title: Photocatalytic carbon dioxide reduction with rhodium-based catalysts in solution and heterogenized within metal-organic frameworks.
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.
authors.affiliation: Laboratoire de Chimie des Processus Biologiques, UMR 8229 CNRS, UPMC Univ Paris 06, Collège de France, 11 Marcelin Berthelot, 75231 Paris Cedex 05, France, Fax: +33 1 44271356 ; Tel: +33 1 44271360.
authors.forename: Matthew B
authors.initials: MB
authors.lastname: Chambers
authors.forename: Xia
authors.initials: X
authors.lastname: Wang
authors.forename: Noémie
authors.initials: N
authors.lastname: Elgrishi
authors.forename: Christopher H
authors.initials: CH
authors.lastname: Hendon
authors.forename: Aron
authors.initials: A
authors.lastname: Walsh
authors.forename: Jonathan
authors.initials: J
authors.lastname: Bonnefoy
authors.forename: Jérôme
authors.initials: J
authors.lastname: Canivet
authors.forename: Elsje Alessandra
authors.initials: EA
authors.lastname: Quadrelli
authors.forename: David
authors.initials: D
authors.lastname: Farrusseng
authors.forename: Caroline
authors.initials: C
authors.lastname: Mellot-Draznieks
authors.forename: Marc
authors.initials: M
authors.lastname: Fontecave
mesh_terms: D015082:2,2'-Dipyridyl / Q000031:analogs & derivatives / Q000737:chemistry / Q000528:radiation effects; D002245:Carbon Dioxide / Q000737:chemistry*; D002384:Catalysis; D056831:Coordination Complexes / Q000737:chemistry* / Q000528:radiation effects; D005561:Formates / Q000737:chemistry*; D008027:Light; D009942:Organometallic Compounds / Q000737:chemistry / Q000528:radiation effects; D010084:Oxidation-Reduction; D017319:Photosensitizing Agents / Q000737:chemistry / Q000528:radiation effects; D012238:Rhodium / Q000737:chemistry* / Q000528:radiation effects; D012996:Solutions
chemical_list: D056831:Coordination Complexes; D005561:Formates; D009942:Organometallic Compounds; D017319:Photosensitizing Agents; D012996:Solutions; C095931:dichlorobis(2,2'-bipyridine)ruthenium; C030544:formic acid; D002245:Carbon Dioxide; D015082:2,2'-Dipyridyl; D012238:Rhodium
keywords: carbon dioxide reduction; hydrogen; metal-organic frameworks; photocatalysis; rhodium