Photothermal Assisted Biomass Oxidation for Pairing Carbon Dioxide Electroreduction with Low Cell Potential

Integrating anodic biomass valorization with carbon dioxide electroreduction (CO2RR) can produce value‐added chemicals on both the cathode and anode; however, anodic oxidation still suffers from high overpotential. Herein, a photothermal‐assisted method was developed to reduce the potential of 5‐hydroxymethyl furfural (HMF) electrooxidation. Capitalizing on the copious oxygen vacancies, defective Co3O4 (D‐Co3O4) exhibited a stronger photothermal effect, delivering a local temperature of 175.47 oC under near infrared light illumination. The photothermal assistance decreased the oxidation potential of HMF from 1.7 V over pristine Co3O4 to 1.37 V over D‐Co3O4 to achieve a target current density of 30 mA cm‐2, with 2,5‐furandicarboxylic acid as the primary product. Mechanistic analysis disclosed that the photothermal effect did not change the HMF oxidation route but greatly enhanced the adsorption capacity of HMF. Meanwhile, faster electron transfer for direct HMF oxidation and the surface conversion to cobalt (oxy)hydroxide, which contributed to indirect HMF oxidation, was observed. Thus, rapid HMF conversion was realized, as evidenced by in situ surface‐enhanced infrared spectroscopy. Upon coupling cathodic CO2RR with an atomically dispersed Ni‐N/C catalyst, the Faradaic efficiencies of CO (cathode) and 2,5‐furandicarboxylic acid (FDCA, anode) exceeded 90.0% under a low cell potential of 1.77 V.