高光催化活性的磷氧桥连TiO2/g-C3N4纳米复合体的合成

doi:10.1016/S1872-2067(17)62850-X

催化学报 ›› 2017, Vol. 38 ›› Issue (6): 1072-1078.DOI: 10.1016/S1872-2067(17)62850-X

高光催化活性的磷氧桥连TiO₂/g-C₃N₄纳米复合体的合成

刘翀^a,b, Fazal Raziq^a, 李志军^a, 曲阳^a, Amir Zada^a, 井立强^a

a. 黑龙江大学功能无机材料化学重点实验室, 黑龙江哈尔滨 150080;
b. 黑龙江科技大学环境与化工学院, 黑龙江哈尔滨 150027

收稿日期:2017-03-23 修回日期:2017-04-19 出版日期:2017-06-18 发布日期:2017-06-08
通讯作者: 井立强
基金资助:
国家自然科学基金项目（U1401245，91622119）；教育部创新团队发展计划项目（IRT1237）；教育部研究项目（213011A）；哈尔滨市优秀青年基金项目（2014RFYXJ002）

Synthesis of TiO₂/g-C₃N₄ nanocomposites with phosphate-oxygen functional bridges for improved photocatalytic activity

Chong Liu^a,b, Fazal Raziq^a, Zhijun Li^a, Yang Qu^a, Amir Zada^a, Liqiang Jing^a

a. Key Laboratory of Functional Inorganic Materials Chemistry, Heilongjiang University, Harbin 150080, Heilongjiang, China;
b. College of Environmental and Chemical Engineering, Heilongjiang University of Science and Technology, Harbin 150027, Heilongjiang, China

Received:2017-03-23 Revised:2017-04-19 Online:2017-06-18 Published:2017-06-08
Supported by:
This work was supported by the National Natural Science Foundation of China (U1401245, 91622119), the Program for Innovative Research Team in Chinese Universities (IRT1237), the Research Project of Chinese Ministry of Education (213011A), and the Science Foundation for Excellent Youth of Harbin City of China (2014RFYXJ002)

摘要/Abstract

摘要：

石墨型氮化碳（g-C₃N₄）是一种新型非金属聚合物半导体材料，具有合理的能带结构、较好的稳定性及卓越的表面性质，因而受到了人们的广泛关注. 目前，它作为光催化剂在降解污染物、光催化分解水产氢和光催化还原CO₂方面正呈现出巨大的应用潜力. 然而，g-C₃N₄可见光响应范围窄、比表面积较小、尤其是光生载流子易复合等缺陷制约着其光催化活性的进一步提高. 针对以上问题，人们对g-C₃N₄进行了大量的改性研究，其中构建能级匹配的纳米半导体/g-C₃N₄异质结复合体是常用的有效改善g-C₃N₄光生电荷分离进而提高其光催化活性的手段. 但现有相关文献往往忽略了复合体界面接触情况对光生电荷转移和分离的影响，从而在一定程度上影响对光催化性能的改善. 本课题组前期工作表明，通过磷氧、硅氧功能桥的建立可加强TiO₂/Fe₂O₃，ZnO/BiVO₄纳米复合物的界面接触，从而促进光生电荷的迁移和分离，进而进一步提高纳米复合体的光催化活性. 这样，通过构建磷氧桥有望改善TiO₂和g-C₃N₄的紧密连接，以促进光生电子由g-C₃N₄向TiO₂的迁移、改善光生载流子的分离，进而更加显著地提高g-C₃N₄的光催化活性. 但是相关工作至今尚未见到报道.
为此，本文通过简单的湿化学法成功地合成了磷氧（P-O）桥连的TiO₂/g-C₃N₄纳米复合体，并研究了P-O功能桥对TiO₂/g-C₃N₄纳米复合体光生电荷分离及其对光催化降解污染物及还原CO₂活性的影响. 结果表明，g-C₃N₄与适量的纳米TiO₂复合，尤其是g-C₃N₄与适量P-O桥连TiO₂的复合可进一步提高g-C₃N₄的光催化活性. 基于气氛调控的表面光电压谱和光致发光谱等的分析，P-O桥连可促使g-C₃N₄的光生电子由g-C₃N₄向TiO₂转移，极大地促进了g-C₃N₄的光生电荷分离，因而使纳米复合体光催化活性大幅提高，其光催化降解2，4-DCP及还原CO₂活性均为g-C₃N₄的3倍. 此外，自由基捕获实验表明，·OH作为空穴调控的直接中间产物，其对2，4-DCP的降解起主导作用.

关键词: TiO₂/g-C₃N₄纳米复合体, 磷氧桥, 电荷转移及分离, 光催化, 二氧化碳转化

Abstract:

One of the most general methods to enhance the separation of photogenerated carriers for g-C₃N₄ is to construct a suitable heterojunctional composite, according to the principle of matching energy levels. The interface contact in the fabricated nanocomposite greatly influences the charge transfer and separation so as to determine the final photocatalytic activities. However, the role of interface contact is often neglected, and is rarely reported to date. Hence, it is possible to further enhance the photocatalytic activity of g-C₃N₄-based nanocomposite by improving the interfacial connection. Herein, phosphate-oxygen (P-O) bridged TiO₂/g-C₃N₄ nanocomposites were successfully synthesized using a simple wet chemical method, and the effects of the P-O functional bridges on the photogenerated charge separation and photocatalytic activity for pollutant degradation and CO₂ reduction were investigated. The photocatalytic activity of g-C₃N₄ was greatly improved upon coupling with an appropriate amount of nanocrystalline TiO₂, especially with P-O bridged TiO₂. Atmosphere-controlled steady-state surface photovoltage spectroscopy and photoluminescence spectroscopy analyses revealed clearly the enhancement of photogenerated charge separation of g-C₃N₄ upon coupling with the P-O bridged TiO₂, resulting from the built P-O bridges between TiO₂ and g-C₃N₄ so as to promote effective transfer of excited electrons from g-C₃N₄ to TiO₂. This enhancement was responsible for the improved photoactivity of the P-O bridged TiO₂/g-C₃N₄ nanocomposite, which exhibited three-time photocatalytic activity enhancement for 2,4-dichlorophenol degradation and CO₂ reduction compared with bare g-C₃N₄. Furthermore, radical-trapping experiments revealed that the ·OH species formed as hole-modulated direct intermediates dominated the photocatalytic degradation of 2,4-dichlorophenol. This work provides a feasible strategy for the design and synthesis of high-performance g-C₃N₄-based nanocomposite photocatalysts for pollutant degradation and CO₂ reduction.

Key words: TiO₂/graphitic carbon nitride nanocomposite, Phosphate-oxygen bridge, Charge transfer and separation, Photocatalysis, Carbon dioxide conversion

刘翀, Fazal Raziq, 李志军, 曲阳, Amir Zada, 井立强. 高光催化活性的磷氧桥连TiO₂/g-C₃N₄纳米复合体的合成[J]. 催化学报, 2017, 38(6): 1072-1078.

Chong Liu, Fazal Raziq, Zhijun Li, Yang Qu, Amir Zada, Liqiang Jing. Synthesis of TiO₂/g-C₃N₄ nanocomposites with phosphate-oxygen functional bridges for improved photocatalytic activity[J]. Chinese Journal of Catalysis, 2017, 38(6): 1072-1078.

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高光催化活性的磷氧桥连TiO₂/g-C₃N₄纳米复合体的合成

Synthesis of TiO₂/g-C₃N₄ nanocomposites with phosphate-oxygen functional bridges for improved photocatalytic activity

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