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。采用化学共沉淀法合成了CdIn2S4/ZnIn2S4微球，然后500°C退火得到降解性能更好的CdIn2S4/ZnIn2S4异质结。SEM、XRD、XPS、BET和UV-Vis DRS对样品进行了表征。观察到异质结外貌为球形，具有典型的介孔结构，表面光电流响应和阻抗测试结果显示其活性显著增强。在光催化降解亚甲基蓝的反应中，退火后的CdIn2S4/ZnIn2S4异质结的光催化活性最佳。反应90 min后，亚甲基蓝(MB)的降解率为96.7%。活性的提高可以归因于催化剂对可见光吸收的增强和光生电荷分离效率的提高。对照实验证明，降解体系中产生的活性物种•O2−在降解过程中起关键作用。预测了异质结光催化降解污染物的机制。本研究合成的复合CdIn2S4/ZnIn2S4异质结对制备高效光催化材料具有借鉴意义，并展示了其在降解污染物方面的良好实用性。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℃ to obtain a CdIn2S4/ZnIn2S4 heterojunction that showed greater degradation performances. Characterizations of the samples 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 degradation rate of 96.7%. Enhancement of photocatalytic activity is attributed to the increase of visible light absorption and excellent separation 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.
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Key words:
- photocatalysis /
- CdIn2S4/ZnIn2S4 /
- heterojunction /
- active species /
- reaction mechanism /
- methylene blue
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图 1 ((a)~(f)) 复合材料的SEM图像；(g) CdIn2S4/ZnIn2S4-2的元素面扫图
Figure 1. ((a)-(f)) SEM images of composites; (g) Element surface scanning diagrams of CdIn2S4/ZnIn2S4-2
图 2 (a) CdIn2S4-1、CdIn2S4-2、ZnIn2S4-1、ZnIn2S4-2、CdIn2S4/ZnIn2S4-1和CdIn2S4/ZnIn2S4-2的XRD图谱；(b) CdIn2S4/ZnIn2S4-2的吸附-脱附等温线(插图为粒径分布图)
Figure 2. (a) XRD patterns of CdIn2S4-1, CdIn2S4-2, ZnIn2S4-1, ZnIn2S4-2, CdIn2S4/ZnIn2S4-1 and CdIn2S4/ZnIn2S4-2; (b) Adsorption desorption isotherm of CdIn2S4/ZnIn2S4-2 (Inset is particle size distribution map)
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) 和Tauc 图 (b)
Figure 3. UV-visible diffuse reflection spectra (a) and Tauc plot (b) of CdIn2S4-1, CdIn2S4-2, ZnIn2S4-1, ZnIn2S4-2, CdIn2S4/ZnIn2S4-1 and CdIn2S4/ZnIn2S4-2 composite material
Eg—Band gap energy; h—Planck constant; F(R)—Kubelka-Munk function; v—Frequency
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 spectra 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、CdIn2S4/ZnIn2S4-2复合材料的电化学表征：(a) 表面光电流响应图谱(SPC)；(b) 电化学阻抗图谱(EIS)
Figure 6. Electrochemical characterization of CdIn2S4-2, ZnIn2S4-2 and CdIn2S4/ZnIn2S4-2 composite materials: (a) Surface photocurrent density curves (SPC); (b) Electrochemical impedance spectroscopy (EIS)
Rs—Solution resistance; Rct—Charge transfer resistance; CPE—Constant phase angle element
图 7 (a) 自由基抑制剂的影响；((b), (c)) CdIn2S4/ZnIn2S4-2原位电子顺磁共振(EPR)光谱；(d) 稳定性分析；(e) CdIn2S4/ZnIn2S4-2反应前后XRD图谱；(f) 亚甲基蓝去除率
Figure 7. (a) Effect of free radical inhibitor; ((b), (c)) Electron paramagnetic resonance (EPR) spectra of CdIn2S4/ZnIn2S4-2 in-situ; (d) Stability analysis; (e) XRD patterns of before and after CdIn2S4/ZnIn2S4-2 reaction; (f) Methylene blue removal rate
EDTA-2Na—Ethylenediamine tetraacetic acid disodium salt; BQ—Benzoquinone; TBA—Tertiary butanol; TOC—Total organic carbon
图 8 CdIn2S4/ZnIn2S4-2的光催化反应机制
Figure 8. Photocatalytic reaction mechanism of CdIn2S4/ZnIn2S4-2
CB—Conduction band; VB—Valence band
表 1 CdIn2S4/ZnIn2S4的EDS数据
Table 1. EDS data of CdIn2S4/ZnIn2S4
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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