盐辅助-超生喷雾热分解法合成中空Bi2WO6纳米微球去除NO的应用

doi:10.1016/S1872-2067(16)62584-6

催化学报 ›› 2017, Vol. 38 ›› Issue (2): 348-356.DOI: 10.1016/S1872-2067(16)62584-6

盐辅助-超生喷雾热分解法合成中空Bi₂WO₆纳米微球去除NO的应用

陈美娟^a, 黄宇^b,c, 李顺诚^d

a 西安交通大学, 人居环境与建筑工程学院;
b 中国科学院地球环境研究所, 中国科学院气溶胶化学与物理重点实验室, 陕西西安 710049;
c 中国科学院地球环境研究所, 黄土与第四纪地质国家重点实验室, 陕西西安 710061;
d 香港理工大学, 土木与环境工程学系

收稿日期:2016-09-15 修回日期:2016-10-18 出版日期:2017-02-18 发布日期:2017-03-14
通讯作者: Yu Huang,Tel/Fax:+86-29-62336261;E-mail:huangyu@ieecas.cn
基金资助:
国家自然科学基金（41503102，41401567，41573138），中国博士后科学基金（2015M572568）.

Salt-assisted Synthesis of Hollow Bi₂WO₆ Microspheres with Superior Photocatalytic Activity for NO Removal

Meijuan Chen^a, Yu Huang^b,c, Shun Cheng Lee^d

a School of Human Settlements and Civil Engineering, Xi'an Jiaotong University, Xi'an 710049, Shaanxi, China;
b Key Lab of Aerosol Chemistry & Physics, Institute of Earth Environment, Chinese Academy of Sciences, Xi'an 710061, Shaanxi, China;
c State Key Lab of Loess and Quaternary Geology(SKLLQG), Institute of Earth Environment, Chinese Academy of Sciences, Xi'an 710061, Shaanxi, China;
d Department of Civil and Environmental Engineering, The Hong Kong Polytechnic University, Hung Hom, Hong Kong, China

Received:2016-09-15 Revised:2016-10-18 Online:2017-02-18 Published:2017-03-14
Contact: 10.1016/S1872-2067(16)62584-6
Supported by:
This work was supported by the National Natural Science Foundation of China (41503102, 41401567, 41573138); the China Postdoctoral Science Foundation (2015M572568).

摘要/Abstract

摘要：

氮氧化物（简称NO_x，包括NO和NO₂等）是形成二次有机气溶胶的重要前体物，其存在会严重影响空气质量并危害人类健康.目前用于NO_x的去除的方法主要有过滤、物理吸附、热催化等.然而，这些技术存在高能耗及产生二次污染等缺点，严重制约其实际应用.近年来，光催化技术作为一种有效处理NO_x的环保技术，因其具备在常温下高效处理低浓度NO_x（大气污染浓度水平）的优点而获得广泛关注.最近，Bi₂WO₆光催化剂因其独特的层状结构以及特有的催化性质，表现出良好的可见光催化性能.Bi₂WO₆光催化性能与催化剂的形貌及尺寸大小密切相关，目前报道的Bi₂WO₆的形貌有片状、颗粒状、花状、中空微球等.其中，由小纳米颗粒堆积成的中空Bi₂WO₆微球因其大的比表面积和高的荷质传输速率，表现出显著优于其它形貌的光催化性能.目前已有少量关于中空结构Bi₂WO₆微球的制备方法的报道，这些方法均需引入纳米球状的“核”作为模板，并在其上生长Bi₂WO₆胶体颗粒，然后去除“核”，从而得到中空结构.譬如，Shang等采用碳纳米球作为“核”制备出Bi₂WO₆微球，再通过煅烧手段去除碳“核”.Thillai与合作者用硅球作为“核”，为了得到中空结构Bi₂WO₆微球，用NaOH将硅“核”刻蚀.然而这类方法均涉及到复杂的制备过程和高昂的运行成本.超生喷雾热分解法是一种常见的制备尺寸可控的纳米球的方法.在之前的工作中，本研究组成功使用超声喷雾热解法制备出具有优良光催化活性的Bi₂WO₆实心微球.我们首次加入NaCl盐为模板，使用简单的超声喷雾热分解方法制备出具有中空结构的Bi₂WO₆微球光催化剂，合成过程无需采用复杂的除“核”手段.一系列表征表明：该微球由直径为41-148 nm的纳米片自组装而成，并在表面形成了不均匀分布的孔结构；并对Bi₂WO₆中空微球的生长机制做了详细的研究，考察了所制备Bi₂WO₆催化剂去除NO的效率.
生长机制研究结果表明，NaCl盐在中空Bi₂WO₆微球的形成过程中发挥着关键性作用：（1）NaCl盐溶液在超生喷雾热分解法的高温过程中形成NaCl单晶并作为“核”模板，参与中空Bi₂WO₆微球的形成；（2）Na⁺离子有助于Bi₂WO₆微球的微结构-纳米片的生长；（3）Cl-离子有利于Bi₂WO₆微球表面微孔的形成；（4）NaCl模板水洗后留下中空结构的Bi₂WO₆微球；（5）NaCl盐也充当着多孔诱发剂，其水洗溢出过程会造成Bi₂WO₆微球表面的孔结构.性能测试表明，以NaCl盐为模板所制备的中空Bi₂WO₆微球表现出优异的光催化性能，其在模拟太阳光下去除NO的效率是未添加模板的1.7倍、以KCl为模板的1.5倍、以Na₂SO₄为模板的1.2倍.BET和DRS分析表明，中空结构Bi₂WO₆微球具有大的比表面积和高的可见光吸收，对提高催化性能起到重要作用.ESR测试结果表明，·OH和·O₂^-是中空Bi₂WO₆微球的光催化反应过程的主要活性物种，·O₂^-的产生有助于提高光催化剂降解NO的耐受性.

关键词: 超声喷雾热分解, 盐模板, Bi₂WO₆中空微球, NO去除

Abstract:

Hollow Bi₂WO₆ microspheres are successfully synthesized by a facile ultrasonic spray pyrolysis (USP) method using NaCl as a salt template. The as-prepared hollow microspheres assembled as nanoplates with dimensions of approximately 41-148 nm and are dispersed with non-uniform pores on the template surface. By swapping the salt template with KCl or Na₂SO₄, different morphologies of Bi₂WO₆ are obtained. The experimental results demonstrate that NaCl plays a key role on the formation of Bi₂WO₆ with hollow structures. The specific growth mechanism of hollow microspheres was studied in detail. The Bi₂WO₆ hollow microspheres exhibit an excellent photocatalytic efficiency for NO removal under solar light irradiation, which is 1.73 times higher than for the Bi₂WO₆ obtained in the absence of any salt template. This enhancement can be ascribed to the simultaneous improvement on the surface area and visible light-harvesting ability from the hollow structures. Electron spin resonance (ESR) results suggest that both radicals of ·OH and ·O₂^- are involved in the photocatalytic process over the BWO-NaCl sample. The production of ·O₂^- radicals offers better durability for NO removal.

Key words: Ultrasonic spray pyrolysis, Salt template, Bi₂WO₆ hollow microsphere, NO removal

陈美娟, 黄宇, 李顺诚. 盐辅助-超生喷雾热分解法合成中空Bi₂WO₆纳米微球去除NO的应用[J]. 催化学报, 2017, 38(2): 348-356.

Meijuan Chen, Yu Huang, Shun Cheng Lee. Salt-assisted Synthesis of Hollow Bi₂WO₆ Microspheres with Superior Photocatalytic Activity for NO Removal[J]. Chinese Journal of Catalysis, 2017, 38(2): 348-356.

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盐辅助-超生喷雾热分解法合成中空Bi₂WO₆纳米微球去除NO的应用

Salt-assisted Synthesis of Hollow Bi₂WO₆ Microspheres with Superior Photocatalytic Activity for NO Removal

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