含S缺陷MoS2的合成及其电化学析氢反应性能研究
Study on synthesis of sulfur-vacancy MoS2 and its electrochemical hydrogen evolution reaction performance
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摘要: 以四硫代钼酸铵和水合肼为原料，通过简单的水热合成与乙醇溶剂热处理相结合的方法制备含S缺陷的MoS2，考查其电化学析氢反应（HER）性能，并利用第一性原理密度泛函理论对其电化学性能进行理论计算，结果表明：S缺陷对MoS2的HER性能具有显著影响，经乙醇溶剂热处理24 h所得样品Eth24h-MoS2的Tafel斜率约为69 mV/dec，达到10 mA/cm2电流密度时其过电位为237 mV，相比原始MoS2均有较大幅度的降低，且具有良好的电化学稳定性；随着S缺陷密度的增加，MoS2的带隙逐渐降低，其导电性改善，缺陷位置和非缺陷位置的H吸附自由能ΔGH均随之迅速降低，且H吸附位点距离S缺陷位置越近，ΔGH越小.Abstract: Using ammonium tetrathiomolybdate and hydrazine hydrate as raw materials,the sulfur-vacancy containing MoS2 was synthesized by simple hydrothermal synthesis combined with subsequent ethanol solvothermal treatment,and its hydrogen evolution reaction (HER) performance was investigated.The electrochemical performance was calculated by first principle density functional theory.The results showed that sulfur-vacancy had obvious effect on HER performance of MoS2.The Tafel slope of the sample Eth24h-MoS2 obtained by ethanol solvothermal treatment for 24 h was 69 mV/dec and the overpotential was 237 mV at current density of 10 mA/cm2,which was significantly lower than that of the original MoS2,and had good electrochemical stability.With the increase of sulfur-vacancy density,the band gap of MoS2 decreased and its conductivity improved.The hydrogen adsorption free energy ΔGH of sulfur-vacancy position and sulfur-vacancy free position decreased rapidly.The closer the hydrogen adsorption site was to the sulfur-vacancy position,the smaller the ΔGH value was.
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