Sun Yu-Wang, Liu Jing-Yao
Institute of Theoretical Chemistry, College of Chemistry, Jilin University, Changchun 130023, P. R. China.
Phys Chem Chem Phys. 2023 Feb 8;25(6):4773-4779. doi: 10.1039/d2cp04385h.
Electrocatalytic CO reduction is a sustainable strategy to convert CO into valuable carbon products. Atomically dispersed single-atom catalysts (SACs) have great potential as effective electrocatalysts for the CO reduction reaction (CORR). Transition metal dichalcogenides (TMDs) are considered to be a kind of promising SAC supports. In this work, ten different 3d TM single atoms (TM = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu and Zn) embedded in PtS with single S-vacancy (TM-PtS) were designed by density functional theory (DFT) as candidate electrocatalysts for the CORR. Possible reaction pathways of CO reduction to different C products were systematically investigated. The results show that for all these TM-PtS SACs, higher selectivity was achieved for CO reduction to C products than for the competing hydrogen evolution. HCOOH is the most favorable reduction product on PtS-S supported Sc, Ti, V, Cr, Mn, Fe and Cu SACs, while multiple C products are generated on Co-, Ni- and Zn-PtS. In particular, it is found that Sc-, V-, Fe-, Co- and Cu-PtS exhibit higher electrocatalytic performance for the CORR than Cu(211). Therefore, these five SACs are promising CORR electrocatalysts.
电催化CO还原是将CO转化为有价值碳产物的可持续策略。原子分散的单原子催化剂（SACs）作为CO还原反应（CORR）的有效电催化剂具有巨大潜力。过渡金属二硫属化物（TMDs）被认为是一种有前景的SAC载体。在这项工作中，通过密度泛函理论（DFT）设计了十种嵌入具有单个S空位的PtS（TM-PtS）中的不同3d过渡金属单原子（TM = Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu和Zn）作为CORR的候选电催化剂。系统研究了CO还原为不同C产物的可能反应途径。结果表明，对于所有这些TM-PtS SACs，CO还原为C产物的选择性高于竞争性析氢反应。HCOOH是PtS-S负载的Sc、Ti、V、Cr、Mn、Fe和Cu SACs上最有利的还原产物，而Co-PtS、Ni-PtS和Zn-PtS上会生成多种C产物。特别地，发现Sc-PtS、V-PtS、Fe-PtS、Co-PtS和Cu-PtS对CORR表现出比Cu(211)更高的电催化性能。因此，这五种SACs是有前景的CORR电催化剂。
