Cu-based catalysts currently offer the most promising route to actively and selectively produce value-added chemicals via electrochemical reduction of CO₂ (eCO₂R); yet further improvements are required for their wide-scale deployment in carbon mitigation efforts. Here, we systematically investigate a family of dilute Cu-based alloys to explore their viability as active and selective catalysts for eCO₂R through a combined theoretical–experimental approach. Using a quantum–classical modeling approach that accounts for dynamic solvation effects, we assess the stability and activity of model single-atom catalysts under eCO₂R conditions. Our calculations identify that the presence of eCO₂R intermediates, such as CO*, H*, and OH*, may dynamically influence the local catalyst surface composition. Additionally, we identify through binding energy descriptors of the CO*, CHO*, and OCCO* dimer intermediates that certain elements, such as group 13 elements (B, Al, and Ga), enhance the selectivity of C₂₊ species relative to pure Cu by facilitating CO dimerization. The theoretical work is corroborated by preliminary testing of eCO₂R activity and selectivity of candidate dilute Cu-based alloy catalyst films prepared by electron beam evaporation in a zero-gap gas diffusion electrode-based reactor. Of all studied alloys, dilute CuAl was found to be the most active and selective toward C₂₊ products like ethylene, consistent with the theoretical predictions. We attribute the improved performance of dilute CuAl alloys to more favorable dimerization reaction energetics of bound CO species relative to that on pure Cu. In a broader context, the results presented here demonstrate the power of our simulation framework in terms of rational catalyst design.

中文翻译：

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评估用于电化学 CO2 还原的稀铜基合金的稳定性和活性

铜基催化剂目前提供了最有前途的途径，通过电化学还原 CO ₂ (eCO ₂ R)主动和选择性地生产增值化学品；然而，它们在碳减排工作中的大规模部署还需要进一步改进。在这里，我们系统地研究了一系列稀释的铜基合金，通过理论-实验相结合的方法探索它们作为 eCO ₂ R 的活性和选择性催化剂的可行性。使用考虑动态溶剂化效应的量子经典建模方法，我们评估了模型单原子催化剂在 eCO ₂ R 条件下的稳定性和活性。我们的计算表明 eCO ₂的存在R 中间体，如 CO*、H* 和 OH*，可能会动态影响局部催化剂表面组成。此外，我们通过 CO*、CHO* 和 OCCO* 二聚体中间体的结合能描述符确定了某些元素，例如第 13 族元素（B、Al 和 Ga），相对于纯元素，增强了 C ₂₊物种的选择性。Cu 通过促进 CO 二聚化。通过在基于零间隙气体扩散电极的反应器中通过电子束蒸发制备的候选稀释 Cu 基合金催化剂薄膜的 eCO ₂ R 活性和选择性的初步测试证实了理论工作。在所有研究的合金中，发现稀释的 CuAl 对 C _{2+ 的}活性和选择性最高乙烯等产物，与理论预测一致。我们将稀释 CuAl 合金的性能改进归因于结合 CO 物种相对于纯 Cu 更有利的二聚反应能量。在更广泛的背景下，此处呈现的结果证明了我们的模拟框架在合理催化剂设计方面的强大功能。