无缺陷和氧缺陷二氧化钛的光催化活性

doi:10.1016/S1872-2067(17)62999-1

催化学报 ›› 2018, Vol. 39 ›› Issue (4): 867-875.DOI: 10.1016/S1872-2067(17)62999-1

• 论文 • 上一篇

无缺陷和氧缺陷二氧化钛的光催化活性

刘书源^a, 戚克振^b,c, 仇萌^d

a 沈阳师范大学化学化工学院能源与环境催化研究所, 辽宁沈阳 110034;
b 沈阳医学院药理教研室, 辽宁沈阳 110034;
c 南开大学化学学院先进能源材料化学教育部重点实验室, 天津 300071;
d 深圳大学光电工程学院, 广东深圳 518060

收稿日期:2017-11-20 修回日期:2017-12-30 出版日期:2018-04-18 发布日期:2018-04-08
通讯作者: 刘书源, 仇萌
基金资助:
国家自然科学基金（51602207）；沈阳医学院博士科研启动基金（20174043）；沈阳医学院大学生科研项目（20160809）；辽宁省博士科研启动基金（201601149，20170520011）.

Photocatalytic performance of TiO₂ nanocrystals with/without oxygen defects

Kezhen Qi^a, Shu-yuan Liu^b,c, Meng Qiu^d

a Institute of Catalysis for Energy and Environment, College of Chemistry and Chemical Engineering, Shenyang Normal University, Shenyang 110034, Liaoning, China;
b Department of Pharmacology, Shenyang Medical College, Shenyang 110034, Liaoning, China;
c Key Laboratory of Advanced Energy Materials Chemistry(Ministry of Education), College of Chemistry, Nankai University, Tianjin 300071, China;
d College of Optoelectronic Engineering, Shenzhen University, Shenzhen 518060, Guangdong, China

Received:2017-11-20 Revised:2017-12-30 Online:2018-04-18 Published:2018-04-08
Contact: 10.1016/S1872-2067(17)62999-1
Supported by:
This work was supported by the National Natural Science Foundation of China (51602207), the Doctoral Scientific Research Foundation of Shenyang Medical College (20174043), the Scientific Research Project for University Students of Shenyang Medical College (20160809), and the Doctoral Scientific Research Foundation of Liaoning Province (201601149, 20170520011).

摘要/Abstract

摘要：

随着全球工业的发展，大量有机污染物排放到水中，已经威胁到人类健康.自1972年Fujishima和Honda发现TiO₂半导体材料可在光照下分解水以来，光催化技术作为一种新型污水处理方法引起广泛重视.近几十年来，光催化已被广泛研究，已成为水体净化领域最有前途的方法之一.TiO₂光催化剂由于具有无毒、耐腐蚀、高稳定和低成本等特点，在光催化领域受到广泛关注，是最具有开发前景的光催化材料之一.然而，TiO₂的禁带较宽，只能吸收仅占太阳光4%的紫外光部分，这严重限制了TiO₂光催化材料对太阳光的有效应用.最新研究结果表明，适量缺陷的存在可以拓展TiO₂对可见光的响应，从而通过提高其对太阳光的利用效率来有效提升TiO₂的光催化活性.因此，研究半导体缺陷与其光催化剂性能的关系，对于提升光催化污染物降解性能具有重要意义.
本工作采用水热法和溶胶-凝胶法分别制备了具有氧缺陷的和无缺陷的TiO₂，用于研究氧缺陷对TiO₂光催化活性的影响.所制备的氧缺陷TiO₂纳米材料为浅蓝色，光的吸收波长向可见光区（~420nm）拓展.拉曼光谱和X射线光电子能谱（XPS）测试均证明溶胶-凝胶法制备的TiO₂中氧空缺位的浓度低于水热合成TiO₂的氧空缺位浓度.光化学测试结果表明，氧缺陷TiO₂在模拟太阳光下的光电流响应增强，这是由于氧缺陷的引入导致能带隙内出现了新的电子态，使得禁带宽度变窄.在光降解亚甲基蓝（MB）的实验中，氧缺陷TiO₂材料表现出更高的光催化活性.根据密度泛函理论（DFT）计算和荧光光谱测试结果，讨论了氧缺陷TiO₂的光催化机理.

关键词: 二氧化钛, 缺陷, 光学性质, 光催化活性, 密度泛函理论计算

Abstract:

To investigate the role of oxygen defects on the photocatalytic activity of TiO₂, the TiO₂ nanocrystals with/without oxygen defects are successfully synthesized by the hydrothermal and sol-gel methods, respectively. The as-prepared TiO₂ nanocrystals with defects are light blue and the absorption edge of light is towards the visible light region (~420 nm). Raman and X-ray photoelectron spectroscopy (XPS) measurements all confirm that the concentration of oxygen vacancies in the TiO₂ synthesized by the sol-gel method is less than that synthesized through the hydrothermal route. The introduction of oxygen defects contributes to a new state in the band gap that narrows the band gap, which is the reason for the extension of light absorption into the visible light region. The photocurrent results confirm that this band-gap narrowing enhances the photocurrent response under simulated solar light irradiation. The TiO₂ with oxygen defects shows a higher photocatalytic activity for decomposition of a methylene blue solution compared with that of the perfect TiO₂ sample. The photocatalytic mechanism is discussed based on the density functional theory calculations and photoluminescence spectroscopy measurements.

Key words: TiO₂, Defect, Optical property, Photocatalytic activity, Density functional theory calculation

刘书源, 戚克振, 仇萌. 无缺陷和氧缺陷二氧化钛的光催化活性[J]. 催化学报, 2018, 39(4): 867-875.

Kezhen Qi, Shu-yuan Liu, Meng Qiu. Photocatalytic performance of TiO₂ nanocrystals with/without oxygen defects[J]. Chinese Journal of Catalysis, 2018, 39(4): 867-875.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(17)62999-1

https://www.cjcatal.com/CN/Y2018/V39/I4/867

参考文献

[1] A. Fujishima, K. Honda, Nature, 1972, 238, 37-38.
[2] J. Kuncewicz, P. Zabek, K. Kruczala, K. Szacilowski, W. Macyk, J. Phys. Chem. C, 2012, 116, 21762-21770.
[3] M. Pacia, P. Warszyński, W. Macyk, Dalton Trans., 2014, 43, 12480-12485.
[4] S. W. Liu, J. Q. Xia, J. G. Yu, ACS Appl. Mater. Interfaces, 2015, 7, 8166-8175.
[5] C. P. Sajan, S. Wageh, A. A. Al-Ghamdi, J. G. Yu, S. W. Cao, Nano Res., 2016, 9, 3-27.
[6] J. Q. Wen, X. Li, W. Liu, Y. P. Fang, J. Xie, Y. H. Xu, Chin. J. Catal., 2015, 36, 2049-2070.
[7] Q. J. Xiang, J. G. Yu, M. Jaroniec, Phys. Chem. Chem. Phys., 2011, 13, 4853-4861.
[8] J. G. Yu, G. P. Dai, Q. J. Xiang, M. Jaroniec, J. Mater. Chem., 2011, 21, 1049-1057.
[9] W. L. Yu, J. F. Zhang, T. Y. Peng, Appl. Catal. B, 2016, 181, 220-227.
[10] M. H. N. Assadi, D. A. H. Hanaor, Appl. Surf. Sci., 2016, 387, 682-689.
[11] T. Xiong, H. W. Huang, Y. J. Sun, F. Dong, J. Mater. Chem. A, 2015, 3, 6118-6127.
[12] S Sakthivel, M. V. Shankar, M. Palanichamy, B. Arabindoo, D. W. Bahnemann, V. Murugesan, Water Res., 2004, 38, 3001-3008.
[13] X. F. Wang, R. Yu, K. Wang, G. Q. Yang, H. G. Yu, Chin. J. Catal., 2015, 36, 2211-2218.
[14] X. F. Zhu, B. Cheng, J. G. Yu, W. Ho, Appl. Surf. Sci., 2016, 364, 808-814.
[15] A. Y. Meng, J. Zhang, D. F. Xu, B. Cheng, J. G. Yu, Appl. Catal. B, 2016, 198, 286-294.
[16] X. Li, J. G. Yu, M. Jaroniec, Chem. Soc. Rev., 2016, 45, 2603-2636.
[17] H. L. Zhao, J. T. Chen, G. Y. Rao, W. Deng, Y. Li, Appl. Surf. Sci., 2017, 404, 49-56.
[18] J. Q. Wen, J. Xie, R. C. Shen, X. Li, X. Y. Luo, H. D. Zhang, A. P. Zhang, G. C. Bi, Dalton Trans., 2017, 46, 1794-1802.
[19] F. Wang, Y. Zhou, P. Li, L. B. Kuai, Z. G. Zou, Chin. J. Catal., 2016, 37, 863-868.
[20] X. L. Wang, S. Shen, Z. C. Feng, C. Li, Chin. J. Catal., 2016, 37, 2059-2068.
[21] Y. F. Li, W. P. Zhang, X. Shen, P. F. Peng, L. B. Xiong, Y. Yu, Chin. J. Catal., 2015, 36, 2229-2236.
[22] L. Pan, J. W. Zhang, X. Jia, Y. H. Ma, X. W. Zhang, L. Wang, J. J. Zou, Chin. J. Catal., 2017, 38, 253-259.
[23] K. Z. Qi, F. Zasada, W. Piskorz, P. Indyka, J. Grybos, M. Trochowski, M. Buchalska, M. Kobielusz, W. Macyk, Z. Sojka, J. Phys. Chem. C, 2016, 120, 5442-5456.
[24] F. J. Wu, W. Liu, J. L. Qiu, J. Z. Li, W. Y. Zhou, Y. P. Fang, S. T. Zhang, X. Li, Appl. Surf. Sci., 2015, 358, 425-435.
[25] K. Z. Qi, R. Selvaraj, T. A. Fahdi, S. Al-Kindy, Y. Kim, G. C. Wang, C. W. Tai, M. Sillanpää, Appl. Surf. Sci., 2016, 387, 750-758.
[26] J. G. Yu, T. T. Ma, G. Liu, B. Cheng, Dalton Trans., 2011, 40, 6635-6644.
[27] W. K. Wang, D. F. Xu, B. Cheng, J. G. Yu, C. J. Jiang, J. Mater. Chem. A, 2017, 5, 5020-5029.
[28] M. R. Hoffmann, S. T. Martin, W. Choi, D. W. Bahnemann, Chem. Rev., 1995, 95, 69-96.
[29] S. U. M. Khan, M. Al-Shahry, W. B. Ingler Jr, Science, 2002, 297, 2243-2245.
[30] Z. Y. Huang, Z. G. Gao, S. M. Gao, Q. Y. Wang, Z. Y. Wang, B. B. Huang, Y. Dai, Chin. J. Catal., 2017, 38, 821-830.
[31] M. S. Akple, J. X. Low, Z. Y. Qin, S. Wageh, A. A. Al-Ghamdi, J. G. Yu, S. W. Liu, Chin. J. Catal., 2015, 36, 2127-2134.
[32] F. Zuo, L. Wang, T. Wu, Z. Y. Zhang, D. Borchardt, P. Y. Feng, J. Am. Chem. Soc., 2010, 132, 11856-11857.
[33] L. Li, H. W. Tian, F. L. Meng, X. Y. Hu, W. T. Zheng, C. Q. Sun, Appl. Surf. Sci., 2014, 317, 568-572.
[34] J. Z. Ma, H. M. Wu, Y. C. Liu, H. He, J. Phys. Chem. C, 2014, 118, 7434-7441.
[35] H. L. Guo, Q. Zhu, X. L. Wu, Y. F. Jiang, X. Xie, A. W. Xu, Nanoscale, 2015, 7, 7216-7223.
[36] K. Z. Qi, B. Cheng, J. G. Yu, W. Ho, J. Alloys Compd., 2017, 727, 792-820.
[37] T. Xiong, W. L. Cen, Y. X. Zhang, F. Dong, ACS Catal., 2016, 6, 2462-2472.
[38] J. Q. Wen, J. Xie, X. B. Chen, X. Li, Appl. Surf. Sci., 2017, 391, 72-123.
[39] Z. W. Zhao, Y. J. Sun, F. Dong, Nanoscale, 2015, 7, 15-37.
[40] Y. C. Huang, B. Long, M. N. Tang, Z. B. Rui, M. S. Balogun, Y. X. Tong, H. B. Ji, Appl. Catal. B, 2016, 181, 779-787.
[41] L. Schwertmann, M. Wark, R. Marschall, RSC Adv., 2013, 3, 18908-18915.
[42] S. Ma, J. Xie, J. Q. Wen, K. L. He, X. Li, W. Liu, X. C. Zhang, Appl. Surf. Sci., 2017, 391, 580-591.
[43] J. Y. Shi, H. N. Cui, Z. X. Liang, X. H. Lu, Y. X. Tong, C. Y. Su, H. Liu, Energy Environ. Sci., 2011, 4, 466-470.
[44] Y. S. Li, Z. L. Tang, J. Y. Zhang, Z. T. Zhang, J. Phys. Chem. C, 2016, 120, 9750-9763.
[45] M. Qiu, D. Q. Zhu, X. C. Bao, J. Y. Wang, X. F. Wang, R. Q. Yang, J. Mater. Chem. A, 2016, 4, 894-900.
[46] G. Kresse, J. Hafner, Phys. Rev. B, 1994, 49, 14251-14269.
[47] G. Kresse, J. Furthmüller, Comput. Mater. Sci., 1996, 6, 15-50.
[48] J. P. Perdew, J. A. Chevary, S. H. Vosko, K. A. Jackson, M. R. Peder-son, D. J. Singh, C. Fiolhais, Phys. Rev. B, 1992, 46, 6671-6687.
[49] P. E. Blöchl, Phys. Rev. B, 1994, 50, 17953-17979.
[50] G. Kresse, D. Joubert, Phys. Rev. B, 1999, 59, 1758-1775.
[51] A. S. Barnard, P. Zapol, L. A. Curtiss, J. Chem. Theory Comput., 2005, 1, 107-116.
[52] H. J. Monkhorst, J. D. Pack, Phys. Rev. B, 1976, 13, 5188-5192.
[53] J. Q. Yan, G. J. Wu, N. J. Guan, L. D. Li, Z. X. Li, X. Z. Cao, Phys. Chem. Chem. Phys., 2013, 15, 10978-10988.
[54] A. S. Barnard, L. A. Curtiss, Nano Lett., 2005, 5, 1261-1266.
[55] G. L. Zhu, T. Q. Lin, X. J. Lü, W. Zhao, C. Y. Yang, Z. Wang, H. Yin, Z. Q. Liu, F. Q. Huang, J. H. Lin, J. Mater. Chem. A, 2013, 1, 9650-9653.
[56] Z. Wang, C. Y. Yang, T. Q. Lin, H. Yin, P. Chen, D. Y. Wan, F. F. Xu, F. Q. Huang, J. H. Lin, X. M. Xie, M. H. Jiang, Energy Environ. Sci., 2013, 6, 3007-3014.
[57] J. H. Zheng, Q. Jiang, J. S. Lian, Appl. Surf. Sci., 2011, 257, 5083-5087.
[58] X. G. Han, H. Z. He, Q. Kuang, X. Zhou, X. H. Zhang, T. Xu, Z. X. Xie, L. S. Zheng, J. Phys. Chem. C, 2009, 113, 584-589.
[59] X. B. Chen, S. S. Mao, Chem. Rev., 2007, 107, 2891-2959.
[60] J. Zhang, F. J. Shi, J. Lin, D. F. Chen, J. M. Gao, Z. X. Huang, X. X. Ding, C. C. Tang, Chem. Mater., 2008, 20, 2937-2941.
[61] A. Naldoni, M. Allieta, S. Santangelo, M. Marelli, F. Fabbri, S. Cappelli, C. L. Bianchi, R. Psaro, V. D. Santo, J. Am. Chem. Soc., 2012, 134, 7600-7603.
[62] Y. Yan, M. Han, A. Konkin, T. Koppe, D. Wang, T. Andreu, G. Chen, U. Vetter, J. R. Morante, P. Schaaf, J. Mater. Chem. A, 2014, 2, 12708-12716.
[63] L, L. Tan, W. J. Ong, S. P. Chai, A. R. Mohamed, Chem. Commun., 2014, 50, 6923-6926.
[64] L. Q. Jing, Y. C. Qu, B. Q. Wang, S. D. Li, B. J. Jiang, L. B. Yang, W. Fu, H. G. Fu, Z. J. Sun, Sol. Energy Mater. Sol. Cells, 2006, 90, 1773-1787.
[65] V. Saxena, D. K. Aswal, M. Kaur, S. P. Koiry, S. K. Gupta, J. V. Yakhmi, R. J. Kshirsagar, S. K. Deshpande, Appl. Phys. Lett., 2007, 90, 043516.

无缺陷和氧缺陷二氧化钛的光催化活性

Photocatalytic performance of TiO₂ nanocrystals with/without oxygen defects

PDF

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

参考文献

相关文章 15

编辑推荐

Metrics

[1]	胡金念, 田玲婵, 王海燕, 孟洋, 梁锦霞, 朱纯, 李隽. MXene负载3d金属单原子高效氮还原电催化剂的理论筛选[J]. 催化学报, 2023, 52(9): 252-262.
[2]	韩璟怡, 管景奇. 通过表面镧改性和体相锰掺杂协助钴尖晶石酸性下析氧[J]. 催化学报, 2023, 51(8): 1-4.
[3]	赵磊, 张震, 朱昭昭, 李平波, 蒋金霞, 杨婷婷, 熊佩, 安旭光, 牛晓滨, 齐学强, 陈俊松, 吴睿. 缺陷氮掺杂碳耦合Co-N₅单原子位点用于高效锌-空气电池[J]. 催化学报, 2023, 51(8): 216-224.
[4]	王潇涵, 田汉, 余旭, 陈立松, 崔香枝, 施剑林. 非晶相电催化剂在电解水领域的研究进展[J]. 催化学报, 2023, 51(8): 5-48.
[5]	乔秀清, 李晨, 王紫昭, 侯东芳, 李东升. TiO_2-_x@C/MoO₂肖特基结: 合理设计及高效电荷分离提升光催化性能[J]. 催化学报, 2023, 51(8): 66-79.
[6]	井会娟, 龙军, 李欢, 傅笑言, 肖建平. 电催化硝酸盐还原合成氨电势相关性的计算见解[J]. 催化学报, 2023, 48(5): 205-213.
[7]	韦之栋, 严嘉玮, 郭伟琦, 上官文峰. 多面体SrTiO₃原位生长N缺陷PCN中的纳米叠层效应助力光催化完全分解水: 内建电场调控的协同机制[J]. 催化学报, 2023, 48(5): 279-289.
[8]	赵志月, 蒋志伟, 黄一哲, Mebrouka Boubeche, Valentina G. Matveeva, Hector F. Garces, 罗惠霞, 严凯. 富空穴CoSi合金无溶剂无碱醇氧化[J]. 催化学报, 2023, 48(5): 175-184.
[9]	姜润, 乔泽龙, 许昊翔, 曹达鹏. 用于氧还原反应的Fe-N-C单原子催化剂的缺陷工程[J]. 催化学报, 2023, 48(5): 224-234.
[10]	刘小妮, 刘晓斌, 李彩霞, 杨波, 王磊. 缺陷工程在金属基电池中的研究进展[J]. 催化学报, 2023, 45(2): 27-87.
[11]	王伟康, 梅少斌, 蒋浩朋, 王乐乐, 唐华, 刘芹芹. 二氧化钛基S型异质结光催化剂的研究进展[J]. 催化学报, 2023, 55(12): 137-158.
[12]	刘成, 刘胡润卿, 余济美, 吴棱, 李朝辉. 高效光催化金属有机框架(MOFs)的构筑策略[J]. 催化学报, 2023, 55(12): 1-19.
[13]	杨竣皓, 安露露, 王双, 张辰浩, 罗官宇, 陈应泉, 杨会颖, 王得丽. 层状双氢氧化物基电解水催化剂的缺陷工程调控策略[J]. 催化学报, 2023, 55(12): 116-136.
[14]	张宁, 杜家毅, 周纳, 王德鹏, 鲍迪, 钟海霞, 张新波. 高价金属钽掺杂无定型氧化铱用于酸性氧析出反应[J]. 催化学报, 2023, 53(10): 134-142.
[15]	李楠, 王传义, 章柯, 吕海钦, 苑明哲, Detlef W. Bahnemann. 光催化转化低浓度NO的进展与展望[J]. 催化学报, 2022, 43(9): 2363-2387.

无缺陷和氧缺陷二氧化钛的光催化活性

Photocatalytic performance of TiO2 nanocrystals with/without oxygen defects

PDF

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

参考文献

相关文章 15

编辑推荐

Metrics

Photocatalytic performance of TiO₂ nanocrystals with/without oxygen defects