Xu Rui, Ren Jun, Shen Xinyue, Zhu Yuan, Shan Yun, Shi Chuan-Guo
School of Chemistry and Chemical Engineering, Nantong University, Nantong 226019, P. R. China.
Nanjing Key Laboratory of Advanced Functional Materials, Nanjing Xiaozhuang University, Nanjing 211171, P. R. China.
ACS Omega. 2022 May 27;7(22):18826-18833. doi: 10.1021/acsomega.2c01772. eCollection 2022 Jun 7.
Enforcing the bimetallic-interface orbital hybridization in single-atom catalysts (SACs) plays a critical role in determining their catalytic activity. However, the electronic state coupling among interacting sites can be affected by surficial strain, but the relative physical mechanism still needs to be understood. Herein, we propose a series of bimetallic-hybridized SACs with structural strain to disclose their interfacial charge transfer and orbital interaction, in which asymmetric superexchange interaction between adjacent Fe and Ni sites can enforce their electronic state coupling by a structural deformation. As a result, the spin-resolved electronic structure, d-band center, and Gibbs free energy can be changed by external strain, leading to a higher reactive activity. Our findings provide a new insight into understanding the contribution of surface strain to enhancing their catalytic activity.
在单原子催化剂（SACs）中强化双金属界面轨道杂化对于决定其催化活性起着关键作用。然而，相互作用位点之间的电子态耦合会受到表面应变的影响，但其相关物理机制仍有待了解。在此，我们提出了一系列具有结构应变的双金属杂化SACs，以揭示其界面电荷转移和轨道相互作用，其中相邻铁和镍位点之间的不对称超交换相互作用可通过结构变形来强化其电子态耦合。结果，自旋分辨电子结构、d带中心和吉布斯自由能可因外部应变而改变，从而导致更高的反应活性。我们的发现为理解表面应变对增强其催化活性的贡献提供了新的见解。
