CO₂ electrochemical reduction to syngas (CO₂RR-to-syngas) is an environment friendly and promising CO₂ utilization technology. However, there are still few efficient catalysts for CO₂RR-to-syngas electrolysis. The crystal orientation regulation is one of the important methods to enhance the activity of catalyst and there is still a lack of systematic research in this field. In this work, a comparative study of the Cu-M bimetal catalysts (BMCs) for CO₂RR-to-syngas is carried out using density functional theory (DFT) calculations to examine the crystal orientation effects. The results indicate that the reaction barrier is significantly changed on different crystal orientations. Gibbs free energy change of the potential limiting step (ΔG_PLS) on the Cu (1 1 0) surface is lower than those on the Cu (1 1 1) and Cu (1 0 0) surfaces. The Cu-Pd catalyst exhibits better catalytic activity for HER than Cu-Ag, Cu-Ni, Cu-Zn, and Cu-Cd catalysts. CO₂RR activity of the Cu-Pd catalyst is better than that of most of the catalysts reported so far. The Cu-Ni catalyst exposing the Cu(1 0 0) surface is the only catalyst which is more favorite to CO₂RR than HER. This work provides guidance for the design of highly efficient catalysts for CO₂RR-to-syngas.

CO ₂电化学还原为合成气（CO ₂ RR-to-syngas）是一种环境友好且有前景的CO ₂利用技术。然而，用于CO ₂ RR-to-syngas电解的有效催化剂仍然很少。晶体取向调控是提高催化剂活性的重要方法之一，该领域尚缺乏系统研究。在这项工作中，针对 CO ₂的 Cu-M 双金属催化剂 (BMC) 的比较研究RR-to-syngas 使用密度泛函理论 (DFT) 计算来检查晶体取向效应。结果表明，反应势垒在不同的晶体取向上发生了显着变化。Cu (1 1 0) 表面的电位限制步长 (Δ G _PLS ) 的吉布斯自由能变化低于 Cu (1 1 1) 和 Cu (1 0 0) 表面的吉布斯自由能变化。Cu-Pd 催化剂对 HER 的催化活性优于 Cu-Ag、Cu-Ni、Cu-Zn 和 Cu-Cd 催化剂。Cu-Pd催化剂的CO ₂ RR活性优于目前报道的大多数催化剂。Cu-Ni催化剂暴露Cu(1 0        0) 表面是唯一比 HER更受 CO ₂ RR喜爱的催化剂。这项工作为设计用于 CO ₂ RR-to-syngas 的高效催化剂提供了指导。