Anodic electrocatalytic conversion of carboxylic acids on thin films of RuO2, IrO2, and Pt

[Display omitted] •Pt foil and thin films (TFs) of RuO2 and IrO2 are active for electrocatalytic decarboxylation (ECDX) of valeric acid at ambient conditions.•Rates of ECDX and O2 evolution increase with potential, while the ECDX selectivity depends also on anode composition.•RuO2-TF is selective toward non-Kolbe products while Pt is selective toward Kolbe products.•The ECDX activity of RuO2-TF is similar to that of Pt foil per geometric area but is one order of magnitude more active per gram of metal.•Turnover frequencies of ECDX were at least one order of magnitude higher than thermocatalytic decarboxylation at 300 °C. The electrocatalytic upgrading of carboxylic acids, abundant biomass-derived molecules, remains a challenging task. Herein, we report an electrocatalytic decarboxylation (ECDX) approach for the conversion of carboxylic acids into paraffins, olefins, and alcohols via (non-)Kolbe electrolysis on thin films (TFs). The ECDX rate, product selectivity, and current efficiency were potential and electrode dependent. For example, the ECDX activity of RuO2-TF was similar to that of Pt foil, but the selectivity to Kolbe products was lower on the former. RuO2-TF showed about five times higher rates for the oxygen evolution reaction than Pt foil, which resulted in lower current efficiency. The ECDX and O2 evolution activities of IrO2-TF were potential dependent, but this electrode was selective to non-Kolbe products with low current efficiency (