Wang Yueyang, Ren Xiaoyan, Jiang Bojie, Deng Meng, Zhao Xingju, Pang Rui, Li S F
School of Physics and Microelectronics, Zhengzhou University, Zhengzhou 450001, China.
J Phys Chem Lett. 2022 Jul 14;13(27):6367-6375. doi: 10.1021/acs.jpclett.2c01605. Epub 2022 Jul 7.
Magnetic single-atom catalysts (MSAC), due to the intrinsic spin degree of freedom, are of particular importance relative to other conventional SAC for applications in various catalytic processes, especially in those cases that involve spin-triplet O. However, the bottleneck issue in this field is the clustering of the SAC during the processes. Here using first-principles calculations we predict that Mn atoms can be readily confined in the interface of the porous g-CN/CeO(111) heterostructure, forming high-performance MSAC for O activation via a delicate synergetic mechanism of charge transfer, mainly provided by the p-block g-CN overlayer mediated by the d-block Mn active site, and spin selection, preserved mainly through active participation of the f-block Ce atoms and/or g-CN, which effectively promotes the CO oxidization. Such a recipe is also demonstrated to be valid for V- and Nb-MSACs, which may shed new light on the design of highly efficient MSACs for various important chemical processes wherein spin-selection matters.
磁性单原子催化剂（MSAC）由于其固有的自旋自由度，相对于其他传统单原子催化剂在各种催化过程中具有特别重要的意义，尤其是在涉及自旋三重态氧的情况下。然而，该领域的瓶颈问题是在过程中单原子催化剂的聚集。在此，我们通过第一性原理计算预测，锰原子可以很容易地被限制在多孔g-CN/CeO(111)异质结构的界面中，通过一种微妙的电荷转移协同机制形成用于氧活化的高性能MSAC，主要由d块锰活性位点介导的p块g-CN覆盖层提供电荷转移，以及主要通过f块铈原子和/或g-CN的积极参与来保持自旋选择，这有效地促进了CO氧化。这种方法也被证明对V-和Nb-MSAC有效，这可能为设计用于各种重要化学过程的高效MSAC提供新的思路，其中自旋选择很重要。
