Electron density modulation of NiCo<sub>2</sub>S<sub>4</sub> nanowires by nitrogen incorporation for highly efficient hydrogen evolution catalysis.

Wu, Yishang; Liu, Xiaojing; Han, Dongdong; Song, Xianyin; Shi, Lei; Song, Yao; Niu, Shuwen; Xie, Yufang et al. · Nat Commun · 2018

basic_science · Level V

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Abstract

Metal sulfides for hydrogen evolution catalysis typically suffer from unfavorable hydrogen desorption properties due to the strong interaction between the adsorbed H and the intensely electronegative sulfur. Here, we demonstrate a general strategy to improve the hydrogen evolution catalysis of metal sulfides by modulating the surface electron densities. The N modulated NiCo<sub>2</sub>S<sub>4</sub> nanowire arrays exhibit an overpotential of 41 mV at 10 mA cm<sup>-2</sup> and a Tafel slope of 37 mV dec<sup>-1</sup>, which are very close to the performance of the benchmark Pt/C in alkaline condition. X-ray photoelectron spectroscopy, synchrotron-based X-ray absorption spectroscopy, and density functional theory studies consistently confirm the surface electron densities of NiCo<sub>2</sub>S<sub>4</sub> have been effectively manipulated by N doping. The capability to modulate the electron densities of the catalytic sites could provide valuable insights for the rational design of highly efficient catalysts for hydrogen evolution and beyond.