Abstract: Electrocatalytic carbon dioxide reduction reaction (CO₂RR) can convert the greenhouse gas CO₂ into high valued multi-carbon (C₂₊) products, providing an effective pathway to achieve carbon neutrality and renewable energy storage. Currently, copper-containing materials are the dominant catalysts for electrocatalytic CO₂ conversion to C₂₊ products. However, the insufficient stability and low single-product selectivity seriously hinder their large-scale application. In recent years, non-copper electrocatalysts have attracted extensive attention for C₂₊ electrosynthesis. This review systematically summarizes the progress on non-copper-based catalysts in electrocatalytic CO₂ reduction to C₂₊ products, and thoroughly analyzes the structure-performance relationships among non-metallic, precious metal, d-block non-copper metal, and p-block metal compounds, particularly in catalyst design, local structural optimization, enhanced CO₂ activation, promoted C-C coupling, and improved stability, revealing the regulatory roles of elemental composition and local coordination environment in steering reaction pathways and product selectivity. However, non-copper catalysts still face challenges including unclear structural evolution and active-site deactivation mechanisms during electrolysis at large current density, and their application in industrial-level electrolysis cell has not yet been realized. Finally, the perspectives are provided on high-throughput screening of advanced catalytic materials, design and construction of high-performance catalytic systems, catalytic process monitoring and mechanistic investigation, and industrial-scale application of stable high-current electrolysis, aiming to provide guidance for the rational design and industrialization of non-copper electrocatalysts.

Key words: electrocatalysis, carbon dioxide reduction reaction, non-copper catalyst, C₂₊ product, review