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开发原料丰富、价格低廉且催化性能优异的析氢反应(HER)催化剂代替Pt基催化剂，对于水分解制氢产业具有非常重要的意义。以廉价的四水合钼酸铵((NH4)_6Mo_7O24·4H_2O)、硫脲(CH_4N_2S)、六水合硝酸锌(Zn(NO3)2·6H_2O)以及葡萄糖(C_6H12O6)为原料，采用常规的水热法成功地制备了具有片状形貌的Zn掺杂1T/2H-Zn@MoS2复合物。采用了X射线衍射仪(XRD)、Raman光谱仪、扫描电子显微镜(SEM)、X射线光电子能谱仪(XPS)对制备的样品进行了详细的表征分析。实验结果表明，Zn掺杂量能够影响MoS2相结构的变化，当Zn与Mo的物质的量之比为1∶500时，制备的MoS2中无ZnS相，而此时Zn原子取代了MoS2中Mo原子的位置。Zn原子的取代使MoS2产生了结构缺陷，活化了1T-MoS2面内活性位点，提高了活性位点密度。实验结果也表明，Zn原子作为电子给体，促使了1T/2H-Zn@MoS2中MoS2的2H相向1T相的转变，使得1T相的占比率提高到了38.6%。因此，1T/2H-Zn@MoS2的HER性能得到了显著增强，在质量浓度0.5 mol/L的H_2SO4溶液中，仅需178.6 mV的过电位就可达到10 mA·cm-2的电流密度，并展现了良好的稳定性。
Abstract：It is of great significance to develop hydrogen evolution reaction(HER) catalysts with abundant raw materials, low price and excellent catalytic performance instead of Pt-based catalysts for hydrogen production by water decomposition. With cheap ammonium molybdate tetrahydrate((NH4)_6Mo_7O24·4H_2O), thiourea(CH_4N_2S), zinc nitrate hexahydrate(Zn(NO3)2·6H_2O) and glucose(C_6H12O6) as raw materials, Zn-doped 1T/2H-Zn@MoS2 composites with flake-like morphology were successfully prepared by conventional hydrothermal method. The prepared samples were characterized and analyzed in detail by X-ray diffractometer(XRD), Raman spectrometer, scanning electron microscope(SEM) and X-ray photoelectron spectrometer(XPS). The experimental results show that the amount of Zn doping can affect the change of the phase structure of MoS2. When the molar ratio of Zn to Mo is 1∶500, there is no ZnS phase in the prepared MoS2. Meanwhile, the Zn atom replaces the position of Mo atom in MoS2, which creates structural defects in MoS2, activates the in-plane active sites of 1T-MoS2 and increases the active site density. The experimental results also show that as electron donors, Zn atoms promote the transformation of the 2H phase to the 1T phase of MoS2 in 1T/2H-Zn@MoS2, which increases the proportion of the 1T phase to 38.6%. Therefore, the HER performance of 1T/2H-Zn@MoS2 is significantly enhanced. In H_2SO4 solution with a mass concentration of 0.5 mol/L, the current density of 10 mA·cm-2 can be reached at only 178.6 mV overpotential, showing good stability.
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基本信息:
DOI：10.13250/j.cnki.wndz.2023.07.007
中图分类号:TQ116.2;TQ426
引用信息:
[1]李季,郑俊鹏,黄启玉,等.Zn掺杂1T/2H-Zn@MoS_2复合材料的制备及其电催化析氢反应性能[J].微纳电子技术,2023,60(07):1037-1046.DOI:10.13250/j.cnki.wndz.2023.07.007.
基金信息:
黔南民族师范学院校级资助项目(2020qnsyzd01,QNYSKYPT2018005);黔南民族师范学院大学创新创业项目(202110670004,202110670006,202210670014); 中国石油化工股份有限公司项目(G6001-21-ZS-0408)
2023-07-15
2023-07-15