CdS量子点修饰TiO2纳米管及光解水产氢性能研究

doi:10.3969/j.issn.1006-396X.2022.04.006

摘要/Abstract

摘要：

二氧化钛（TiO₂）是一种传统的光催化剂材料，但由于其自身带隙宽(3.2 eV)及光生载流子易复合,往往需要通过贵金属或过渡金属掺杂、阴离子掺杂、构建异质结等手段增强其对太阳光的有效吸收，促使光生载流子分离并抑制其复合。采用两步法构建TiO₂/CdS异质结，首先通过多重电压阳极氧化法制备结构化的TiO₂纳米管阵列，再以TiO₂纳米管为基底，通过化学浴沉积法在TiO₂纳米管管壁内外均匀生长CdS量子点。通过X射线衍射、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线光电子能谱(XPS)和紫外?可见光谱(UV?VIS)对TiO₂/CdS异质结组成、形貌和光学性质进行了表征。结果表明，构建的TiO₂?CdS异质结有效抑制光生载流子复合，促进激发电子的转移，提高光催化产氢效率；样品TiO₂(1.0)?CdS(1.0)产氢效率达到1.30 mmol/（g $?$ h），是CdS量子点的1.67倍。最后，基于实验分析提出了可见光光解水制氢过程中光生电子在TiO₂?CdS上的转移机制。

关键词: TiO₂纳米管, CdS量子点, 异质结, 载流子分离, 光解水制氢

Abstract:

Titanium dioxide (TiO₂) is a traditional photocatalyst material.However, due to its wide band gap (3.2 eV) and the easy recombination of photogenerated carriers,it is necessary to enhance the effective absorption of sunlight,promote the separation of photogenerated carriers,and inhibit their recombination by doping noble metals,transition metals,anions and constructing heterojunctions.TiO₂/CdS heterojunctions were prepared in two steps.Firstly,TiO₂ nanotube arrays were prepared by multiple voltage anodization.Then,with TiO₂ nanotubes as the base,CdS quantum dots were uniformly deposited inside and outside the nanotubes through chemical bath deposition.The composition,morphology,and optical properties of TiO₂/CdS heterojunctions were characterized by X?ray diffraction,scanning electron microscopy (SEM),transmission electron microscopy (TEM),X?ray photoelectron spectroscopy (XPS),and UV?visible spectroscopy (UV?VIS).The prepared TiO₂/CdS heterojunctions effectively inhibited the recombination of photogenerated carriers,promoted the transfer of excited electrons,and improved the hydrogen production efficiency by photocatalysis.The hydrogen production efficiency of sample TiO₂(1.0)?CdS(1.0) reached 1.30 mmol/（g $?$ h）,which was 1.67 times that of CdS quantum dots.Finally,according to the experimental analysis,the transfer mechanism of photogenerated electrons on TiO₂/CdS during photocatalytic water splitting for hydrogen was proposed.

Key words: TiO₂nanotubes, CdS quantum dots, Heterojunction, Carrier separation, Photocatalytic water splitting for hydrogen

中图分类号:

TQ134.1

余志超, 汤振国, 张楠, 崔泽岳, 胡林河, 李刚. CdS量子点修饰TiO₂纳米管及光解水产氢性能研究[J]. 石油化工高等学校学报, 2022, 35(4): 38-45.

Zhichao Yu, Zhenguo Tang, Nan Zhang, Zeyue Cui, Linhe Hu, Gang Li. TiO₂ Nanotubes Modified by CdS Quantum Dots and Performance of Photocatalytic Water Splitting for Hydrogen[J]. Journal of Petrochemical Universities, 2022, 35(4): 38-45.

图/表 11

图1 TiO2?CdS催化剂制备过程示意图

Fig.1 Diagram for the preparation of TiO2?CdS

图2 TiO2纳米管、CdS量子点及TiO2(1.0)?CdS(1.0)的XRD图谱

Fig.2 XRD images of TiO2 nanotubes,CdS quantum dots and TiO2(1.0)?CdS(1.0)

图3 TiO2纳米管负载CdS前后的SEM图及TiO2(1.0)?CdS(1.0)的HRTEM图和SAED图

Fig.3 SEM images of TiO2 nanotubes before and after loading CdS and HRTEM and SAED images of TiO2 (1.0)?CdS (1.0)

图4 TiO2(1.0)?CdS(1.0)中Ti、O、Cd、S的XPS能谱图

Fig.4 X?ray photoelectron spectroscopy (XPS) spectra of Ti，O，Cd，S for TiO2(1.0)?CdS(1.0)

图5 TiO2纳米管、TiO2(1.0)?CdS(1.0)的N2吸附?脱附等温曲线及孔径分布

Fig.5 The N2 adsorption–desorption isotherms and the pore size distribution of TiO2 nanotubes and TiO2(1.0)?CdS(1.0)

图6 TiO2纳米管、CdS量子点及TiO2(1.0)?CdS(1.0)的紫外可见漫反射吸收光谱图及其Tauc图

Fig.6 UV?Vis absorption spectra and the corresponding Tauc diagram of TiO2 nanotubes,CdS quantum dots and TiO2(1.0)-CdS(1.0)

图7 TiO2纳米管、CdS量子点及不同质量比的TiO2?CdS催化剂的产氢量及产氢效率对比

Fig.7 Hydrogen production and hydrogen efficiency of TiO2 nanotubes,CdS quantum dots and TiO2/CdS with different mass ratios

图8 TiO2(1.0)?CdS(1.0)催化剂循环稳定性测试结果

Fig.8 Cyclic stability testing of TiO2(1.0)?CdS(1.0)

图9 TiO2纳米管和TiO2(1.0)?CdS(1.0)在370 nm激发下的光致发光光谱

Fig.9 Photoluminescence emission spectra with an excitation wavelength of TiO2 nanotubes and TiO2(1.0)?CdS(1.0)

图10 循环测试后TiO2(1.0)?CdS(1.0)的SEM和XRD谱图

Fig. 10 SEM and XRD plot after cyclic hydrogen production testing of TiO2(1.0)?CdS(1.0)

图11 TiO2?CdS异质结的能带结构及电荷转移图

Fig.11 The energy band spectrum and charge transfer of TiO2?CdS heterojunction

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CdS量子点修饰TiO₂纳米管及光解水产氢性能研究

TiO₂ Nanotubes Modified by CdS Quantum Dots and Performance of Photocatalytic Water Splitting for Hydrogen

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