A systematic DFT study on production selectivity of Cu single-crystal surfaces are performed at electrochemical interfaces to gain the origin of CO₂ electroreduction into C₁ and C₂ species. The results show that CO is a common intermediate on Cu(111) and Cu(100) surfaces, and its further reduction is the crucial selectivity-determining step. Simultaneously, a Langmuir-Hinshelwood mechanism is proposed for CO dimerization and the reason for pathway selectivity is explained by geometry analysis. The present studies will provide theoretical support for C₁ and C₂ species formation mechanisms and the rational design of Cu-based alloy electrocatalysts that are active at a lower overpotential.

在电化学界面上对Cu单晶表面的生产选择性进行了系统的DFT研究，以了解将CO ₂电还原成C ₁和C ₂物种的起源。结果表明，CO是Cu（111）和Cu（100）表面上的常见中间体，其进一步还原是决定选择性的关键步骤。同时，提出了Langmuir-Hinshelwood机理用于CO二聚，并通过几何分析解释了途径选择性的原因。本研究将为C ₁和C ₂物种的形成机理提供理论依据，并为在较低的超电势下具有活性的Cu基合金电催化剂的合理设计提供依据。