催化学报

催化学报 ›› 2019, Vol. 40 ›› Issue (3): 380-389.DOI: 10.1016/S1872-2067(18)63166-3

• 论文 • 上一篇    下一篇

利用有机助剂提高TiO2光催化产氢和降解性能

沈珺a, 王瑞b, 刘芹芹b, 杨小飞c, 唐华c, 杨进b   

  1. a 苏州卫生职业技术学院药学院, 江苏苏州 215009;
    b 江苏大学材料科学与工程学院, 江苏镇江 212013;
    c 南京林业大学理学院化学系, 江苏南京 212237
  • 收稿日期:2018-08-31 修回日期:2018-09-21 出版日期:2019-03-18 发布日期:2019-02-22
  • 通讯作者: 刘芹芹
  • 基金资助:

    国家自然科学基金（51672113，51602132）；江苏省六大人才高峰计划（2015-XCL-026）；江苏省自然科学基金（BK20171299）；江苏大学"青年骨干教师培训工程"青年学术带头人培育人选（5521220009）；江苏省卫生计生委2016年度青年科研课题（Q201609）.

Accelerating photocatalytic hydrogen evolution and pollutant degradation by coupling organic co-catalysts with TiO2

Jun Shena, Rui Wangb, Qinqin Liub, Xiaofei Yangc, Hua Tangc, Jin Yangb   

  1. a School of Pharmacy, Suzhou Vocational Health College, Suzhou 215009, Jiangsu, China;
    b School of Materials Science and Engineering, Jiangsu University, Zhenjiang 212013, Jiangsu, China;
    c Department of Chemistry, College of Science, Nanjing Forestry University, Nanjing 210037, Jiangsu, China
  • Received:2018-08-31 Revised:2018-09-21 Online:2019-03-18 Published:2019-02-22
  • Supported by:

    This work was supported by the National Natural Science Foundation of China (51672113, 51602132), the Six Talent Peaks Project in Jiangsu Province (2015-XCL-026), the Natural Science Foundation of Jiangsu Province (BK20171299), the Training Project of Jiangsu University for Young Cadre Teachers (5521220009), and the Youth Research Project of Jiangsu Health and Family Planning Commission in 2016 (Q201609).

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摘要：

采用助催化剂加速光催化材料中空穴-电子对的分离提高光催化效率的有效方法.本文以有机分子草酰胺（OA）作为新型助催化剂来促进TiO2光催化材料的光生载流子分离，从而增强其光催化H2释放和染料降解性能.最佳TiO2-OA复合光催化剂上H2的析出和罗丹明B的光催化效率分别达到2371 μmol g-1 h-1和1.43×10-2 min-1，分别是TiO2的2.4和3.8倍.系统研究了光催化增强的可能机理，并提出OA凭借其π-共轭结构作为助催化剂，不仅增强了TiO2的光吸收，而且促进了空穴转移，因而达到了加速电荷分离的效果.
利用湿化学法合成了TiO2-OA光催化材料，并采用X射线衍射（XRD）、X射线光电子能谱（XPS）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）、红外光谱（FT-IR）以及紫外-可见漫反射光谱（UV-vis）等表征方法对该催化剂的结构特征、微观形貌和光学性能进行分析，并研究了TiO2-OA复合材料的光催化性能.SEM和TEM结果表明，TiO2-OA呈方形，尺寸约为30 nm.OA含量为30 wt%的TiO2-OA样品在用于制氢的光催化水分解反应中表现最佳.同时研究了TiO2-OA光催化剂的光催化机理，用对苯醌、乙二胺四乙酸二钠和正丁醇进行了自由基捕捉剂实验.结果表明，羟基自由基在降解有机染料过程中起主要作用.通过光电流测试、材料价带导带位置计算以及·O2和·OH定量实验并结合文献分析认为，掺入具有独特π-共轭结构的OA可以提供空穴转移位点，从而极大地促进TiO2和OA之间光生电子-空穴的分离和转移.本工作可能为构建具有新型有机助催化剂的高效光催化体系开辟了一条新途径.

关键词: 二氧化钛, 草酰胺, 助催化剂, 光催化, 制氢, 染料降解

Abstract:

Accelerating the separation efficiency of photoexcited electron-hole pairs with the help of highly active co-catalysts has proven to be a promising approach for improving photocatalytic activity. Thus far, the most developed co-catalysts for semiconductor-based photocatalysis are inorganic materials; the employment of a specific organic molecule as a co-catalyst for photocatalytic hydrogen evolution and pollutant photodegradation is rare and still remains a challenging task. Herein, we report on the use of an organic molecule, oxamide (OA), as a novel co-catalyst to enhance electron-hole separation, photocatalytic H2 evolution, and dye degradation over TiO2 nanosheets. OA-modified TiO2 samples were prepared by a wet chemical route and demonstrated improved light absorption in the visible-light region and more efficient charge transport. The photocatalytic performance of H2 evolution from water splitting and rhodamine B (RhB) degradation for an optimal OA-modified TiO2 photocatalyst reached 2.37 mmol g-1 h-1 and 1.43×10-2 min-1, respectively, which were 2.4 and 3.8 times higher than those of pristine TiO2, respectively. A possible mechanism is proposed, in which the specific π-conjugated structure of OA is suggested to play a key role in the enhancement of the charge transfer and catalytic capability of TiO2. This work may provide advanced insight into the development of a variety of metal-free organic molecules as functional co-catalysts for improved solar-to-fuel conversion and environmental remediation.

Key words: TiO2, Oxamide, Co-catalyst, Photocatalysis, Hydrogen evolution, Dye degradation