基于WO3-x量子点和TiO2构建高效Z型光催化产氢催化剂

引用本文: 潘伦, 张靖雯, 贾旭, 马煜航, 张香文, 王莅, 邹吉军. 基于WO_3-x量子点和TiO₂构建高效Z型光催化产氢催化剂[J]. 催化学报, 2017, 38(2): 253-259. doi: 10.1016/S1872-2067(16)62576-7 shu

Citation: Lun Pan, Jingwen Zhang, Xu Jia, Yu-Hang Ma, Xiangwen Zhang, Li Wang, Ji-Jun Zou. Highly efficient Z-scheme WO_3-x quantum dots/TiO₂ for photocatalytic hydrogen generation[J]. Chinese Journal of Catalysis, 2017, 38(2): 253-259. doi: 10.1016/S1872-2067(16)62576-7 shu

基于WO_3-x量子点和TiO₂构建高效Z型光催化产氢催化剂

a 天津大学化工学院绿色合成与转化教育部重点实验室, 天津 300072;
b 天津化学化工协同创新中心, 天津 300072
基金项目:
国家自然科学基金（21506156，21676193）；天津市自然科学基金（15JCZDJC37300，16JCQNJC05200）.

摘要: TiO₂具有高效、廉价、无毒及光化学稳定性好等优点，因而被广泛应用于光能转化和利用领域，如太阳能电池、光催化分解水制氢和环境污染物降解等.但是，TiO₂仍然存在一些缺陷制约了其应用，其中，最关键的问题是光生电荷分离效率低.因此，人们对其进行了掺杂、异质结构建和Z型结构建等来解决这一问题，其中Z型结近年来备受关注.
全固体Z型结的构建目前主要有两种方式：PSI-C-PSII和PSI-PSII.前者PSI与PSII间要插入中间导电层（如Au、rGO等）来实现界面欧姆接触；后者则无中间层，而是基于界面设计来实现欧姆接触.本文以构建PSI-PSII Z型结为目标，以TiO₂和WO₃为基础半导体材料，采用原位溶剂热生长的方法构建WO₃量子点/TiO₂结构，借助氢气还原反应在界面处引入氧缺陷.采用透射电子显微镜、X射线衍射和拉曼光谱研究了复合晶体结构，采用X射线光电子能谱、紫外可见光谱和荧光光谱等手段研究了Z型结的界面结构和能带结构.结合光催化分解水产氢活性来建立Z型结结构与光催化性能的关联关系.
表征结果表明，在TiO₂上进行原位溶剂热成核反应可点缀WO₃量子点，并且量子点粒径随W前驱体用量的增加而变大.两种半导体材料为TiO₂锐钛矿和WO₃晶体结构，且WO₃的XRD特征峰和Raman特征吸收峰会随W前驱体用量增加而变大.通过对WO₃/TiO₂进行氢气还原处理，使其表面形成大量W⁵⁺和氧缺陷，一方面提高了催化剂对可见光的吸收，另一方面在界面形成欧姆接触，实现了Z型结构的构建.Z型结构实现了光催化分解水产氢反应，其中WTH10光催化活性最好.本文为新型Z型光催化剂的设计和构建提供了新思路和策略.

关键词:

English

Highly efficient Z-scheme WO_3-x quantum dots/TiO₂ for photocatalytic hydrogen generation

a Key Laboratory for Green Chemical Technology of Ministry of Education, School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China;
b Collaborative Innovative Center of Chemical Science and Engineering(Tianjin), Tianjin 300072, China
Received Date: 28 August 2016
Revised Date: 15 October 2016
Available Online: 02 March 2017
Fund Project:
This work was supported by the National Natural Science Foundation of China (21506156, 21676193) and the Tianjin Municipal Natural Science Foundation (15JCZDJC37300, 16JCQNJC05200).

Abstract: Z-scheme semiconductors are a promising class of photocatalysts for hydrogen generation. In this work, Z-scheme semiconductors composed of WO_3-x quantum dots supported on TiO₂ (WO_3-x QDs/TiO₂) were fabricated by solvothermal and hydrogen-reduction methods. Characterization by transmission electron microscopy and X-ray diffraction indicated that the amount and size of the WO_3-x QDs could be tuned by modulating the addition of the W precursor. Evidence from X-ray photoelectron spectroscopy and photoluminescence spectroscopy suggested that the hydrogen reduction of the composite induced the formation of oxygen vacancy (W⁵⁺/VO) defects in WO₃. These defects led to ohmic contact between WO_3-x and TiO₂, which altered the charge-transfer pathway from type II heterojunction to Z-scheme, and maintained the highly reductive and oxidative ability of TiO₂ and WO_3-x, respectively. Therefore, the Z-scheme sample showed 1.3-fold higher photoactivity than pure TiO₂ in hydrogen generation. These results suggest that the formation of W⁵⁺/VO defects at the interface is highly beneficial for the fabrication of Z-scheme photocatalysts.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

基于WO_3-x量子点和TiO₂构建高效Z型光催化产氢催化剂

English

Highly efficient Z-scheme WO_3-x quantum dots/TiO₂ for photocatalytic hydrogen generation

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