一步水热合成铜纳米颗粒负载二氧化钛复合纳米管及其可见光催化活性

引用本文: 赵鹏君, 吴荣, 侯娟, 常爱民, 关芳, 张博. 一步水热合成铜纳米颗粒负载二氧化钛复合纳米管及其可见光催化活性[J]. 物理化学学报, 2012, 28(08): 1971-1977. doi: 10.3866/PKU.WHXB201206111 shu

Citation: ZHAO Peng-Jun, WU Rong, HOU Juan, CHANG Ai-min, GUAN Fang, ZHANG Bo. One-Step Hydrothermal Synthesis and Visible-Light Photocatalytic Activity of Ultrafine Cu-Nanodot-Modified TiO₂ Nanotubes[J]. Acta Physico-Chimica Sinica, 2012, 28(08): 1971-1977. doi: 10.3866/PKU.WHXB201206111 shu

一步水热合成铜纳米颗粒负载二氧化钛复合纳米管及其可见光催化活性

赵鹏君 ^1,2, ,
吴荣 ^1, ,
侯娟 ^1,2, ,
常爱民 ^1, ,
关芳 ^1,2, ,
张博 ^1,2,

基金项目:
中国科学院&ldquo

西部之光&rdquo

联合学者项目(LHXZ200902) (LHXZ200902)

中国博士后科研基金项目(20100471679, 201104704)资助 (20100471679, 201104704)

摘要:

采用一步水热法合成了Cu纳米粒子负载二氧化钛纳米管材料. 利用透射电子显微镜(TEM)、X射线衍射仪(XRD)、能谱仪(EDS)等对材料的相组成、形貌以及形成过程进行了研究. 制得的Cu-TiO₂复合纳米材料长度约为100 nm, 直径10-15 nm, 其上负载的Cu纳米粒子尺寸约为5 nm. BET比表面积测试表明实验制备的Cu-TiO₂复合纳米管的比表面积为154.67 m²·g^-1. 通过调节水热反应时间和钛前驱体种类, 研究了该复合纳米管材料的形成机制. 结果表明: 非晶态的钛源对于成功一步合成Cu-TiO₂复合纳米管至关重要. 同时, 实验中观察到铜纳米粒子的尺寸随水热反应时间延长而减小(反奥氏陈化过程), 这一现象有助于纳米粒子的可控合成.紫外-可见吸收光谱表明该复合纳米管在350-800 nm范围内有较强的吸收, 并在550-600 nm范围观察到Cu的表面等离子激元吸收带. Cu-TiO₂界面处形成的肖特基势垒有助于加快光生载流子的输运, 提高光生电子-空穴对的分离效率. 光催化实验表明Cu-TiO₂复合纳米管在可见光下具有较高的催化活性.

关键词:

English

One-Step Hydrothermal Synthesis and Visible-Light Photocatalytic Activity of Ultrafine Cu-Nanodot-Modified TiO₂ Nanotubes

1.
1. Xinjiang Key Laboratory of Electronic Information Materials and Devices, Xinjiang Technical Institute of Physics & Chemistry, Chinese Academy of Sciences, Urumqi 830011, P. R. China;
2. Graduate University of Chinese Academy of Sciences, Beijing 100049, P. R. China
Received Date: 28 March 2012
Available Online: 10 July 2012
Fund Project:
中国科学院&ldquo

西部之光&rdquo

联合学者项目(LHXZ200902)

中国博士后科研基金项目(20100471679, 201104704)资助

Abstract:

One dimensional titanate nanotubes modified with copper nanospheres were synthesized through a facile one-step hydrothermal process. Transmission electron microscope (TEM), X-ray diffraction (XRD), and energy dispersive spectrometry (EDS) were used to monitor the changes in the morphology and phases during the hydrothermal process. The diameter of the Cu-TiO₂ composite nanotubes was 10-15 nm and their lengths were ca 100 nm, the dimension of the covered Cu nanoparticles was about 5 nm. Brunauer-Emmett-Teller (BET) tests revealed the specific surface area of the Cu-TiO₂ composite nanotubes to be 154.67 m²·g^-1. The formation process and mechanism of the composite nanotubes were surveyed by adjusting the hydrothermal duration and titanium precursor. The results revealed that an amorphous titanium precursor is essential for the successful formation of this unique topography and phase composition. Anti-Ostwald ripening, a decrease in the dimensions of the copper nanospheres with hydrothermal time, was observed in the TEM images, which is of benefit to helps keep the particles on the nanoscale. The UV-Vis spectrum of the as-prepared material exhibits a strong absorption at 350-800 nm in the visible band compared with commercial TiO₂ nanopowders. The plasmonic absorption of metallic copper particles between 550 and 600 nm is seen in the UV-Vis spectrum. Schottky barriers between copper-TiO₂ interfaces make this kind of material a potential agent in speeding up electron transport rates and slowing recombination rates. Photocatalytic experiments demonstrated this unique Cu-TiO₂ composite nanotube material has a high photocatalytic activity under visible-light irradiation.

Key words:

1. [1]
  
  (1) Yella, A.; Lee, H.W.; Tsao, H. N.; Yi, C.; Chandiran, A. K.;Nazeeruddin, M. K.; Diau, E.W.; Yeh, C. Y.; Zakeeruddin, S.M.; Grätzel, M. Science 2011, 334, 629. doi: 10.1126/science.1209688
  (1) Yella, A.; Lee, H.W.; Tsao, H. N.; Yi, C.; Chandiran, A. K.;Nazeeruddin, M. K.; Diau, E.W.; Yeh, C. Y.; Zakeeruddin, S.M.; Grätzel, M. Science 2011, 334, 629. doi: 10.1126/science.1209688
2. [2]
  (2) Xu, P. C.; Liu, Y.;Wei, J. H.; Xiong, R.; Pan, C. X.; Shi, J. Acta Phys. -Chim. Sin. 2010, 26, 2261. [许平昌, 柳阳, 魏建红,熊锐, 潘春旭, 石兢. 物理化学学报, 2010, 26, 2261.] doi: 10.3866/PKU.WHXB20100815(2) Xu, P. C.; Liu, Y.;Wei, J. H.; Xiong, R.; Pan, C. X.; Shi, J. Acta Phys. -Chim. Sin. 2010, 26, 2261. [许平昌, 柳阳, 魏建红,熊锐, 潘春旭, 石兢. 物理化学学报, 2010, 26, 2261.] doi: 10.3866/PKU.WHXB20100815
3. [3]
  (3) Zhang,W.; Zou, L.;Wang, L. Appl. Catal. A 2009, 371, 1.doi: 10.1016/j.apcata.2009.09.038(3) Zhang,W.; Zou, L.;Wang, L. Appl. Catal. A 2009, 371, 1.doi: 10.1016/j.apcata.2009.09.038
4. [4]
  (4) Chen, J. S.; Tan, Y. L.; Li, C. M.; Cheah, Y. L.; Luan, D.;Madhavi, S.; Boey, F. Y. C.; Archer, L. A.; Lou, X.W. J. Am. Chem. Soc. 2010, 132, 6124. doi: 10.1021/ja100102y(4) Chen, J. S.; Tan, Y. L.; Li, C. M.; Cheah, Y. L.; Luan, D.;Madhavi, S.; Boey, F. Y. C.; Archer, L. A.; Lou, X.W. J. Am. Chem. Soc. 2010, 132, 6124. doi: 10.1021/ja100102y
5. [5]
  (5) Li, N.; Liu, G.; Zhen, C.; Li, F.; Zhang, L.; Chen, H. M. Adv. Funct. Mater. 2011, 21, 1717. doi: 10.1002/adfm.201002295(5) Li, N.; Liu, G.; Zhen, C.; Li, F.; Zhang, L.; Chen, H. M. Adv. Funct. Mater. 2011, 21, 1717. doi: 10.1002/adfm.201002295
6. [6]
  (6) Wang, N.; Han, L.; He, H.; Park, N. H.; Koumoto, K. Energy Environ. Sci. 2011, 4, 3676. doi: 10.1039/c1ee01646f(6) Wang, N.; Han, L.; He, H.; Park, N. H.; Koumoto, K. Energy Environ. Sci. 2011, 4, 3676. doi: 10.1039/c1ee01646f
7. [7]
  (7) Attar, A. S.; Ghamsari, M. S.; Hajiesmaeilbaigi, F.; Mirdamadi,S.; Katagiri, K.; Koumoto, K. Mater. Chem. Phys. 2009, 113,856. doi: 10.1016/j.matchemphys.2008.08.040(7) Attar, A. S.; Ghamsari, M. S.; Hajiesmaeilbaigi, F.; Mirdamadi,S.; Katagiri, K.; Koumoto, K. Mater. Chem. Phys. 2009, 113,856. doi: 10.1016/j.matchemphys.2008.08.040
8. [8]
  (8) Wang, D.; Yu, B.;Wang, C.; Zhou, F.; Liu,W. Adv. Mater. 2009,21, 1964. doi: 10.1002/adma.200801996(8) Wang, D.; Yu, B.;Wang, C.; Zhou, F.; Liu,W. Adv. Mater. 2009,21, 1964. doi: 10.1002/adma.200801996
9. [9]
  (9) Dai, L.; Sow, C. H.; Lim, C. T.; Cheong,W. C. D.; Tan, V. B. C.Nano Lett. 2009, 9, 576. doi: 10.1021/nl8027284(9) Dai, L.; Sow, C. H.; Lim, C. T.; Cheong,W. C. D.; Tan, V. B. C.Nano Lett. 2009, 9, 576. doi: 10.1021/nl8027284
10. [10]
  (10) Lekeufack, D. D.; Brioude, A.; Mouti, A.; Alauzun, J. G.;Stadelmann, P.; Coleman, A.W.; Miele, P. Chem. Commun.2010, 46, 4544. doi: 10.1039/c0cc00935k(10) Lekeufack, D. D.; Brioude, A.; Mouti, A.; Alauzun, J. G.;Stadelmann, P.; Coleman, A.W.; Miele, P. Chem. Commun.2010, 46, 4544. doi: 10.1039/c0cc00935k
11. [11]
  (11) Yuan, J.;Wang, Y.; Chen, Y.; Yang,W.; Yao, J.; Cao, Y. Appl. Surf. Sci. 2011, 257, 7335. doi: 10.1016/j.apsusc.2011.03.139(11) Yuan, J.;Wang, Y.; Chen, Y.; Yang,W.; Yao, J.; Cao, Y. Appl. Surf. Sci. 2011, 257, 7335. doi: 10.1016/j.apsusc.2011.03.139
12. [12]
  (12) Sathish, M.; Viswanathan, B.; Viswanath, R. P.; pinath, C. S.Chem. Mater. 2005, 17, 6349. doi: 10.1021/cm052047v(12) Sathish, M.; Viswanathan, B.; Viswanath, R. P.; pinath, C. S.Chem. Mater. 2005, 17, 6349. doi: 10.1021/cm052047v
13. [13]
  (13) Liu, G.;Wang, X.; Chen, Z.; Cheng, H. M.; Lu, G. Q. J. Colloid Interface Sci. 2009, 329, 331. doi: 10.1016/j.jcis.2008.09.061(13) Liu, G.;Wang, X.; Chen, Z.; Cheng, H. M.; Lu, G. Q. J. Colloid Interface Sci. 2009, 329, 331. doi: 10.1016/j.jcis.2008.09.061
14. [14]
  (14) Xu, L.; Tang, C. Q.; Huang, Z. B. Acta Phys. -Chim. Sin. 2010,26, 1401. [徐凌, 唐超群, 黄宗斌. 物理化学学报, 2010,26, 1401.] doi: 10.3866/PKU.WHXB20100526(14) Xu, L.; Tang, C. Q.; Huang, Z. B. Acta Phys. -Chim. Sin. 2010,26, 1401. [徐凌, 唐超群, 黄宗斌. 物理化学学报, 2010,26, 1401.] doi: 10.3866/PKU.WHXB20100526
15. [15]
  (15) Gao, X.; Zhu, H.; Pan, G.; Ye, S.; Lan, Y.;Wu, F.; Song, D.J. Phys. Chem. B 2004, 108, 2868. doi: 10.1021/jp036821i(15) Gao, X.; Zhu, H.; Pan, G.; Ye, S.; Lan, Y.;Wu, F.; Song, D.J. Phys. Chem. B 2004, 108, 2868. doi: 10.1021/jp036821i
16. [16]
  (16) Lei, B. X.; Liao, J. Y.; Zhang, R.;Wang, J.; Su, C. Y.; Kuang, D.B. J. Phys. Chem. C 2010, 114, 15228.(16) Lei, B. X.; Liao, J. Y.; Zhang, R.;Wang, J.; Su, C. Y.; Kuang, D.B. J. Phys. Chem. C 2010, 114, 15228.
17. [17]
  (17) Zhu, K.; Vinzant, T. B.; Neale, N. R.; Frank, A. J. Nano Lett.2007, 7, 3739. doi: 10.1021/nl072145a(17) Zhu, K.; Vinzant, T. B.; Neale, N. R.; Frank, A. J. Nano Lett.2007, 7, 3739. doi: 10.1021/nl072145a
18. [18]
  (18) Huang, B.; Yang, Y.; Chen, X.; Ye, D. Catal. Commun. 2010, 11,844. doi: 10.1016/j.catcom.2010.03.006(18) Huang, B.; Yang, Y.; Chen, X.; Ye, D. Catal. Commun. 2010, 11,844. doi: 10.1016/j.catcom.2010.03.006
19. [19]
  (19) Viana, B. C.; Ferreira, O. P.; Filho, A. G. S.; Rodrigues, C. M.;Moraes, S. G.; Filho, J. M.; Alves, O. L. J. Phys. Chem. C 2009,113, 20234. doi: 10.1021/jp9068043(19) Viana, B. C.; Ferreira, O. P.; Filho, A. G. S.; Rodrigues, C. M.;Moraes, S. G.; Filho, J. M.; Alves, O. L. J. Phys. Chem. C 2009,113, 20234. doi: 10.1021/jp9068043
20. [20]
  (20) Chu, S.; Zheng, X.; Kong, F.;Wu, G.; Luo, L.; Guo, Y.; Liu, H.;Wang, Y.; Yu, H.; Zou, Z.; Liu, Z. Mater. Chem. Phys. 2011,129, 1184. doi: 10.1016/j.matchemphys.2011.06.004(20) Chu, S.; Zheng, X.; Kong, F.;Wu, G.; Luo, L.; Guo, Y.; Liu, H.;Wang, Y.; Yu, H.; Zou, Z.; Liu, Z. Mater. Chem. Phys. 2011,129, 1184. doi: 10.1016/j.matchemphys.2011.06.004
21. [21]
  (21) Zhao, G., Lei, Y.; Zhang, Y.; Li, H.; Liu, M. J. Phys. Chem. C2008, 112, 14786. doi: 10.1021/jp712054c(21) Zhao, G., Lei, Y.; Zhang, Y.; Li, H.; Liu, M. J. Phys. Chem. C2008, 112, 14786. doi: 10.1021/jp712054c
22. [22]
  (22) Chien, S.; Liou, Y. C.; Kuo, M. C. Synthetic Metals 2005, 152,333. doi: 10.1016/j.synthmet.2005.07.254(22) Chien, S.; Liou, Y. C.; Kuo, M. C. Synthetic Metals 2005, 152,333. doi: 10.1016/j.synthmet.2005.07.254
23. [23]
  (23) Wang, C.; Yin, L.; Zhang, L.; Liu, N.; Lun, N.; Qi, Y. ACS Appl. Mater. Interfaces 2010, 2, 3373. doi: 10.1021/am100834x(23) Wang, C.; Yin, L.; Zhang, L.; Liu, N.; Lun, N.; Qi, Y. ACS Appl. Mater. Interfaces 2010, 2, 3373. doi: 10.1021/am100834x
24. [24]
  (24) Macak, J. M.; Schmidt-Stein, F.; Schmuki, P. Electrochem. Commun. 2007, 9, 1783. doi: 10.1016/j.elecom.2007.04.002(24) Macak, J. M.; Schmidt-Stein, F.; Schmuki, P. Electrochem. Commun. 2007, 9, 1783. doi: 10.1016/j.elecom.2007.04.002
25. [25]
  (25) Zeng, H.; Cai,W.; Liu, P.; Xu, X.; Zhou, H.; Klingshirn, C.;Kalt, H. ACS Nano 2008, 2, 1661. doi: 10.1021/nn800353q(25) Zeng, H.; Cai,W.; Liu, P.; Xu, X.; Zhou, H.; Klingshirn, C.;Kalt, H. ACS Nano 2008, 2, 1661. doi: 10.1021/nn800353q
26. [26]
  (26) Kumar, V.; Adamson, D. H.; Prudhomme, R. K. Small 2010, 6,2907. doi: 10.1002/smll.201001199(26) Kumar, V.; Adamson, D. H.; Prudhomme, R. K. Small 2010, 6,2907. doi: 10.1002/smll.201001199
27. [27]
  (27) Jia,W.; Douglas, E. P. J. Mater. Chem. 2004, 14, 744. doi: 10.1039/b311917c(27) Jia,W.; Douglas, E. P. J. Mater. Chem. 2004, 14, 744. doi: 10.1039/b311917c
28. [28]
  (28) Nakahira, A.; Kubo, T.; Numako, C. Inorg. Chem. 2010, 49,5845. doi: 10.1021/ic9025816(28) Nakahira, A.; Kubo, T.; Numako, C. Inorg. Chem. 2010, 49,5845. doi: 10.1021/ic9025816
29. [29]
  (29) Huang, J.; Cao, Y.; Huang, Q.; He, H.; Liu, Y.; Guo,W.; Hong,M. Cryst. Growth Des. 2009, 9, 3632. doi: 10.1021/cg900381h(29) Huang, J.; Cao, Y.; Huang, Q.; He, H.; Liu, Y.; Guo,W.; Hong,M. Cryst. Growth Des. 2009, 9, 3632. doi: 10.1021/cg900381h
30. [30]
  (30) Yao, B. D.; Chan, Y. F.; Zhang, X. Y.; Zhang,W. F.; Yang, Z. Y.;Wang, N. Appl. Phys. Lett. 2003, 82, 281. doi: 10.1063/1.1537518(30) Yao, B. D.; Chan, Y. F.; Zhang, X. Y.; Zhang,W. F.; Yang, Z. Y.;Wang, N. Appl. Phys. Lett. 2003, 82, 281. doi: 10.1063/1.1537518
31. [31]
  (31) Kochkar, H.; Lakhdhar, N.; Berhault, G.; Bausach, M.; Ghorbel,A. J. Phys. Chem. C 2009, 113, 1672. doi: 10.1021/jp809131z(31) Kochkar, H.; Lakhdhar, N.; Berhault, G.; Bausach, M.; Ghorbel,A. J. Phys. Chem. C 2009, 113, 1672. doi: 10.1021/jp809131z
32. [32]
  (32) Xu, S.; Ng, J.; Zhang, X.; Bai, H.; Sun, D. D. Int. J. Hydrog. Energy 2010, 35, 5254. doi: 10.1016/j.ijhydene.2010.02.129(32) Xu, S.; Ng, J.; Zhang, X.; Bai, H.; Sun, D. D. Int. J. Hydrog. Energy 2010, 35, 5254. doi: 10.1016/j.ijhydene.2010.02.129
33. [33]
  (33) Boccuzzi, F.; Coluccia, S.; Martra, G.; Ravasio, N. J. Catal.1999, 184, 316. doi: 10.1006/jcat.1999.2428(33) Boccuzzi, F.; Coluccia, S.; Martra, G.; Ravasio, N. J. Catal.1999, 184, 316. doi: 10.1006/jcat.1999.2428
34. [34]
  (34) Balogh, L.; Tomalia, D. A. J. Am. Chem. Soc. 1998, 120, 7355.doi: 10.1021/ja980861w(34) Balogh, L.; Tomalia, D. A. J. Am. Chem. Soc. 1998, 120, 7355.doi: 10.1021/ja980861w
35. [35]
  (35) Doremus, R. H.; Rao, P. J. Mater. Res. 1996, 11, 2384.(35) Doremus, R. H.; Rao, P. J. Mater. Res. 1996, 11, 2384.
36. [36]
  (36) Pestryakov, A. N.; Petranovskii, V. P.; Kryazho, A.; Ozhereliev,O.; Pfcander, N.; Knop-Gericke, A. Chem. Phys. Lett. 2004,385, 173. doi: 10.1016/j.cplett.2003.12.077
  (36) Pestryakov, A. N.; Petranovskii, V. P.; Kryazho, A.; Ozhereliev,O.; Pfcander, N.; Knop-Gericke, A. Chem. Phys. Lett. 2004,385, 173. doi: 10.1016/j.cplett.2003.12.077

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

一步水热合成铜纳米颗粒负载二氧化钛复合纳米管及其可见光催化活性

English

One-Step Hydrothermal Synthesis and Visible-Light Photocatalytic Activity of Ultrafine Cu-Nanodot-Modified TiO₂ Nanotubes

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

一步水热合成铜纳米颗粒负载二氧化钛复合纳米管及其可见光催化活性

English

One-Step Hydrothermal Synthesis and Visible-Light Photocatalytic Activity of Ultrafine Cu-Nanodot-Modified TiO2 Nanotubes

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

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One-Step Hydrothermal Synthesis and Visible-Light Photocatalytic Activity of Ultrafine Cu-Nanodot-Modified TiO₂ Nanotubes

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