Engineering Organic Molecule-Copper Interfaces for Selective C₂₊ Production in CO₂ Electroreduction

The electrochemical carbon dioxide reduction reaction (CO₂RR) serves as a crucial bridge linking CO₂ utilization, renewable electricity, and chemical production. Driven by intermittent clean energy sources such as wind and solar power, it can convert CO₂ into high-value chemicals and fuels under ambient temperature and pressure and is therefore regarded as a promising route for artificial carbon recycling and sustainable manufacturing of chemicals. Copper (Cu) is currently the only metal capable of deep CO₂ reduction to multicarbon (C₂₊) products in aqueous electrolytes. However, the product selectivity and catalytic stability of Cu-based catalysts still demand further improvement. In recent years, organic molecule modification strategies have emerged as an effective approach to optimizing Cu-based CO₂RR catalysts and have attracted increasing attention. Organic molecules can form favorable organic-inorganic interfaces with the Cu surface through various interactions, promoting the formation of C₂₊ products via multiple mechanisms. This review summarizes the recent advances in constructing efficient Cu-based catalysts for CO₂RR through organic molecule modification strategy. By reviewing the fundamentals for C₂₊ formation over Cu-based catalysts, this paper first sorts out the interfacial structures and interactions between the organic molecules and Cu surfaces. Then, the underlying mechanisms of the well-defined organic molecule-Cu interfaces for enhanced CO₂RR performance are discussed, including the modulation of surface charge and oxidation state of Cu, the tuning of the local microenvironments, and the synergies for activating CO₂ or stabilizing key intermediates. Furthermore, current research challenges and future prospects associated with the engineering of organic molecule-Cu interfaces are outlined, aiming to provide insights for the rational design of Cu-based catalysts for CO₂RR.