构建2D-2D TiO<sub>2</sub>纳米片/层状WS<sub>2</sub>异质结用以增强可见光响应光催化活性

引用本文: 吴勇川, 刘中敏, 李亚茹, 陈继涛, 主曦曦, 那平. 构建2D-2D TiO₂纳米片/层状WS₂异质结用以增强可见光响应光催化活性[J]. 催化学报, 2019, 40(1): 60-69. doi: 10.1016/S1872-2067(18)63170-5 shu

Citation: Yongchuan Wu, Zhongmin liu, Yaru Li, Jitao Chen, Xixi Zhu, Ping Na. Construction of 2D-2D TiO₂ nanosheet/layered WS₂ heterojunctions with enhanced visible-light-responsive photocatalytic activity[J]. Chinese Journal of Catalysis, 2019, 40(1): 60-69. doi: 10.1016/S1872-2067(18)63170-5 shu

构建2D-2D TiO₂纳米片/层状WS₂异质结用以增强可见光响应光催化活性

吴勇川 ^a, ,
刘中敏 ^b, ,
李亚茹 ^a, ,
陈继涛 ^a, ,
主曦曦 ^c, ,
那平 ^a,

a 天津大学化工学院, 天津 300350;
b 德州大学化学与化学工程学院, 山东德州 253023;
c 山东科技大学化学与环境工程学院, 山东青岛 266590
基金项目:
国家高技术研究发展计划（863计划，2012AA063504）；国家自然科学基金（U1407116，21511130020，21276193）；天津市自然科学基金（13JCZDJC35600）.

摘要: 自Fujishima等首次报道以来，TiO₂作为一种重要的光催化剂引起了人们的广泛关注.迄今为止，研究人员已经开发出了各种形貌的具有不同晶型结构的TiO₂，并用于光催化降解有机污染物.然而，TiO₂的宽禁带（3.2eV）使其难以被可见光激活，导致对太阳光的利用效率低下.而且，在光催化反应中，低的量子效率无法满足实际应用.因此，开发具有可见光响应的高催化活性的TiO₂基催化剂具有重要意义.集成复合材料、纳米材料和界面的优势构建纳米复合材料已成为提高TiO₂光催化活性的重要策略.WS₂具有典型的类石墨烯层状结构和窄的带隙（1.35eV），且其导带高于TiO₂的导带，适合作为助催化剂修饰TiO₂，使其具备可见光响应光催化活性.
本文采用一步水热法，以二维（2D）TiO₂纳米片作基质材料，直接在其表面原位生长WS₂层，制得了2D-2D TiO₂纳米片/层状WS₂（TNS/WS₂）异质结.XRD及Raman结果表明，层状WS₂与TiO₂纳米片紧密结合在一起，且两者之间形成了W=O键.TEM结果显示，层状WS₂以面-面堆叠方式均匀地包覆在TiO₂纳米片表面，包覆层数约为4层.光催化性能测试结果表明，可见光照射下，TNS/WS₂异质结对RhB的光催化降解能力高于原始TiO₂纳米片和层状WS₂，光催化活性得到明显增强.
紫外可见光谱试验结果显示，层状WS₂的引入极大地增强了异质结的光吸收性能.PL光谱测试表明，TNS/WS₂异质结具有更高效的载流子分离效率.为了进一步证实是光吸收性能的提升还是载流子分离效率的增强对光催化性能提起其主要作用，本文还研究了3D-2D TiO₂空心微球/层状WS₂（THS/WS₂）复合材料.结果表明，TNS/WS₂异质结比THS/WS₂复合材料具有更高效的光生电子和空穴的分离能力.从而证明了TiO₂纳米片与层状WS₂之间完美的2D-2D纳米界面和紧密的界面结合，显著增加了载流子分离效率，因此光催化活性得到明显提高.
为了研究TNS/WS₂异质结光催化剂的光催化机理，采用重铬酸钾、草酸铵、叔丁醇和对苯醌作自由基猝灭剂进行了自由基捕捉剂实验.结果表明，空穴在RhB降解过程中起主要作用，超氧自由基起次要作用.基于自由基猝灭实验结果和带隙结构分析，提出了TNS/WS₂异质结对RhB的光催化机理为双转移光催化机理.可见，界面异质结工程化可能是制备高效和环境稳定的光催化剂的新思路.

关键词:

English

Construction of 2D-2D TiO₂ nanosheet/layered WS₂ heterojunctions with enhanced visible-light-responsive photocatalytic activity

a School of Chemical Engineering and Technology, Tianjin University, Tianjin 300350, China;
b College of Chemistry and Chemical Engineering, Dezhou University, Dezhou 253023, Shandong, China;
c College of Chemistry and Environmental Engineering, Shandong University of Science and Technology, Qingdao 266590, Shandong, China
Received Date: 21 July 2018
Revised Date: 21 September 2018
Fund Project:
This work was supported by the National High Technology Research and Development Program of China (863 Program, 2012AA063504), the National Natural Science Foundation of China (U1407116, 21511130020, 21276193), and the Tianjin Municipal Natural Science Foundation (13JCZDJC35600).

Abstract: Constructing nanocomposites that combine the advantages of composite materials, nanomaterials, and interfaces has been regarded as an important strategy to improve the photocatalytic activity of TiO₂. In this study, 2D-2D TiO₂ nanosheet/layered WS₂ (TNS/WS₂) heterojunctions were prepared via a hydrothermal method. The structure and morphology of the photocatalysts were systematically characterized. Layered WS₂ (~4 layers) was wrapped on the surface of TiO₂ nanosheets with a plate-to-plate stacked structure and connected with each other by W=O bonds. The as-prepared TNS/WS₂ heterojunctions showed higher photocatalytic activity for the degradation of RhB under visible-light irradiation, than pristine TiO₂ nanosheets and layered WS₂. The improvement of photocatalytic activity was primarily attributed to enhanced charge separation efficiency, which originated from the perfect 2D-2D nanointerfaces and intimate interfacial contacts between TiO₂ nanosheets and layered WS₂. Based on experimental results, a double-transfer photocatalytic mechanism for the TNS/WS₂ heterojunctions was proposed and discussed. This work provides new insights for synthesizing highly efficient and environmentally stable photocatalysts by engineering the surface heterojunctions.

Key words:

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构建2D-2D TiO₂纳米片/层状WS₂异质结用以增强可见光响应光催化活性

English

Construction of 2D-2D TiO₂ nanosheet/layered WS₂ heterojunctions with enhanced visible-light-responsive photocatalytic activity

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

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中国化学会秘书处

构建2D-2D TiO2纳米片/层状WS2异质结用以增强可见光响应光催化活性

English

Construction of 2D-2D TiO2 nanosheet/layered WS2 heterojunctions with enhanced visible-light-responsive photocatalytic activity

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

构建2D-2D TiO₂纳米片/层状WS₂异质结用以增强可见光响应光催化活性

Construction of 2D-2D TiO₂ nanosheet/layered WS₂ heterojunctions with enhanced visible-light-responsive photocatalytic activity

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