Abstract：
Small Cu clusters are excellent candidates for the electrocatalytic reduction of carbon dioxide (CO2RR), and their catalytic performance is expected to be significantly influenced by the interaction between the substrate and cluster. In this study, we systematically investigate the CO2RR for a Cu3 cluster anchored on Janus MoSX (X = Se, Te) substrates using density functional theory calculations. These substrates feature a broken vertical mirror symmetry, which generates spontaneous out-of-plane polarization and offers two distinct polar surfaces to support the Cu3 cluster. Our findings reveal that the CO2RR performance on the Cu3 cluster is strongly influenced by the polarization direction and strength of the MoSX (X = Se, Te) substrates. Notably, the Cu3 cluster supported on the S-terminated MoSTe surface (Cu3(S)@MoSTe) demonstrates the highest CO2RR activity, producing methane. These results underscore the pivotal role of substrate polarization in modulating the binding strength of reactants and reaction intermediates, thereby enhancing the CO2RR efficiency.
摘要：
小Cu团簇是二氧化碳（CO2RR）电催化还原的优秀候选物，它们的催化性能预计会受到底物和团簇之间相互作用的显著影响。在这项研究中,我们系统地研究了锚定在JanusMoSX上的Cu3簇的CO2RR(X=Se，Te)使用密度泛函理论计算的基底。这些基板的特征是破碎的垂直镜像对称，它产生自发的面外极化，并提供两个不同的极性表面来支持Cu3团簇。我们的发现表明，Cu3团簇上的CO2RR性能受MoSX的极化方向和强度的强烈影响（X=Se，Te)基底。值得注意的是,S终止的MoSTe表面上支持的Cu3簇（Cu3（S）@MoSTe）显示出最高的CO2RR活性，产生甲烷。这些结果强调了底物极化在调节反应物和反应中间体的结合强度方面的关键作用。从而提高CO2RR效率。
