磷钨酸钾模板法制备高活性二氧化钛空心微球

doi:10.1016/S1872-2067(15)60987-1

催化学报 ›› 2015, Vol. 36 ›› Issue (12): 2237-2243.DOI: 10.1016/S1872-2067(15)60987-1

磷钨酸钾模板法制备高活性二氧化钛空心微球

蓝俊峰^b, 伍晓锋^a, 吕康乐^a, 司玲玲^a, 邓克俭^a

a 中南民族大学催化材料科学国家民委-教育部共建重点实验室, 湖北武汉 430074;
b 广西科技师范学院化学与生命科学系, 广西柳州 545004

收稿日期:2015-08-27 修回日期:2015-09-20 出版日期:2015-12-02 发布日期:2015-12-07
通讯作者: 吕康乐, 邓克俭
基金资助:
教育部“新世纪优秀人才支持计划”(NCET-12-0668);国家自然科学基金(21373275,20977114).

Fabrication of TiO₂ hollow microspheres using K₃PW₁₂O₄₀ as template

Junfeng Lan^b, Xiaofeng Wu^a, Kangle Lü^a, Lingling Si^a, Kejian Deng^a

a Key Laboratory of Catalysis and Materials Science of the State Ethnic Affairs Commission & Ministry of Education, South-Central University for Nationalities, Wuhan 430074, Hubei, China;
b Department of Chemistry and Life Science, Guangxi Science and Technology Normal University, Liuzhou 545004, Guangxi, China

Received:2015-08-27 Revised:2015-09-20 Online:2015-12-02 Published:2015-12-07
Supported by:
This work was supported by Program for New Century Excellent Talents in University (NCET-12-0668) and the National Natural Science Foundation of China (21373275, 120977114).

摘要/Abstract

摘要：

TiO₂空心微球因具有低密度、高活性、易分离而有利于多次重复使用的优点而广受关注.本文介绍一种无氟制备TiO₂空心微球的简单方法——磷钨酸钾(K₃PW₁₂O₄₀)模板法.首先,将H₃PW₁₂O₄₀和KCl溶液混匀,得到白色牛奶状的K₃PW₁₂O₄₀模板(式(1)),然后在磁力搅拌下加入一定量的Ti(SO₄)₂粉末,加热至大约125℃开始回流.回流8h后,过滤洗涤.滤饼分散在强NaOH溶液中,原位除去K₃PW₁₂O₄₀模板(式(2)).最后,将催化剂洗涤到滤液为中性,干燥后即得到TiO₂空心微球.
3KCl + H₃PW₁₂O₄₀ = K₃PW₁₂O₄₀↓ + 3HCl (1)
K₃PW₁₂O₄₀ + 24NaOH = 12Na₂WO₄ + K₃PO₄ + 12 H₂O (2)
Ti(SO₄)₂ + 2H₂O = TiO₂ + 2H₂SO₄ (3)
我们将所制备的TiO₂空心微球,采用X射线衍射、透射电子显微镜、扫描电子显微镜、傅立叶红外光谱、固体粉末漫反射和X射线光电子能谱等进行了表征.采用紫外光催化降解阴离子染料(活性嫣红X3B)来评价催化剂的性能.
实验结果显示:(1)所制TiO₂空心微球直径在0.5-1.0μm;(2)磷钨酸钾模板剂充当晶核,有利于空心微球的晶化;(3)加入的高浓度硫酸钛,水解产生大量的硫酸,抑制硫酸钛水解,不利于TiO₂空心微球的晶化(式(3));(4)催化剂的活性随着硫酸钛量的增加而先增后降.4mmol硫酸钛用量的TiO₂空心微球具有最高的光催化活性,是TiO₂颗粒样品(无磷钨酸钾模板法制备)的2.1倍.
用该方法制备的TiO₂空心微球活性高可归因于以下主要原因:(1)TiO₂空心微球独特的孔结构;(2)良好的晶化程度(TiO₂样品晶化度越高,越有利于光生载流子的分离,抑制复合);(3)样品残余磷钨酸钾模板和TiO₂之间存在光生电子转移,有利于空心微球TiO₂活性的提高.该法具有操作简单、重复性好、易于批量制备的等优点,有望广泛应用于(光)催化、电化学、分离与纯化以及药物缓释等领域.

关键词: 二氧化钛, 空心微球, 磷钨酸钾, 模板, 降解

Abstract:

Fabrication of TiO₂ hollow microspheres (TiO₂-HMSs) has attracted considerable attention owing to their low density, high photoreactivity, and easy to separate and reuse. A fluoride-free method for the fabrication of TiO₂-HMSs is reported by refluxing a mixed solution of H₃PW₁₂O₄₀ (0.4 mmol), KCl (2.5 mmol) and Ti(SO₄)₂ (2-25 mmol) at 125 ℃ for 8 h, followed by decomposition of the K₃PW₁₂O₄₀ (KPW) template in basic solution. The prepared TiO₂-HMSs are characterized by X-ray diffraction, transmission electron microscopy, scanning electron microscopy, Fourier transform infrared spectroscopy, ultraviolet-visible diffuse reflectance spectroscopy and X-ray photoelectron spectroscopy. The activities of the photocatalysts are evaluated by photocatalytic degradation of Brilliant Red X-3B, an anionic dye, under UV irradiation. It is observed that the TiO₂-HMSs exhibit diameters of approximately 0.5-1 μm, and the photocatalytic activity of TiO₂-HMSs initially increases and then decreases with an increasing amount of Ti(SO₄)₂. The TiO₂-HMSs prepared in the presence of 4 mmol Ti(SO₄)₂ exhibit the highest photocatalytic activity, which is 2.1 times higher than TiO₂ nanoparticles (prepared in the absence of the KPW template). The enhanced photocatalytic activity of the prepared TiO₂-HMSs is ascribed to the improved crystallization, coupling effect between TiO₂ and the residual KPW template, and the unique hollow structures of TiO₂-HMSs.

Key words: Titania, Hollow microsphere, K₃PW₁₂O₄₀, Template, Degradation

蓝俊峰, 伍晓锋, 吕康乐, 司玲玲, 邓克俭. 磷钨酸钾模板法制备高活性二氧化钛空心微球[J]. 催化学报, 2015, 36(12): 2237-2243.

Junfeng Lan, Xiaofeng Wu, Kangle Lü, Lingling Si, Kejian Deng. Fabrication of TiO₂ hollow microspheres using K₃PW₁₂O₄₀ as template[J]. Chinese Journal of Catalysis, 2015, 36(12): 2237-2243.

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https://www.cjcatal.com/CN/Y2015/V36/I12/2237

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磷钨酸钾模板法制备高活性二氧化钛空心微球

Fabrication of TiO₂ hollow microspheres using K₃PW₁₂O₄₀ as template

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磷钨酸钾模板法制备高活性二氧化钛空心微球

Fabrication of TiO2 hollow microspheres using K3PW12O40 as template

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Fabrication of TiO₂ hollow microspheres using K₃PW₁₂O₄₀ as template