Li Xiaojiao, Jiang Liyun, Zhou Yilei, Yu Qi
School of Materials Science and Engineering, and Shaanxi Laboratory of Catalysis, Shaanxi University of Technology, Hanzhong 723001, China.
Department of Chemistry and Key Laboratory of Organic Optoelectronics & Molecular Engineering of Ministry of Education, Tsinghua University, Beijing 100084, China.
Langmuir. 2024 Jul 15. doi: 10.1021/acs.langmuir.4c01246.
In recent years, single-atom alloy catalysts (SAAs) have received much attention due to the combination of structural features of both single-atom and alloy catalysts, as well as their efficient catalytic activity, high selectivity, and high stability in various chemical reactions. In this work, we designed a series of Cu-based SAAs by doping isolated 3d transition metal (TM) atoms on the surface of Cu(111) (TM = Fe, Co, Ru, Rh, Os and Ir), in which Ir/Cu(111) SAAs are considered to be the most stable among 3d-series SAAs due to their optimal binding energy (). The density of states of SAAs have been systematically investigated to further discuss structural properties. Based on density functional theory calculations, the activity and selectivity of Ir/Cu(111) SAAs are investigated for electrocatalytic CO reduction reaction (CORR). The initial hydrogenation of CO on Ir/Cu(111) SAAs can form *CO intermediates, which will be further to CH production by the pathway of *CO → *CHO → *CHOH → *CHOH → *CH → *CH → CH. This study provides theoretical insights for the rational design of selective Cu-based monatomic alloy catalysts.
近年来，单原子合金催化剂（SAA）因其兼具单原子催化剂和合金催化剂的结构特点，以及在各种化学反应中具有高效的催化活性、高选择性和高稳定性而备受关注。在本工作中，我们通过在Cu(111)表面掺杂孤立的3d过渡金属（TM）原子（TM = Fe、Co、Ru、Rh、Os和Ir）设计了一系列铜基SAA，其中Ir/Cu(111) SAA因其最佳结合能被认为是3d系列SAA中最稳定的。对SAA的态密度进行了系统研究以进一步讨论其结构性质。基于密度泛函理论计算，研究了Ir/Cu(111) SAA对电催化CO还原反应（CORR）的活性和选择性。CO在Ir/Cu(111) SAA上的初始氢化可形成CO中间体，其将通过CO→*CHO→*CHOH→*CHOH→*CH→*CH→CH的途径进一步生成CH。本研究为选择性铜基单原子合金催化剂的合理设计提供了理论见解。
