Ordered Copper Triangular Atomic Sites for Industrial‐Grade Electromethanation of CO <sub>2</sub> via Self‐Regulated Adsorption of Reactants
Fanglei Yao, Yuntong Sun, Long Nie, Cheng Zhang, Hongwei Shou, Zhiming Li, Xiaoping Gao, Jin Wang
Abstract
Abstract Copper single‐atom catalysts have shown considerable potential for electrocatalytic CO 2 reduction reaction (CO 2 RR) to methane but face constraints of low selectivity at industrial‐grade current densities (>400 mA cm −2 ) and limited economic viability. Herein, we report an ion exchange strategy to precisely construct ordered Cu triangular atomic sites loaded on poly(heptazine imide) (Cu TAS/PHI), achieving a methane Faradaic efficiency (FE) of 80.5% at 400 mA cm −2 and >60% across 100–800 mA cm −2 . Remarkably, it enables CO 2 deuteration to high‐value methane‐ d 4 with an FE of 75.1% at 700 mA cm −2 and an estimated annual return on investment of 425.35%. In situ spectroscopy and theoretical calculations demonstrate that Cu triangular atomic sites enable strengthened adsorption and activation of CO 2 , as well as balanced proton supply via self‐regulated adsorption of reactants, thus favoring CO 2 deep hydrogenation over hydrogen evolution. Moreover, Cu TAS/PHI unlocks an energetically favorable *C(OH) 2 pathway, circumventing the conventional *CO pathway that typically yields diverse CO 2 RR products. This work demonstrates a strategy to construct ordered multiatomic sites for highly selective CO 2 RR at industrial‐grade current density and highlights the extraordinary financial potential of electrocatalytic CO 2 RR to produce high‐value deuterated chemicals.