Ordered Porous Nitrogen-Doped Carbon Matrix with Atomically Dispersed Cobalt Sites as an Efficient Catalyst for Dehydrogenation and Transfer Hydrogenation of N-Heterocycles

Yunhu Han; Ziyun Wang; Ruirui Xu; Wei Zhang; Wenxing Chen; Lirong Zheng; Jian Zhang; Jun Luo; Konglin Wu; Youqi Zhu; Chen Chen; Qing Peng; Qiang Liu; P Hu; Dingsheng Wang; Yadong Li

doi:10.1002/anie.201805467

Ordered Porous Nitrogen-Doped Carbon Matrix with Atomically Dispersed Cobalt Sites as an Efficient Catalyst for Dehydrogenation and Transfer Hydrogenation of N-Heterocycles

Angew Chem Int Ed Engl. 2018 Aug 27;57(35):11262-11266. doi: 10.1002/anie.201805467. Epub 2018 Aug 1.

Authors

Yunhu Han¹, Ziyun Wang², Ruirui Xu³, Wei Zhang¹, Wenxing Chen¹, Lirong Zheng⁴, Jian Zhang¹, Jun Luo⁵, Konglin Wu¹, Youqi Zhu¹, Chen Chen¹, Qing Peng¹, Qiang Liu¹, P Hu², Dingsheng Wang¹, Yadong Li¹

Affiliations

¹ Department of Chemistry, Tsinghua University, Beijing, 100084, China.
² School of Chemistry and Chemical Engineering, The Queen's University of Belfast, Belfast, BT9 5AG, UK.
³ School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi'an, 710000, China.
⁴ Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing, 100084, China.
⁵ Center for Electron Microscopy, Tianjin University of Technology, Tianjin, 300384, China.

PMID: 29978942
DOI: 10.1002/anie.201805467

Abstract

Single-atom catalysts (SACs) have been explored widely as potential substitutes for homogeneous catalysts. Isolated cobalt single-atom sites were stabilized on an ordered porous nitrogen-doped carbon matrix (ISAS-Co/OPNC). ISAS-Co/OPNC is a highly efficient catalyst for acceptorless dehydrogenation of N-heterocycles to release H₂ . ISAS-Co/OPNC also exhibits excellent catalytic activity for the reverse transfer hydrogenation (or hydrogenation) of N-heterocycles to store H₂ , using formic acid or external hydrogen as a hydrogen source. The catalytic performance of ISAS-Co/OPNC in both reactions surpasses previously reported homogeneous and heterogeneous precious-metal catalysts. The reaction mechanisms are systematically investigated using first-principles calculations and it is suggested that the Eley-Rideal mechanism is dominant.

Keywords: N-doped carbon; atomically dispersed sites; dehydrogenation; hydrogenation; transfer hydrogenation.