离子交换法制备高光催化活性Bi2WO6@Bi2S3异质结纳米片

引用本文: 黄婷婷, 李雨涵, 伍晓峰, 吕康乐, 李覃, 李玫, 杜冬云, 叶恒朋. 离子交换法制备高光催化活性Bi₂WO₆@Bi₂S₃异质结纳米片[J]. 催化学报, 2018, 39(4): 718-727. doi: 10.1016/S1872-2067(17)62913-9 shu

Citation: Tingting Huang, Yuhan Li, Xiaofeng Wu, Kangle Lv, Qin Li, Mei Li, Dongyun Du, Hengpeng Ye. In-situ transformation of Bi₂WO₆ to highly photoreactive Bi₂WO₆@Bi₂S₃ nanoplate via ion exchange[J]. Chinese Journal of Catalysis, 2018, 39(4): 718-727. doi: 10.1016/S1872-2067(17)62913-9 shu

离子交换法制备高光催化活性Bi₂WO₆@Bi₂S₃异质结纳米片

黄婷婷 ^a, ,
李雨涵 ^a,b, ,
伍晓峰 ^a, ,
吕康乐 ^a, ,
李覃 ^a, ,
李玫 ^a, ,
杜冬云 ^a, ,
叶恒朋 ^a,

a 中南民族大学资源与环境学院催化材料科学湖北省重点实验室, 湖北武汉 430074;
b 香港教育大学科学与环境系, 香港
基金项目:
国家自然科学基金（51672312，21571192，21373275）；武汉市科技计划（2016010101010018，2015070504020220）；"十二五"国家科技支撑计划（2015BAB01B01）；中南民族大学自然科学基金（XTZ15016，CZP17062）.

摘要: 社会经济快速发展的同时，也带来了日益严峻的环境污染问题.半导体光催化氧化技术因节能环保而在环境领域有广阔的应用前景.作为最具有代表性的半导体光催化材料，TiO₂因为其禁带宽度（3.2eV）比较大，只能被紫外光激发，因而对太阳能的利用率较低.作为一种最简单的含铋层状氧化物，Bi₂WO₆的禁带宽度（2.7eV）相对较小，可以部分利用太阳光中的可见光，因而受到广大研究者的青睐.但是，Bi₂WO₆光催化材料的可见光响应范围较窄，仅能被波长小于450nm的光激发，且激发后的光生载流子容易复合，导致光催化效率不高.因此，迫切需要对Bi₂WO₆光催化材料进行结构修饰与改性，采用拓展其光响应范围和抑制载流子复合，来提高其光催化活性.
本文采用离子交换法原位合成了具有核-壳结构的Bi₂S₃@Bi₂WO₆纳米片，充分利用Bi₂S₃优良的可见光响应性能和半导体异质结光催化剂的构建，来提高Bi₂WO₆的光催化活性.结果表明，随着Na₂S·9H₂O用量从0增加到1.5g，所得催化剂的光活性不断提高，X3B的降解速率常数由0.40×10^-3 min^-1增加到6.6×10^-3 min^-1，催化剂活性提高了16.5倍.当进一步增加Na2S·9H2O的用量时（1.5-3.0g），复合催化剂的光活性下降.这是由于过多Na2S·9H2O的引入导致在催化剂表面生成了没有光活性的NaBiS₂层（Bi₂S₃+Na₂S=2NaBiS₂），占据了催化剂的活性位点，阻碍了染料分子与催化剂的直接接触.Bi₂WO₆@Bi₂S₃异质结纳米片光活性的提高，可归因于Bi₂S₃的敏化作用极大拓展了复合催化剂的光响应范围；另一方面，Bi₂WO₆和Bi₂S₃两者之间的半导体异质结效应有效促进了光生载流子在空间的有效分离，抑制了光生电子-空穴的复合，从而提高了复合催化剂的催化效率.本研究为其他半导体复合材料的原位生长制备提供了新的思路.

关键词:

English

In-situ transformation of Bi₂WO₆ to highly photoreactive Bi₂WO₆@Bi₂S₃ nanoplate via ion exchange

a Key Laboratory of Catalysis and Materials Science of the State Ethnic Affairs Commission & Ministry of Education, Hubei Province, College of Resources and Environmental Science, South-Central University for Nationalities, Wuhan 430074, Hubei, China;
b Department of Science and Environmental Studies, The Education University of Hong Kong, Tai Po, N. T., Hong Kong, China
Received Date: 22 October 2017
Revised Date: 26 November 2017
Fund Project:
This work was supported by the National Natural Science Foundation of China (51672312, 21571192, 21373275), the Science and Technology Program of Wuhan (2016010101010018, 2015070504020220), the Key Project in the National Science & Technology Pillar Program during the Twelfth Five-Year Plan Period (2015BAB01B01), and the Natural Science Foundation of South-Central University for Nationalities (XTZ15016, CZP17062).

Abstract: As a two dimensional (2D) visible-light-responsive semiconductor photocatalyst, the photoreactivity of Bi₂WO₆ is not high enough for practical application owing to its limited response to visible light and rapid recombination of photogenerated electron-hole pairs. In this paper, 2D core-shell structured Bi₂WO₆@Bi₂S₃ nanoplates were prepared by calcination of a mixture of Bi₂WO₆ (1.3 g) and a certain amount of Na₂S·9H₂O (0-3.0 g) at 350℃ for 2 h. The reactivity of the resulting photocatalyst materials was evaluated by photocatalytic degradation of Brilliant Red X-3B (X3B), an anionic dye, under visible light irradiation (λ > 420 nm). As the amount of Na₂S·9H₂O was increased from 0 to 1.5 g, the degradation rate constant of X3B sharply increased from 0.40×10^-3 to 6.6×10^-3 min^-1. The enhanced photocatalytic activity of Bi₂WO₆@Bi₂S₃ was attributed to the photosensitization of Bi₂S₃, which greatly extended the light-responsive range from the visible to the NIR, and the formation of a heterojunction, which retarded the recombination rate of photogenerated electron-hole pairs. However, further increases in the amount of Na₂S·9H₂O (from 1.5 to 3.0 g) resulted in a decrease of the photocatalytic activity of the Bi₂WO₆@Bi₂S₃ nanoplates owing to the formation of a photo-inactive NaBiS₂ layer covering the Bi₂WO₆ surface.

Key words:

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离子交换法制备高光催化活性Bi₂WO₆@Bi₂S₃异质结纳米片

English

In-situ transformation of Bi₂WO₆ to highly photoreactive Bi₂WO₆@Bi₂S₃ nanoplate via ion exchange

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