非贵金属单原子催化剂Ni_(1)/MoS_(2)的电子结构及CO_(2)还原电催化性能  

Theoretical studies of non-noble metal single-atom catalyst Ni1/MoS_(2):Electronic structure and electrocatalytic CO_(2) reduction

作　　者：于琦 Qi Yu(School of Materials Science and Engineering,Shaanxi Laboratory of Catalysis,Shaanxi University of Technology,Hanzhong 723001,China)

机构地区：[1]School of Materials Science and Engineering,Shaanxi Laboratory of Catalysis,Shaanxi University of Technology,Hanzhong 723001,China

出　　处：《Science China Materials》2023年第3期1079-1088,共10页中国科学（材料科学（英文版）

基　　金：supported by the National Natural Science Foundation of China(92061109;the Natural Science Basic Research Program of Shaanxi(2021JCW-20 and S2020-JC-WT-0001);the Open Project Program of Fujian Key Laboratory of Functional Marine Sensing Materials(MJUKF-FMSM202002);Guangdong Provincial Key Laboratory of Catalysis(2020B121201002).

摘　　要：单原子催化剂(SACs)因其在化学反应中具有高选择性及催化活性,近年来在多相催化领域已引起广泛关注.本文采用第一性原理理论计算,对MoS_(2)负载的非贵金属SACs进行计算化学筛选,考察了3d金属单原子(M=Sc,Ti,V,Cr,Mn,Fe,Co,Ni,Cu,Zn)负载的SACs的稳定性我们发现,Ni_(1)/MoS_(2)催化剂具有最佳的结合能,在此3d系列催化剂结构中最稳定.为分析SACs的稳定性与成键作用,本文系统地研究了Ni_(1)/MoS_(2)的电子结构,包括使用自旋密度、电荷密度差分(CDD)、电子局域化函数(ELF)、能带结构、态密度(DOS)以及局部晶体轨道哈密顿量(COHP).此外,还应用分子中原子的固态量子理论(QTAIM)进一步表征了Ni–S、Ni–Mo及Mo–S键的共价性与离子性.此外,为研究Ni_(1)/MoS_(2)的电催化应用,对CO_(2)还原反应(CO_(2)RR)制甲醇的反应机理与路径进行了分析.计算表明,Ni_(1)/MoS_(2)对于CO_(2)RR具有较高的催化活性本文为MoS_(2)基功能材料高效SACs的设计提供了理论依据.Single-atom catalysts(SACs) have aroused significant interest in heterogeneous catalysis in recent years because of their high catalytic selectivity and tunable activity in various chemical reactions. Herein, non-noble metal SACs with 3d-series metal single atoms(M1)(M = Sc, Ti, V, Cr, Mn,Fe, Co, Ni, Cu, Zn) supported on MoS_(2)are computationally screened by using first-principles quantum-chemical theory.The Ni_(1)/MoS_(2)catalyst is found to be the most stable among those 3d-series SACs due to the optimal binding energy. In order to provide a fundamental understanding of the intrinsic stability and bonding interaction between the metal single atoms and MoS_(2)support, the electronic structure, including the spin density populations, charge density difference(CDD),electron localization function(ELF), band structure, density of states(DOS), and crystal orbital Hamiltonian populations(COHP) are systematically examined. The solid-state quantum theory of atoms in molecules(QTAIM) is also applied to further characterize the Ni–S and Mo–S covalent and ionic bonding nature between the metal single atoms and support.It is found that in addition to Ni–S bonding, there exists significant Ni–Mo bonding that is critical for the electronic structure, stability, and catalytic properties of Ni_(1)/MoS_(2)catalyst. As a typical application of this Ni_(1)/MoS_(2)catalyst, the electrocatalytic mechanism and reaction pathway of CO_(2)reduction reaction(CO_(2)RR) on Ni_(1)/MoS_(2)catalyst have been investigated. The MoS_(2)-supported Ni single atoms are found to exhibit high catalytic activity for CO_(2)RR to methanol. The calculational results provide theoretical insights towards the design of highly efficient SACs on MoS_(2)-based functional materials.

关 键 词：单原子催化剂 哈密顿量 第一性原理 量子理论 自旋密度 催化剂结构 多相催化 共价性 

分 类 号：O643.36[理学—物理化学]