TY - JOUR
T1 - Photocatalytic carbon dioxide reduction with rhodium-based catalysts in solution and heterogenized within metal-organic frameworks
AU - Chambers, Matthew B.
AU - Wang, Xia
AU - Elgrishi, Noémie
AU - Hendon, Christopher H.
AU - Walsh, Aron
AU - Bonnefoy, Jonathan
AU - Canivet, Jérôme
AU - Quadrelli, Elsje Alessandra
AU - Farrusseng, David
AU - Mellot-draznieks, Caroline
AU - Fontecave, Marc
PY - 2015/1/22
Y1 - 2015/1/22
N2 - 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.
AB - 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.
UR - http://dx.doi.org/10.1002/cssc.201403345
U2 - 10.1002/cssc.201403345
DO - 10.1002/cssc.201403345
M3 - Article
SN - 1864-5631
VL - 8
SP - 603
EP - 608
JO - ChemSusChem
JF - ChemSusChem
IS - 4
ER -