Decreasing the coordinated N atoms in a single-atom Cu catalyst to achieve selective transfer hydrogenation of alkynes

Xuge Zhang; He Lin; Jian Zhang; Yajun Qiu; Zedong Zhang; Qi Xu; Ge Meng; Wensheng Yan; Lin Gu; Lirong Zheng; Dingsheng Wang; Yadong Li

doi:10.1039/d1sc04344g

Decreasing the coordinated N atoms in a single-atom Cu catalyst to achieve selective transfer hydrogenation of alkynes

Chem Sci. 2021 Oct 19;12(43):14599-14605. doi: 10.1039/d1sc04344g. eCollection 2021 Nov 10.

Authors

Xuge Zhang^{1

2}, He Lin³, Jian Zhang², Yajun Qiu¹, Zedong Zhang¹, Qi Xu¹, Ge Meng², Wensheng Yan⁴, Lin Gu⁵, Lirong Zheng⁶, Dingsheng Wang¹, Yadong Li¹

Affiliations

¹ Department of Chemistry, Tsinghua University Beijing 100084 China wangdingsheng@mail.tsinghua.edu.cn.
² College of Chemistry and Materials Engineering, Wenzhou University Wenzhou Zhejiang 325035 China zhangjian@wzu.edu.cn.
³ State Key Laboratory of Chemistry and Utilization of Carbon Based Energy Resources, Key Laboratory of Advanced Functional Materials, Autonomous Region, Institute of Applied Chemistry, College of Chemistry, Xinjiang University Urumqi 830046 Xinjiang China.
⁴ National Synchrotron Radiation Laboratory, CAS Center for Excellence in Nanoscience, University of Science and Technology of China Hefei 230029 China.
⁵ Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences Beijing 100190 China.
⁶ Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences Beijing 100049 China.

Abstract

Single-atom (SA) catalysts have attracted broad attention due to their distinctive catalytic properties in diverse reactions. Increasing the unsaturated coordination sites of active centers is a valid and challenging approach to improve the performance of such catalysts. Herein, we report an oxide compounding strategy to decrease the N coordination number of a SA Cu catalyst by reducing the thickness of the N-doped carbon carrier with a lower density of N atoms. The SA Cu catalyst with a more unsaturated N coordination structure can achieve transfer hydrogenation of alkynes with good activity and selectivity, which is disabled over the common N coordinated SA Cu catalyst on pure CN. It is found that individual Cu centers coordinated by fewer N atoms can accelerate the hydrogen transfer from ammonia-borane and still leave proper adsorption sites for alkynes to realize the entire hydrogenation reaction. This work will open up new opportunities to modulate the unsaturated coordination structure of SA catalysts for creating better-performing heterogeneous catalysts.