Conductive Zeolite Supported Indium–Tin Alloy Nanoclusters for Selective and Scalable Formic Acid Electrosynthesis

Abstract Upgrading excess CO 2 toward the electrosynthesis of formic acid is of significant research and commercial interest. However, simultaneously achieving high selectivity and industrially relevant current densities of CO 2 ‐to‐formate conversion remains a grand challenge for practical implementations. Here, an electrically conductive zeolite support is strategically designed by implanting Sn ions into the skeleton structure of a zeolite Y, which impregnates ultrasmall In 0.2 Sn 0.8 alloy nanoclusters into the supercages of the tailored 12‐ring framework. The prominent electronic and geometric interactions between In 0.2 Sn 0.8 nanoalloy and zeolite support lead to the delocalization of electron density that enhances orbital hybridizations between In active site and *OCHO intermediate. Thus, the energy barrier for the rate‐limiting *OCHO formation step is reduced, facilitating the electrocatalytic hydrogenation of CO 2 to formic acid. Accordingly, the developed zeolite electrocatalyst achieves an industrial‐level partial current density of 322 mA cm −2 and remarkable Faradaic efficiency of 98.2% for formate production and stably maintains Faradaic efficiency above 93% at an industrially relevant current density for over 102 h. This work opens up new opportunities of conductive zeolite‐based electrocatalysts for industrial‐level formic acid electrosynthesis from CO 2 electrolysis and toward practically accessible electrocatalysis and energy conversion.