具有可见光增强芬顿活性的II型2D/2D Cu2ZnSnS4/Bi2WO6异质结

引用本文: 郭莉, 张开来, 韩宣宣, 赵强, 张媛媛, 戚勉, 王丹军, 付峰. 具有可见光增强芬顿活性的II型2D/2D Cu₂ZnSnS₄/Bi₂WO₆异质结[J]. 催化学报, 2020, 41(3): 503-513. doi: S1872-2067(19)63524-2 shu

Citation: Li Guo, Kailai Zhang, Xuanxuan Han, Qiang Zhao, Yuanyuan Zhang, Mian Qi, Danjun Wang, Feng Fu. 2D/2D type-II Cu₂ZnSnS₄/Bi₂WO₆ heterojunctions to promote visible-light-driven photo-Fenton catalytic activity[J]. Chinese Journal of Catalysis, 2020, 41(3): 503-513. doi: S1872-2067(19)63524-2 shu

具有可见光增强芬顿活性的II型2D/2D Cu₂ZnSnS₄/Bi₂WO₆异质结

延安大学化学与化工学院, 陕西省化学反应工程重点实验室, 陕西延安 716000
基金项目:
国家自然科学基金（21663030，21666039）；北京化工大学有机-无机复合材料国家重点实验室开放项目（oic-201901009）；陕西省科技厅（2018TSCXL-NY-02-01，2013K11-08，2013SZS20-P01）；延安市科技局工业攻关项目（2018KG-04）；延安大学研究生创新项目（YCX201988）.

摘要: 高级氧化工艺（AOPs）是一种处理有机污染物的极具吸引力的技术.大量的前期研究工作集中在通过芬顿反应（Fenton）降解有机污染物.然而，芬顿反应需要在酸性条件下进行，必须在其过程中进行预处理.同时，反应后产生的含铁污泥需要进一步处理以满足排放要求，从而限制了芬顿反应的发展.作为另一种AOPs，光催化技术因反应条件温和、操作简单和选择性好等优点受到广泛关注.研究表明，各种铁基和铜半导体光催化材料形成光-芬顿（Photo-Fenton）系统，可有效解决芬顿反应中高价金属离子/低价金属离子的循环问题.为了充分利用芬顿氧化技术和光催化氧化技术在降解有机污染物方面的各自优势，构建具有宽太阳光谱响应的新型光芬顿催化剂具有重要意义.
由于其独特的层状结构和优越的有机物光催化性能，Bi₂WO₆作为结构最为简单的钙钛矿型层状氧化物，其禁带宽度为2.6-2.8eV，可响应可见光，已成研究最多的光催化材料之一.研究表明，将Bi₂WO₆与合适的助催化剂耦合以构建异质结是提高光生载流子分离效率、拓宽Bi₂WO₆可见光响应范围的一种有效策略.在众多的窄带隙半导体助催化材料中，Cu₂ZnSnS₄作为一种p-型窄带隙半导体，可以响应可见光甚至近红外光.近年来，已经广泛报道了Cu₂ZnSnS₄可以作为与其他半导体光催化剂进行结合以提高光催化活性的有效助催化剂.
在本文中，新型Cu₂ZnSnS₄/Bi₂WO₆（CZTS/BWO）异质结构通过简单的二次溶剂热法构建.异质结的成功形成得到了一系列表征方法的证实，比如XPS和HR-TEM.光催化活性结果表明，制备的CZTS/BWO异质结对有机污染物的降解具有优异的光催化性能，特别是当CZTS相对于异质结中BWO的质量分数为2%时.此外，加入过氧化氢（H₂O₂）可进一步提高染料和抗生素的降解效率.增强的光催化和光芬顿降解性能主要是由于BWO的引入，其提供了更多的活性位点，扩展了太阳光谱响应范围并加速了Cu（II）/Cu（I）的循环.催化剂的催化活性在经过四次循环实验后并没有显著降低.最终我们合理假设了光催化和光-芬顿催化机理.本项研究可为设计新型光-芬顿催化剂提供新的视角，即共同利用光催化活性和芬顿活性进行废水中残留有机物的净化.

关键词:

English

2D/2D type-II Cu₂ZnSnS₄/Bi₂WO₆ heterojunctions to promote visible-light-driven photo-Fenton catalytic activity

Shaanxi Key Laboratory of Chemical Reaction Engineering, College of Chemistry&Chemical Engineering, Yan'an University, Yan'an 716000, Shaanxi, China
Received Date: 06 August 2019
Revised Date: 23 September 2019
Fund Project:
This work was supported by the National Natural Science Foundation of China (21663030, 21666039), the Open Project of State Key Laboratory of Organic-Inorganic Composites Beijing Key Laboratory, Beijing University of Chemical Technology (oic-201901009), the Project of Science & Technology Office of Shannxi Province (2018TSCXL-NY-02-01, 2013K11-08, 2013SZS20-P01), Industrial Key Project of Yan'an Science and Technology Bureau (2018KG-04), and the Project of Yan'an Science Graduate Innovation Project of Yan'an University (YCX201988).

Abstract: In this work, a set of novel Cu₂ZnSnS₄/Bi₂WO₆ (CZTS/BWO) two-dimensional (2D)/two-dimensional (2D) type-II heterojunctions with different CZTS weight ratios (1%, 2%, and 5%) were successfully synthesized via a brief secondary solvothermal process. The successful formation of the heterojunctions was affirmed by characterization methods such as X-ray photoelectron spectroscopy and high-resolution transmission electron microscopy. The photocatalytic activity results showed that the prepared CZTS/BWO heterojunctions had excellent photocatalytic behaviors for organic degradation, especially when the mass fraction of CZTS with respect to BWO in the composite was 2%. Moreover, the addition of hydrogen peroxide (H₂O₂) could further improve the dye and antibiotic degradation efficiencies. The reinforced photocatalytic and photo-Fenton degradation performance were primarily attributable to the introduction of BWO, which afforded increased active sites, expanded the solar spectral response range, and accelerated the cycle of Cu(II)/Cu(I); after four cycling times, its catalytic activity did not decrease significantly. In addition, reasonable hypotheses of the photocatalytic and photo-Fenton catalytic mechanisms were formulated. This study is expected to provide a visual approach for designing a novel photo-Fenton catalyst to jointly utilize the photocatalytic and Fenton activities, which can be better applied to the purification of residual organics in wastewater.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

具有可见光增强芬顿活性的II型2D/2D Cu₂ZnSnS₄/Bi₂WO₆异质结

English

2D/2D type-II Cu₂ZnSnS₄/Bi₂WO₆ heterojunctions to promote visible-light-driven photo-Fenton catalytic activity

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