A Pair-Electrosynthesis for Formate at Ultra-Low Voltage Via Coupling of CO2 Reduction and Formaldehyde Oxidation

Formate can be synthesized electrochemically by CO2 reduction reaction (CO2RR) or formaldehyde oxidation reaction (FOR). The CO2RR approach suffers from kinetic-sluggish oxygen evolution reaction at the anode. To this end, an electrochemical system combining cathodic CO2RR with anodic FOR was developed, which enables the formate electrosynthesis at ultra-low voltage. Cathodic CO2RR employing the BiOCl electrode in H-cell exhibited formate Faradaic efficiency (FE) higher than 90% within a wide potential range from - 0.48 to - 1.32 VRHE. In flow cell, the current density of 100 mA cm-2 was achieved at - 0.67 VRHE. The anodic FOR using the Cu2O electrode displayed a low onset potential of - 0.13 VRHE and nearly 100% formate and H2 selectivity from 0.05 to 0.35 VRHE. The CO2RR and FOR were constructed in a flow cell through membrane electrode assembly for the electrosynthesis of formate, where the CO2RR//FOR delivered an enhanced current density of 100 mA cm-2 at 0.86 V. This work provides a promising pair-electrosynthesis of value-added chemicals with high FE and low energy consumption.