Harnessing Electrocatalytic Coupling of Carbon Dioxide and Methanol for High‐Efficiency Formic Acid Production

Abstract The coupling of electrocatalytic CO 2 reduction (ECR) and methanol oxidation reaction (MOR) presents a promising strategy for simultaneous cogeneration of formic acid (FA) at both cathode and anode. However, sluggish kinetics, low selectivity and efficiency hinder practical application. Herein, we demonstrate an integrated ECR||MOR system employing CuBi cathode and NiCo anode for energy‐efficient FA cogeneration. The CuBi alloy achieves high Faradaic efficiencies (FE > 90%) for FA generation over an extensive potential range (>400 mV), attributed to the accelerated formation of HCOO * intermediates in facilitating FA production. Meanwhile, the NiCo alloy reached a remarkable FE of 97.5% for FA generation at 1.4 V versus reversible hydrogen electrode, benefiting from rapid HCOO * intermediate formation that effectively mitigates CO toxicity. This unique system delivered a current density of 10 mA cm −2 at a voltage of 2.07 V, representing a substantial reduction of 320 mV compared to water electrolysis. Across a wide operational voltage window (2.0–2.8 V), the system consistently delivered total Faradaic efficiencies ranging between 189% and 192%, alongside exceptional FA production capacities surpassing 400 g kWh −1 , which significantly outperformed traditional methods (∼220 g kWh −1 ). This work provides an efficient pathway for low‐energy CO 2 utilization and sustainable FA production.