介孔TiO2/WO3空心球的制备及其可见光光催化性能

doi:10.15541/jim20160377

无机材料学报 ›› 2017, Vol. 32 ›› Issue (4): 365-371.DOI: 10.15541/jim20160377

介孔TiO₂/WO₃空心球的制备及其可见光光催化性能

喻洋¹, 佟明兴¹, 何玉兰¹, 陈辉¹, 高静^{1, 2}, 李国华^{1, 2}

(浙江工业大学 1. 化学工程学院; 2. 绿色化学合成技术国家重点实验室培训基地, 杭州 310014)

收稿日期:2016-06-15 修回日期:2016-09-12 出版日期:2017-04-20 网络出版日期:2017-03-24
作者简介:喻洋(1989–), 男, 硕士研究生. E-mail: 2111401151@zjut.edu.cn
基金资助:
国家自然科学基金(21173193, 21301154);浙江省自然科学基金(Y4080209, Y406094);宁波市自然科学基金(2014A610116)

Preparation and Visible-light Photocatalytic Performance of Mesoporous Hollow TiO₂/WO₃ Spheres

YU Yang¹, TONG Ming-Xing¹, HE Yu-Lan¹, CHEN Hui¹, GAO Jing^{1, 2}, LI Guo-Hua^{1, 2}

(1. School of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, China; 2. State Key Laboratory Breeding Base of Green Chemistry Synthesis Technology, Hangzhou 310014, China)

Received:2016-06-15 Revised:2016-09-12 Published:2017-04-20 Online:2017-03-24
About author:YU Yang. E-mail: 2111401151@zjut.edu.cn
Supported by:
National Natural Science Foundation of China (21173193, 21301154);Natural Science Foundation of Zhejiang Provience(Y4080209, Y406094);Natural Science Foundation of Ningbo (2014A610116)

摘要/Abstract

摘要：

以硫酸氧钛和偏钨酸铵为前驱体, 以柠檬酸作为络合剂, 采用喷雾干燥-高温煅烧两步法制备了介孔TiO₂/WO₃空心球复合材料。利用SEM、TEM、BET、XRD、UV-Vis DRS等手段对样品的形貌、微结构、比表面积、晶相组成和光学性能进行了表征和分析, 以亚甲基蓝为模拟降解物考察其光催化性能。结果表明: 复合材料为介孔空心球状结构, 球体分散好, 直径主要分布在1 μm左右; 球壁由纳米颗粒和空隙构成, 随着煅烧温度的升高, 颗粒粒径不断增大, 空隙孔径不断增大。性能研究结果表明, TiO₂与WO₃复合后, 样品对光的吸收范围扩展到了可见光区域, 这有利于提高太阳光的利用率; 当前驱体中WO₃含量为3mol%, 样品的煅烧温度为500℃时, 复合材料具有最好的光催化性能: 对亚甲基蓝降解率可达99.1%, 而P25的降解率仅为29.5%。

关键词: 二氧化钛, 三氧化钨, 介孔空心球, 光催化, 亚甲基蓝

Abstract:

By using titanyl sulfate and ammonia metatungstate (AMT) as precursors and citric acid as a complexing agent, mesoporous hollow spheres of TiO₂/WO₃ composites were prepared via a two-step approach, which included a spray-drying process followed by a high-temperature calcination course. The morphologies, microstructures, surface area, crystal phase, and optical properties of the composites were characterized by SEM, TEM, BET, XRD and UV-Vis DRS. The results showed that the TiO₂/WO₃ composites were well-dispersed mesoporous hollow spheres with diameters around 1 μm, of which the wall consisted of nanoparticles and mesopores. What’s more, nanoparticles and mesopores increased with the calcination temperature. UV-Vis DRS analysis showed that the absorption spectra of TiO₂/WO₃ composites could extend from ultraviolet region to visible region, which was helpful to improve the utilization efficiency of sunlight. In addition, photocatalytic activities of the prepared samples were investigated by photo-degradation of methylene blue (MB). It’s found that the composite containing 3% molar ratio of WO₃ with calcination temperature of 500^oC showed the best photocatalytic activity. The degradation efficiency of MB with this composite could reach 99.1%, much higher than that of P25, which was only 29.5% under the same conditions.

Key words: titania dioxide, tungsten trioxide, mesoporous hollow sphere, photocatalytic, methylene blue

中图分类号:

O643

喻洋, 佟明兴, 何玉兰, 陈辉, 高静, 李国华. 介孔TiO₂/WO₃空心球的制备及其可见光光催化性能[J]. 无机材料学报, 2017, 32(4): 365-371.

YU Yang, TONG Ming-Xing, HE Yu-Lan, CHEN Hui, GAO Jing, LI Guo-Hua. Preparation and Visible-light Photocatalytic Performance of Mesoporous Hollow TiO₂/WO₃ Spheres[J]. Journal of Inorganic Materials, 2017, 32(4): 365-371.

图/表 9

图1 不同煅烧温度下样品的XRD图谱

Fig. 1 XRD patterns of samples calcined at different temperatures(a) 435℃; (b) 500℃; (c) 600℃; (d) 700℃

表1 煅烧温度与锐钛矿晶粒大小的关系

Table 1 Relationship between calcination temperature and grain size of anatase

Temperature/℃	Size/nm
500	9.8
600	21.5
700	48.3

图2 不同煅烧温度下样品的SEM照片

Fig. 2 SEM images of samples calcined at different temperatures(a, e) 435℃; (b, f) 500℃; (c, g) 600℃; (d, h) 700℃

图3 TiO2/WO3样品的N2吸附-脱附等温线和孔径微分分布曲线

Fig. 3 Nitrogen adsorption-desorption isotherms and pore distribution curves of the TiO2/WO3 composites

图4 500℃煅烧得到的TiO2/WO3复合材料的TEM照片

Fig. 4 TEM images of TiO2/WO3 composite calcined at 500℃with 3mol% WO3(a, b) TEM images of TiO2/WO3 composites ; (c, d) HRTEM images of TiO2/WO3 composites

图5 不同温度煅烧得到的TiO2/WO3复合材料的UV-Vis吸收光谱

Fig. 5 UV-Vis DRS absorption spectra of TiO2/WO3 composites calcined at different temperatures(a) 435℃; (b) 500℃; (c) 600℃; (d) 700℃; (e) P25

图6 不同温度煅烧得到的TiO2/WO3样品的可见光光催化性能

Fig. 6 Photocatalytic activities of TiO2/WO3 composites calcined at different temperatures

图7 不同WO3摩尔百分比的TiO2/WO3样品的可见光光催化性能

Fig. 7 Photocatalytic activities of TiO2/WO3 composites with different WO3 percentages

图8 TiO2/WO3复合材料光生电子与空穴有效分离机理示意图

Fig. 8 Separated mechanism of photogenerated electrons- holes in TiO2/WO3 composites

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介孔TiO₂/WO₃空心球的制备及其可见光光催化性能

Preparation and Visible-light Photocatalytic Performance of Mesoporous Hollow TiO₂/WO₃ Spheres

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