Advances in the carbon dioxide electroreduction to ethanol

The increasingly severe issue of global carbon cycle imbalance caused by carbon dioxide emissions has made the electrochemical CO2 reduction reaction (ECO2RR) a highly promising and attractive approach to maintaining the dynamic balance of the carbon cycle. In particular, the synthesis of ethanol as a high value-added fuel to address the energy crisis has garnered widespread attention. However, the diversity of reaction mechanisms, the complexity of competing reactions, and the limitations of current density have made the path to ethanol production challenging. Here, by analyzing the latest achievements in ECO2RR for ethanol generation, we summarize optimization strategies and future directions, focusing on three key aspects. First, combining in situ characterizations and theoretical calculations, we elucidate the dynamic evolution of intermediates and the formation mechanisms of ethanol, including the emergence and progression of *CO dimerization and *CO insertion pathways. Second, we comprehensively evaluate the design strategies for both Cu-based and non-Cubased catalysts, focusing on four major aspects: crystal facet regulation, surface morphology, alloy effects, and support effects for Cu-based catalysts. For non-Cu-based catalysts, we explore metal-based and metal-free systems to broaden the catalyst design strategies. Then, interface engineering for CO2 electroreduction to ethanol is discussed. Additionally, we provide a detailed discussion on improving mass transfer efficiency and optimizing the interfacial microenvironment, encompassing the selection and regulation of electrolytes (aqueous solutions, organic solvents, and ionic liquids), electrode structure design, and electrolyzer selection. Finally, we outline the prospects and challenges in this field. The industrial-scale production of ethanol should be the future direction, and we hope that the insights provided will not only promote high CO2 conversion but also accelerate the goal of large-scale ethanol production.