Tuning Strategies of Indium‐Based Catalysts for Electrocatalytic Carbon Dioxide Reduction

In electrocatalytic carbon dioxide reduction (CO 2 RR), indium (In)‐based catalysts with low toxicity and environmental benefits are renowned for their specific high selectivity for formic acid and intrinsic inertia for the competing hydrogen evolution reaction. However, recent studies have reported various products over In‐based catalysts showing comparable or even higher selectivity for carbon monoxide (CO) than for formic acid (HCOOH), puzzling the reaction pathway for CO 2 reduction. This article presents a comprehensive review of recent studies on electrocatalytic CO 2 RR over In‐based catalysts highlighting the formation pathway of specific products. First, the mechanism of electrocatalytic CO 2 RR with the multiple reaction pathways is concluded considering the relationship between reaction intermediates and selectivity. Furthermore, the regulation strategies for multiple product formation are summarized, including crystalline phase engineering, alloying, nanostructuring, and structural modulation of In single atom, where the effect of key intermediates (*COOH, *OOCH, and *OCHO) on product generation is systematically discussed to achieve high selectivity. Finally, the intrinsic regulation mechanisms of these strategies are analyzed and the challenges and opportunities for the development of next‐generation In‐based catalysts are proposed.