高活性Ag修饰TiO2空心八面体光催化剂的简易模板诱导合成

doi:10.1016/S1872-2067(15)60978-0

催化学报 ›› 2015, Vol. 36 ›› Issue (12): 2211-2218.DOI: 10.1016/S1872-2067(15)60978-0

高活性Ag修饰TiO₂空心八面体光催化剂的简易模板诱导合成

王雪飞^a, 余锐^a, 王康^a, 杨桂全^a, 余火根^a,b

a 武汉理工大学化学、化工与生命科学学院, 湖北武汉 430070;
b 武汉理工大学硅酸盐国家重点实验室, 湖北武汉 430070

收稿日期:2015-08-27 修回日期:2015-09-22 出版日期:2015-12-02 发布日期:2015-12-07
通讯作者: 余火根
基金资助:
国家自然科学基金(51208396, 21277107, 21477094, 51472192); 新世纪优秀人才支持计划(NCET-13-0944); 中央高校基本科研业务费专项基金(WUT 2014-1α-003, 2014-VII-037, 2015IB002).

Facile template-induced synthesis of Ag-modified TiO₂ hollow octahedra with high photocatalytic activity

Xuefei Wang^a, Rui Yu^a, Kang Wang^a, Guiquan Yang^a, Huogen Yu^a,b

a School of Chemistry, Chemical Engineering and Life Sciences, Wuhan University of Technology, Wuhan 430070, Hubei, China;
b State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Wuhan 430070, Hubei, China

Received:2015-08-27 Revised:2015-09-22 Online:2015-12-02 Published:2015-12-07
Supported by:
This work was supported by the National Natural Science Foundation of China (51208396, 21277107, 21477094, and 51472192), the Program for New Century Excellent Talents in University (NCET-13-0944), and the Fundamental Research Funds for the Central Universities (WUT 2014-1α-003, 2014-VII-037, and 2015IB002).

摘要/Abstract

摘要：

贵金属修饰的TiO₂空心纳米光催化材料由于具有大的比表面积、低的质量密度、良好的表面渗透性、强的光吸收能力以及界面电荷的快速转移,因而表现出优异的光催化性能.为了制备结构可控且精良的贵金属修饰TiO₂空心纳米光催化材料,人们先后采用湿化学法、高温固相法、声化学法及光化学沉积法等.由于在制备过程中涉及多种异相材料的合成和结构控制,因此上述合成方法通常需要复杂且多步过程(有些过程甚至很容易导致结构破坏),从而限制了其在光催化领域的实际应用.
本文开发了一种简单的模板诱导法,成功制备了Ag纳米粒子修饰的TiO₂空心八面体光催化剂.合成过程包括模板指导沉积和原位模板溶解.以Ag₂O八面体为模板,TiF₄水溶液为前驱体,首先通过TiF₄水解形成TiO₂纳米粒子沉积在Ag₂O模板表面,而TiF₄水解产生的酸性HF水溶液可原位溶解碱性的Ag₂O模板,从而一步制得TiO₂空心八面体.同时,利用Ag₂O以及Ag⁺离子的光敏特性,在光照条件下使Ag₂O和Ag⁺离子生成Ag纳米颗粒,直接沉积在TiO₂空心八面体的内外表面,得到Ag/TiO₂光催化剂.由此可见,该合成方法具有明显的步骤少的优点.扫描电镜、透射电镜、能量散射和紫外-可见光谱等表征结果表明成功制得内外Ag纳米粒子修饰的TiO₂空心八面体光催化剂,其中TiO₂空心八面体的壁厚约为25nm,边长约为1μm,而修饰在其表面的Ag纳米粒子尺寸仅为5-10nm.此外,通过控制TiF₄前驱体浓度,还可制备核壳结构的Ag₂O@TiO₂八面体以及不同壁厚Ag修饰的TiO₂空心八面体,表明该方法在Ag/TiO₂形貌合成上的多样性和可控性.
为了获得良好的光催化活性,对制备的Ag纳米粒子修饰的TiO₂空心八面体光催化剂进行了不同温度的热处理.X射线衍射结果表明,即使在600℃高温下,制备的Ag/TiO₂空心八面体光催化剂依然能够保持原有的特殊形貌和锐钛矿TiO₂晶型.该温度明显高于TiO₂从锐钛矿向金红石转变的温度.这说明合成的Ag/TiO₂能在保持高活性锐钛矿相的同时获得更好的结晶性.这可能是由于分散在TiO₂原始晶粒周围的Ag纳米粒子能阻止其进一步长大,从而抑制了其晶型转变.不同样品光催化降解甲基橙的结果表明,经600℃高温热处理的样品表现出最高的光催化活性,相应的反应速率常数为0.11min^-1.这应得益于该光催化剂具有以下三个特点:(1)TiO₂空心八面体的薄壁结构能够缩短光照条件下光生电子和空穴从内部扩散到表面的距离;(2)由于贵金属Ag纳米粒子沉积在TiO₂薄壁的内外两个表面以及TiO₂和Ag形成肖脱基势垒,因此在它们接触的界面上能够发生更快的界面电荷转移;(3)高温处理导致TiO₂良好的晶化以及高活性锐钛矿TiO₂晶型的保持.

关键词: 光催化, 银, 二氧化钛, 空心八面体, 界面电荷转移, 模板

Abstract:

Noble metal/titania hollow nanomaterials usually exhibit excellent photocatalytic activity because of their high specific surface area, low density, good surface permeability, strong light-harvesting capacity, and rapid interfacial charge transfer. However, the present preparation methods usually include complicated and multistep procedures, which can cause damage to the hollow nanostructures. In this paper, a facile template-induced synthesis, based on a template-directed deposition and in situ template-sacrificial dissolution, was employed to prepare Ag-modified TiO₂ (Ag/TiO₂) hollow octahedra using Ag₂O octahedra as templates and TiF₄ as the precursor. In the synthetic strategy, the shells of TiO₂ hollow octahedra were formed by coating TiO₂ nanoparticles on the surface of Ag₂O templates based on the template-directed deposition. Simultaneously, the Ag₂O templates can be in situ removed by dissolving the Ag₂O octahedral template in HF solution produced via the hydrolysis reaction of TiF₄ in the reaction system. In addition, Ag nanoparticles were deposited on the inside and outside surfaces of TiO₂ shells by effectively using the photosensitive properties of Ag₂O and Ag⁺ ions under light irradiation, along with the formation of TiO₂ hollow octahedra. The Ag/TiO₂ hollow octahedra exhibited high photocatalytic activity because of their (1) short diffusion distances between photogenerated electrons and holes because of the thin shells of Ag/TiO₂ hollow octahedral, (2) deposition of Ag nanoparticles on the inside and outside surfaces of TiO₂ shells, and (3) rapid interfacial charge transfer between TiO₂ shells and Ag nanoparticles. This work may also provide new insights into preparing other Ag-modified and hollow nanostructured photocatalysts.

Key words: Photocatalysis, Silver, Titanium dioxide, Hollow octahedral, Interfacial charge transfer, Template

王雪飞, 余锐, 王康, 杨桂全, 余火根. 高活性Ag修饰TiO₂空心八面体光催化剂的简易模板诱导合成[J]. 催化学报, 2015, 36(12): 2211-2218.

Xuefei Wang, Rui Yu, Kang Wang, Guiquan Yang, Huogen Yu . Facile template-induced synthesis of Ag-modified TiO₂ hollow octahedra with high photocatalytic activity[J]. Chinese Journal of Catalysis, 2015, 36(12): 2211-2218.

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高活性Ag修饰TiO₂空心八面体光催化剂的简易模板诱导合成

Facile template-induced synthesis of Ag-modified TiO₂ hollow octahedra with high photocatalytic activity

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