Tailoring the d-Band Centers Enables Co4 N Nanosheets To Be Highly Active for Hydrogen Evolution Catalysis

Zhiyan Chen; Yao Song; Jinyan Cai; Xusheng Zheng; Dongdong Han; Yishang Wu; Yipeng Zang; Shuwen Niu; Yun Liu; Junfa Zhu; Xiaojing Liu; Gongming Wang

doi:10.1002/anie.201801834

Tailoring the d-Band Centers Enables Co₄ N Nanosheets To Be Highly Active for Hydrogen Evolution Catalysis

Angew Chem Int Ed Engl. 2018 Apr 23;57(18):5076-5080. doi: 10.1002/anie.201801834. Epub 2018 Mar 23.

Authors

Zhiyan Chen^{1

2}, Yao Song^{1

2}, Jinyan Cai¹, Xusheng Zheng³, Dongdong Han¹, Yishang Wu^{1

2}, Yipeng Zang¹, Shuwen Niu¹, Yun Liu¹, Junfa Zhu³, Xiaojing Liu¹, Gongming Wang¹

Affiliations

¹ Department of Chemistry, University of Science & Technology of China, Hefei, Anhui, 230026, P. R. China.
² School of Materials Science and Engineering, Central South University of Forestry and Technology, Changsha, 410004, P. R. China.
³ National Synchrotron Radiation Laboratory, University of Science and Technology of China, Hefei, 230029, P. R. China.

PMID: 29498161
DOI: 10.1002/anie.201801834

Abstract

Endowing materials with specific functions that are not readily available is always of great importance, but extremely challenging. Co₄ N, with its beneficial metallic characteristics, has been proved to be highly active for the oxidation of water, while it is notoriously poor for catalyzing the hydrogen evolution reaction (HER), because of its unfavorable d-band energy level. Herein, we successfully endow Co₄ N with prominent HER catalytic capability by tailoring the positions of the d-band center through transition-metal doping. The V-doped Co₄ N nanosheets display an overpotential of 37 mV at 10 mA cm^-2 , which is substantially better than Co₄ N and even close to the benchmark Pt/C catalysts. XANES, UPS, and DFT calculations consistently reveal the enhanced performance is attributed to the downshift of the d-band center, which helps facilitate the H desorption. This concept could provide valuable insights into the design of other catalysts for HER and beyond.

Keywords: Co4N; d band center; heterogeneous catalysis; hydrogen evolution reaction; transition metals.

Publication types

Research Support, Non-U.S. Gov't