Bipolar Formate Production: From Catalyst Design to Electrolyzer Construction

ABSTRACT In recent years, bipolar formate production (BFP) has emerged as a cutting‐edge electrocatalytic technology that simultaneously generates high‐value formate at both the cathode via CO 2 reduction reaction (CO 2 RR) and the anode via various organic oxidation reactions (OORs). This transformative approach is receiving unprecedented attention because it overcomes the sluggish kinetics, high energy consumption, and low economic viability of traditional CO 2 RR systems impeded by the anodic oxygen evolution reaction (OER). Therefore, it is urgently necessary to systematically review the state‐of‐the‐art advances of BFP. In this review, we first clarify the predominant anodic OOR pathways enabling dual formate synthesis, including the oxidation of methanol, ethylene glycol (from plastic waste), glycerol, formaldehyde, and glucose. Second, we comprehensively elaborate on the innovative catalyst design strategies and reaction mechanisms for these pathways, alongside advanced electrolyzer constructions. Finally, we propose critical outlooks on the core challenges for industrialization, providing theoretical guidance and novel design principles for developing highly selective catalysts and scalable, sustainable BFP systems.