石墨烯/电气石/二氧化钛复合材料的制备及其光催化降解异丙醇性能

催化学报 ›› 2017, Vol. 38 ›› Issue (8): 1307-1314.

石墨烯/电气石/二氧化钛复合材料的制备及其光催化降解异丙醇性能

尹利利^a, 赵明^a, 胡慧林^a, 叶金花^a,b,c, 王德法^a,b

a 天津大学-日本国立物质材料研究机构国际合作实验室, 先进陶瓷与加工技术教育部重点实验室, 天津市材料复合与功能化重点实验室, 天津大学材料科学与工程学院, 天津 300072, 中国;
b 天津化学化工协同创新中心, 天津 300072, 中国;
c 日本国立物质材料研究机构, 筑波茨城305-0044, 日本

收稿日期:2016-12-29 修回日期:2017-01-28 出版日期:2017-08-18 发布日期:2017-08-04
通讯作者: 王德法
基金资助:
国家重点基础研究发展计划（973计划，2014CB239300）；国家自然科学基金（51572191）；天津市自然科学基金（13JCYBJC16600）.

Synthesis of graphene/tourmaline/TiO₂ composites with enhanced activity for photocatalytic degradation of 2-propanol

Lili Yin^a, Ming Zhao^a, Huilin Hu^a, Jinhua Ye^a,b,c, Defa Wang^a,b

a TJU-NIMS International Collaboration Laboratory, Key Laboratory of Advanced Ceramics and Machining Technology of Ministry of Education, Tianjin Key Laboratory of Composite and Functional Materials, School of Materials Science and Engineering, Tianjin University, Tianjin 300072, China;
b Collaborative Innovation Center of Chemical Science and Engineering(Tianjin), Tianjin 300072, China;
c International Center of Materials Nanoarchitectonics(WPI-MANA), National Institute for Materials Science(NIMS), Tsukuba, Ibaraki 305-0044, Japan

Received:2016-12-29 Revised:2017-01-28 Online:2017-08-18 Published:2017-08-04
Supported by:
This work was supported by the National Basic Research Program of China (973 Program, 2014CB239300), the National Natural Science Foundation of China (51572191), and the Natural Science Foundation of Tianjin (13JCYBJC16600).

摘要/Abstract

摘要：

光催化是一种理想的应对全球能源短缺和环境污染问题的绿色化学技术，可以实现有机物降解、水分解和二氧化碳光还原等.光催化反应效率受诸多因素影响，其中光生载流子（电子和空穴）的分离和传输具有至关重要的作用.以往研究表明，构筑多元复合光催化材料体系有利于光生电子和空穴有效分离和传递，促进催化剂表面的还原和氧化反应，从而提高其光催化效率.基于以上考虑，我们提出了一种新型的石墨烯/电气石/TiO₂三元复合光催化材料体系，其中TiO₂因其价格低廉、无毒和抗光腐蚀等优点而被广泛用作光催化材料；石墨烯（G）拥有独特的二维结构、高的电子迁移率、大的比表面积，是一种优异的催化剂载体；电气石（T）的一个重要性质是表面存在自发极化的静电场，该静电场将会影响光激发载流子的分离、传递和光催化反应过程.
利用水热法合成了不同成分的石墨烯/电气石/TiO₂三元复合材料体系.为了对比研究石墨烯表面电荷性质的影响，其中一组的石墨烯（氧化石墨）为直接采用改良的Hummers法所制备，其表面带负电；另一组的石墨烯经聚二烯丙基二甲基氯化铵（PDDA）修饰，使其表面带正电.X射线衍射结果显示，三元复合材料中TiO₂为锐钛矿相，其结晶性没有因为与石墨烯和电气石的复合而受到影响.扫描和透射电子显微分析表明，TiO₂的平均颗粒大小为15 nm左右，并且与石墨烯和电气石均匀复合.傅里叶变换红外光谱和zeta电位表征分析证实，PDDA可以有效地对石墨烯进行功能化改性，使其表面带正电.紫外-可见分光光谱显示，石墨烯/电气石/TiO₂三元复合材料与TiO₂的吸收带边一致，复合材料中石墨烯和电气石并没有改变TiO₂的光吸收特征.
光催化降解异丙醇实验表明，石墨烯/电气石/TiO₂三元复合材料优于单纯的TiO₂、石墨烯/TiO₂以及电气石/TiO₂二元复合材料，当石墨烯和电气石的质量百分比分别为0.5%和5%时，三元复合材料降解异丙醇产生丙酮的速率达到最高（223 μmol/h）.特别值得指出的是，由表面带负电的石墨烯组成的复合材料比由带正电荷的PDDA-石墨烯组成的复合材料具有更高的光催化性能，原因如下：在水溶液中显示正zeta电位值的TiO₂与带负电的石墨烯/电气石复合物静电吸引而均匀紧密复合，有利于TiO₂中光生电子和空穴的快速分离和传递，从而使得石墨烯/电气石/TiO₂三元复合材料具有较高的光催化性能；而带正电的PDDA-石墨烯/电气石复合物和TiO₂颗粒相互排斥而不宜复合，导致PDDA-石墨烯基复合材料的光催化活性降低.机理研究揭示，在三元复合材料光催化降解异丙醇的反应中起主要作用的是光生电子和空穴.基于以上研究结果，我们提出了三元复合材料光催化降解异丙醇的反应机理.

关键词: 光催化, 石墨烯, 电气石, 二氧化钛, 复合材料, 异丙醇, 降解

Abstract:

We report the construction of a graphene/tourmaline/TiO₂ (G/T/TiO₂) composite system with enhanced charge-carrier separation, and therefore enhanced photocatalytic properties, based on tailoring the surface-charged state of graphene and/or by introducing an external electric field arising from tourmaline. A simple two-step hydrothermal method was used to synthesize G/T/TiO₂ composites and poly(diallyldimethylammonium chloride)-G/T/TiO₂ composites. In the photocatalytic degradation of 2-propanol (IPA), the catalytic activity of the composite containing negatively charged graphene was higher than of the composite containing positively charged graphene. The highest acetone evolution rate (223 μmol/h) was achieved using the ternary composite with the optimum composition, i.e., G0.5/T5/TiO₂ (0.5 wt% graphene and 5 wt% tourmaline). The involvement of tourmaline and graphene in the composite is believed to facilitate the separation and transportation of electrons and holes photogenerated in TiO₂. This synergetic effect could account for the enhanced photocatalytic activity of the G/T/TiO₂ composite. A mechanistic study indicated that O₂^·- radicals and holes were the main reactive oxygen species in photocatalytic degradation of IPA.

Key words: Photocatalysis, Graphene, Tourmaline, TiO₂, Composite, 2-Propanol, Degradation

尹利利, 赵明, 胡慧林, 叶金花, 王德法. 石墨烯/电气石/二氧化钛复合材料的制备及其光催化降解异丙醇性能[J]. 催化学报, 2017, 38(8): 1307-1314.

Lili Yin, Ming Zhao, Huilin Hu, Jinhua Ye, Defa Wang. Synthesis of graphene/tourmaline/TiO₂ composites with enhanced activity for photocatalytic degradation of 2-propanol[J]. Chinese Journal of Catalysis, 2017, 38(8): 1307-1314.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.cjcatal.com/CN/

https://www.cjcatal.com/CN/Y2017/V38/I8/1307

参考文献

[1] A. Fujishima, K. Honda, Nature, 1972, 238, 37-38.
[2] M. R. Hoffmann, S. T. Martin, W. Choi, D. W. Bahnemann, Chem. Rev., 1995, 95, 69-96.
[3] A. L. Linsebigler, G. Q. Lu, J. T. Yates, Chem. Rev., 1995, 95, 735-758.
[4] A. Fujishima, K. Hashimoto, T. Watanabe, TiO₂ Photocatalysis:Fundamentals and Applications, BKC Inc., Tokyo, Japan, 1999.
[5] A. Paracchino, V. Laporte, K. Sivula, M. Grätzel, E. Thimsen, Nature Mater., 2011, 10, 456-461.
[6] H. Tong, S. X. Ouyang, Y. P. Bi, N. Umezawa, M. Oshikiri, J. H. Ye, Adv. Mater., 2012, 24, 229-251.
[7] A. J. Cowan, J. R. Durrant, Chem. Soc. Rev., 2013, 42, 2281-2293.
[8] A. Kudo, Y. Miseki, Chem. Soc. Rev., 2009, 38, 253-278.
[9] K. Maeda, K. Domen, J. Phys. Chem. Lett., 2010, 1, 2655-2661.
[10] R. G. Li, F. X. Zhang, D. E. Wang, J. X. Yang, M. R. Li, J. Zhu, X. Zhou, H. X. Han, C. Li, Nature Commun., 2013, 4, 1432/1-7.
[11] D. F. Wang, Z. G. Zou, J. H. Ye, Chem. Mater., 2005, 17, 3255-3261.
[12] D. F. Wang, J. K. Baral, H. G. Zhao, B. A. Gonfa, V. V. Truong, M. A. El Khakani, R. Izquierdo, D. L. Ma, Adv. Funct. Mater., 2011, 21, 4010-4018.
[13] D. F. Wang, H. G. Zhao, N. Q. Wu, M. A. El Khakani, D. L. Ma, J. Phys. Chem. Lett., 2010, 1, 1030-1035.
[14] Y. P. Yuan, L. W. Ruan, J. Barber, S. C. Joachim Loo, C. Xue, Energy Environ. Sci., 2014, 7, 3934-3951.
[15] R. Marschall, Adv. Funct. Mater., 2014, 24, 2421-2440.
[16] J. W. Tang, H. D. Quan, J. H. Ye, Chem. Mater., 2007, 19, 116-122.
[17] M. Grandcolas, J. H. Ye, Sci. Technol. Adv. Mater., 2010, 11, 055001/-1055001/6.
[18] H. Xu, S. X. Ouyang, P. Li, T. Kako, J. H. Ye, ACS Appl. Mater. Interf., 2013, 5, 1348-1354.
[19] R. Z. Ma, T. Sasaki, Adv. Mater., 2010, 22, 5082-5104.
[20] D. Voiry, M. Salehi, R. Silva, T. Fujita, M. W. Chen, T. Asefa, V. B. Shenoy, G. Eda, M. Chhowalla, Nano Lett., 2013, 13, 6222-6227.
[21] Q. Li, B. D. Guo, J. G. Yu, J. R. Ran, B. H. Zhang, H. J. Yan, J. R. Gong, J. Am. Chem. Soc., 2011, 133, 10878-10884.
[22] Q. J. Xiang, B. Cheng, J. G. Yu, Angew. Chem. Int. Ed., 2015, 54, 11350-11366.
[23] H. Zhang, X. J. Lü, Y. M. Li, Y. Wang, J. H. Li, ACS Nano, 2010, 4, 380-386.
[24] Q. J. Xiang, J. G. Yu, M. Jaroniec, J. Am. Chem. Soc., 2012, 134, 6575-6578
[25] W. Ackermann, Ann. Phys., 1915, 46, 197-220.
[26] R. R. Yeredla, H. F. Xu, J. Phys. Chem. C, 2008, 112, 532-539.
[27] S. Yamaguchi, Appl. Phys. A, 1983, 31, 183-185.
[28] K. X. Li, T. Chen, L. S. Yan, Y. H. Dai, Z. M. Huang, H. Q. Guo, L. X. Jiang, X. H. Gao, J. J. Xiong, D. Y. Song, Catal. Commun., 2012, 28, 196-201.
[29] S. Y. Wang, D. S. Yu, L. M. Dai, D. W. Chang, J. B. Baek, ACS Nano, 2011, 5, 6202-6209.
[30] X. K. Cai, T. C. Ozawa, A. Funatsu, R. Z. Ma, Y. Ebina, T. Sasaki, J. Am. Chem. Soc., 2015, 137, 2844-2847.
[31] W. S. Hummers Jr., R. E. Offeman, J. Am. Chem. Soc., 1958, 80, 1339-1339.
[32] D. F. Wang, T. Kako, J. H. Ye, J. Phys. Chem. C, 2009, 113, 3785-3792.
[33] S. W. Liu, J. G. Yu, M. Jaroniec, J. Am. Chem. Soc., 2010, 132, 11914-11916.
[34] W. F. Zhang, Y. L. He, M. S. Zhang, Z. Yin, Q. Chen, J. Phys. D, 2000, 33, 912-916.
[35] X. Y. Zhang, H. P. Li, X. L. Cui, Y. H. Lin, J. Mater. Chem., 2010, 20, 2801-2806.
[36] K. Chang, Z. W. Mei, T. Wang, Q. Kang, S. X. Ouyang, J. H. Ye, ACS Nano, 2014, 8, 7078-7087.
[37] H. R. Zhu, L. Gao, X. L. Jiang, R. Liu, Y. T. Wei, Y. L. Wang, Y. L. Zhao, Z. F. Chai, X. Y. Gao, Chem. Commun., 2014, 50, 3695-3698.
[38] S. Y. Wang, X. Wang, S. P. Jiang, Phys. Chem. Chem. Phys., 2011, 13, 6883-6891.
[39] K. Suttiponparnit, J. K. Jiang, M. Sahu, P. Biswas, S. Suvachit-tanont, T. Charinpanitkul, Nanoscale Res. Lett., 2011, 6, 27.
[40] B. P. Vinayan, R. Nagar, V. Raman, N. Rajalakshmi, K. S. Dhathathreyan, S. Ramaprabhu, J. Mater. Chem., 2012, 22, 9949-9956.
[41] N. L. Yang, Y. Zhang, J. E. Halpert, J. Zhai, D. Wang, L. Jiang, Small, 2012, 8, 1762-1770.
[42] Y. Ohko, K. Hashimoto, A. Fujishima, J. Phys. Chem. A, 1997, 101, 8057-8062.
[43] S. X. Ouyang, J. H. Ye, J. Am. Chem. Soc., 2011, 133, 7757-7763.