Enhanced Activity of C2N-Supported Single Co Atom Catalyst by Single Atom Promoter

Wenhui Zhong; Guozhen Zhang; Yachao Zhang; Chuanyi Jia; Tongtong Yang; Shentong Ji; Oleg V Prezhdo; Jianyong Yuan; Yi Luo; Jun Jiang

doi:10.1021/acs.jpclett.9b02906

Enhanced Activity of C₂N-Supported Single Co Atom Catalyst by Single Atom Promoter

J Phys Chem Lett. 2019 Nov 21;10(22):7009-7014. doi: 10.1021/acs.jpclett.9b02906. Epub 2019 Nov 1.

Authors

Wenhui Zhong^{1

2}, Guozhen Zhang³, Yachao Zhang², Chuanyi Jia², Tongtong Yang³, Shentong Ji², Oleg V Prezhdo⁴, Jianyong Yuan⁵, Yi Luo³, Jun Jiang³

Affiliations

¹ School of Chemical Engineering , Guizhou Institute of Technology , Guiyang , Guizhou 550003 , China.
² Guizhou Provincial Key Laboratory of Computational Nano-Material Science, Institute of Applied Physics , Guizhou Education University , Guiyang , Guizhou 550018 , China.
³ Hefei National Laboratory for Physical Sciences at the Microscale, iChEM (Collaborative Innovation Center of Chemistry for Energy Materials), CAS Center for Excellence in Nanoscience, School of Chemistry and Materials Science , University of Science and Technology of China Hefei , Anhui 230026 , China.
⁴ Department of Chemistry , University of Southern California , Los Angeles , California 90089 , United States.
⁵ Key Laboratory for Ultrafine Materials of Ministry of Education and Shanghai Key Laboratory of Advanced Polymeric Materials, School of Materials Science and Engineering , East China University of Science and Technology , Shanghai 200237 , China.

PMID: 31660736
DOI: 10.1021/acs.jpclett.9b02906

Abstract

The remarkable chemical activity of metal single-atom catalysts (SACs) lies in their unique electronic states associated with the low-coordination nature of single-atom sites. Yet, electronic state manipulation normally requires direct contact with other atoms, which inevitably changes the low-coordination environment. Herein, we found by first-principle calculations that the activity of a Co SAC for HCOOH dehydrogenation is appreciably enhanced via electronic state manipulation by a noncontact single atom promoter. A Co atom and a Sn/Ge/Pb atom are anchored in the same cavity of a graphitic C₂N monolayer. Surprisingly, the nonbonded promoter makes two far splitting spin states of Co almost degenerate via charge redistribution of C₂N support. Further, the high-spin Co gives a remarkably low reaction barrier comparable to Pt or Pd catalysts. Our results demonstrate that the activity of a SAC can be tuned via a noncontact promoter, casting new insights into electronic state modulation of SACs on graphene-like support.