Lewis acidity-triggered active reconstruction sustains industrial-scale CO2-to-Formate conversion beyond 1500 h

Abstract The electrochemical upgrading of CO2 remains hindered by its unsatisfied durability to meet industrial requests, which is in part due to the passive reconstruction of catalyst during dynamic operation. Prior research primarily focuses on suppressing such reconstruction with modest improvement in durability. Herein, we innovatively propose an active reconstruction (AR) strategy that employs Lewis acid, as a seed, to trigger rapid reconstruction, thereby enabling on-demand reconfiguration into dynamically stable rich-low-coordination sites through in-situ regeneration of defect sites for industrial-scale CO2-to-formate electrolysis. Combined experimental and theoretical results reveal a linear-like tailoring relationship between Lewis acidity and reconstruction kinetics, allowing precise control of unsaturated-coordinated sites to achieve high activity and enhancing the metal-oxygen bond order to improve intrinsic stability, which applies to various catalysts. Meanwhile, low-coordinated sites also optimize the interfacial H2O/CO2 microenvironment via enhancing *CO2·- intermediates adsorption and regulating 2H (2-coordinated Hydrogen-bonded) interfacial water ratio. The optimized AR-ITO (active-reconstruction In1.8Sn0.2O3/In9Sn) catalyst delivers a high FEformate of 91% at 1 A cm-2 and achieves an unprecedented durability of up to 1500 h at 300 mA cm-2 (1.5 A) with the maintained FEformate of 92% in MEA electrolyzer. Our findings highlight the superiority of a controlled activated reconstruction strategy for industrial CO2RR applications.