一步水热合成In2S3/CdIn2S4异质结微球及其光催化性能

doi:10.11949/0438-1157.20191475

化工学报 ›› 2020, Vol. 71 ›› Issue (8): 3602-3613.DOI: 10.11949/0438-1157.20191475

• 催化、动力学与反应器 • 上一篇下一篇

一步水热合成In₂S₃/CdIn₂S₄异质结微球及其光催化性能

张开莲¹(),杨凯^1,⁴(),李笑笑¹,梁若雯²,管婕¹,李文强¹,黄健¹,余长林³(),戴文新⁴()

^1.江西理工大学化学化工学院，江西赣州 341000
^2.宁德师范学院绿色能源与环境催化福建省高校重点实验室，福建宁德 352100
^3.广东石油化工学院环境科学与工程学院，广东茂名 525000
^4.福州大学能源与环境光催化国家重点实验室，福建福州 350108

收稿日期:2019-12-05 修回日期:2020-06-02 出版日期:2020-08-05 发布日期:2020-08-05
通讯作者: 杨凯,余长林,戴文新
作者简介:张开莲（1994—），女，硕士研究生，2068058875@qq.com
基金资助:
国家自然科学基金项目(21962006);江西省自然科学基金重点项目(20192ACBL21011);江西理工大学清江优秀人才支持计划项目;江西省自然科学基金项目(20181BAB213010);福州大学国家重点实验室开放基金项目(SKLPEE-KF201712);宁德师范学院绿色能源与环境催化福建省高校重点实验室基金项目(FJ-GEEC201901);广东石油化工学院环境重点实验室开放基金项目(2018B030322017)

One-step hydrothermal synthesis of In₂S₃/CdIn₂S₄ heterojunction microsphere and its photocatalytic performance

Kailian ZHANG¹(),Kai YANG^1,⁴(),Xiaoxiao LI¹,Ruowen LIANG²,Jie GUAN¹,Wenqiang LI¹,Jian HUANG¹,Changlin YU³(),Wenxin DAI⁴()

^1.College of Chemistry and Chemical Engineering, Jiangxi University of Science and Technology, Ganzhou 341000, Jiangxi, China
^2.Key Laboratory of Green Energy and Environment Catalysis, Fujian Province University, Ningde Normal University, Ningde 352100, Fujian, China
^3.School of Environmental and Engineering, Guangdong University of Petrochemical Technology, Maoming 525000, Guangdong, China
^4.State Key Laboratory of Photocatalysis on Energy and Environment, Fuzhou University, Fuzhou 350108，Fujian, China

Received:2019-12-05 Revised:2020-06-02 Online:2020-08-05 Published:2020-08-05
Contact: Kai YANG,Changlin YU,Wenxin DAI

摘要/Abstract

摘要：

利用一步水热法成功制备了In₂S₃/CdIn₂S₄异质结微球催化剂，通过降解甲基橙(MO)、酸性橙Ⅱ(AOⅡ) 和罗丹明B(RhB)来评价所制备催化剂的活性。实验结果表明，In₂S₃/CdIn₂S₄异质结微球对MO、AOⅡ和RhB的光催化降解率分别达到了87%、75%和96%，明显高于催化剂In₂S₃和CdIn₂S₄。瞬态光电流和阻抗测试结果表明，In₂S₃/CdIn₂S₄异质结微球受光激发产生的电子空穴对能快速得到分离。捕获主要活性物种实验表明，该反应体系中主要是超氧自由基和空穴起关键性作用。In₂S₃/CdIn₂S₄异质结微球催化剂重复使用四次，其催化能力依然保持较高水平。In₂S₃/CdIn₂S₄异质结微球活性的增强归因于异质结的形成有助于电子的转移，从而降低了电子空穴对的复合概率。并且合适的能带结构有助于产生大量的光生电子，电子与活性氧的结合最终引起氧化能力的增强。

关键词: In₂S₃/CdIn₂S₄, 一步水热法, 异质结, 降解, 自由基

Abstract:

In₂S₃/CdIn₂S₄ heterojunction microspheres were successfully prepared by one-step hydrothermal method, and then the photocatalytic performances were evaluated by the photocatalytic degradation of MO, AOⅡ and RhB. The consequence presented that the photocatalytic activity of In₂S₃/CdIn₂S₄was significantly higher than those of In₂S₃ and CdIn₂S₄ catalysts, which could decompose 87%中MO, 75% AOⅡ and 96% RhB, respectively. The photogenerated electrons and holes could be separated quickly over In₂S₃/CdIn₂S₄ heterojunction microspheres, drawing a conclusion from transient photocurrent response and impedance test. The experiments captured by the main active radicals showed that the superoxide radicals and holes played a key irreplaceable role in the reaction system. Meanwhile, the stability is still at a high level after four successive cycles over In₂S₃/CdIn₂S₄ heterojunction microspheres. The enhancing activity can attribute to the heterojunction, which can contribute to the electron transfer and conclusively suppress the recombination of the electrons/holes pairs. In addition, a suitable energy band structure helps to generate a large number of photo-generated electrons, and the combination of electrons and active oxygen ultimately leads to the enhancement of oxidation ability.

Key words: In₂S₃/CdIn₂S₄, one-step hydrothermal method, heterojunction, degradation, radicals

中图分类号:

TQ 028.8

张开莲, 杨凯, 李笑笑, 梁若雯, 管婕, 李文强, 黄健, 余长林, 戴文新. 一步水热合成In₂S₃/CdIn₂S₄异质结微球及其光催化性能[J]. 化工学报, 2020, 71(8): 3602-3613.

Kailian ZHANG, Kai YANG, Xiaoxiao LI, Ruowen LIANG, Jie GUAN, Wenqiang LI, Jian HUANG, Changlin YU, Wenxin DAI. One-step hydrothermal synthesis of In₂S₃/CdIn₂S₄ heterojunction microsphere and its photocatalytic performance[J]. CIESC Journal, 2020, 71(8): 3602-3613.

图/表 15

图1 所制备样品的XRD谱图和局部放大图

Fig.1 XRD patterns and magnified patterns of all prepared samples

图2 In2S3、CdIn2S4、In2S3/CdIn2S4的扫描电镜图

Fig.2 SEM images of In2S3，CdIn2S4 and In2S3/CdIn2S4

图3 In2S3、CdIn2S4、In2S3/CdIn2S4的透射电镜图和高分辨透射电镜图

Fig.3 TEM and HRTEM of In2S3,CdIn2S4, In2S3/CdIn2S4

图4 催化剂In2S3/CdIn2S4的元素面扫图

Fig.4 Elemental mapping images of In2S3/CdIn2S4 photocatalyst

图5 N2吸附-脱附等温线和孔径分布曲线

Fig.5 N2 absorption-desorption isotherms and corresponding pore-size distribution curves

表1 样品的比表面积、孔容和孔径

Table 1 Specific surface area, pore volume and pore diameter of samples

样品	比表面积/(m²/g)	孔容/(cm³/g)	孔径/nm
In₂S₃	23.78	0.128	21.53
CdIn₂S₄	7.47	0.055	29.46
In₂S₃/CdIn₂S₄	7.09	0.062	35.22

图6 样品的FT-IR图

Fig.6 FT-IR spectra of samples

图7 CdIn2S4和ln2S3/CdIn2S4异质结的 XPS 谱图

Fig.7 XPS spectra of CdIn2S4 and ln2S3/CdIn2S4 heterojunction

图8 催化剂的紫外-可见漫反射吸收光谱和光学带隙分布

Fig.8 UV-Vis diffuse absorption spectra of all catalysts and optical bandgap distribution

图9 催化剂的光催化性能比较

Fig.9 Comparison of photocatalytic performances over as-prepared productions

图10 催化剂的瞬态光电流响应和阻抗测试

Fig.10 Transient photocurrent response and impedance testing for all catalysts

图11 样品In2S3、CdIn2S4和In2S3/CdIn2S4的PL谱

Fig.11 PL spectra of In2S3, CdIn2S4 and In2S3/CdIn2S4 samples

图12 催化剂In2S3/CdIn2S4稳定性测试

Fig.12 Stability test of In2S3/CdIn2S4 sample

图13 异质结In2S3/CdIn2S4捕获主要活性物种实验

Fig.13 Trapping experiments for major active species over heterojunction In2S3/CdIn2S4

图14 In2S3/CdIn2S4异质结光催化降解污染物机理

Fig.14 Proposed mechanism of enhancement photocatalytic activity over In2S3/CdIn2S4 heterojunction

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一步水热合成In₂S₃/CdIn₂S₄异质结微球及其光催化性能

One-step hydrothermal synthesis of In₂S₃/CdIn₂S₄ heterojunction microsphere and its photocatalytic performance

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Metrics

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