Preparation and Photocatalytic Properties of Novel Composite CdIn2S4/ZnIn2S4 Heterojunction
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摘要:
探索高效、稳定的光催化剂是实现实用化太阳能光催化降解污染物的永恒追求。具有二维超薄层状结构的ZnIn2S4表现出优异的性能，不仅具有高能带结构，而且还具有优异的光学性质。此外，ZnIn2S4的制备简单，超薄的ZnIn2S4可以很容易地附着在半导体表面。然而，由于光催化时ZnIn2S4具有较高的电荷复合效率，导致活性很低。半导体之间结合构建异质结的方法可以有效抑制光生电荷的复合。例如，具有层次化的CdIn2S4/石墨烯纳米异质结构已经被制备成作为太阳能制氢的光催化剂。因此，构建异质结是减少光生电荷复合的一种有效途径。本文采用一种简便的无模板化学共沉淀法在160°C下制备了CdIn2S4/ZnIn2S4-1,然后在500°C经管式炉退火得到CdIn2S4/ZnIn2S4-2。以亚甲基蓝为污染物，研究了异质结材料在可见光下的光催化性能,可见光光源下对亚甲基蓝90min降解率为96.7%。为了研究电子-空穴对的分离和迁移，还进行了暂态光电流响应测试和电化学阻抗谱(EIS)测试了光电化学性质。最后，根据自由基淬灭实验结果提出了可能的降解机制。 (a)不同材料在可见光照射下的光催化降解曲线, (b) CdIn2S4/ZnIn2S4-2降解亚甲基蓝的UV-Vis光谱随光照时间的变化 Abstract: Exploring efficient and stable photocatalysts is an ongoing pursuit in effective solar photocatalytic degradation of pollutants. Through a chemical coprecipitation method, CdIn2S4/ZnIn2S4 microspheres were synthesized and then further annealed at 500°C to obtain a CdIn2S4/ZnIn2S4 heterojunction that showed greater degradation performances. Characterization of the sample through SEM, XRD, XPS, BET and UV-Vis DRS determined that the heterojunction had the spherical appearance and typical mesoporous structure. The surface photocurrent response and EIS showed significantly enhanced catalytic activity. CdIn2S4/ZnIn2S4 heterojunction catalysts displayed the best photocatalytic activity in the degradation of methylene blue (MB) after 90 min of illumination, yielding a 96.7% degradation rate. Enhancement of photocatalytic activity is attributed to the increase of visible light absorption and excellent separation of ability of h+-e- pair. A control experiment revealed that the active species ·O2- played a significant role in the degradation process. Based on these findings, a mechanism for the photocatalytic degradation of pollutants via CdIn2S4/ZnIn2S4 heterojunction was predicted. The composite CdIn2S4/ZnIn2S4 heterojunction synthesized in this study has reference significance for the preparation of high-efficient photocatalytic materials, and shows its good practicability in the degradation of pollutants.-
Key words:
- photocatalysis /
- CdIn2S4/ZnIn2S4 /
- heterojunction /
- active species /
- reaction mechanism /
- methylene blue
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图 1 (a)-(f)材料SEM图；(g)CdIn2S4/ZnIn2S4-2的元素面扫图
Figure 1. (a)-(f) Material SEM diagram; (g) Element surface scanning diagram of CdIn2S4/ZnIn2S4-2
图 2 (a)X射线衍射谱图，(b)CdIn2S4/ZnIn2S4-2的吸附-脱附等温线
Figure 2. (a)X-ray diffraction spectrum，(b)Adsorption desorption isotherm of CdIn2S4/ZnIn2S4-2
图 3 CdIn2S4-1、CdIn2S4-2、ZnIn2S4-1、ZnIn2S4-2、CdIn2S4/ZnIn2S4-1和CdIn2S4/ZnIn2S4-2复合材料的紫外-可见漫反射光谱(a)，Tanc plot (b)
Figure 3. (a) UV-visible diffuse reflection spectrum, (b) Tanc plot of CdIn2S4-1、CdIn2S4-2、ZnIn2S4-1、ZnIn2S4-2、CdIn2S4/ZnIn2S4-1 and CdIn2S4/ZnIn2S4-2 composite material
图 5 (a)不同材料在可见光照射下的光催化降解曲线, (b)CdIn2S4/ZnIn2S4-2降解 MB的UV-Vis光谱随光照时间的变化, (c) 不同材料光催化降解MB的动力学(C0和C分别为污染物的初始浓度和降解反应过程中某时刻的浓度), (d)相应的反应常数k
Figure 5. (a) Photocatalytic degradation curve of different materials under visible light irradiation, (b) UV Vis spectrum of CdIn2S4/ZnIn2S4-2 degrading MB changes with light time, (c) kinetics of photocatalytic degradation of MB by different materials (C0 and C are the initial concentration of pollutants and the concentration at a certain time during the degradation reaction) (d) corresponding reaction constant k
图 6 CdIn2S4-2、ZnIn2S4-2、和CdIn2S4/ZnIn2S4-2复合材料的电化学表征: (a)SPC, (b)EIS
Figure 6. Electrochemical Characterization of CdIn2S4-2、ZnIn2S4-2 and CdIn2S4/ZnIn2S4-2 composite material (a)SPC, (b)EIS
图 7 (a)自由基抑制剂的影响，(b)和(c)CdIn2S4/ZnIn2S4-2原位EPR光谱,(d)稳定性分析，(e)CdIn2S4/ZnIn2S4-2反应前后XRD;(f)亚甲基蓝去除率Fig. 7(a) Effect of free radical inhibitor, (b) and (c) CdIn2S4/ZnIn2S4-2 in-situ EPR spectrum, (d) stability analysis, (e) XRD before and after CdIn2S4/ZnIn2S4-2 reaction; (f) Methylene blue removal rate
图 8 CdIn2S4/ZnIn2S4-2的光催化反应机制
Figure 8. Photocatalytic reaction mechanism of CdIn2S4/ZnIn2S4-2
表 1 CdIn2S4/ZnIn2S4 EDS能谱
Table 1. CdIn2S4/ZnIn2S4 EDS
Atonic Cd Zn In S CdIn2S4/ZnIn2S4-1 9.94% 3.93% 55.19% 30.94% CdIn2S4/ZnIn2S4-2 10.06% 3.84% 55.18% 30.92% 
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