In2O3/Ag：ZnIn2S4“Type Ⅱ”型异质结构材料的制备及可见光催化性能

doi:10.11949/0438-1157.20220238

摘要/Abstract

摘要：

采用低温油浴的方法，制备出具有“Type Ⅱ”异质结构的In₂O₃/Ag:ZnIn₂S₄复合材料光催化剂。使用X射线粉末衍射（XRD）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、X射线光电子能谱（XPS）、紫外-可见漫反射光谱（UV-Vis DRS）以及光电化学测试（PEC）等技术对物相、形貌结构、元素化合状态、光响应特性等方面进行探究。在可见光照射下进行光解水制氢和光降解甲基橙（MO）实验来评价光催化剂的光催化活性，结果表明，粉末状光催化剂 In₂O₃/40.0%（质量分数）Ag:ZnIn₂S₄的光催化制氢速率达到 21.85 μmol·h^-1，约是In₂O₃和Ag:ZnIn₂S₄的57.5倍和1.5倍。在可见光下的降解MO实验中，In₂O₃/40.0% Ag:ZnIn₂S₄光降解速率为0.3466 min^-1，分别约是In₂O₃和Ag:ZnIn₂S₄的105倍和2.1倍。这主要归因于In₂O₃和Ag:ZnIn₂S₄之间形成的“Type Ⅱ”异质结构，促使光生载流子的快速迁移和分离。

关键词: 催化剂, 复合材料, 降解, 制氢, ZnIn₂S₄, In₂O₃

Abstract:

The Ag:ZnIn₂S₄nanosheets were grown internal and external surface of hollow In₂O₃microtubes, with the reasonable design and construction of a visible light-responsive In₂O₃/ $A g : Z n I n 2 S 4$ _{tubular heterostructure photocatalysts. The samples were prepared by a low-temperature oil bath method to ensure the uniform distribution of each component. Experimental preparation process: firstly, In(NO₃)₃ and 1,4-benzenedicarboxylic acid were dissolved in N,N-dimethylformamide (DMF) and placed in a low-temperature oil bath to obtain the precursor In-MIL-68. To synthesize the hexagonal In₂O₃ microtubes, In-MIL-68 was placed in a crucible, and then kept at a constant temperature of 500℃ for 2 h in a muffle furnace. Growth of Ag:ZnIn₂S₄ nanosheets on both inner and outer surfaces of In₂O₃microtubes was achieved by a low temperature hydrothermal method. X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), UV-visible diffuse reflection spectroscopy (UV-Vis DRS), and photoelectric chemical analysis (PEC) were used to investigate the phase, morphology, elemental combination state and light response characteristics of photocatalysts. After rigorous comparison and analysis, the optimized In₂O₃/40.0%(mass) $A g : Z n I n 2 S 4$ sample exhibited an excellent rate of H₂production (21.85 μmol·h^-1) under visible light irradiation, which was 57.5 times and 1.5 times higher than that of pure In₂O₃(0.38 μmol·h^-1) and Ag:ZnIn₂S₄(14.79 μmol·h^-1). Simultaneously, in the experiment of MO degradation under visible light irradiation, the photodegradation rate of In₂O₃/40.0% Ag:ZnIn₂S₄ was 0.3466 min^-1, about 105 times and 2.1 times of In₂O₃ (0.0033 min^-1) and Ag:ZnIn₂S₄(0.1669 min^-1), respectively. These improvements are because of synergetic effect of compact heterojunction by unveiling a greater number of catalytically active sites and effectively enhancing charge-carrier separation and relocation. This is mainly attributed to the “Type Ⅱ” heterostructure formed between In₂O₃and Ag:ZnIn₂S₄, which promotes the rapid migration and separation of photogenerated carriers.}

Key words: catalyst, composites, degradation, hydrogen production, ZnIn₂S₄, In₂O₃

中图分类号:

TQ 028.8

徐振和, 李泓江, 高雨, 礼峥, 张含烟, 徐宝彤, 丁茯, 孙亚光. In₂O₃/Ag：ZnIn₂S₄“Type Ⅱ”型异质结构材料的制备及可见光催化性能[J]. 化工学报, 2022, 73(8): 3625-3635.

Zhenhe XU, Hongjiang LI, Yu GAO, Zheng LI, Hanyan ZHANG, Baotong XU, Fu DING, Yaguang SUN. Preparation of In₂O₃/Ag:ZnIn₂S₄ “Type Ⅱ” heterogeneous structure materials for visible light catalysis[J]. CIESC Journal, 2022, 73(8): 3625-3635.

图/表 9

图1 In2O3/Ag:ZnIn2S4复合材料的制备过程

Fig.1 Schematic illustration of the fabrication process of In2O3/Ag:ZnIn2S4 composites

图2 In-MIL-68的SEM图像，In2O3的TEM图像，In2O3/40.0% Ag:ZnIn2S4的TEM、HRTEM、HAADF-STEM图像及元素映射图像和EDS能谱分析

Fig.2 SEM image of In-MIL-68, TEM image of In2O3, TEM, HRTEM, HAADF-STEM image and element mapping image of In2O3/40.0% Ag:ZnIn2S4 and EDS analysis

图3 样品的XRD谱图

Fig.3 XRD patterns of samples

图4 样品的XPS谱图

Fig.4 XPS spectra of samples

图5 样品的紫外-可见漫反射吸收光谱、光学带隙分布和VB XPS谱图

Fig.5 UV-Vis DRS analysis, optical bandgap distribution and VB XPS spectra of samples

图6 样品的光解水制氢性能表征

Fig.6 Characterization of hydrogen production by photocatalytic water splitting

图7 样品的光催化降解MO性能表征

Fig.7 Characterization of photocatalytic degradation of MO

图8 样品的阻抗测试和瞬态光电流响应

Fig.8 Impedance testing and transient photocurrent response of samples

图9 样品的光催化反应机理

Fig.9 Photocatalytic reaction mechanism of samples

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In₂O₃/Ag：ZnIn₂S₄“Type Ⅱ”型异质结构材料的制备及可见光催化性能

Preparation of In₂O₃/Ag:ZnIn₂S₄ “Type Ⅱ” heterogeneous structure materials for visible light catalysis

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