A Unique Ru-N4-P Coordinated Structure Synergistically Waking Up the Nonmetal P Active Site for Hydrogen Production

Chuanqiang Wu; Shiqing Ding; Daobin Liu; Dongdong Li; Shuangming Chen; Huijuan Wang; Zeming Qi; Binghui Ge; Li Song

doi:10.34133/2020/5860712

A Unique Ru-N₄-P Coordinated Structure Synergistically Waking Up the Nonmetal P Active Site for Hydrogen Production

Research (Wash D C). 2020 Aug 28:2020:5860712. doi: 10.34133/2020/5860712. eCollection 2020.

Authors

Chuanqiang Wu^{1

2}, Shiqing Ding¹, Daobin Liu¹, Dongdong Li³, Shuangming Chen¹, Huijuan Wang⁴, Zeming Qi¹, Binghui Ge², Li Song¹

Affiliations

¹ National Synchrotron Radiation Laboratory, CAS Center for Excellence in Nanoscience, University of Science and Technology of China, Hefei, Anhui 230029, China.
² Institutes of Physical Science and Information Technology, Anhui University, Hefei 230601, China.
³ Institute of Amorphous Matter Science, School of Materials Science and Engineering, Hefei University of Technology, Hefei, Anhui 230009, China.
⁴ Experimental Center of Engineering and Material Science, University of Science and Technology of China, Hefei 230026, China.

Abstract

Numerous experiments have demonstrated that the metal atom is the active center of monoatomic catalysts for hydrogen evolution reaction (HER), while the active sites of nonmetal doped atoms are often neglected. By combining theoretical prediction and experimental verification, we designed a unique ternary Ru-N₄-P coordination structure constructed by monodispersed Ru atoms supported on N,P dual-doped graphene for highly efficient hydrogen evolution in acid solution. The density functional theory calculations indicate that the charge polarization will lead to the most charge accumulation at P atoms, which results in a distinct nonmetallic P active sites with the moderate H∗ adsorption energy. Notably, these P atoms mainly supply highly efficient catalytic sites with ultrasmall absorption energy of 0.007 eV. Correspondingly, the Ru-N₄-P demonstrated outstanding HER performance not only in an acidic condition but also in alkaline environment. Notably, the performance of Ru-NPC catalyst at high current is even superior to the commercial Pt/C catalysts, whether in acidic or alkaline medium. Our in situ synchrotron radiation infrared spectra demonstrate that a P-H_ads intermediate is continually emerging on the Ru-NPC catalyst, actively proving the nonmetallic P catalytically active site in HER that is very different with previously reported metallic sites.