SiO2@Ag@SiO2@TiO2核壳结构的制备及其光催化降解性能

doi:10.15541/jim20210685

无机材料学报 ›› 2022, Vol. 37 ›› Issue (7): 750-756.DOI: 10.15541/jim20210685 CSTR: 32189.14.10.15541/jim20210685

SiO₂@Ag@SiO₂@TiO₂核壳结构的制备及其光催化降解性能

迟聪聪(), 屈盼盼, 任超男, 许馨, 白飞飞, 张丹洁

陕西科技大学轻化工程国家级实验教学中心, 陕西省造纸技术及特种纸品开发重点实验室, 中国轻工业纸基功能材料重点实验室, 中国轻工业功能印刷与运输包装重点实验室, 西安 710021

收稿日期:2021-11-08 修回日期:2021-12-22 出版日期:2022-07-20 网络出版日期:2022-01-06
作者简介:迟聪聪(1981-), 女, 副教授. E-mail: congcongchi@163.com
基金资助:
国家自然科学基金重点项目(31600476);省级大学生创新创业训练计划(S202110708106);陕西省提升公众科学素质计划(2021PSL68)

Preparation of SiO₂@Ag@SiO₂@TiO₂ Core-shell Structure and Its Photocatalytic Degradation Property

CHI Congcong(), QU Panpan, REN Chaonan, XU Xin, BAI Feifei, ZHANG Danjie

National Demonstration Center for Experimental Light Chemistry Engineering Education, Shaanxi Province Key Laboratory of Papermaking Technology and Specialty Paper, Key Laboratory of Paper based Functional Materials of China National Light Industry, Key Laboratory of Functional Printing and Transport Packaging of China National Light Industry, Shaanxi University of Science & Technology, Xi'an 710021, China

Received:2021-11-08 Revised:2021-12-22 Published:2022-07-20 Online:2022-01-06
About author:CHI Congcong (1981-), female, associate professor. E-mail: congcongchi@163.com
Supported by:
National Natural Science Foundation of China(31600476);Provincial College Students’ Innovation and Entrepreneurship Training Program Project(S202110708106);Shanxi Provincial Project to Improve the Scientific Quality of the Public(2021PSL68)

摘要/Abstract

摘要：

光催化是一种绿色且高效的降解染料污染物的方式, 在水污染治理中应用广泛。本研究以SiO₂为核层, 依次采用氧化还原法、改进的Stöber法及水热法合成SiO₂@Ag@SiO₂@TiO₂多层核壳结构作为光催化剂用于染料污染物降解, 并探讨了硝酸银(AgNO₃)、正硅酸乙酯(TEOS)、钛酸四丁酯(TBOT)等用量对包覆效果的影响。采用不同表征手段对样品的微观形貌、物相结构、孔结构参数和光电性能进行分析表征。结果表明, 当AgNO₃、TEOS、TBOT与SiO₂的质量比为5 : 2.4 : 6 : 1, 多层核壳结构每层均达到最优包覆效果。与SiO₂@TiO₂和SiO₂@Ag@TiO₂催化剂相比较, SiO₂@Ag@SiO₂@TiO₂核壳结构的光催化剂具有更佳的光催化活性, 光照45 min可降解93%的MB溶液, 经4次循环后其光催化效率为90%。

关键词: 核壳结构, 光催化, 二氧化钛, 亚甲基蓝

Abstract:

Photocatalytic degradation is an eco-friendly and high-efficiency way to degrade dye pollutants which has broad application prospects in water pollution control. In this study, the multi-layer core-shell structure of SiO₂@Ag@SiO₂@TiO₂ was synthesized by different methods as a photocatalyst for pollutant degradation, with oxidation-reduction method, modified Stöber method and hydrothermal method in turn. Effect of silver nitrate (AgNO₃), tetraethyl orthosilicate (TEOS) and tetrabutyl titanate (TBOT) on the coating effect were discussed. Microstructure, phase structure, pore structure parameters and photoelectrical properties of SiO₂-based multi-layer core-shell structure were systematically analyzed by various characterization methods while its degradation performance of methylene blue (MB) was also studied and discussed. The results show that when the mass ratio of AgNO₃, TEOS and TBOT to SiO₂ is 5 : 2.4 : 6 : 1, each layer of the multi-layer cored shell structure achieves the optimal coating effect. Compared with SiO₂@TiO₂ and SiO₂@Ag@TiO₂, the core-shell structure of SiO₂@Ag@SiO₂@TiO₂ photocatalyst has the best photocatalytic activity. Its photocatalytic degradation efficiency is close to 93% after simulated visible light irradiation for 45 min, and degradation efficiency keeps at 90% after 4 cycles of recycling tests.

Key words: core-shell structure, photocatalysis, titanium dioxide, methylene blue

中图分类号:

TB333

迟聪聪, 屈盼盼, 任超男, 许馨, 白飞飞, 张丹洁. SiO₂@Ag@SiO₂@TiO₂核壳结构的制备及其光催化降解性能[J]. 无机材料学报, 2022, 37(7): 750-756.

CHI Congcong, QU Panpan, REN Chaonan, XU Xin, BAI Feifei, ZHANG Danjie. Preparation of SiO₂@Ag@SiO₂@TiO₂ Core-shell Structure and Its Photocatalytic Degradation Property[J]. Journal of Inorganic Materials, 2022, 37(7): 750-756.

图/表 12

图1 SiO2@Ag@SiO2@TiO2微球的制备流程图

Fig.1 Schematic diagram for synthesizing SiO2@Ag@SiO2@TiO2 microspheres

图2 不同AgNO3/SiO2质量比制备SiO2@Ag微球的SEM照片

Fig. 2 SEM images of SiO2@Ag microspheres prepared with different AgNO3/SiO2 mass ratios (a) 2 : 1; (b) 3 : 1; (c) 4 : 1; (d) 5 : 1

图3 SiO2@Ag微球的(a) STEM照片, (b) 选定区域EDS能谱, (c) TEM照片和(d) HRTEM照片

Fig. 3 STEM image (a), EDS pattern of selected region (b), TEM image (c), and HRTEM image (d) of SiO2@Ag microspheres

图4 500 ℃高温处理前(a)和后(b) SiO2@Ag微球的SEM照片

Fig. 4 SEM images of SiO2@Ag microspheres before (a) and after (b) thermal-treated at 500 ℃

图5 不同TEOS/SiO2质量比制备的SiO2@Ag@SiO2微球的SEM照片

Fig. 5 SEM images of SiO2@Ag@SiO2 microspheres prepared with different TEOS/SiO2 mass ratios (a) 0.9 : 1; (b) 1.4 : 1; (c) 1.9 : 1; (d) 2.4 : 1

图6 不同TBOT/SiO2质量比制备SiO2@Ag@TiO2微球的SEM照片

Fig. 6 SEM images of SiO2@Ag@TiO2 microspheres with different TBOT/SiO2 mass ratios (a) 3 : 1; (b) 4 : 1; (c) 5 : 1; (d) 6 : 1; (e) 7 : 1; (f) 8 : 1

图7 SiO2@Ag@SiO2@TiO2微球的(a) TEM照片, (b) EDS能谱, (c) HRTEM照片和(d) O, Si, Ag和Ti的元素分布

Fig. 7 (a) TEM image, (b) EDS pattern, (c) HRTEM image and corresponding elemental mapping of O, Si, Ag and Ti of SiO2@Ag@SiO2@TiO2 microspheres

图8 不同SiO2基微球的XRD谱图

Fig. 8 XRD patterns of different SiO2-based microspheres

表1 不同微球的孔结构参数

Table 1 Pore structure parameters of different microspheres

Sample	S_BET/ (m²·g^-1)	Pore volume/ (cm³·g^-1)	Average pore size/nm
SiO₂	18.95	0.23	56.20
SiO₂@Ag	23.87	0.38	62.78
SiO₂@Ag@TiO₂	48.36	0.23	15.85
SiO₂@Ag@SiO₂@TiO₂	81.36	0.25	10.37

图9 不同SiO2基微球的氮气吸脱附曲线

Fig. 9 Nitrogen adsorption-desorption isotherms of different SiO2-based microspheres

图10 不同样品ln(At/A0)随时间的变化曲线和SiO2@Ag@SiO2@TiO2降解MB的循环测试(插图)

Fig. 10 ln(At/A0)-t curves of different samples and cyclic tests of MB degradation by SiO2@Ag@SiO2@TiO2 (insert)

图11 不同样品的瞬态光电流响应(a)和电化学阻抗谱(b)

Fig. 11 Transient photocurrent responses (a) and electrochemical impedance spectra (b) of different samples

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SiO₂@Ag@SiO₂@TiO₂核壳结构的制备及其光催化降解性能

Preparation of SiO₂@Ag@SiO₂@TiO₂ Core-shell Structure and Its Photocatalytic Degradation Property

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