自牺牲型金属有机框架衍生In2S3多级孔结构纳米材料强化光催化性能

doi:10.1016/S1872-2067(24)60003-3

催化学报 ›› 2024, Vol. 59: 204-213.DOI: 10.1016/S1872-2067(24)60003-3

自牺牲型金属有机框架衍生In₂S₃多级孔结构纳米材料强化光催化性能

杨婷婷^a^,¹, 王彬^a^,^b^,¹, 朱剑豪^b, 夏杰祥^a^,^*(), 李华明^a^,^*()

^a江苏大学化学化工学院, 能源研究院, 江苏镇江 212013
^b香港城市大学物理系, 材料科学与工程系, 生物医学工程系, 香港

收稿日期:2023-12-14 接受日期:2024-02-08 出版日期:2024-04-18 发布日期:2024-04-15
通讯作者: *电子邮箱: xjx@ujs.edu.cn (夏杰祥), lhm@ujs.edu.cn (李华明).
作者简介:
¹共同第一作者.
基金资助:
国家自然科学基金(22108106);国家自然科学基金(22108108);中国博士后科学基金(2022M721380);香港城市大学捐赠研究补助金(DON-RMG 9229021)

Self-sacrificing MOF-derived hierarchical porous In₂S₃ nanostructures with enhanced photocatalytic performance

Tingting Yang^a^,¹, Bin Wang^a^,^b^,¹, Paul K. Chu^b, Jiexiang Xia^a^,^*(), Huaming Li^a^,^*()

^aSchool of Chemistry and Chemical Engineering, Institute for Energy Research, Jiangsu University, Zhenjiang 212013, Jiangsu, China
^bDepartment of Physics, Department of Materials Science and Engineering, and Department of Biomedical Engineering, City University of Hong Kong, Tat Chee Avenue, Kowloon, Hong Kong, China

Received:2023-12-14 Accepted:2024-02-08 Online:2024-04-18 Published:2024-04-15
Contact: *xjx@ujs.edu.cn (J. Xia); lhm@ujs.edu.cn (H. Li).
About author:
¹Contributed equally to this work.
Supported by:
The National Natural Science Foundation of China(22108106);The National Natural Science Foundation of China(22108108);The China Postdoctoral Science Foundation(2022M721380);City University of Hong Kong Donation Research(DON-RMG 9229021)

摘要/Abstract

摘要：

半导体基光催化是减少对化石燃料的依赖和解决环境污染问题的有前景的策略之一. 在光催化有机污染物降解领域, 硫化物材料备受关注. 其中, In₂S₃催化剂因展现较好的催化活性及经济可行性, 而被认为是光催化降解的理想催化剂之一. 然而, 采用传统煅烧法制备的In₂S₃催化剂由于比表面积小, 暴露的活性位点有限, 进而限制了其催化活性的进一步提升. 因此, 制备具有较大比表面积和多活性位点的In₂S₃基催化剂, 对于推动光催化降解有机污染物领域的发展具有重要的意义.

本文通过构建分级多孔结构的光催化剂, 以增强材料的光吸收性能并优化光生载流子的迁移和分离, 从而提升光催化降解有机污染物的性能. 利用In基金属有机骨架(MOFs)作为自我牺牲模板, 通过硫化制备了包括空心纳米管、微管、中空球和十二面体在内的多种分级In₂S₃光催化剂. 分级多孔结构不仅增强了入射光的多次折射和反射, 还提供了更大的表面积, 从而提高了光生载流子的光利用率和相分离效率. 实验结果表明, 这些材料的光催化效率远高于块状和商用In₂S₃. 通过X射线光电子能谱、X射线衍射等手段验证了不同形貌分级多孔In₂S₃材料的成功制备. 紫外-可见漫反射光谱结果表明, 所有催化剂均可吸收部分可见光, 结合莫特肖特基曲线和XPS价带谱结果, 说明催化剂的导带、价带位置均满足光催化降解有机污染物的要求. 光致发光光谱、光电流强度曲线和电化学阻抗曲线等研究表明, 分级多孔结构有效促进了光生载流子的分离和迁移. 光催化降解罗丹明B(RhB)和四环素(TC)性能评价结果表明, 与块状和商用In₂S₃相比, 具有分级多孔结构的In₂S₃材料表现出更好的光催化降解活性. 其中, 空心In₂S₃纳米管(HNTs)具有最佳的光催化性能, 在光照1.5和2 h后, In₂S₃-HNT可以去除约50%的TC和95%的RhB, 其RhB的降解速率分别是块状和商业In₂S₃的135.6倍和446.9倍, TC的降解速率分别是块状和商业级In₂S₃的7.8倍和36.5倍. 电子顺磁共振和自由基捕获实验结果表明, 在光催化降解过程中, 空穴、超氧自由基以及单线态氧是主要的活性物种. 特别是, 当In₂S₃-HNT受到光照时, 其独特的分级多孔结构使得光生电子和空穴对能够有效分离, 这使得In₂S₃-HNT可以积累更多的活性氧自由基, 从而显著提升了其光催化降解有机污染物的性能.

综上, 本文采用新型自牺牲模板法, 制备了金属有机框架衍生In₂S₃多级孔结构纳米材料. 通过精准调控In₂S₃催化剂的形貌, 有效提升了光催化降解有机污染物性能. 该方法在高效光催化剂的制备上展现了显著潜力, 为设计高性能的光催化降解材料提供参考.

关键词: 硫化铟, 金属有机框架, 形貌调控, 光催化, 污染物降解

Abstract:

Fabrication of porous hierarchical structures is an effective method to improve the photo-absorption capability of photocatalysts by enhancing the photogenerated charge separation and transfer. In-based metal-organic frameworks (MOFs) are utilized as self-sacrificial templates to synthesize various hierarchical In₂S₃ photocatalysts including hollow nanotubes/microtubes/ spheres and dodecahedrons by the sulfidation process. The porous hierarchical structures improve multiple refraction and reflection of the incident light, provide larger surface areas, and increase the light utilization and phase separation efficiency of the photogenerated carriers. As a result, the photocatalytic efficiency is much higher than that of the bulk and commercial In₂S₃. In particular, the hollow In₂S₃ nanotubes (HNTs) have the best photocatalytic properties boosting degradation rates of organic pollutants that are 135.6 and 446.9 times than those of the bulk and commercial-grade In₂S₃, respectively. Theoretical calculations, optical/electrical characterization, and free radical trapping experiments reveal that under the condition of light, the photogenerated electron hole pairs produced in In₂S₃-HNT can effectively separate due to its hierarchical porous structure. So, the In₂S₃-HNT can accumulate more reactive oxygen radicals. This novel self-sacrificial template method has large potential in the design and fabrication of hierarchical high-efficiency photocatalysts.

Key words: In₂S₃, Metal-organic framework, Morphological control, Photocatalysis, Pollutants degradation

杨婷婷, 王彬, 朱剑豪, 夏杰祥, 李华明. 自牺牲型金属有机框架衍生In₂S₃多级孔结构纳米材料强化光催化性能[J]. 催化学报, 2024, 59: 204-213.

Tingting Yang, Bin Wang, Paul K. Chu, Jiexiang Xia, Huaming Li. Self-sacrificing MOF-derived hierarchical porous In₂S₃ nanostructures with enhanced photocatalytic performance[J]. Chinese Journal of Catalysis, 2024, 59: 204-213.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(24)60003-3

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图/表 6

Scheme 1. Schematic illustration of the synthesis of the hierarchical In2S3 structures.

Fig. 1. SEM and TEM images of In(OH)3 (a,b), In2S3-HNT (c,d), MIL-68-In (f,g), In2S3-HMT (h,i), In(OH)(2,5-PDC) (k,l), In2S3-HS (m,n), In-rho-ZMOFs (p,q), and In2S3-PD (r,s). HR-TEM images of In2S3-HNT (e), In2S3-HMT (j), In2S3-HS (o), and In2S3-PD (t).

Fig. 2. N2 adsorption-desorption isotherms (a), XRD patterns (b), XPS In 3d (c) and S 2p (d) spectra of In2S3-HNT, In2S3-HMT, In2S3-HS, and In2S3-PD. (e) Calculated DOS. (f) Band structure of In2S3. UV-vis DRS and bandgaps (g), XPS valence-band spectra (h), and Mott-Schottky plots (i) of In2S3-HNT, In2S3-HMT, In2S3-HS, and In2S3-PD.

Fig. 3. Photocatalytic properties for degradation of RhB (a) and TC (b) under visible light irradiation. (c) Reaction kinetics for degradation of RhB and TC. Interference experiments for Positive ions (d), Negative ions (e), and pH (f) for RhB degradation in the presence of In2S3-HNT. EIS spectra (g), Photocurrent curves (h), and PL spectra (i) of In2S3-HNT, In2S3-HMT, In2S3-HS, and In2S3-PD.

Fig. 4. Possible degradation routes of RhB (a) and TC (b) in In2S3-HNT. Growing situation (c) and average length (d) of mung bean seeds in deionized water as well as solution before and after photocatalytic degradation.

Fig. 5. (a-c) Comparison of the photocatalytic activities of In2S3-HNT for the degradation of RhB (a) and TC (b) with or without adding TBA, TEOA, Trp, and N2 under visible light irradiation. ESR spectra of electrons (d), holes (e), DMPO-·O2- (f), DMPO-·1O2 (g), and DMPO-·OH (h) of In2S3-HNT, In2S3-HMT, In2S3-HS, and In2S3-PD. (i) Mechanism and role of In2S3 in photocatalytic degradation.

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自牺牲型金属有机框架衍生In₂S₃多级孔结构纳米材料强化光催化性能

Self-sacrificing MOF-derived hierarchical porous In₂S₃ nanostructures with enhanced photocatalytic performance

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