Electrocatalytic and Solar‐Driven CO2 Reduction to CO with a Molecular Manganese Catalyst Immobilized on Mesoporous TiO2. Issue 26 (25th April 2016)

• Record Type: Journal Article
• Authors: Rosser, Timothy E.; Windle, Christopher D.; Reisner, Erwin
• Is Part Of: Angewandte Chemie international edition. Volume 55:Issue 26(2016)
• Page Start: 7388
• Page End: 7392
• Publication Date: 2016-04-25
• Subjects: carbon dioxide -- electrocatalysis -- hybrid materials -- manganese -- reduction; Chemistry -- Periodicals; 540
• DOI: 10.1002/anie.201601038
• Languages: English
• ISSNs: 1433-7851

Abstract

Abstract: Electrocatalytic CO2 reduction to CO was achieved with a novel Mn complex, fac ‐[MnBr(4, 4′‐bis(phosphonic acid)‐2, 2′‐bipyridine)(CO)3 ] (MnP ), immobilized on a mesoporous TiO2 electrode. A benchmark turnover number of 112±17 was attained with these TiO2 |MnP electrodes after 2 h electrolysis. Post‐catalysis IR spectroscopy demonstrated that the molecular structure of theMnP catalyst was retained. UV/vis spectroscopy confirmed that an active Mn–Mn dimer was formed during catalysis on the TiO2 electrode, showing the dynamic formation of a catalytically active dimer on an electrode surface. Finally, we combined the light‐protected TiO2 |MnP cathode with a CdS‐sensitized photoanode to enable solar‐light‐driven CO2 reduction with the light‐sensitiveMnP catalyst. Abstract : One small step for Mn : A Mn catalyst immobilized on TiO2 gave electrocatalytic CO2 reduction with a turnover number of 112. The low overpotential of 420 mV is a result of dimerization of the catalyst on the mesoporous electrode. The heterogeneous hybrid cathode was used in a photoelectrochemical cell enabling solar‐driven CO production by a photo‐unstable Mn catalyst for the first time.