赖氨酸辅助高分散金粒子修饰氮掺杂TiO2纳米管催化剂的合成及光催化性能

doi:10.7503/cjcu20160377

高等学校化学学报 ›› 2016, Vol. 37 ›› Issue (11): 2034.doi: 10.7503/cjcu20160377

赖氨酸辅助高分散金粒子修饰氮掺杂TiO₂纳米管催化剂的合成及光催化性能

安会琴¹(), 于育才¹, 闫琳¹, 吴婷婷¹, 李晓峰¹, 贺晓凌¹, 赵莉芝², 黄唯平³()

1. 天津工业大学环境与化学工程学院, 省部共建分离膜与膜过程国家重点实验室, 天津 300387
2. 天津工业大学材料科学与工程学院, 天津 300387
3. 南开大学先进能源材料化学教育部重点实验室, 天津 300071

收稿日期:2016-05-26 出版日期:2016-11-10 发布日期:2016-10-20
作者简介:联系人简介: 安会琴, 女, 博士, 讲师, 主要从事无机功能材料合成研究. E-mail: anhuiqinhebei@163.com; 黄唯平, 男, 博士, 教授, 主要从事无机合成及材料催化研究. E-mail: hwp914@nankai.edu.cn
基金资助:
国家自然科学基金(批准号: 21501131, 21373120)、天津工业大学国家级大学生创新创业训练计划项目(批准号: 201510058021)和天津市科技特派员项目(批准号: 15JCTPJC57500)资助

Synthesis of Highly Dispersed Au Nanoparticles Modified N-Doped TiO₂ Nanotubes by the Assist of Lysine and Their Photocatalytic Activity^†

AN Huiqin^1,^*, YU Yucai¹, YAN Lin¹, WU Tingting¹, LI Xiaofeng¹, HE Xiaoling¹, ZHAO Lizhi², HUANG Weiping^3,^*

1. School of Environmental and Chemical Engineering, State Key Laboratory of Separation Membranes and Membrane Processes, Tianjin Polytechnic University, Tianjin 300387, China
2. School of Materials Science and Engineering, Tianjin Polytechnic University, Tianjin 300387, China
3. Key Laboratory of Advanced Energy Materials Chemistry, Ministry of Enducation,Nankai University, Tianjin 300071, China

Received:2016-05-26 Online:2016-11-10 Published:2016-10-20
Contact: AN Huiqin,HUANG Weiping E-mail:anhuiqinhebei@163.com;hwp914@nankai.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.21501131, 21373120), the National Training Program of Innovation and Entrepreneurship for Undergraduates of Tianjin Polytechnic University, China(No.201510058021) and the Science and Technology Correspondent Project of Tianjin, China(No.15JCTPJC57500)

摘要/Abstract

摘要：

通过溶胶-凝胶法联合水热合成法制备了氮掺杂TiO₂纳米管, 并以该纳米管为载体, 采用绿色无毒的赖氨酸作为链接剂和螯合剂, 一步实现金粒子在TiO₂纳米管上的高度分散, 制备得到高分散金粒子修饰氮掺杂TiO₂纳米管催化剂(Au/N-TiO₂纳米管). 表征了产物的形貌、结构、光学特性及组成, 通过紫外光下甲基橙水溶液的光降解率评价产物的光催化活性, 讨论了氮掺杂量、金负载量、赖氨酸及焙烧对合成催化剂光催化性能的影响. 结果显示, 在赖氨酸存在下, 金粒子在TiO₂纳米管上呈高度分散状态, 未发生聚集. 且与纯TiO₂纳米管相比, Au/N-TiO₂纳米管显示出更高的光催化活性. Au/N-TiO₂纳米管的高催化活性是由于氮掺杂后引起的TiO₂带隙能窄化、金粒子在载体上的高分散状态及金与TiO₂形成的肖特恩势垒引起的低电子-空穴复合率共同作用导致的.

关键词: 二氧化钛纳米管, 氮掺杂, 金粒子, 赖氨酸, 光降解甲基橙

Abstract:

N-doped TiO₂ nanotubes were synthesized by the combination of sol-gel and hydrothermal methods firstly; and then Au nanoparticles were deposited on the N-doped TiO₂ nanotubes by a simple one-pot process with lysine as both the linker and capping agent. The morphology, structure, optical absorption and composition of the samples were characterized by means of TEM, XRD, UV-Vis and XPS. The photodegradation rates of methyl orange under UV light irradiation were used to evaluate the photocatalytic activities of samples. The effects of N content, Au content, lysine and calcination on the photocatalytic activities of Au/N-doped TiO₂ nanotubes were discussed. The results exhibit that Au nanoparticles capped by lysine are highly dispersed on the support without any aggregation and the obtained sample exhibits higher photocatalytic activity in comparison with pure TiO₂ nanotubes. The improved photocatalytic activity is attributed to the narrower band gap of N-doped TiO₂, the high dispersion of Au nanoparticles and the reduced recombination of photogenerated electrons and holes caused by the formation of metal-semiconductor Schottky junction between Au and TiO₂.

Key words: TiO2 nanotube, N doping, Au nanoparticle, Lysine, Photodegradation of methyl orange

中图分类号:

O644
O611.4

TrendMD:

安会琴, 于育才, 闫琳, 吴婷婷, 李晓峰, 贺晓凌, 赵莉芝, 黄唯平. 赖氨酸辅助高分散金粒子修饰氮掺杂TiO₂纳米管催化剂的合成及光催化性能. 高等学校化学学报, 2016, 37(11): 2034.

AN Huiqin, YU Yucai, YAN Lin, WU Tingting, LI Xiaofeng, HE Xiaoling, ZHAO Lizhi, HUANG Weiping. Synthesis of Highly Dispersed Au Nanoparticles Modified N-Doped TiO₂ Nanotubes by the Assist of Lysine and Their Photocatalytic Activity^†. Chem. J. Chinese Universities, 2016, 37(11): 2034.

图/表 12

Fig.1 Procedure for the deposition of Au on N-doped TiO2 nanotubes by the assist of lysine

Fig.2 XRD patterns of TiO2 nanotubes(a) and N-doped TiO2 nanotubes with different N contents(b, c)w(N): b. 1.0%; c. 2.0%.

Fig.3 XRD patterns of TiO2 nanotubes(a) and 1.0% N-doped TiO2 nanotubes with different Au loadings(b—d)w(Au): b. 2.0%; c. 3.0%; d. 4.0%.

Fig.4 Wide XPS spectrum of Au/N-TiO2 nanotubes with 1.0% N and 3.0% Au loading(A) and high resolution XPS spectra for Ti2p(B), N1s(C), Au4f(D), C1s(E) and O1s(F)

Fig.5 HRTEM(A) and TEM(B) images of 1.0% N-TiO2 nanotubes and HRTEM images of Au/N-TiO2 nanotubes with 1.0% N and 3.0% Au loading in the presence(C) and absence(D) of lysine

Fig.6 UV-Vis absorption spectra of TiO2 nanotubes(a) and 1.0% N-doped TiO2 nanotubes(b)

Fig.7 Photocatalytic activity of N-doped TiO2 nanotubes with different N contents(A) and comparison of photocatalytic activities of 1.0% N-doped TiO2 nanotubes(a) and pure TiO2 nanotubes(b)(B) toward MO degradation(A) w(N): a. 0.5%; b. 1.0%; c. 2.0%.

Fig.8 Schematic diagram of N-doped TiO2 nanotubes after light activation

Fig.9 Photocatalytic activity of Au/N-TiO2 nanotubes(1.0% N) with different Au contentsw(Au): a. 2.0%; b. 3.0%; c. 4.0%.

Fig.10 Schematic diagram for the charge separation and photodegradation of Au/N-TiO2 nanotubes(Ef: Fermi energy)

Fig.11 Photocatalytic activity of Au/N-TiO2 nanotubes with 1.0% N and 3.0% Au loading synthesized in the presence(a) and absence(b) of lysine

Fig.12 Photocatalytic activity of Au/N-TiO2 nanotubes with 1.0% N and 3.0% Au loading calcined at 300 ℃(a) and without calcination(b)

参考文献 31

[1]	Liu, X. , Chen, Y. , Rao S., H. , Pang G., S. , Chem. Res. Chinese Universities, 2015, 31( 5), 688- 692
[2]	Widchaya, R. , Araya, T. , Ratchaneekorm, W. , Chem. Res. Chinese Universities, 2014, 30( 1), 149- 156
[3]	Shi Y., K. , Hu X., J. , Zhu B., L. , Zhang S., M. , Huang W., P. , Chem. Res. Chinese Universities, 2015, 31( 5), 851- 857
[4]	安会琴, 朱宝林, 吴红艳, 张明, 王淑荣, 张守民, 吴世华, 黄唯平. 高等学校化学学报, 2008, 29(3), 439- 444
	An H., Q. , Zhu B., L. , Wu H., Y. , Zhang, M. , Wang S., R. , Zhang S., M. , Wu. S., H. , Huang W., P. , Chem. J. Chinese Universities, 2008, 29( 3), 439- 444 (
[5]	Kasuga, T. , Hiramatsu, M. , Hoson, A. , Sekino, T. , Niihara, K. , Langmuir, 1998, 14( 12), 3160- 3163
[6]	Valentin C., D. , Finazzi, E. , Pacchioni, G. , Selloni, A. , Livraghi, S. , Paganini M., C. , Giamello, E. , Chem. Phys., 2007, 339( 1-3), 44- 56
[7]	Iliev, V. , Tomova, D. , Bilyarska, L. , Tyuliev, G. , J. Mol. Catal. A, 2007, 263( 1/2), 32- 38
[8]	Yu, Y. , Wu H., H. , Zhu B., L. , Wang S., R. , Huang W., P. , Wu S., H. , Zhang S., M. , Catal. Lett., 2008, 121( 1), 165- 171
[9]	Cantau, C. , Pigot, T. , Dupin, J. , Lacombe, S. , J. Photoch. Photobio. A, 2010, 216( 2/3), 201- 208
[10]	Pelaez, M. , de la Cruz A., A. , Stathatos, E. , Falaras, P. , Dionysiou D., D. , Catal. Today, 2009, 144( 1/2), 19- 25
[11]	Zhu B., L. , Li K., R. , Feng Y., F. , Zhang S., M. , Wu S., H. , Huang W., P. , Catal. Lett., 2007, 118( 1), 55- 58
[12]	An H., Q. , He X., L. , Li J., Q. , Zhao L., Z. , Chang, C. , Zhang S., H. , Huang W., P. , New J. Chem., 2015, 39( 6), 4611- 4623
[13]	Iliev, V. , Tomova, D. , Todorovska, R. , Oliver, D. , Petrov, L. , Todorovsky, D. , Uzunova-Bujnova, M. , Appl. Catal. A: Gen., 2006, 313( 2), 115- 121
[14]	An H., Q. , Zhou, J. , Li J., X. , Zhu B., L. , Wang S., R. , Zhang S., M. , Wu S., H. , Huang W., P. , Catal. Commun., 2009, 11( 3), 175- 179
[15]	Hashmi A. S., K. , Hutchings G., J. , Angew. Chem. Int. Ed., 2006, 45( 47), 7896- 7936
[16]	Wen, D. , Guo S., J. , Zhai J., F. , Deng, L. , Ren, W. , Dong S., J. , J. Phys. Chem. C, 2009, 113( 30), 13023- 13028
[17]	Guo S., J. , Dong S., J. , Wang E., K. , J. Phys. Chem. C, 2009, 113( 14), 5485- 5492
[18]	Zhong Z., Y. , Lin, J. , Teh S., P. , Teo, J. , Dautzenberg F., M. , Adv. Funct. Mater., 2007, 17( 8), 1402- 1408
[19]	Zhang, J. , Liu, X. , Wang, L. , Yang, T. , Guo, X. , Wu, S. , Wang, S. , Zhang, S. , J. Phys. Chem. C, 2011, 115( 13), 5352- 5357
[20]	Zhang, J. , Liu X., H. , Guo X., Z. , Wu S., H. , Wang S., R. , Chem. Eur. J., 2010, 16( 27), 8108- 8116
[21]	Wang Z., P. , Cai W., M. , Hong X., T. , Zhao X., L. , Xu, F. , Cai C., G. , Appl. Catal. B, 2005, 57( 3), 223- 231
[22]	Chen, Y. , Zhang, S. , Yu, Y. , Wu, H. , Wang, S. , Zhu, B. , Huang, W. , Wu, S. , J. Disper. Sci. Technol., 2008, 29( 2), 245- 249
[23]	An H., Q. , Hu X., J. , Zhu B., L. , Song J., J. , Zhao W., L. , Zhang S., M. , Huang W., P. , Mater. Sci.-Poland, 2013, 31( 4), 531- 542
[24]	Sun, L. , Zhao, Z. , Zhou, Y. , Liu, L. , Nanoscale, 2012, 4( 2), 613- 620
[25]	Sathish, M. , Viswanathan, B. , Viswanath R., P. , Gopinath C., S. , Chem. Mater., 2005, 17( 25), 6349- 6353
[26]	Zhao, L. , Chen, X. , Wang, X. , Zhang, Y. , Wei, W. , Sun, Y. , Antonietti, M. , Titirici M., M. , Adv. Mater., 2010, 22( 30), 3317- 3321
[27]	Xiang, Q. , Yu, J. , Jaroniec, M. , Nanoscale, 2011, 3( 9), 3670- 3678
[28]	Wang W., S. , Wang D., H. , Qu W., G. , Lu L., Q. , Xu A., W. , J. Phys. Chem. C, 2012, 116( 37), 19893- 19901
[29]	Yang X., X. , Cao C., D. , Erickson, L. , Hohn, K. , Maghirang, R. , Klabunde, K. , Appl. Catal. B, 2009, 91( 3/4), 657- 662
[30]	Mubeen, S. , Lee, J. , Singh, N. , Kramer, S. , Stucky G., D. , Moskovits, M. , Nat. Nanotechnol., 2013, 8, 247- 251
[31]	McFarland E., W. , Tang, J. , Nature, 2003, 421( 6923), 616- 618

赖氨酸辅助高分散金粒子修饰氮掺杂TiO₂纳米管催化剂的合成及光催化性能

Synthesis of Highly Dispersed Au Nanoparticles Modified N-Doped TiO₂ Nanotubes by the Assist of Lysine and Their Photocatalytic Activity^†

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 12

参考文献 31

相关文章 15

编辑推荐

Metrics

本文评价

[1]	范建玲, 唐灏, 秦凤娟, 许文静, 谷鸿飞, 裴加景, 陈文星. 氮掺杂超薄碳纳米片复合铂钌单原子合金催化剂的电化学析氢性能[J]. 高等学校化学学报, 2022, 43(9): 20220366.
[2]	郝宏蕾, 孟繁雨, 李若钰, 李迎秋, 贾明君, 张文祥, 袁晓玲. 生物质基氮掺杂多孔炭材料的制备及对水中亚甲基蓝的吸附性能[J]. 高等学校化学学报, 2022, 43(6): 20220055.
[3]	侯从聪, 王惠颖, 李婷婷, 张志明, 常春蕊, 安立宝. N-CNTs/NiCo-LDH复合材料的制备及电化学性能[J]. 高等学校化学学报, 2022, 43(10): 20220351.
[4]	姜珊, 申倩倩, 李琦, 贾虎生, 薛晋波. Pd增强缺陷态TiO₂纳米管阵列的光催化产氢性能[J]. 高等学校化学学报, 2022, 43(10): 20220206.
[5]	马丽娟, 高升启, 荣祎斐, 贾建峰, 武海顺. Sc, Ti, V修饰B/N掺杂单缺陷石墨烯的储氢研究[J]. 高等学校化学学报, 2021, 42(9): 2842.
[6]	刘志刚, 李家宝, 杨剑, 马浩, 王赪胤, 郭鑫, 汪国秀. 新型石墨化氮化碳/锡/氮掺杂碳复合物的制备及储钠性能[J]. 高等学校化学学报, 2021, 42(2): 633.
[7]	熊俊宇, 王姗姗, 许颜清, 胡长文. 原子级分散Fe-N-C温和条件下选择性氧化催化特性[J]. 高等学校化学学报, 2020, 41(6): 1262.
[8]	王霞, 刘彦吉, 贾永锋, 吉磊, 胡全丽, 段莉梅, 刘景海. 含氮多孔纳米碳纤维的制备及对锂硫电池容量的提高[J]. 高等学校化学学报, 2020, 41(4): 829.
[9]	王煜瑶, 张强, 于吉红. 多级孔NaX分子筛的合成及CO₂吸附性能[J]. 高等学校化学学报, 2020, 41(4): 616.
[10]	闫松, 张成武, 袁芳, 秦传玉. 氮掺杂碳纳米管的合成及活化过一硫酸盐的性能与机理[J]. 高等学校化学学报, 2020, 41(11): 2503.
[11]	王婷婷, 李元, 杨莉莉, 鲍昌昊, 程寒. 碳纤维微电极负载金纳米粒子用于芦荟多糖的在体动态监测[J]. 高等学校化学学报, 2020, 41(1): 87.
[12]	赵文采, 韩丽丽, 彭颖君, 王晓静, 刘晟宇, 李鹏飞, 黄宜兵, 陈育新. 碱性氨基酸对螺旋型抗菌肽生物活性的影响[J]. 高等学校化学学报, 2018, 39(4): 681.
[13]	华承贺, 马红超, 董晓丽, 张秀芳. α-Bi₂O₃纳米管/氮掺杂碳量子点复合材料的合成及光催化性能[J]. 高等学校化学学报, 2018, 39(2): 200.
[14]	赵麒, 何婉莹, 段莉洁, 张瑜, 于双江, 高光辉. 基于席夫碱键的可注射糖肽水凝胶的制备及性能[J]. 高等学校化学学报, 2016, 37(9): 1750.
[15]	俞丁凌, 张博文, 何兴权. 三维氮掺杂石墨烯气凝胶负载钴酞菁作为高效的氧气还原反应催化剂[J]. 高等学校化学学报, 2016, 37(12): 2176.