离子刻蚀法制备具有高效催化性能的m-Bi2O4/BiOCl p-n异质结催化剂

doi:10.1016/S1872-2067(18)63142-0

催化学报 ›› 2018, Vol. 39 ›› Issue (11): 1792-1803.DOI: 10.1016/S1872-2067(18)63142-0

离子刻蚀法制备具有高效催化性能的m-Bi₂O₄/BiOCl p-n异质结催化剂

王隽秀^a, 张振宗^a, 汪曦^a, 沈奕^a, 郭永福^a, Po Keung Wong^b, 白仁碧^a

a 苏州科技大学分离净化材料与技术研发中心, 江苏苏州 215009;
b 香港中文大学生命科学学院, 香港沙田

收稿日期:2018-05-23 修回日期:2018-07-20 出版日期:2018-11-18 发布日期:2018-09-01
通讯作者: 郭永福, 白仁碧
基金资助:
国家自然科学基金（51578354）；苏州科技局科技计划项目（SS201667）；江苏省六大人才高峰（2016-JNHB-067）；江苏省青蓝工程.

Synthesis of novel p-n heterojunction m-Bi₂O₄/BiOCl nanocomposite with excellent photocatalytic activity through ion-etching method

Junxiu Wang^a, Zhenzong Zhang^a, Xi Wang^a, Yi Shen^a, Yongfu Guo^a, Po Keung Wong^b, Renbi Bai^a

a Center for Separation and Purification Materials & Technologies, Suzhou University of Science and Technology, Suzhou 215009, Jiangsu, China;
b School of Life Science, The Chinese University of Hong Kong, Shatin, Hong Kong, China

Received:2018-05-23 Revised:2018-07-20 Online:2018-11-18 Published:2018-09-01
Contact: 10.1016/S1872-2067(18)63142-0
Supported by:
This work was supported by the National Natural Science Foundation of China (51578354), Suzhou Science and Technology Bureau (SS201667), Six Talent Peaks Program (2016-JNHB-067), and Qing Lan Project of Jiangsu Province.

摘要/Abstract

摘要：

光催化技术作为一种绿色的环境修复方法而备受关注，它直接利用太阳光作为能源，可有效地降解有机污染物.铋系化合物具有化学稳定性强、抑制光腐蚀、无毒和来源广泛等优点，被认为是一种环境友好的光催化剂，广泛用于降解染料、苯酚和其他有机污染物.BiOCl具有独特的内部结构，可形成内电场促进电子和空穴的移动，抑制其复合.但是BiOCl本身带隙能过大，只能被紫外光激发，对光的利用率较低，限制了其在环境治理中的应用.近两年来发现，m-Bi₂O₄带隙能小，可吸收大波长的可见光，催化性能好.为充分发挥m-Bi₂O₄的优异性质，改善BiOCl的性能，本文将BiOCl与m-Bi₂O₄复合制得新型催化剂，降低催化剂的带隙能，增强对光的吸收，提高量子效率，促进光生载流子的分离，抑制电子-空穴复合，从而提高催化剂性能，加速降解反应进程.
本文通过离子刻蚀法制备具有p-n异质结的m-Bi₂O₄/BiOCl复合催化剂，通过调节HCl的加入量制得不同比例的催化剂，并考察了其在可见光下催化降解MO（甲基橙）的性能.结果表明，m-Bi₂O₄/BiOCl复合催化剂在可见光下表现出优异的光催化降解MO和四环素的性能，反应10内min可降解95%的MO，反应150min内四环素的降解率为85.5%；该复合催化剂对MO和四环素的光降解效率分别是纯BiOCl的52.3和4.9倍.活性自由基捕获实验表明，空穴在光催化降解过程中起最主要的作用，其次是超氧自由基，羟基自由基对降解反应也起到一定的作用.
采用XRD，SEM，EDS，TEM，SAED，FT-IR，Raman，XPS，BET，UV-vis和光电流等表征方法分析了催化剂的结构、形貌、化学组成、元素价态、孔结构、带隙能、光学性质和载流子复合效率.结果表明，与BiOCl的斜四方体相比，m-Bi₂O₄/BiOCl复合催化剂呈现纳米片状结构，氯离子进入晶格的内部，颜色也由BiOCl原来的深褐色变为黄色.m-Bi₂O₄/BiOCl为介孔结构，比表面积为112.90m²/g，其吸收波长红移，由紫外光扩展至可见光区域，带隙能也由3.2降低为1.87eV，能带弯曲形成p-n异质结，提高了电子-空穴的转移效率，抑制其复合；m-Bi₂O₄/BiOCl的光电流密度高于m-Bi₂O₄和BiOCl，电子-空穴的分离效率更高，因而其催化性能更优越.

关键词: 四氧化二铋, 光催化, 甲基橙, 四环素, 降解机理

Abstract:

A novel p-n heterostructure photocatalyst m-Bi₂O₄/BiOCl was successfully synthetized through a facile ion-etching method. Via adjusting the added volume of HCl solution, a series of different ratios of composite photocatalysts were obtained. The as-prepared samples of physical, chemical and optical characteristics were examined by X-ray diffraction, scanning electron microscope, transmission electron microscope, energy dispersive X-ray spectroscopy, selected-area electron diffraction, Fourier transform infrared absorption, Raman microscope, N₂ adsorption-desorption, X-ray photoelectron spectroscopy and UV-vis spectrum technologies. The photocatalysts showed high degradation rate and complete mineralization ability for methyl orange and tetracycline solution under visible light. The reaction rate constant of m-Bi₂O₄/BiOCl for methyl orange was 52.28 times higher than that of BiOCl. The characterization presented a good stability of materials. Furthermore, the photocurrent response test certified that the heterostructure effectively accelerated the separation and migration of photo-generated carries. The scavenger experiments evidenced that hole (h⁺) and superoxide radical (·O₂^-) were the primary active radicals. A possible photocatalytic mechanism was proposed. This work provided an alternative photocatalyst applied to water environmental remediation.

Key words: Dibismuth tetroxide, Photocatalysis, Methylene orange, Tetracycline, Degradation mechanism

王隽秀, 张振宗, 汪曦, 沈奕, 郭永福, Po Keung Wong, 白仁碧. 离子刻蚀法制备具有高效催化性能的m-Bi₂O₄/BiOCl p-n异质结催化剂[J]. 催化学报, 2018, 39(11): 1792-1803.

Junxiu Wang, Zhenzong Zhang, Xi Wang, Yi Shen, Yongfu Guo, Po Keung Wong, Renbi Bai. Synthesis of novel p-n heterojunction m-Bi₂O₄/BiOCl nanocomposite with excellent photocatalytic activity through ion-etching method[J]. Chinese Journal of Catalysis, 2018, 39(11): 1792-1803.

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离子刻蚀法制备具有高效催化性能的m-Bi₂O₄/BiOCl p-n异质结催化剂

Synthesis of novel p-n heterojunction m-Bi₂O₄/BiOCl nanocomposite with excellent photocatalytic activity through ion-etching method

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