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

参考文献 21

1	Wang M，Ioccozia J，Sun L，et al.Inorganic⁃modified semiconductor TiO₂ nanotube arrays for photocatalysis［J］.Energy & Environmental Science，2014，7（7）：2182⁃2202.
2	王宁，赵振涛，马坤怡，等.矿物材料负载TiO₂光催化研究进展［J］.辽宁石油化工大学学报，2021，41（3）：1⁃9.
	Wang N，Zhao Z T，Ma K Y，et al.Research progress of photocatalysis of TiO₂ supported on mineral materials［J］.Journal of Liaoning Petrochemical University，2021，41（3）：1⁃9.
3	Wang Y，Chen J，Zhang X，et al.N⁃doped rutile TiO₂/C hybrids with enhanced charge transfer capability derived from NH₂⁃MIL⁃125（Ti） for the photocatalytic degradation of tetracycline［J］.Materials Research Bulletin，2022，155：111968.
4	Cheng Y，Gao J，Shi Q，et al.In situ electrochemical reduced Au loaded black TiO₂ nanotubes for visible light photocatalysis［J］.Journal of Alloys and Compounds，2022，901：163562.
5	Lee H，Jang H S，Kim N Y，et al.Cu⁃doped TiO₂ hollow nanostructures for the enhanced photocatalysis under visible light conditions［J］.Journal of Industrial and Engineering Chemistry，2021，99：352⁃363.
6	Drmosh Q A，Hezam A，Hendi A H Y，et al.Ternary Bi₂S₃/MoS₂/TiO₂ with double Z⁃scheme configuration as high performance photocatalyst［J］.Applied Surface Science，2020，499：143938.
7	Dong J，Huang J，Wang A，et al.Vertically⁃aligned Pt⁃decorated MoS₂ nanosheets coated on TiO₂ nanotube arrays enable high⁃efficiency solar⁃light energy utilization for photocatalysis and self⁃cleaning SERS devices［J］.Nano Energy，2020，71：104579.
8	Zhang M，Xu Y，Gong Z，et al.Enhanced charge collection and photocatalysis performance of CdS and PbS nanoclusters co⁃sensitized TiO₂porous film［J］.Journal of Alloys and Compounds，2015，649：190⁃195.
9	Ong W L，Ho G W.Enhanced photocatalytic performance of TiO₂ hierarchical spheres decorated with Ag₂S nanoparticles［J］.Procedia Engineering，2016，141：7⁃14.
10	Hou J，Huang B，Kong L，et al.One⁃pot hydrothermal synthesis of CdS–CuS decorated TiO₂ NTs for improved photocatalytic dye degradation and hydrogen production［J］.Ceramics International，2021，47（21）：30860⁃30868.
11	Wu Z，Yuan D，Lin S，et al.Enhanced photoelectrocatalytic activity of Bi₂S₃–TiO₂ nanotube arrays hetero⁃structure under visible light irradiation［J］.International Journal of Hydrogen Energy，2020，45（56）：32012⁃32021.
12	Yu B，Meng F，Zhou T，et al.Construction of hollow TiO₂/CuS nanoboxes for boosting full⁃spectrum driven photocatalytic hydrogen evolution and environmental remediation［J］.Ceramics International，2021，47（7，Part A）：8849⁃8858.
13	Nasir J A，Rehman Z U，Shah S N A，et al.Recent developments and perspectives in CdS⁃based photocatalysts for water splitting［J］.Journal of Materials Chemistry A，2020，8（40）：20752⁃20780.
14	Yu Y，Ren J，Meng M.Photocatalytic hydrogen evolution on graphene quantum dots anchored TiO₂ nanotubes⁃array［J］.International Journal of Hydrogen Energy，2013，38（28）：12266⁃12272.
15	Zhu Y，Wang Y，Chen Z，et al.Visible light induced photocatalysis on CdS quantum dots decorated TiO₂nanotube arrays［J］.Applied Catalysis A：General，2015，498：159⁃166.
16	楚家玉.CdS基异质结构催化剂的构筑及光催化产氢性能［D］.哈尔滨：哈尔滨工业大学，2020.
17	Zhou P，Le Z，Xie Y，et al.Studies on facile synthesis and properties of mesoporous CdS/TiO₂composite for photocatalysis applications［J］.Journal of Alloys and Compounds，2017，692：170⁃177.
18	Liu Y，Zhou H，Zhou B，et al.Highly stable CdS⁃modified short TiO₂ nanotube array electrode for efficient visible⁃light hydrogen generation［J］.International Journal of Hydrogen Energy，2011，36（1）：167⁃174.
19	Hou W，Chen C，Wang Y，et al.Cerium versus zirconium UiO66 metal–organic frameworks coupled with CdS for H₂evolution under visible light［J］.Catalysis Science & Technology，2022，12（12）：4012⁃4019.
20	周月娥，陈雪冰，张静.内建电场调控光生电荷分离效率的研究进展［J］.石油化工高等学校学报，2021，34（3）：1⁃6.
	Zhou Y E，Chen X B，Zhang J.Research progress on the regulation of photogenerated charge separation by built⁃in electric field［J］.Journal of Petrochemical Universities，2021，34（3）：1⁃6.
21	Kumar Yadav S，Jeevanandam P.Thermal decomposition approach for the synthesis of CdS–TiO₂ nanocomposites and their catalytic activity towards degradation of rhodamine B and reduction of Cr（VI）［J］.Ceramics International，2015，41（2）：2160⁃2179.

[1]	李哲, 王芳芳, 陈常东. 一步水热法合成Mn₃O₄/CuMnO₂及其光芬顿反应性能的研究[J]. 石油化工高等学校学报, 2024, 37(3): 73-80.
[2]	张若男, 何仕婕, 王晓蓉, 王芳芳, 陈常东. BaTiO₃⁃TiO₂复合体的软化学制备及其性能研究[J]. 石油化工高等学校学报, 2022, 35(4): 46-51.
[3]	梁红玉,李建中,田彦文,邹赫,胡绍争. 不同g-C₃N₄/WO₃异质结材料的制备及其光催化性能研究[J]. 石油化工高等学校学报, 2018, 31(01): 23-29.

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

HTML

PDF

可视化

摘要/Abstract

引用本文

使用本文

图/表 11

参考文献 21

相关文章 3

编辑推荐

Metrics