Efficient hydrogen production and photocatalytic reduction of nitrobenzene over a visible-light-responsive metal–organic framework photocatalyst

Toyao, Takashi; Saito, Masakazu; Horiuchi, Yu; Mochizuki, Katsura; Iwata, Masaya; Higashimura, Hideyuki; Matsuoka, Makoto

doi:10.1039/c3cy00211j

Cited by 204 publications

(103 citation statements)

References 53 publications

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“…25 The photogenerated electrons in the CdS semiconductor under visible-light irradiation can be accepted by Ni 2 P, thereby decreasing the recombination probability of the photoexcited electron-hole pairs. 26 On the other hand, with the total weight of hybrid catalysts increasing, the efficiency of reduction turn better obviously (see SEI †, Table S1, entries [8][9][10][11][12][13]. There is no doubt that the more Ni 2 P/CdS the more active catalytic sites can be provided for reduction reaction.…”

Section: Highly Efficient and Selective Photocatalytic Reduction Of Nmentioning

confidence: 99%

Highly efficient and selective photocatalytic reduction of nitroarenes using the Ni₂P/CdS catalyst under visible-light irradiation

Gao

Chen

et al. 2015

Chem. Commun.

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A highly efficient and selective heterogeneous photocatalytic system for nitro reduction to amino organics was established using CdS, Ni2P and Na2S/Na2SO3 as a photosensitizer, a cocatalyst and a sacrificial electron donor in aqueous solution, respectively. Two competing pathways for photocatalytic H2 production and nitro reduction were found. Also, the reduction of nitroarenes to aniline was confirmed to proceed through both the direct and condensation routes.

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Section: Highly Efficient and Selective Photocatalytic Reduction Of Nmentioning

confidence: 99%

Highly efficient and selective photocatalytic reduction of nitroarenes using the Ni₂P/CdS catalyst under visible-light irradiation

Gao

Chen

et al. 2015

Chem. Commun.

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“…13 In the presence of triethanolamine (TEOA), visible-light irradiation of NH 2 -MIL-125 results in the catalytic reduction of nitrobenzene to aniline, 15 CO 2 to formate, 13 and protons (aq) to H 2 . 14,15,26 …”

Section: ■Introductionmentioning

confidence: 99%

Bulk-to-Surface Proton-Coupled Electron Transfer Reactivity of the Metal–Organic Framework MIL-125

et al. 2018

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Stoichiometric proton-coupled electron transfer (PCET) reactions of the metal−organic framework (MOF) MIL-125, Ti8O8(OH)4(bdc)6 (bdc = terephthalate), are described. In the presence of UV light and 2-propanol, MIL-125 was photoreduced to a maximum of 2(e−/H+) per Ti8 node. This stoichiometry was shown by subsequent titration of the photoreduced material with the 2,4,6-tri-tert-butylphenoxyl radical. This reaction occurred by PCET to give the corresponding phenol and the original, oxidized MOF. The high level of charging, and the independence of charging amount with particle size of the MOF samples, shows that the MOF was photocharged throughout the bulk and not only at the surface. NMR studies showed that the product phenol is too large to fit in the pores, so the phenoxyl reaction must have occurred at the surface. Attempts to oxidize photoreduced MIL-125 with pure electron acceptors resulted in multiple products, underscoring the importance of removing e− and H+ together. Our results require that the e− and H+ stored within the MOF architecture must both be mobile to transfer to the surface for reaction. Analogous studies on the soluble cluster Ti8O8(OOCtBu)16 support the notion that reduction occurs at the Ti8 MOF nodes and furthermore that this reduction occurs via e−/H+ (H-atom) equivalents. The soluble cluster also suggests degradation pathways for the MOFs under extended irradiation. The methods described are a facile characterization technique to study redox-active materials and should be broadly applicable to, for example, porous materials like MOFs.

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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.…”

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

confidence: 99%

“…24,25,[27][28][29] Inspired by natural photosynthesis, we envisioned a multi-component system that would allow for efficient photon-capture, charge-separation, electron-transport and catalytic turnover at different locations of a guest@MOF composite. This would offer efficient charge transfer between a stable, photo-active MOF structure and the encapsulated proton reduction catalyst under visible-light illumination.…”

Section: -26mentioning

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.

371

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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Efficient hydrogen production and photocatalytic reduction of nitrobenzene over a visible-light-responsive metal–organic framework photocatalyst

Cited by 204 publications

References 53 publications

Highly efficient and selective photocatalytic reduction of nitroarenes using the Ni₂P/CdS catalyst under visible-light irradiation

Highly efficient and selective photocatalytic reduction of nitroarenes using the Ni₂P/CdS catalyst under visible-light irradiation

Bulk-to-Surface Proton-Coupled Electron Transfer Reactivity of the Metal–Organic Framework MIL-125

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

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Efficient hydrogen production and photocatalytic reduction of nitrobenzene over a visible-light-responsive metal–organic framework photocatalyst

Cited by 204 publications

References 53 publications

Highly efficient and selective photocatalytic reduction of nitroarenes using the Ni2P/CdS catalyst under visible-light irradiation

Highly efficient and selective photocatalytic reduction of nitroarenes using the Ni2P/CdS catalyst under visible-light irradiation

Bulk-to-Surface Proton-Coupled Electron Transfer Reactivity of the Metal–Organic Framework MIL-125

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

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Highly efficient and selective photocatalytic reduction of nitroarenes using the Ni₂P/CdS catalyst under visible-light irradiation

Highly efficient and selective photocatalytic reduction of nitroarenes using the Ni₂P/CdS catalyst under visible-light irradiation

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