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Metal Organic Frameworks in Heterogeneous Catalysis: Recent Metal–Organic Frameworks in Heterogeneous Catalysis: Recent Progress, New Trends, and Future Perspectives Item Type Article Authors Bavykina, Anastasiya; Kolobov, Nikita; Khan, Il Son; Bau, Jeremy; Galilea, Adrian; Gascon, Jorge Citation Bavykina, A., Kolobov, N., Khan, I. S., Bau, J. A., Ramirez, A., & Gascon, J. (2020). Metal–Organic Frameworks in Heterogeneous Catalysis: Recent Progress, New Trends, and Future Perspectives. Chemical Reviews. doi:10.1021/ acs.chemrev.9b00685 Eprint version Post-print DOI 10.1021/acs.chemrev.9b00685 Publisher American Chemical Society (ACS) Journal Chemical Reviews Rights This document is the Accepted Manuscript version of a Published Work that appeared in final form in Chemical Reviews, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://pubs.acs.org/doi/10.1021/acs.chemrev.9b00685. Download date 25/09/2021 22:24:52 Link to Item http://hdl.handle.net/10754/662392 Metal Organic Frameworks in Heterogeneous Catalysis: Recent Progress, New Trends and Future Perspectives Anastasiya Bavykina,† Nikita Kolobov,† Il Son Khan,† Jeremy A. Bau,† Adrian Ramirez† and Jorge Gascon *† † King Abdullah University of Science and Technology, KAUST Catalysis Center (KCC), Advanced Catalytic Materials, Thuwal, 23955-6900, Saudi Arabia [email protected] Abstract More than 95% (in volume) of all today’s chemical products are manufactured through catalytic processes, making research into more efficient catalytic materials a thrilling and very dynamic research field. In this regard, Metal Organic Frameworks (MOFs) offer great opportunities for the rational design of new catalytic solids, as highlighted by the unprecedented number of publications appearing over the last decade. In this review, the recent advances in the application of MOFs in heterogeneous catalysis are discussed. MOFs with intrinsic thermo-catalytic activity, as hosts for the incorporation of metal nanoparticles, as precursors for the manufacture of composite catalysts and those active in photo and electrocatalytic processes are critically reviewed. The review is wrapped up with our personal view on future research directions. 1 1. Introduction .......................................................................................................................... 4 2 MOFs with intrinsic catalytic activity ................................................................................. 7 2.1 Catalysis on open metal sites and non-decorated frameworks ...................................... 8 2.2 Catalysis on defects ....................................................................................................... 13 2.3 Catalysis on decorated MOFs (de novo synthesis or post treatment) ......................... 21 2.3.1 CO2 conversion ....................................................................................................... 22 2.3.2 C-H bond activation ................................................................................................ 29 2.3.3 Other reactions ....................................................................................................... 32 3 MOFs as supports for metal nanoparticles ...................................................................... 45 3.1 Synthesis ........................................................................................................................ 47 3.1.1 “Ship in a bottle” MNP/MOF................................................................................. 49 3.1.1.1 CVD. ................................................................................................................ 49 3.1.1.2 Solid grinding................................................................................................... 50 3.1.1.3 Solution impregnation. ..................................................................................... 50 3.1.1.4 Double solvent approach.................................................................................. 52 3.1.1.5 One-pot synthesis. ............................................................................................ 53 3.1.2 Colloidal deposition ................................................................................................ 54 3.1.3 “Bottle around ship” or “templated synthesis” ..................................................... 55 3.1.4 Thermal decomposition ........................................................................................... 56 3.1.5 Spray drying ............................................................................................................ 57 3.1.6 Other methods ......................................................................................................... 58 3.2 Catalysis ......................................................................................................................... 59 3.2.1 CO related chemistry .............................................................................................. 59 3.2.2 CO2 utilization ........................................................................................................ 62 3.2.3 Dehydrogenation..................................................................................................... 64 3.2.4 Hydrogenation reactions ........................................................................................ 65 3.2.5 Oxidation of alcohols and carbonyl compounds .................................................... 67 3.2.6 Organic coupling reactions .................................................................................... 68 4 MOF-mediated materials in heterogeneous catalysis ...................................................... 69 4.1 Synthesis routes for MOF-mediated catalysts.............................................................. 71 4.2 Catalytic applications of MOF-mediated catalysts ...................................................... 77 5 Electrocatalysis on MOFs................................................................................................... 90 5.1 MOFs as electrocatalysts .............................................................................................. 91 5.1.1 O2 evolution ............................................................................................................ 91 5.1.2 H2 evolution ............................................................................................................ 97 2 5.1.3 O2 reduction .......................................................................................................... 101 5.1.4 CO2 reduction ....................................................................................................... 103 5.2 Derived electrocatalysts............................................................................................... 106 5.2.1 Strategies for materials – OER ............................................................................. 106 5.2.2 Strategies for materials – HER ............................................................................. 109 5.2.3 Strategies for materials – ORR ............................................................................. 111 5.2.4 General strategies – heterostructures ................................................................... 112 5.2.5 General strategies – controlled decomposition of MOFs to preserve ideal structural features .......................................................................................................... 113 5.2.6 General strategies – 2D MOF decomposition ...................................................... 115 6 Photocatalysis .................................................................................................................... 116 6.1 MOFs in photocatalysis .............................................................................................. 117 6.1.1 MOF-based photocatalysts ................................................................................... 117 6.1.2 Single-site MOF photocatalyst ............................................................................. 118 6.1.3 MOFs as supports ................................................................................................. 120 6.1.4 MOF-derived photocatalysts ................................................................................ 122 6.1.5 Composites ............................................................................................................ 125 6.2 Most studied photocatalytic processes on MOF-related materials............................ 130 6.2.1 Hydrogen and oxygen evolution, overall water splitting ...................................... 131 6.2.2 CO2 reduction ....................................................................................................... 137 6.2.3 Pollutant treatment ............................................................................................... 143 7 Outlook, challenges and future perspectives .................................................................. 147 3 1. Introduction A catalyst is a substance that increases the rate of a chemical reaction towards equilibrium without being appreciably consumed. The word “catalysis” stems from Greek: “κατα” that means “down” and “λυσισ” that means “loosening”. In the eastern culture, the Chinese characters for catalyst refer to a marriage broker.1 By using the adequate catalyst, one or a set of desired reactions proceed with
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