MoS2修饰ZnIn2S4微米球复合光催化剂的制备及光催化制氢活性增强研究

doi:10.1016/S1872-2067(17)62981-4

摘要/Abstract

摘要：

开发高效、稳定的半导体光催化材料是太阳能光催化制氢领域的研究热点，ZnIn₂S₄因其合适的能隙、带边电势位置以及稳定、低毒等优点而受到广泛关注.但在实际应用中，单纯的ZnIn₂S₄光催化制氢活性仍较低，主要原因是ZnIn₂S₄受激产生光生电子-空穴对后，载流子的传输、分离效果不理想，易在体相或表面复合；再者是单一的ZnIn₂S₄表面缺少催化反应产氢的活性位点.为提高催化活性，通常在催化剂的表面负载一定量的贵金属作为助催化剂，但由于贵金属成本高和稀缺性，限制了其实际的应用.因此，开发低成本、储量丰富、高效的非贵金属助催化剂来增强ZnIn₂S₄的光催化制氢活性具有显著意义.
最近研究表明，具有层状结构的MoS₂可被作为一种非贵金属助催化剂应用于光催化制氢，且已取得了优异的光催化制氢效果.理论计算得出，暴露在MoS₂边缘的不饱和S原子具有与质子H⁺很强的键合作用，从而使其能够作为活性位点便利地产生氢气.因而将MoS₂负载于ZnIn₂S₄的表面，可进一步提高ZnIn₂S₄的光催化制氢活性.
本文采用二步水热法制备了MoS₂负载于ZnIn₂S₄微球表面的MoS₂/ZnIn₂S₄复合光催化剂.采用X-射线衍射、场发射扫描电子显微镜、透射电子显微镜、X射线光电子能谱、Raman光谱、紫外-可见漫反射吸收光谱、氮气吸附-脱附测试和荧光光谱等技术对所得样品进行了表征.以乳酸作为牺牲试剂考察了MoS₂负载量对光催化制氢活性的影响.结果显示，当MoS₂含量为1 wt%时，MoS₂/ZnIn₂S₄复合光催化剂的光催化产氢活性最高，达343 μmol/h，是单纯ZnIn₂S₄的14.9倍.此外，对1 wt% MoS₂/ZnIn₂S₄样品进行光催化制氢的长效循环测试表明，该样品在可见光下能够保持稳定、有效的光催化制氢性能.据此提出一个可能的增强光催化制氢活性机理：适量的MoS₂可以促进ZnIn₂S₄表面光生载流子的有效传输和分离，从而延长载流子的寿命.

关键词: 复合物, 助催化剂, 光催化产氢, 电荷载流子, 分离

Abstract:

MoS₂/ZnIn₂S₄ composites with MoS₂ anchored on the surface of ZnIn₂S₄ microspheres were synthesized by a two-step hydrothermal process. The obtained samples were characterized by X-ray diffraction, field emission scanning electron microscopy, energy dispersive X-ray spectroscopy, high-resolution transmission electron microscopy, X-ray photoelectron spectroscopy, Raman spectroscopy, ultraviolet-visible diffuse reflectance absorption spectroscopy, nitrogen adsorption-desorption measurements, photoluminescence spectroscopy, and photoelectrochemical tests. The influence of the loading of MoS₂ on the photocatalytic H₂ evolution activity was investigated using lactic acid as a sacrificial reagent. A H₂ evolution rate of 343 μmol/h was achieved under visible light irradiation over the 1 wt% MoS₂/ZnIn₂S₄ composite, corresponding to an apparent quantum efficiency of about 3.85% at 420 nm monochromatic light. The marked improvement of the photocatalytic H₂ evolution activity compared with ZnIn₂S₄ can be ascribed to efficient transfer and separation of photogenerated charge carriers and facilitation of the photocatalytic H₂ evolution reaction at the MoS₂ active sites.

Key words: Composite, Cocatalyst, Photocatalytic hydrogen evolution, Charge carrier, Separation

柴波, 刘纯, 王春蕾, 闫俊涛, 任占冬. MoS₂修饰ZnIn₂S₄微米球复合光催化剂的制备及光催化制氢活性增强研究[J]. 催化学报, 2017, 38(12): 2067-2075.

Bo Chai, Chun Liu, Chunlei Wang, Juntao Yan, Zhandong Ren. Photocatalytic hydrogen evolution activity over MoS₂/ZnIn₂S₄ microspheres[J]. Chinese Journal of Catalysis, 2017, 38(12): 2067-2075.

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MoS₂修饰ZnIn₂S₄微米球复合光催化剂的制备及光催化制氢活性增强研究

Photocatalytic hydrogen evolution activity over MoS₂/ZnIn₂S₄ microspheres

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