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Efficient and Robust Hydrogen Evolution: Phosphorus Nitride Imide Nanotubes as Supports for Anchoring Single Ruthenium Sites
Author(s) -
Yang Jian,
Chen Bingxu,
Liu Xiaokang,
Liu Wei,
Li Zhijun,
Dong Juncai,
Chen Wenxing,
Yan Wensheng,
Yao Tao,
Duan Xuezhi,
Wu Yuen,
Li Yadong
Publication year - 2018
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201804854
Subject(s) - overpotential , ruthenium , tafel equation , materials science , density functional theory , catalysis , chemistry , computational chemistry , electrochemistry , organic chemistry , electrode
Amorphous phosphorus nitride imide nanotubes (HPN) are reported as a novel substrate to stabilize materials containing single‐metal sites. Abundant dangling unsaturated P vacancies play a role in stabilization. Ruthenium single atoms (SAs) are successfully anchored by strong coordination interactions between the d orbitals of Ru and the lone pair electrons of N located in the HPN matrix. The atomic dispersion of Ru atoms can be distinguished by X‐ray absorption fine structure measurements and spherical aberration correction electron microscopy. Importantly, Ru SAs@PN is an excellent electrocatalyst for the hydrogen evolution reaction (HER) in 0.5 m H 2 SO 4 , delivering a low overpotential of 24 mV at 10 mA cm −2 and a Tafel slope of 38 mV dec −1 . The catalyst exhibits robust stability in a constant current test at a large current density of 162 mA cm −2 for more than 24 hours, and is operative for 5000 cycles in a cyclic voltammetry test. Additionally, Ru SAs@PN presents a turnover frequency (TOF) of 1.67 H 2 s −1 at 25 mV, and 4.29 H 2 s −1 at 50 mV, in 0.5 m H 2 SO 4 solution, outperforming most of the reported hydrogen evolution catalysts. Density functional theory (DFT) calculations further demonstrate that the Gibbs free energy of adsorbed H* over the Ru SAs on PN is much closer to zero compared with the Ru/C and Ru SAs supported on carbon and C 3 N 4 , thus considerably facilitating the overall HER performance.