1. Photocatalytic carbon dioxide reduction with rhodium-based catalysts in solution and heterogenized within metal-organic frameworks.
- Author
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Chambers MB, Wang X, Elgrishi N, Hendon CH, Walsh A, Bonnefoy J, Canivet J, Quadrelli EA, Farrusseng D, Mellot-Draznieks C, and Fontecave M
- Subjects
- 2,2'-Dipyridyl analogs & derivatives, 2,2'-Dipyridyl chemistry, 2,2'-Dipyridyl radiation effects, Catalysis, Coordination Complexes radiation effects, Light, Organometallic Compounds chemistry, Organometallic Compounds radiation effects, Oxidation-Reduction, Photosensitizing Agents chemistry, Photosensitizing Agents radiation effects, Rhodium radiation effects, Solutions, Carbon Dioxide chemistry, Coordination Complexes chemistry, Formates chemistry, Rhodium chemistry
- Abstract
The first photosensitization of a rhodium-based catalytic system for CO2 reduction is reported, with formate as the sole carbon-containing product. Formate has wide industrial applications and is seen as valuable within fuel cell technologies as well as an interesting H2 -storage compound. Heterogenization of molecular rhodium catalysts is accomplished via the synthesis, post-synthetic linker exchange, and characterization of a new metal-organic framework (MOF) Cp*Rh@UiO-67. While the catalytic activities of the homogeneous and heterogeneous systems are found to be comparable, the MOF-based system is more stable and selective. Furthermore it can be recycled without loss of activity. For formate production, an optimal catalyst loading of ∼10 % molar Rh incorporation is determined. Increased incorporation of rhodium catalyst favors thermal decomposition of formate into H2 . There is no precedent for a MOF catalyzing the latter reaction so far., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)
- Published
- 2015
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