Dopant-Induced Electron Localization Drives Direct Current Kolbe Coupling of Biomass-Derived Carboxylic Acids

The Kolbe coupling of biomass-derived carboxylic acids presents a promising route for sustainable production of value-added chemicals. However, conventional direct current (DC) Kolbe electrolysis typically cleaves functional groups in carboxylic acids, significantly hindering its broader application. Herein, we demonstrate that dopant-induced electron localization in activated carbon (AC) facilitates decarboxylative coupling while preserving functional integrity. Experimental and theoretical results reveal that nitrogen doping in AC (N-AC) modulates the local electronic structure and enhances the adsorption capacity of carboxylic acids. Notably, N-AC exhibits a 10-fold increase in the conversion of 10-undecenoic acid compared to AC, with a selectivity of up to 60 ± 2% for the coupling product. More importantly, N-AC effectively catalyzes carboxylic acids with diverse functional groups. This study provides new insights into the structure–property relationship of N-doped carbon and advances the practical implementation of Kolbe electrolysis for biomass valorization.