单分散SnO<sub>2</sub>中空微纳米球的制备和性质

引用本文: 蔡宏敏, 任素贞, 王萌, 贾翠英. 单分散SnO₂中空微纳米球的制备和性质[J]. 物理化学学报, doi: 10.3866/PKU.WHXB201302051 shu

Citation: CAI Hong-Min, REN Su-Zhen, WANG Meng, JIA Cui-Ying. Preparation and Properties of Monodisperse SnO₂ Hollow Micro/Nano Spheres[J]. Acta Physico-Chimica Sinica, doi: 10.3866/PKU.WHXB201302051 shu

单分散SnO₂中空微纳米球的制备和性质

基金项目:
国家自然科学基金(21176043)资助项目 (21176043)

摘要:

模板法是制备无机中空微纳米球的重要方法之一. 本文以苯乙烯为单体, 通过乳液聚合得到粒径约为620 nm的单分散聚苯乙烯(PS)微球. 以磺化后的聚苯乙烯(PSS)微球为模板, 利用阴阳离子静电吸附作用, 将PSS与前驱体SnSO₄中的Sn²⁺结合. 通过Sn²⁺在乙醇-水介质中的水解作用得到核-壳复合结构, 再经高温煅烧, 得到SnO₂中空微纳米球. 实验对前驱体的浓度、表面活性剂的用量、反应时间及模板选择等方面做了研究,通过扫描电镜(SEM)、X 射线衍射(XRD)、红外(IR) 光谱、热重分析(TGA)、H₂ 程序升温还原(H₂-TPR)、Brunauer-Emmett-Teller (BET)比表面积等技术深入探究SnO₂中空微纳米球的结构, 并对比中空SnO₂与实心粒子的氧化还原特性. BET和H₂-TPR显示将SnO₂制备成微纳米空心球后其比表面积增大, 表面氧空位明显增多, 氧化活性明显提高. 从IR 及XRD推断核-壳结构形成机理, 进而优化出简单合理的实验方案, 获得表面光滑、结构致密, 包覆厚度可控的SnO₂中空微纳米球.

关键词:

English

Preparation and Properties of Monodisperse SnO₂ Hollow Micro/Nano Spheres

1.
1 College of Chemistry, Dalian University of Technology, Dalian, 116024, Liaoning Province, P. R. China;
2 The experiment center of Chemistry, Dalian University of Technology, Dalian, 116024, Liaoning Province, P. R. China
Received Date: 26 November 2012
Available Online: 25 March 2013
Fund Project:
国家自然科学基金(21176043)资助项目

Abstract:

Templating is one of the most important methods for preparation of inorganic hollow micro/ nano spheres. We prepared monodisperse polystyrene (PS) microspheres having a diameter of 620 nm by the emulsion polymerization of styrene. Sulfonated polystyrene (PSS) microspheres were used as a template, through electrostatic adsorption of anions and cations, for modification with Sn²⁺ from SnSO₄ precursor. The core-shell composite structures thereby produced through Sn²⁺ hydrolysis in an ethanolwater medium were calcined at high temperature to remove PSS and to obtain SnO₂ hollow micro/nano spheres. We investigated the effects of precursor concentration, amount of surfactant, reaction time, and templates choice. Scanning electron microscopy (SEM), X-ray diffraction (XRD), infrared (IR) spectroscopy, thermogravimetric analysis (TGA), H₂ temperature programmed reduction (H₂-TPR), Brunauer-Emmett-Teller (BET) measurement, and other technical probes were used to detect the structure and properties of the prepared SnO₂ hollow micro/nano spheres, and compared them with those of solid SnO₂. BET and H₂-TPR showed that the hollow SnO₂ micro/nano spheres had improved specific surface area, surface oxygen vacancies, and oxidation activity. We inferred the growth mechanism of the core-shell structure from IR spectroscopy and XRD pattern and optimized the simple and reasonable synthesis procedure to obtain SnO₂ hollow micro/nano spheres which had smooth surface, compact structure, and well controlled cladding thickness.

Key words:

1. [1]
  
  (1) (a) Zhu, Y.; Shi, J.; Shen,W.; Dong, X.; Feng, J.; Ruan, M.; Li,Y. Angew. Chem. 2005, 117 (32), 5213.
  (1) (a) Zhu, Y.; Shi, J.; Shen,W.; Dong, X.; Feng, J.; Ruan, M.; Li,Y. Angew. Chem. 2005, 117 (32), 5213.
2. [2]
  (b) Zhu, Y.; Shi, J.; Shen,W.; Dong, X.; Feng, J.; Ruan, M.; Li,Y. Angew. Chem. Int. Edit. 2005, 44, 5083.(b) Zhu, Y.; Shi, J.; Shen,W.; Dong, X.; Feng, J.; Ruan, M.; Li,Y. Angew. Chem. Int. Edit. 2005, 44, 5083.
3. [3]
  (2) Zhang,W. M.; Hu, J. S.; Guo, Y. G.; Zheng, S. F.; Zhong, L. S.;Song,W. G.;Wan, L. J. Adv. Mater. 2008, 20 (6), 1160. doi: 10.1002/adma.v20:6(2) Zhang,W. M.; Hu, J. S.; Guo, Y. G.; Zheng, S. F.; Zhong, L. S.;Song,W. G.;Wan, L. J. Adv. Mater. 2008, 20 (6), 1160. doi: 10.1002/adma.v20:6
4. [4]
  (3) Cai,W. Q.; Yu, J. G.; Cheng, B.; Su, B. L.; Jaroniec, M. J. Phys.Chem. C 2009, 113, 14739. doi: 10.1021/jp904570z(3) Cai,W. Q.; Yu, J. G.; Cheng, B.; Su, B. L.; Jaroniec, M. J. Phys.Chem. C 2009, 113, 14739. doi: 10.1021/jp904570z
5. [5]
  (4) Yu, K.;Wu, Z.; Zhao, Q.; Li, B.; Xie, Y. J. Phys. Chem. C 2008,112 (7), 2244. doi: 10.1021/jp711880e(4) Yu, K.;Wu, Z.; Zhao, Q.; Li, B.; Xie, Y. J. Phys. Chem. C 2008,112 (7), 2244. doi: 10.1021/jp711880e
6. [6]
  (5) Wu, P.; Du, N.; Zhang, H.; Zhai, C. X.; Yang, D. R. ACS Appl.Mater. Interfaces 2011, 3, 1946. doi: 10.1021/am200168w(5) Wu, P.; Du, N.; Zhang, H.; Zhai, C. X.; Yang, D. R. ACS Appl.Mater. Interfaces 2011, 3, 1946. doi: 10.1021/am200168w
7. [7]
  (6) Zheng, L. R.; Zheng, Y. H.; Chen, C. Q.; Zhan, Y. Y.; Lin, X. Y.;Zheng, Q.;Wei, K. M.; Zhu, J. F. Inorg. Chem. 2009, 48, 1819.doi: 10.1021/ic802293p(6) Zheng, L. R.; Zheng, Y. H.; Chen, C. Q.; Zhan, Y. Y.; Lin, X. Y.;Zheng, Q.;Wei, K. M.; Zhu, J. F. Inorg. Chem. 2009, 48, 1819.doi: 10.1021/ic802293p
8. [8]
  (7) Li,W. B.; Bu, Y. Y.; Yu, J. Q. Acta Phys. -Chim. Sin. 2012, 28 (11), 2676. [李卫兵, 补钰煜, 于建强. 物理化学学报, 2012,28 (11), 2676.] doi: 10.3866/PKU.WHXB201207101(7) Li,W. B.; Bu, Y. Y.; Yu, J. Q. Acta Phys. -Chim. Sin. 2012, 28 (11), 2676. [李卫兵, 补钰煜, 于建强. 物理化学学报, 2012,28 (11), 2676.] doi: 10.3866/PKU.WHXB201207101
9. [9]
  (8) Rao, G. S.; Cheng, M. Q.; Zhong, Y.; Deng, X. C.; Yi, F.; Chen,Z. R.; Zhong, Q. L.; Fan, F. R.; Ren, B.; Tian, Z. Q. ActaPhys. -Chim. Sin. 2011, 27 (10), 2373. [饶贵仕, 程美琴,钟艳, 邓小聪, 易飞, 陈治仁, 钟起玲, 范凤茹, 任斌,田中群. 物理化学学报, 2011, 27 (10), 2373.] doi: 10.3866/PKU.WHXB20111008(8) Rao, G. S.; Cheng, M. Q.; Zhong, Y.; Deng, X. C.; Yi, F.; Chen,Z. R.; Zhong, Q. L.; Fan, F. R.; Ren, B.; Tian, Z. Q. ActaPhys. -Chim. Sin. 2011, 27 (10), 2373. [饶贵仕, 程美琴,钟艳, 邓小聪, 易飞, 陈治仁, 钟起玲, 范凤茹, 任斌,田中群. 物理化学学报, 2011, 27 (10), 2373.] doi: 10.3866/PKU.WHXB20111008
10. [10]
  (9) Xiao, L. F.; Li, J. P.; Li, Q.; Zhang, L. Z. J. Solid State Electr.2010, 14, 931.(9) Xiao, L. F.; Li, J. P.; Li, Q.; Zhang, L. Z. J. Solid State Electr.2010, 14, 931.
11. [11]
  (10) Zhao, Q.; Xie, Y.; Dong, T.; Zhang, Z. J. Phys. Chem. C 2007,111 (31), 11598. doi: 10.1021/jp072858h(10) Zhao, Q.; Xie, Y.; Dong, T.; Zhang, Z. J. Phys. Chem. C 2007,111 (31), 11598. doi: 10.1021/jp072858h
12. [12]
  (11) Liu, J.; Zhang, L.; Shi, S.; Chen, S.; Zhou, N.; Zhang, Z.;Cheng, Z.; Zhu, X. Langmuir 2010, 26 (18), 14806. doi: 10.1021/la102994g(11) Liu, J.; Zhang, L.; Shi, S.; Chen, S.; Zhou, N.; Zhang, Z.;Cheng, Z.; Zhu, X. Langmuir 2010, 26 (18), 14806. doi: 10.1021/la102994g
13. [13]
  (12) Kobayashi, Y.; Salgueirino-Maceira, V.; Liz-Marzan, L. M.Chem. Mater. 2001, 13 (5), 1630. doi: 10.1021/cm001240g(12) Kobayashi, Y.; Salgueirino-Maceira, V.; Liz-Marzan, L. M.Chem. Mater. 2001, 13 (5), 1630. doi: 10.1021/cm001240g
14. [14]
  (13) Liu, R.; Yang, S.;Wang, F.; Lu, X.; Yang, Z.; Ding, B. ACSAppl. Mater. Interfaces 2012, 4, 1537. doi: 10.1021/am201756m(13) Liu, R.; Yang, S.;Wang, F.; Lu, X.; Yang, Z.; Ding, B. ACSAppl. Mater. Interfaces 2012, 4, 1537. doi: 10.1021/am201756m
15. [15]
  (14) Tierno, P.; edel,W. A. J. Phys. Chem. B 2006, 110 (7), 3043.doi: 10.1021/jp054213s(14) Tierno, P.; edel,W. A. J. Phys. Chem. B 2006, 110 (7), 3043.doi: 10.1021/jp054213s
16. [16]
  (15) Chen, M.;Wu, L.; Zhou, S.; You, B. Adv. Mater. 2006, 18 (6),801.(15) Chen, M.;Wu, L.; Zhou, S.; You, B. Adv. Mater. 2006, 18 (6),801.
17. [17]
  (16) Jang, I.; Sung, J.; Choi, H.; Chin, I. Synth. Met. 2005, 152 (1-3), 9. doi: 10.1016/j.synthmet.2005.07.087(16) Jang, I.; Sung, J.; Choi, H.; Chin, I. Synth. Met. 2005, 152 (1-3), 9. doi: 10.1016/j.synthmet.2005.07.087
18. [18]
  (17) Li, M.; Lu, Q.; Nuli, Y.; Qian, X. Electrochem. Solid-State Lett.2007, 10 (8), K33.(17) Li, M.; Lu, Q.; Nuli, Y.; Qian, X. Electrochem. Solid-State Lett.2007, 10 (8), K33.
19. [19]
  (18) Holland, B. T.; Blanford, C. F.; Do, T.; Stein, A. Chem. Mater.1999, 11 (3), 795. doi: 10.1021/cm980666g(18) Holland, B. T.; Blanford, C. F.; Do, T.; Stein, A. Chem. Mater.1999, 11 (3), 795. doi: 10.1021/cm980666g
20. [20]
  (19) (a) Yang, Z.; Niu, Z.; Lu, Y.; Hu, Z.; Han, C. C. Angew. Chem.Int. Edit. 2003, 42, 1943. doi: 10.1002/anie.200250443(19) (a) Yang, Z.; Niu, Z.; Lu, Y.; Hu, Z.; Han, C. C. Angew. Chem.Int. Edit. 2003, 42, 1943. doi: 10.1002/anie.200250443
21. [21]
  (b) Yang, Z.; Niu, Z.; Lu, Y.; Hu, Z.; Han, C. C. Angew. Chem.2003, 115 (17), 1987.(b) Yang, Z.; Niu, Z.; Lu, Y.; Hu, Z.; Han, C. C. Angew. Chem.2003, 115 (17), 1987.
22. [22]
  (20) Cai, J. Y.; Lü, S.; Sun,W. D. J. Northeast Norm. Univ., Nat. Sci.Ed. 2009, 41 (2), 135. [蔡建岩, 吕卅, 孙闻东. 东北师大学报: 自然科学版, 2009, 41 (2), 135.](20) Cai, J. Y.; Lü, S.; Sun,W. D. J. Northeast Norm. Univ., Nat. Sci.Ed. 2009, 41 (2), 135. [蔡建岩, 吕卅, 孙闻东. 东北师大学报: 自然科学版, 2009, 41 (2), 135.]
23. [23]
  (21) (a) Yoon, K.; Yang, Y.; Lu, P.;Wan, D. H.; Peng, H. C.; Masias,K. S.; Fanson, P. T.; Campbell, C. T.; Xia, Y. N. Angew. Chem.2012, 124 (38), 9681. doi: 10.1002/ange.v124.38(21) (a) Yoon, K.; Yang, Y.; Lu, P.;Wan, D. H.; Peng, H. C.; Masias,K. S.; Fanson, P. T.; Campbell, C. T.; Xia, Y. N. Angew. Chem.2012, 124 (38), 9681. doi: 10.1002/ange.v124.38
24. [24]
  (b) Yoon, K.; Yang, Y.; Lu, P.;Wan, D. H.; Peng, H. C.; Masias,K. S.; Fanson, P. T.; Campbell, C. T.; Xia, Y. N. Angew. Chem.Int. Edit. 2012, 51, 9543.(b) Yoon, K.; Yang, Y.; Lu, P.;Wan, D. H.; Peng, H. C.; Masias,K. S.; Fanson, P. T.; Campbell, C. T.; Xia, Y. N. Angew. Chem.Int. Edit. 2012, 51, 9543.
25. [25]
  (22) Huang, Y.; Li, M. Materials Review 2006, 20 (10), 143.[黄怡, 李梅. 材料导报, 2006, 20 (10), 143.](22) Huang, Y.; Li, M. Materials Review 2006, 20 (10), 143.[黄怡, 李梅. 材料导报, 2006, 20 (10), 143.]
26. [26]
  (23) Li, G.; Xi, S. P.; Liu, Z. X.; Huang, Y. E. Spectroscopy andSpectral Analysis 1999, 19 (3), 289. [李谷, 席世平, 刘振兴, 黄月娥. 光谱学与光谱分析, 1999, 19 (3), 289.](23) Li, G.; Xi, S. P.; Liu, Z. X.; Huang, Y. E. Spectroscopy andSpectral Analysis 1999, 19 (3), 289. [李谷, 席世平, 刘振兴, 黄月娥. 光谱学与光谱分析, 1999, 19 (3), 289.]
27. [27]
  (24) Shi, L.; Lin, H. Langmuir 2010, 26 (24), 18718. doi: 10.1021/la103769d(24) Shi, L.; Lin, H. Langmuir 2010, 26 (24), 18718. doi: 10.1021/la103769d
28. [28]
  (25) Zhao, H. Y.; Zhao, Z. Z.; Zhao, Y. F.; Liu, Q. J. Chin. J. Catal.2010, 31 (1), 44. [赵鹤云, 赵忠泽, 赵义芬, 柳清菊. 催化学报, 2010, 31 (1), 44.]
  (25) Zhao, H. Y.; Zhao, Z. Z.; Zhao, Y. F.; Liu, Q. J. Chin. J. Catal.2010, 31 (1), 44. [赵鹤云, 赵忠泽, 赵义芬, 柳清菊. 催化学报, 2010, 31 (1), 44.]

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

单分散SnO₂中空微纳米球的制备和性质

English

Preparation and Properties of Monodisperse SnO₂ Hollow Micro/Nano Spheres

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