Progress in Cu-Based Catalyst Design for Sustained Electrocatalytic CO₂ to C₂₊ Conversion

The electrocatalytic conversion of CO₂ into valuable multi-carbon (C₂₊) products using Cu-based catalysts has attracted significant attention. This review provides a comprehensive overview of recent advances in Cu-based catalyst design to improve C₂₊ selectivity and operational stability. It begins with an analysis of the fundamental reaction pathways for C₂₊ formation, encompassing both established and emerging mechanisms, which offer critical insights for catalyst design. In situ techniques, essential for validating these pathways by real-time observation of intermediates and material evolution, are also introduced. A key focus of this review is placed on how to enhance C₂₊ selectivity through intermediates manipulation, particularly emphasizing catalytic site construction to promote C─C coupling via increasing ^*CO coverage and optimizing protonation. Additionally, the challenge of maintaining catalytic activity under reaction conditions is discussed, highlighting the reduction of active charged Cu species and materials reconstruction as major obstacles. To address these, the review describes recent strategies to preserve active sites and control materials evolution, including novel catalyst design and the utilization and mitigation of reconstruction. By presenting these developments and the challenges ahead, this review aims to guide future materials design for CO₂ conversion. © 2025 The Author(s). Advanced Science published by Wiley-VCH GmbH.