近日，中国科学技术大学刘进勋团队报道了富电子亚纳米Cu簇促进CO-CO在CO₂电还原中的耦合。相关论文于2026年1月22日发表在《美国化学会志》上。

负载于功能基底上的亚纳米铜簇，已成为电化学二氧化碳还原制备多碳产物的理想催化剂，但其优异碳碳耦合活性的机理起源尚不明确。

研究组结合机器学习加速的大正则蒙特卡洛采样与大正则密度泛函理论，揭示了石墨相氮化碳负载的Cu₈簇如何促进一氧化碳二聚化过程。在逐渐负移的电势下，一氧化碳吸附在热力学上更有利，而甲酸盐吸附受到抑制，从而同时提升了碳碳键形成的内在反应活性与统计可能性。相较于扩展的Cu(100)表面，Cu₈簇通过纯粹的顶位吸附CO表现出更低的CO-CO耦合能垒，这主要归因于其配位不饱和的铜原子会引起更大的零点电势正向位移，并积累更多过剩电子电荷。

这些因素通过场-偶极耦合作用增强Cu-OCCO轨道杂化，并借助强静电相互作用稳定OCCO中间体。尽管部分亚稳态Cu₈异构体本身具有催化活性，但在实际工况下，因具有更高分布概率与更优动力学特性，CO饱和的全局能量最低构型Cu₈(CO)₁₅物种占据主导。该研究结果揭示了电子结构与簇几何构型在调控电子转移与中间体稳定过程中的关键作用，为跨电催化平台提升高价值产物生成效率提供了普适性设计原则。

附：英文原文

Title: Electron-Rich Subnanometer Cu Clusters Facilitate CO–CO Coupling in CO2 Electroreduction

Author: Jinze Zhu, Jia-Lan Chen, Xin-Ze Qi, Jian-Wen Zhao, Xue-Chun Jiang, Wei-Xue Li, Jin-Xun Liu

Issue&Volume: January 22, 2026

Abstract: Subnanometer copper clusters supported on functional substrates have emerged as promising catalysts for electrochemical CO2 reduction (eCO2RR) to multicarbon (C2+) products. However, the mechanistic origin of their superior C–C coupling activity remains elusive. Here, we combine machine learning–accelerated grand canonical Monte Carlo sampling with grand canonical density functional theory to reveal how the electronic and structural features of the g-C3N4-supported Cu8 cluster promote CO–CO dimerization. Under increasingly negative potentials, CO adsorption is thermodynamically favored, whereas formate adsorption is suppressed, increasing both the intrinsic reactivity and the statistical likelihood of C–C bond formation. Relative to an extended Cu(100) surface, Cu8 clusters exhibit lower CO–CO coupling barriers via purely top-bound CO adsorption. This is driven by their undercoordinated Cu atoms, which incur a larger positive shift in the potential of zero charge (UPZC) and accumulate more excess electronic charge. These factors enhance Cu–OCCO orbital hybridization and stabilize the OCCO intermediate through strong electrostatic interactions induced by field–dipole coupling. Although some metastable Cu8 isomers are intrinsically active, CO-saturated global-minimum Cu8(CO)15 species dominate under operating conditions because of their high population and favorable kinetics. Our findings highlight the critical roles of the electronic structure and cluster geometry in mediating electron transfer and intermediate stabilization, yielding transferable design rules to enhance valuable-product formation across electrocatalytic platforms.

DOI: 10.1021/jacs.5c12495

Source: https://pubs.acs.org/doi/abs/10.1021/jacs.5c12495