过渡金属掺杂构建超细二氧化钛的表面缺陷以提升光催化产氢活性

doi:10.1016/S1872-2067(18)63044-X

催化学报 ›› 2018, Vol. 39 ›› Issue (3): 542-548.DOI: 10.1016/S1872-2067(18)63044-X

• 论文 • 上一篇

过渡金属掺杂构建超细二氧化钛的表面缺陷以提升光催化产氢活性

刘祺凤^a, 张倩^a, 刘丙蕊^a, 李仕友^b, 马晶军^a,c

a 河北农业大学理工学院, 河北黄骅 061100;
b 南华大学污染控制与资源化技术湖南省重点实验室, 湖南衡阳 421001;
c 河北省农产品加工工程技术研究中心, 河北保定 071001

收稿日期:2018-01-23 修回日期:2018-02-05 出版日期:2018-03-18 发布日期:2018-03-10
通讯作者: 李仕友, 马晶军
基金资助:
河北省食品科学与工程学科"双一流"建设资金项目（2018SPGCA18）；河北省高等学校青年拔尖人才计划项目（自然科学类，BJ2017026）；河北农业大学引进博士专项（ZD201709）.

Building surface defects by doping with transition metal on ultrafine TiO₂ to enhance the photocatalytic H₂ production activity

Qi-Feng Liu^a, Qian Zhang^a, Bing-Rui Liu^a, Shiyou Li^b, Jing-Jun Ma^a,c

a College of Science and Technology, Agricultural University of Hebei, Huanghua 061100, Hebei, China;
b Hunan Provincial Key Laboratory of Pollution Control and Resources Technology, University of South China, Hengyang 421001, Hunan, China;
c Hebei Agricultural Products Processing Engineering Technology Research Center, Baoding 071001, Hebei, China

Received:2018-01-23 Revised:2018-02-05 Online:2018-03-18 Published:2018-03-10
Contact: 10.1016/S1872-2067(18)63044-X
Supported by:
This work was supported by the Double First-rate Subject-Food Science and Engineering Program of Hebei Province (2018SPGCA18), Young Tip-top Talents Plan of Universities and Colleges in Hebei Province of China (BJ2017026), and the Specific Foundation for Doctor in Hebei Agriculture University of China (ZD201709).

摘要/Abstract

摘要：

载流子分离效率低和光吸收范围窄是制约二氧化钛光催化产氢活性的两个关键因素.研究表明，一定浓度的表面缺陷既有利于光生载流子传递到表面缺陷位点，抑制载流子的复合，又可以扩展光催化剂的光谱吸收范围，从而提高光催化活性.本文利用低成本过渡金属（Co，Ni，Cu和Mn）掺杂在超细二氧化钛表面，构建了表面缺陷（氧空位和金属阳离子取代缺陷）.相对于原始的缺陷很少的二氧化钛，表面缺陷的二氧化钛活性可以提升3-4倍，而且可见光产氢速率高达3.4 μmol/h，在365 nm处的表观量子效率达到36.9%，这些结果都远远高于商业的P25 TiO₂.我们认为，光催化产氢活性的明显提升可以归结为更快速的电荷分离和更好的光吸收.可见，利用过渡金属进行热液处理来实现表面掺杂是一种非常简便有效构建表面缺陷的方法.

关键词: 构建表面缺陷, 超细二氧化钛, 低成本过渡金属, 表面掺杂, 光催化产氢

Abstract:

Inefficient charge separation and limited light absorption are two critical issues associated with high-efficiency photocatalytic H₂ production using TiO₂. Surface defects within a certain concentration range in photocatalyst materials are beneficial for photocatalytic activity. In this study, surface defects (oxygen vacancies and metal cation replacement defects) were induced with a facile and effective approach by surface doping with low-cost transition metals (Co, Ni, Cu, and Mn) on ultrafine TiO₂. The obtained surface-defective TiO₂ exhibited a 3-4-fold improved activity compared to that of the original ultrafine TiO_2. In addition, a H₂ production rate of 3.4 μmol/h was obtained using visible light (λ > 420 nm) irradiation. The apparent quantum yield (AQY) at 365 nm reached 36.9% over TiO₂-Cu, significantly more than the commercial P25 TiO₂. The enhancement of photocatalytic H₂ production activity can be attributed to improved rapid charge separation efficiency and expanded light absorption window. This hydrothermal treatment with transition metal was proven to be a very facile and effective method for obtaining surface defects.

Key words: Construction of surface defects, Ultrafine TiO₂, Low-cost transition metal, Surface doping, Photocatalytic H₂ production

刘祺凤, 张倩, 刘丙蕊, 李仕友, 马晶军. 过渡金属掺杂构建超细二氧化钛的表面缺陷以提升光催化产氢活性[J]. 催化学报, 2018, 39(3): 542-548.

Qi-Feng Liu, Qian Zhang, Bing-Rui Liu, Shiyou Li, Jing-Jun Ma. Building surface defects by doping with transition metal on ultrafine TiO₂ to enhance the photocatalytic H₂ production activity[J]. Chinese Journal of Catalysis, 2018, 39(3): 542-548.

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过渡金属掺杂构建超细二氧化钛的表面缺陷以提升光催化产氢活性

Building surface defects by doping with transition metal on ultrafine TiO₂ to enhance the photocatalytic H₂ production activity

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过渡金属掺杂构建超细二氧化钛的表面缺陷以提升光催化产氢活性

Building surface defects by doping with transition metal on ultrafine TiO2 to enhance the photocatalytic H2 production activity

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Building surface defects by doping with transition metal on ultrafine TiO₂ to enhance the photocatalytic H₂ production activity