Rational Design Strategies for Electrocatalytic CO₂ Reduction: From Nanostructured Metals to Metal-Free and Molecular Catalysts 

Mingxia Zhang  Yue Li  Yani Hua ^{（Corresponding Author）}

School of Chemical Engineering and Technology, Xi’an Jiaotong University, Xi’an P. R. China，710049；

Abstract：The electrochemical CO₂ reduction reaction (CO₂RR) is a promising strategy for converting carbon dioxide into value-added fuels and chemicals using renewable electricity. This review summarizes recent advances in CO2RR catalysts, focusing on metal-based nanostructured catalysts, metal-free catalysts, and molecular metal complex catalysts. Key design strategies, including nanostructure engineering, heteroatom doping, defect regulation, coordination-environment tuning, and framework optimization, are discussed in relation to catalytic activity, selectivity, and stability. Particular attention is paid to structure-performance relationships, reaction mechanisms, and product distribution. Major challenges, including limited selectivity, poor durability, competing hydrogen evolution, and difficulty in identifying true active sites, are also discussed. Finally, future perspectives for the design of efficient and stable electrocatalysts for practical CO2 electrolysis are proposed.

Keywords: Electrochemical CO2 reduction; CO2RR; Electrocatalysts; Catalyst design strategies

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