三明治结构钌插层二氧化钛光催化四环素降解性能研究

doi:10.15541/jim20230457

无机材料学报 ›› 2024, Vol. 39 ›› Issue (4): 383-389.DOI: 10.15541/jim20230457

三明治结构钌插层二氧化钛光催化四环素降解性能研究

王兆阳¹(), 秦鹏², 蒋胤¹, 冯小波¹, 杨培志¹(), 黄富强³()

1.云南师范大学可再生能源材料先进技术与制备教育部重点实验室, 昆明 650500
2.中国科学院上海硅酸盐研究所, 高性能陶瓷与超微结构国家重点实验室, 上海200050
3.上海交通大学材料科学与工程学院, 金属基复合材料国家重点实验室, 上海 200240

收稿日期:2023-10-07 修回日期:2023-12-13 出版日期:2024-04-20 网络出版日期:2023-12-25
通讯作者: 杨培志, 研究员. E-mail: pzhyang@hotmail.com;
黄富强, 教授. E-mail: huangfq@sjtu.edu.cn
作者简介:王兆阳(1999-), 男, 硕士研究生. E-mail: wang1143882613@163.com
基金资助:
国家自然科学基金(U1802257);国家自然科学基金(12264057);云南省基础研究重点基金(202201AS070023);“兴滇英才支持计划” “春城计划”高层次人才引进培养工程(2022SCP005)

Sandwich Structured Ru@TiO₂ Composite for Efficient Photocatalytic Tetracycline Degradation

WANG Zhaoyang¹(), QIN Peng², JIANG Yin¹, FENG Xiaobo¹, YANG Peizhi¹(), HUANG Fuqiang³()

1. Key Laboratory of Advanced Technique & Preparation for Renewable Energy Materials, Ministry of Education, Yunnan Normal University, Kunming 650500, China
2. State Key Laboratory of High Performance Ceramics and Superfine Microstructure, Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China
3. State Key Lab of Metal Matrix Composites, School of Materials Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China

Received:2023-10-07 Revised:2023-12-13 Published:2024-04-20 Online:2023-12-25
Contact: YANG Peizhi, professor. E-mail: pzhyang@hotmail.com;
HUANG Fuqiang, professor. E-mail: huangfq@sjtu.edu.cn
About author:WANG Zhaoyang (1999-), male, Master candidate. E-mail: wang1143882613@163.com
Supported by:
National Natural Science Foundation of China(U1802257);National Natural Science Foundation of China(12264057);Key Foundation of Basic Research of Yunnan Province(202201AS070023);“Yunnan Revitalization Talent Support Program” and “Spring City Plan” Introduction and Training Project of High-level Talent(2022SCP005)

摘要/Abstract

摘要：

纳米TiO₂具有高催化活性、高化学稳定性、成本低廉和安全无毒等优势, 是目前广泛使用的一类光催化剂, 但较大的禁带宽度和较高的光生电子-空穴复合速率使其光子利用率偏低。本研究利用微刻蚀法设计合成了二维TiO₂纳米片, 并进一步与Ru复合, 构建了三明治结构Ru@TiO₂高效光催化剂。采用不同表征手段研究了三明治结构Ru@TiO₂的表面形貌、电子结构、光电特性和光降解盐酸四环素的性能。结果表明: 插入Ru将TiO₂的光响应范围由紫外光区拓展至整个可见-近红外光区, 光子吸收和载流子分离效率得以提升,同时提高了体系光催化活性。模拟太阳光(AM 1.5G, 100 mW·cm^-2)照射80 min, 三明治结构Ru@TiO₂高效光催化剂对盐酸四环素的降解效果出色, 降解效率达到91.91%。本研究为TiO₂基高效光催化剂结构设计提供了一条有效途径。

关键词: 层状二氧化钛, 钌插层, 光催化, 盐酸四环素

Abstract:

TiO₂ nanomaterials are widely used photocatalysts due to high photocatalytic activity, good chemical stability, low cost, and nontoxicity. However, its lower photon utilization efficiency is still limited by larger bandgap width and higher recombination rate between photon and hole. In this study, two-dimensional TiO₂ nanosheets were synthesized via microetching, which were then inserted by ruthenium atoms to form an efficient photocatalyst Ru@TiO₂with sandwich structure. The surface morphology, electronic structure, photoelectric properties, and photocatalytic degradation performance of tetracycline hydrochloride of Ru@TiO₂ sandwich structure were investigated using different measurements. Results indicated that the material’s photoresponse range extended from UV to visible- near-infrared regions, improving photon absorption and carrier separation efficiency while enhancing photocatalytic activity. Under simulated sunlight irradiation (AM 1.5 G, 100 mW·cm^-2) for 80 min, sandwich structured Ru@TiO₂ efficient photocatalyst exhibited superior degradation performance on tetracycline hydrochloride with a degradation efficiency up to 91.91%. This work offers an effective way for the construction of efficient TiO₂based photocatalysts.

Key words: layered titanium dioxide, ruthenium intercalation, photocatalysis, tetracycline hydrochloride

中图分类号:

X703

王兆阳, 秦鹏, 蒋胤, 冯小波, 杨培志, 黄富强. 三明治结构钌插层二氧化钛光催化四环素降解性能研究[J]. 无机材料学报, 2024, 39(4): 383-389.

WANG Zhaoyang, QIN Peng, JIANG Yin, FENG Xiaobo, YANG Peizhi, HUANG Fuqiang. Sandwich Structured Ru@TiO₂ Composite for Efficient Photocatalytic Tetracycline Degradation[J]. Journal of Inorganic Materials, 2024, 39(4): 383-389.

图/表 6

图1 三明治结构L-Ru@TiO2的合成示意图

Fig. 1 Schematic diagram of preparation of sandwich structured L-Ru@TiO2

图2 不同条件制备的前驱体K2Ti4O9的XRD图谱

Fig. 2 XRD patterns of precursor K2Ti4O9 prepared under different conditions

图3 L-TiO2和L-Ru@TiO2的XRD、XPS、EPR和BET表征

Fig. 3 XRD, XPS, EPR, and BET characterizations of L-TiO2 and L-Ru@TiO2 (a) XRD patterns; (b) Ru3d XPS spectrum of L-Ru@TiO2; (c) O1s, and (d) Ti2p XPS spectra; (e) EPR spectra; (f) Nitrogen adsorption and desorption isotherms and corresponding pore size distribution curves. 1 Gs=10-4 T

图4 L-TiO2和L-Ru@TiO2的形貌表征

Fig. 4 Morphology characterization of L-TiO2 and L-Ru@TiO2 (a,b,d,e) TEM images of (a, b) L-TiO2 and (d, e) L-Ru@TiO2; (c, f) HRTEM images of (c) L-TiO2 and (f) L-Ru@TiO2 with insets showing lattice fringes of TiO2 (105); (g, h) HAADF images and (i) element distributions for L-Ru@TiO2

图5 L-TiO2和L-Ru@TiO2的光电特性

Fig. 5 Photoelectric properties of L-TiO2 and L-Ru@TiO2 (a) UV-Vis absorption spectra; (b) PL spectra; (c) Transient photocurrent responses; (d) Work functions

图6 L-TiO2和L-Ru@TiO2的催化降解性能

Fig. 6 Catalytic degradation performance of L-TiO2 and L-Ru@TiO2 (a) TC degradation and (b) TC photodegradation kinetics curves of photocatalytic raw materials TiO2, L-TiO2 and L-Ru@TiO2 under simulated sunlight; (c, d) Photocatalytic degradation efficiencies of TC by L-Ru@TiO2 at different (c) temperatures and (d) wavelengths; (e, f) Photocatalytic degradation efficiencies of TC in active species trapping experiment by L-Ru@TiO2 (Initial conditions: AO 1 mmol/L, LA 0.5 mmol/L)

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三明治结构钌插层二氧化钛光催化四环素降解性能研究

Sandwich Structured Ru@TiO₂ Composite for Efficient Photocatalytic Tetracycline Degradation

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三明治结构钌插层二氧化钛光催化四环素降解性能研究

Sandwich Structured Ru@TiO2 Composite for Efficient Photocatalytic Tetracycline Degradation

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Sandwich Structured Ru@TiO₂ Composite for Efficient Photocatalytic Tetracycline Degradation