Asymmetric coordination effect is an important concept in heterogeneous catalysis where both catalytic activity and product selectivity are serious influenced. However, this effect has rarely been understood because of the difficult in characterizing detailed coordination information. Here, by employing a theoretical study on electrocatalytic CO₂ reduction reaction (ECO₂RR) towards HCOOH over Ti₃C₂O₂-based NS/NN co-coordinated transition metal single atom catalysts (TM-NS/NN-Ti₃C₂O₂ SACs), we show that asymmetric coordination environments have great impact on the electronic structure of the active center. Both electron transferring ability and spin polarization of the active center are vital to optimize the adsorption and hydrogenation of key intermediates. As a result, both catalytic activity and product selectivity can be maximized. V-NN-Ti₃C₂O₂ are predicted to promote high-throughput HCOOH generation process at operation applied potential of −0.32 with considerable electrochemical stability, surpassing most reported catalysts. This work demonstrates V-NN-Ti₃C₂O₂ as high-performance ECO₂RR catalysts, and highlights that the introduction of the concept of asymmetric coordination effect may offer a new insight into the rational design of more efficient SACs.

不对称配位效应是多相催化中的一个重要概念，它严重影响催化活性和产物选择性。然而，由于难以描述详细的协调信息，这种效应很少被理解。在此，通过对Ti ₃ C ₂ O ₂基NS/NN共配位过渡金属单原子催化剂（TM-NS/NN-Ti ₃ C ）上电催化CO ₂还原反应（ECO ₂ RR）生成HCOOH的理论研究₂ O ₂ SACs），我们表明不对称配位环境对活性中心的电子结构有很大影响。活性中心的电子转移能力和自旋极化对于优化关键中间体的吸附和氢化至关重要。因此，催化活性和产物选择性都可以最大化。 V-NN-Ti ₃ C ₂ O ₂预计可在-0.32的操作施加电位下促进高通量HCOOH生成过程，并具有相当大的电化学稳定性，超过大多数报道的催化剂。这项工作证明了V-NN-Ti ₃ C ₂ O ₂作为高性能ECO ₂ RR催化剂，并强调引入不对称配位效应概念可能为更高效SAC的合理设计提供新的见解。