Engineering Electrochemical Surface for Efficient Carbon Dioxide Upgrade

Abstract Electrochemical CO₂ conversion offers an attractive route for recycling CO₂ with economic and environmental benefits, while the catalytic materials and electrode structures still require further improvements for scale‐up application. Electrocatalytic surface and near‐surface engineering (ESE) has great potential to advance CO₂ reduction reactions (CO₂RR) with improved activity, selectivity, energetic efficiency, stability, and reduced overpotentials. This review initially provides a panorama of ESE effects to give a clear perspective and leverage their advantages, including surface electronic effects, ensemble effects, strain effects, and local environment effects. Additionally, relevant in situ spectroscopic characterization techniques to detect, and theoretical computational approaches to reveal these ESE effects are presented. Typical ESE strategies are also summarized, e.g., in situ surface reconstruction, surface morphology control, surface modifications, etc. Rational manipulations of specific ESE approaches or combinations of them are critical to designing composite catalysts and electrodes, consequently promoting sustainable development and steadily increasing the prosperity of this field.