Shi Jinlei, Yang Fengyuan, Zhao Xingju, Ren Xiaoyan, Tang Yanan, Li Shunfang
College of Physics and Electronic Engineering, Zhengzhou Normal University, Zhengzhou 450044, China.
School of Physics and Microelectronics, Zhengzhou University, Zhengzhou, Henan 450001, China.
Phys Chem Chem Phys. 2024 Jun 12;26(23):16459-16465. doi: 10.1039/d4cp00352g.
Developing high-loading spin-polarized p-block-element-based single-atom catalysts (p-SACs) upon defect-free substrates for various chemical reactions wherein spin selection matters is generally considered a formidable challenge because of the difficulty of creating high densities of underpinning stable defects and the delocalized electronic features of p-block elements. Here our first-principles calculations establish that the defect-free rutile TiO(110) wide-bandgap semiconducting anchoring support can stabilize and localize the wavefunctions of p-block metal elements (Sb and Bi) strong ionic bonding, forming spin-polarized -SACs. Cooperated by the underlying d-block Ti atoms a delicate spin donation-back-donation mechanism, the p-block single-atom reactive center Sb(Bi) exhibits excellent catalysis for spin-triplet O activation and CO oxidation in alignment with Wigner's spin selection rule, with a low rate-limiting reaction barrier of ∼0.6 eV. This work is crucial in establishing high-loading reactive centers of high-performance p-SACs for various important physical processes and chemical reactions, especially wherein the spin degree of freedom matters, , spin catalysis.
在无缺陷衬底上开发用于各种自旋选择起重要作用的化学反应的高负载自旋极化p族元素基单原子催化剂（p-SACs）通常被认为是一项艰巨的挑战，因为难以形成高密度的稳定缺陷以及p族元素的离域电子特性。在此，我们的第一性原理计算表明，无缺陷的金红石型TiO(110)宽带隙半导体锚定载体可以通过强离子键稳定并局域化p族金属元素（Sb和Bi）的波函数，形成自旋极化的-SACs。在底层d族Ti原子的配合下，通过微妙的自旋给予-反馈机制，p族单原子反应中心Sb（Bi）与维格纳自旋选择规则一致，对自旋三重态O活化和CO氧化表现出优异的催化作用，其限速反应势垒低至约0.6 eV。这项工作对于为各种重要物理过程和化学反应建立高性能p-SACs的高负载反应中心至关重要，特别是在自旋自由度起重要作用的情况下，即自旋催化。
