Citation: DENG Jie, TAO Jie, WU Tao, TAO Hai-Jun. Growth Mechanism and Characterization of Flexible TiO2 Nanowhisker Films Hydrothermally Synthesized in Dilute Alkaline Solution[J]. Acta Physico-Chimica Sinica, doi: 10.3866/PKU.WHXB201302041
稀碱溶液中水热法制备柔性TiO2纳米须薄膜的生长机制及表征
以柔性不锈钢基底上经磁控溅射沉积的钛膜为钛源, 在1 mol·L-1的低浓度NaOH溶液中水热法制备了朝基底上方取向生长的大长径比柔性TiO2纳米须薄膜, 考察了钛膜沉积条件对纳米须薄膜的影响, 系统研究了水热反应条件对薄膜生长过程的影响及TiO2纳米须薄膜的形成机制. 通过场发射扫描电镜(FESEM)、X射线能谱仪(EDS)、高分辨透射电子显微镜(HRTEM)、X射线衍射仪(XRD)等对样品进行了表征. 结果表明, 与室温沉积的钛膜相比, 600 ℃下沉积的钛膜水热后得到的纳米线薄膜与基底的附着力更好. 所得TiO2纳米须为单晶锐钛矿, 经由Na2Ti2O4(OH)2、H2Ti2O5·H2O转变而来. 纳米须形成于水热阶段, 平行于Na2Ti2O4(OH)2的(100)晶面择优取向生长, 纳米须经历了纳米片→纳米线束→纳米线的裂解生长过程. 朝基底上方取向生长的纳米须薄膜的形成是低浓度NaOH溶液与较高水热温度(220 ℃)协同作用的结果. 进一步在Na2SO4溶液中研究了薄膜电极的光电化学性能, 结果表明, TiO2纳米须薄膜的光电性能明显优于零维纳米颗粒薄膜和二维纳米片薄膜, 显示了良好的应用前景.
English
Growth Mechanism and Characterization of Flexible TiO2 Nanowhisker Films Hydrothermally Synthesized in Dilute Alkaline Solution
Flexible oriented TiO2 nanowhisker films with large aspect ratios were hydrothermally prepared in 1 mol·L-1 NaOH solution from Ti film deposited by magnetron sputtering on a flexible stainless steel substrate. The influence of the Ti film deposition conditions on the resulting TiO2 nanowhisker films was investigated. We also systematically studied the effects of the hydrothermal parameters on the nanowhisker films and their growth mechanism. The samples were characterized by field emission scanning electron microscopy (FESEM), energy dispersive X-ray spectrometry (EDS), X-ray diffraction (XRD), and high resolution transmission electron microscopy (HRTEM). The results showed that nanowhisker film prepared from Ti film deposited at 600 ° C had stronger adhesion to the substrate compared with that prepared from Ti film deposited at room temperature. The as-prepared TiO2 nanowhiskers were single crystalline anatase and were the result of transformation of Ti into Na2Ti2O4(OH)2 and H2Ti2O5·H2O. The nanowhiskers took shape during the hydrothermal synthesis, preferably oriented parallel to (100) crystal face of Na2Ti2O4(OH)2, and experienced splitting conversion from nanobelts to nanowire harnesses and nanowires. The formation of vertical nanowhisker films was ascribed to a cooperative effect of the dilute NaOH solution and the higher hydrothermal temperature (220 ° C). The photoelectrochemical properties of the films were investigated in Na2SO4 solution, and the results showed that the as-prepared TiO2 nanowhisker film exhibited better photoelectrochemical properties than those of zero-dimensional nanoparticle films and two-dimensional nanobelt films, indicating a od potential for practical application.
-
Key words:
-
TiO2
- / Nanowhisker
- / Thin film
- / Hydrothermal synthesis
- / Flexible stainless steel substrate
- / Photoelectrical property
-
-
[1]
(1) O'Regan, B.; Grätzel, M. Nature 1991, 353, 737. doi: 10.1038/353737a0
(1) O'Regan, B.; Grätzel, M. Nature 1991, 353, 737. doi: 10.1038/353737a0
-
[2]
(2) Lee, S.; Cho, I.; Lee, J. H.; Kim, D. H.; Kim, D.W.; Kim, J. Y.;Shin, H.; Lee, J.; Jung, H. S.; Park, N.; Kim, K.; Ko, M. J.;Hong, K. S. Chem. Mater. 2010, 22, 1958. doi: 10.1021/cm902842k(2) Lee, S.; Cho, I.; Lee, J. H.; Kim, D. H.; Kim, D.W.; Kim, J. Y.;Shin, H.; Lee, J.; Jung, H. S.; Park, N.; Kim, K.; Ko, M. J.;Hong, K. S. Chem. Mater. 2010, 22, 1958. doi: 10.1021/cm902842k
-
[3]
(3) Li, T. C.; Fabregat-Santia , F.; Farha, O. K.; Spokoyny, A. M.;Raga, S. R.; Bisquert, J.; Mirkin, C. A.; Marks, T. J.; Hupp, J. T.J. Phys. Chem. C 2011, 115, 11257. doi: 10.1021/jp112139h(3) Li, T. C.; Fabregat-Santia , F.; Farha, O. K.; Spokoyny, A. M.;Raga, S. R.; Bisquert, J.; Mirkin, C. A.; Marks, T. J.; Hupp, J. T.J. Phys. Chem. C 2011, 115, 11257. doi: 10.1021/jp112139h
-
[4]
(4) Chang, M. L.; Li, X. J. Acta Phys. -Chim. Sin. 2012, 28, 1368.[常萌蕾, 李新军. 物理化学学报, 2012, 28, 1368.] doi: 10.3866/PKU.WHXB201203161(4) Chang, M. L.; Li, X. J. Acta Phys. -Chim. Sin. 2012, 28, 1368.[常萌蕾, 李新军. 物理化学学报, 2012, 28, 1368.] doi: 10.3866/PKU.WHXB201203161
-
[5]
(5) Shi, J.; Chen, S.;Wang, S.;Wu, P.; Xu, G. Journal of MolecularCatalysis A: Chemical 2009, 303, 141. doi: 10.1016/j.molcata.2009.01.016(5) Shi, J.; Chen, S.;Wang, S.;Wu, P.; Xu, G. Journal of MolecularCatalysis A: Chemical 2009, 303, 141. doi: 10.1016/j.molcata.2009.01.016
-
[6]
(6) Reyes-Garcia, E. A.; Sun, Y.; Reyes-Gil, K. R.; Raftery, D. SolidState Nuclear Magnetic Resonance 2009, 35, 74. doi: 10.1016/j.ssnmr.2009.02.004(6) Reyes-Garcia, E. A.; Sun, Y.; Reyes-Gil, K. R.; Raftery, D. SolidState Nuclear Magnetic Resonance 2009, 35, 74. doi: 10.1016/j.ssnmr.2009.02.004
-
[7]
(7) Yu, H.; Irie, H.; Shimodaira, Y.; Hosogi, Y.; Kuroda, Y.;Miyauchi, M.; Hashimoto, K. J. Phys. Chem. C 2010, 114,16481. doi: 10.1021/jp1071956(7) Yu, H.; Irie, H.; Shimodaira, Y.; Hosogi, Y.; Kuroda, Y.;Miyauchi, M.; Hashimoto, K. J. Phys. Chem. C 2010, 114,16481. doi: 10.1021/jp1071956
-
[8]
(8) Lin, S.; Li, D.;Wu, J.; Li, X.; Akbar, S. A. Sensors andActuators B: Chemical 2011, 156, 505. doi: 10.1016/j.snb.2011.02.046(8) Lin, S.; Li, D.;Wu, J.; Li, X.; Akbar, S. A. Sensors andActuators B: Chemical 2011, 156, 505. doi: 10.1016/j.snb.2011.02.046
-
[9]
(9) García-Berríos, E.; Gao, T.;Walker, D.; Brunschwig, B. S.;Lewis, N. S. Sensors and Actuators B: Chemical 2011, 158, 17.doi: 10.1016/j.snb.2011.04.022(9) García-Berríos, E.; Gao, T.;Walker, D.; Brunschwig, B. S.;Lewis, N. S. Sensors and Actuators B: Chemical 2011, 158, 17.doi: 10.1016/j.snb.2011.04.022
-
[10]
(10) Zhang, Q.; Chou, T. P.; Russo, B.; Jenekhe, S. A.; Cao, G.Angew. Chem. Int. Edit. 2008, 47, 2402.(10) Zhang, Q.; Chou, T. P.; Russo, B.; Jenekhe, S. A.; Cao, G.Angew. Chem. Int. Edit. 2008, 47, 2402.
-
[11]
(11) Sauvage, F.; Fonzo, F. D.; Bassi, A. L.; Casari, C. S.; Russo, V.;Divitini, G.; Ducati, C.; Bottani, C. E.; Comte, P.; Grätzel, M.Nano Lett. 2010, 10, 2562. doi: 10.1021/nl101198b(11) Sauvage, F.; Fonzo, F. D.; Bassi, A. L.; Casari, C. S.; Russo, V.;Divitini, G.; Ducati, C.; Bottani, C. E.; Comte, P.; Grätzel, M.Nano Lett. 2010, 10, 2562. doi: 10.1021/nl101198b
-
[12]
(12) Smith,W.; Mao, S.; Lu, G.; Catlett, A.; Chen, J.; Zhao, Y. Chem.Phys. Lett. 2010, 485, 171. doi: 10.1016/j.cplett.2009.12.041(12) Smith,W.; Mao, S.; Lu, G.; Catlett, A.; Chen, J.; Zhao, Y. Chem.Phys. Lett. 2010, 485, 171. doi: 10.1016/j.cplett.2009.12.041
-
[13]
(13) Li, H. H.; Chen, R. F.; Ma, Z.; Zhang, S. L.; An, Z. F.; Huang,W. Acta Phys. -Chim. Sin. 2011, 27, 1017. [李欢欢, 陈润锋,马琮, 张胜兰, 安众福, 黄维. 物理化学学报, 2011, 27,1017.] doi: 10.3866/PKU.WHXB20110514(13) Li, H. H.; Chen, R. F.; Ma, Z.; Zhang, S. L.; An, Z. F.; Huang,W. Acta Phys. -Chim. Sin. 2011, 27, 1017. [李欢欢, 陈润锋,马琮, 张胜兰, 安众福, 黄维. 物理化学学报, 2011, 27,1017.] doi: 10.3866/PKU.WHXB20110514
-
[14]
(14) Feng, X.; Zhai, J.; Jiang, L. Angew. Chem. Int. Edit. 2005, 44,5115.(14) Feng, X.; Zhai, J.; Jiang, L. Angew. Chem. Int. Edit. 2005, 44,5115.
-
[15]
(15) Feng, X.; Shankar, K.; Varghese, O. K.; Paulose, M.; Latempa,T. J.; Grimes, C. A. Nano Lett. 2008, 8, 3781. doi: 10.1021/nl802096a(15) Feng, X.; Shankar, K.; Varghese, O. K.; Paulose, M.; Latempa,T. J.; Grimes, C. A. Nano Lett. 2008, 8, 3781. doi: 10.1021/nl802096a
-
[16]
(16) Li, Y.; Guo, M.; Zhang, M.;Wang, X. Materials ResearchBulletin 2009, 44, 1232. doi: 10.1016/j.materresbull.2009.01.009(16) Li, Y.; Guo, M.; Zhang, M.;Wang, X. Materials ResearchBulletin 2009, 44, 1232. doi: 10.1016/j.materresbull.2009.01.009
-
[17]
(17) Liu, B.; Aydil, E. S. J. Am. Chem. Soc. 2009, 131, 3985. doi: 10.1021/ja8078972(17) Liu, B.; Aydil, E. S. J. Am. Chem. Soc. 2009, 131, 3985. doi: 10.1021/ja8078972
-
[18]
(18) Vernardou, D.; Kalogerakis, G.; Stratakis, E.; Kenanakis, G.;Koudoumas, E.; Katsarakis, N. Solid State Science 2009, 11,1499. doi: 10.1016/j.solidstatesciences.2009.05.014(18) Vernardou, D.; Kalogerakis, G.; Stratakis, E.; Kenanakis, G.;Koudoumas, E.; Katsarakis, N. Solid State Science 2009, 11,1499. doi: 10.1016/j.solidstatesciences.2009.05.014
-
[19]
(19) Kumar, A.; Madaria, A. R.; Zhou, C. J. Phys. Chem. C 2010,114, 7787. doi: 10.1021/jp100491h(19) Kumar, A.; Madaria, A. R.; Zhou, C. J. Phys. Chem. C 2010,114, 7787. doi: 10.1021/jp100491h
-
[20]
(20) Zeng, Q.;Wu, L.; Zhang, Y.; Qi, B.; Zhi, J. Scripta Materialia2010, 62, 810. doi: 10.1016/j.scriptamat.2010.01.054(20) Zeng, Q.;Wu, L.; Zhang, Y.; Qi, B.; Zhi, J. Scripta Materialia2010, 62, 810. doi: 10.1016/j.scriptamat.2010.01.054
-
[21]
(21) Peng, X.; Chen, A. Adv. Funct. Mater. 2006, 16, 1355.(21) Peng, X.; Chen, A. Adv. Funct. Mater. 2006, 16, 1355.
-
[22]
(22) Kitano, M.; Mitsui, R.; Eddy, D. R.; El-Bahy, Z. M. A.;Matsuoka, M.; Ueshima, M.; Anpo, M. Catal. Lett. 2007, 119,217. doi: 10.1007/s10562-007-9243-1(22) Kitano, M.; Mitsui, R.; Eddy, D. R.; El-Bahy, Z. M. A.;Matsuoka, M.; Ueshima, M.; Anpo, M. Catal. Lett. 2007, 119,217. doi: 10.1007/s10562-007-9243-1
-
[23]
(23) Boercker, J. E.; Enache-Pommer, E.; Aydil, E. S.Nanotechnology 2008, 19, 095604. doi: 10.1088/0957-4484/19/9/095604(23) Boercker, J. E.; Enache-Pommer, E.; Aydil, E. S.Nanotechnology 2008, 19, 095604. doi: 10.1088/0957-4484/19/9/095604
-
[24]
(24) Dong, X.; Tao, J.; Li, Y. Y.;Wang, T.; Zhu, H. Acta Phys. -Chim.Sin. 2009, 25, 1874. [董祥, 陶杰, 李莹滢, 汪涛,朱宏. 物理化学学报, 2009, 25, 1874.] doi: 10.3866/PKU.WHXB20090913(24) Dong, X.; Tao, J.; Li, Y. Y.;Wang, T.; Zhu, H. Acta Phys. -Chim.Sin. 2009, 25, 1874. [董祥, 陶杰, 李莹滢, 汪涛,朱宏. 物理化学学报, 2009, 25, 1874.] doi: 10.3866/PKU.WHXB20090913
-
[25]
(25) Chi, B.; Victorio, E. S.; Jin, T. J. Nanosci. Nanotechnol. 2007, 7,668. doi: 10.1166/jnn.2007.147(25) Chi, B.; Victorio, E. S.; Jin, T. J. Nanosci. Nanotechnol. 2007, 7,668. doi: 10.1166/jnn.2007.147
-
[26]
(26) Guo, Y.; Lee, N.; Oh, H.; Yoon, C.; Park, K.; Lee, H.; Lee, K.;Kim, S. Nanotechnology 2007, 18, 295608. doi: 10.1088/0957-4484/18/29/295608(26) Guo, Y.; Lee, N.; Oh, H.; Yoon, C.; Park, K.; Lee, H.; Lee, K.;Kim, S. Nanotechnology 2007, 18, 295608. doi: 10.1088/0957-4484/18/29/295608
-
[27]
(27) Liu, B.; Boercker, J. E.; Aydil, E. S. Nanotechnology 2008, 19,505604. doi: 10.1088/0957-4484/19/50/505604(27) Liu, B.; Boercker, J. E.; Aydil, E. S. Nanotechnology 2008, 19,505604. doi: 10.1088/0957-4484/19/50/505604
-
[28]
(28) Liao, J.; Lei, B.; Chen, H.; Kuang, D.; Su, C. Energy Environ.Sci. 2012, 5, 5750. doi: 10.1039/c1ee02766b(28) Liao, J.; Lei, B.; Chen, H.; Kuang, D.; Su, C. Energy Environ.Sci. 2012, 5, 5750. doi: 10.1039/c1ee02766b
-
[29]
(29) Kang, M. G.; Park, N.; Ryu, K. S.; Chang, S. H.; Kim, K. Sol.Energy Mater. Sol. Cells 2006, 90, 574. doi: 10.1016/j.solmat.2005.04.025(29) Kang, M. G.; Park, N.; Ryu, K. S.; Chang, S. H.; Kim, K. Sol.Energy Mater. Sol. Cells 2006, 90, 574. doi: 10.1016/j.solmat.2005.04.025
-
[30]
(30) Kang, H.; Lee, C.; Kim, D.; Kim, J.; Choi,W.; Kim, H. AppliedCatalysis B: Environmental 2011, 104, 6. doi: 10.1016/j.apcatb.2011.03.010(30) Kang, H.; Lee, C.; Kim, D.; Kim, J.; Choi,W.; Kim, H. AppliedCatalysis B: Environmental 2011, 104, 6. doi: 10.1016/j.apcatb.2011.03.010
-
[31]
(31) Vijayakumar, V.; Pasquier, A. D.; Birnie, D. P., III. Sol. EnergyMater. Sol. Cells 2011, 95, 2120. doi: 10.1016/j.solmat.2011.03.010(31) Vijayakumar, V.; Pasquier, A. D.; Birnie, D. P., III. Sol. EnergyMater. Sol. Cells 2011, 95, 2120. doi: 10.1016/j.solmat.2011.03.010
-
[32]
(32) Wu, T.; Tao, J.; Deng, J.; Tang, Y. X.; Zhu, H.; Gao, P. ActaPhys. -Chim. Sin. 2010, 26, 3087. [吴涛, 陶杰, 邓杰,汤育欣, 朱宏, 高鹏. 物理化学学报, 2010, 26, 3087.] doi: 10.3866/PKU.WHXB20101103(32) Wu, T.; Tao, J.; Deng, J.; Tang, Y. X.; Zhu, H.; Gao, P. ActaPhys. -Chim. Sin. 2010, 26, 3087. [吴涛, 陶杰, 邓杰,汤育欣, 朱宏, 高鹏. 物理化学学报, 2010, 26, 3087.] doi: 10.3866/PKU.WHXB20101103
-
[33]
(33) Yang, J.; Jin, Z.;Wang, X.; Li,W.; Zhang, J.; Zhang, S.; Guo,X.; Zhang, Z. Dalton Trans. 2003, 3898.(33) Yang, J.; Jin, Z.;Wang, X.; Li,W.; Zhang, J.; Zhang, S.; Guo,X.; Zhang, Z. Dalton Trans. 2003, 3898.
-
[34]
(34) Zhang, M.; Jin, Z.; Zhang, J.; Guo, X.; Yang, J.; Li,W.;Wang,X.; Zhang, Z. Journal of Molecular Catalysis A: Chemical2004, 217, 203. doi: 10.1016/j.molcata.2004.03.032(34) Zhang, M.; Jin, Z.; Zhang, J.; Guo, X.; Yang, J.; Li,W.;Wang,X.; Zhang, Z. Journal of Molecular Catalysis A: Chemical2004, 217, 203. doi: 10.1016/j.molcata.2004.03.032
-
[35]
(35) Xing, C.; Jing, D.; Liu, M.; Guo, L. Materials Research Bulletin2009, 44, 442. doi: 10.1016/j.materresbull.2008.04.016(35) Xing, C.; Jing, D.; Liu, M.; Guo, L. Materials Research Bulletin2009, 44, 442. doi: 10.1016/j.materresbull.2008.04.016
-
[36]
(36) Xie, T. S.; Du, H.; Meng, X. M.; Sun, C.;Wen, L. S. ActaMetallurgica Sinica 2001, 37, 113. [谢天生, 杜昊, 孟祥敏,孙超, 闻立时. 金属学报, 2001, 37, 113.](36) Xie, T. S.; Du, H.; Meng, X. M.; Sun, C.;Wen, L. S. ActaMetallurgica Sinica 2001, 37, 113. [谢天生, 杜昊, 孟祥敏,孙超, 闻立时. 金属学报, 2001, 37, 113.]
-
[37]
(37) Wang, K. M.; Zhang, C. S.; Li, M.; Zhou, Y.;Wang, Y. Q.;Wang, X.; Peng, Y. C.; Liu, B. T. Journal of Synthetic Crystals2010, 39, 135. [王宽冒, 张沧生, 李曼, 周阳, 王玉强,王侠, 彭英才, 刘保亭. 人工晶体学报, 2010, 39, 135.](37) Wang, K. M.; Zhang, C. S.; Li, M.; Zhou, Y.;Wang, Y. Q.;Wang, X.; Peng, Y. C.; Liu, B. T. Journal of Synthetic Crystals2010, 39, 135. [王宽冒, 张沧生, 李曼, 周阳, 王玉强,王侠, 彭英才, 刘保亭. 人工晶体学报, 2010, 39, 135.]
-
[38]
(38) Zhu, K.; Vinzant, T. B.; Neale, N. R.; Frank, A. J. Nano Lett.2007, 7, 3739. doi: 10.1021/nl072145a(38) Zhu, K.; Vinzant, T. B.; Neale, N. R.; Frank, A. J. Nano Lett.2007, 7, 3739. doi: 10.1021/nl072145a
-
[39]
(39) Zhuo, Y.;Wu, C.; Han, S.; Chi, B.; Pu, J.; Jin, T.; Jian, L.J. Nanosci. Nanotechnol. 2011, 11, 2298. doi: 10.1166/jnn.2011.3573(39) Zhuo, Y.;Wu, C.; Han, S.; Chi, B.; Pu, J.; Jin, T.; Jian, L.J. Nanosci. Nanotechnol. 2011, 11, 2298. doi: 10.1166/jnn.2011.3573
-
[40]
(40) Wu, D.; Liu, J.; Zhao, X.; Li, A.; Chen, Y.; Ming, N. Chem.Mater. 2006, 18, 547. doi: 10.1021/cm0519075(40) Wu, D.; Liu, J.; Zhao, X.; Li, A.; Chen, Y.; Ming, N. Chem.Mater. 2006, 18, 547. doi: 10.1021/cm0519075
-
[41]
(41) Huang, J.; Cao, Y.; Huang, Q.; He, H.; Liu, Y.; Guo,W.; Hong,M. Crystal Growth & Design 2009, 9, 3632. doi: 10.1021/cg900381h(41) Huang, J.; Cao, Y.; Huang, Q.; He, H.; Liu, Y.; Guo,W.; Hong,M. Crystal Growth & Design 2009, 9, 3632. doi: 10.1021/cg900381h
-
[42]
(42) Wang,W.; Lin, H.; Li, J.;Wang, N. J. Am. Ceram. Soc. 2008,91, 628. doi: 10.1111/jace.2008.91.issue-2
(42) Wang,W.; Lin, H.; Li, J.;Wang, N. J. Am. Ceram. Soc. 2008,91, 628. doi: 10.1111/jace.2008.91.issue-2
-
[1]
-
扫一扫看文章
计量
- PDF下载量: 1090
- 文章访问数: 1723
- HTML全文浏览量: 94

下载: