93.Electron-Efficient Formate Electrosynthesis from CO2 and Biomass-Derived Carbohydrates in a Zero-Gap Electrolyzer

Yue Ren, Ming Xu, Kang Zou, Wei Kong, Zhenhua Li, Xianggui Kong, Lirong Zheng, Zishan Han, Chunyu Zhang, Hua Zhou*, Mingfei Shao*, Haohong Duan*
Angewandte Chemie International Edition, 2026, e3951875
DOI: 10.1002/anie.3951875

Abstract
Paired electrolysis is being actively developed for co-producing valuable chemicals by leveraging electron transfer at bipolar electrodes. In electrochemical CO₂ reduction to formate, if the reaction is coupled with oxygen evolution reaction, formate experiences severe crossover and oxidation to CO₂ over anode in membrane electrode assembly (MEA) electrolyzer. We reported a convergent electrolysis that produces formate at bipolar electrodes by coupling CO₂ reduction with biomass-derived carbohydrate (for example, glucose) oxidation, maximizing the electron efficiency toward formate (0.88 formate per e⁻) and suppressing oxidation of crossed formate at anode. This convergent electrolysis shows low electricity consumption for formate production (76.5 Wh mol⁻¹ at 100 mA cm⁻²), lower than that of conventional CO₂ reduction (180−350 Wh mol⁻¹). Furthermore, we extended the convergent electrolysis to acetate production by coupling electrochemical CO reduction with waste polylactic acid plastic oxidation. This work offers a framework for the rational design of paired electrolysis for low electricity consumption of chemical production.