Abstract
The development of efficient noble-metal-free hydrogen evolution catalysts is quite appealing with the aim of providing cost-competitive hydrogen. Herein, nickel sulfides (NiSx) with tunable NiS/Ni3S4 molar ratios were synthesized via a simple hydrothermal method. Detailed electrochemical studies under neutral conditions indicated that the electrocatalytic property of NiSx catalysts was determined by the composition. Notably, the NiSx sample with the NiS/Ni3S4 molar ratio of 1.0 exhibited the lowest overpotential and charge-transfer resistance. As analyzed from the Tafel plots, the rate-determining step of NiSx catalysts for hydrogen generation was the Volmer step, in which the proton adsorption played a key role. Theoretical calculation revealed that NiS and Ni3S4 exhibited the metallic behaviors with different work functions. Consequently, the NiSx sample with the NiS/Ni3S4 molar ratio of 1.0 owned the most adsorbed protons, which led to the highest electrocatalytic property. Meanwhile, NiSx was demonst...
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