Efficient photoelectrochemical Kolbe C-C coupling at BiVO4 electrodes under visible light irradiation

Electrochemical Kolbe C-C coupling of carboxylic acids at Pt electrodes has been studied for over 150 years and remains relevant today because renewable electricity is envisaged to make an increasing contribution to clean chemical processes and carboxylic acids are readily available precursors for chemical synthesis. Traditional electrochemical Kolbe occurs typically at very high potential (>10 V) which is required to achieve high selectivity for C-C coupling. Here we describe porous BiVO4 photoelectrodes that mediate C-C Kolbe coupling with near quantitative faradaic efficiency under visible light irradiation at <2 V. High substrate concentrations are also found to stabilise the double layer avoiding the need for additional supporting electrolyte. Comparison with related literature describing photocatalytic Kolbe C-C coupling shows that the apparent quantum yield can be raised from <1% to 12% demonstrating the distinct advantage of using photoelectrochemistry in this system.