence: 99%

Co@NH₂-MIL-125(Ti): cobaloxime-derived metal–organic framework-based composite for light-driven H₂ production

Nasalevich

Becker

Ramos‐Fernández

et al. 2015

Energy Environ. Sci.

382

258

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“…For instance, J. Long et al 68 reported that under visible light irradiation, UiO-66-NH 2 catalyzes the aerobic oxidation of alcohols, olefines and cyclic alkanes. In benzyl alcohol, cyclohexanol and hexyl alcohol oxidation catalysis, 100% selectivity is achieved for these substrates (entry 13, Table 2) , but the conversion rate highly depends on the activation energy of α-C-H bonds.…”

Section: Hydroxylation Of Phenolmentioning

confidence: 99%

Metal-Organic Frameworks as Selective or Chiral Oxidation Catalysts

2014

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Since the discovery of Metal Organic Frameworks (MOFs) in the early 1990, the amount of new structures has grown exponentially. A MOF typically consists of inorganic nodes that are connected by organic linkers to form crystalline, highly porous structures. MOFs have attracted a lot of attention lately, as the versatile design of such materials holds promises of interesting applications in various fields. In this review, we will focus on the use of MOFs as heterogeneous oxidation catalysts. MOFs are very promising candidates to replace homogeneous catalysts by sustainable and stable heterogeneous catalysts. The catalytic active function can be either the active metal sites of the MOF itself or can be introduced as an extra functionality in the linker, a dopant or a "ship-in-a-bottle" complex. As the pore size, pore shape and functionality of MOFs can be designed in numerous ways, shape selectivity and even chiral selectivity can be created. In this review, we will present an overview on the state of the art of the use of MOFs as a heterogeneous catalyst in liquid phase oxidation reactions.

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“…These studies reveal that the change of organic ligand is an effective method to regulate band gap of MOF. Although in recent years many efforts have been made to modify the organic ligands of MOFs, 5,9,11,20,21 the effects of ligand functionalization on the photocatalytic properties of MOFs are still unclear. It is obvious that a better understanding the mechanism of ligand modification is important to develop new MOF-based photocatalysts.…”

Section: Introductionmentioning

confidence: 99%

“…Especially, many investigations have demonstrated that MOF materials are promising catalysts in photocatalysis. 5,6,[9][10][11][12][13][14][15][16] As one of the most popular MOF, 1,[5][6][7] the titanium-based MIL-125 can catalyze the oxidation of alcohols to aldehydes under the UV irradiation, indicating that MIL-125 is an active photocatalyst. 10 However, because of the large optical band gap (3.6 eV), 10 MIL-125 is only active under UV irradiation.…”

Section: Introductionmentioning

confidence: 99%

“…Therefore, it is necessary to modify the organic ligands or 5,16 After introducing the amine group, the band gap of MIL-125 is obviously reduced to about 2.6 eV, 12,18,19 and similar decreasing of the band gap by amine-functionalization is also observed for zirconium-based MOF (NH 2 -Uio-66). 11 A recent investigation indicates that the number of amine group also has obviously influence on the photocatalytic performances of NH 2 -MIL-125. 20 By a combined experimental and computational study, Hendon et al have explored the band structure of MIL-125 and the impact of different functional groups on the BDC linker, 21 and the obvious decreasing of band gap after introducing one or two NH 2 groups is also achieved.…”

Section: Introductionmentioning

confidence: 99%

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Effects of ligand functionalization on the photocatalytic properties of titanium-based MOF: A density functional theory study

et al. 2018

AIP Advances

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The first principle calculations have been performed to investigate the geometries, band structures and optical absorptions of a series of MIL-125 MOFs, in which the 1,4-benzenedicarboxylate (BDC) linkers are modified by different types and amounts of chemical groups, including NH2, OH, and NO2. Our results indicate that new energy bands will appear in the band gap of pristine MIL-125 after introducing new group into BDC linker, but the components of these band gap states and the valence band edge position are sensitive to the type of functional group as well as the corresponding amount. Especially, only the incorporation of amino group can obviously decrease the band gap of MIL-125, and the further reduction of the band gap can be observed if the amount of NH2 is increased. Although MIL-125 functionalized by NH2 group exhibits relatively weak or no activity for the photocatalytic O2 evolution by splitting water, such ligand modification can effectively improve the efficiency in H2 production because now the optical absorption in the visible light region is significantly enhanced. Furthermore, the adsorption of water molecule becomes more favorable after introducing of amino group, which is also beneficial for the water-splitting reaction. The present study can provide theoretical insights to design new photocatalysts based on MIL-125.

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Amine-functionalized zirconium metal–organic framework as efficient visible-light photocatalyst for aerobic organic transformations

Cited by 422 publications

References 22 publications

Co@NH₂-MIL-125(Ti): cobaloxime-derived metal–organic framework-based composite for light-driven H₂ production

Co@NH₂-MIL-125(Ti): cobaloxime-derived metal–organic framework-based composite for light-driven H₂ production

Metal-Organic Frameworks as Selective or Chiral Oxidation Catalysts

Effects of ligand functionalization on the photocatalytic properties of titanium-based MOF: A density functional theory study

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Amine-functionalized zirconium metal–organic framework as efficient visible-light photocatalyst for aerobic organic transformations

Cited by 422 publications

References 22 publications

Co@NH2-MIL-125(Ti): cobaloxime-derived metal–organic framework-based composite for light-driven H2 production

Co@NH2-MIL-125(Ti): cobaloxime-derived metal–organic framework-based composite for light-driven H2 production

Metal-Organic Frameworks as Selective or Chiral Oxidation Catalysts

Effects of ligand functionalization on the photocatalytic properties of titanium-based MOF: A density functional theory study

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Co@NH₂-MIL-125(Ti): cobaloxime-derived metal–organic framework-based composite for light-driven H₂ production

Co@NH₂-MIL-125(Ti): cobaloxime-derived metal–organic framework-based composite for light-driven H₂ production