Citation: ZHAO Wei-Rong, XI Hai-Ping, LIAO Qiu-Wen. Cu-Doped Titania Nanotubes for Visible-Light Photocatalytic Mineralization of Toluene[J]. Acta Physico-Chimica Sinica, 2013, 29(10): 2232-2238. doi: 10.3866/PKU.WHXB201308291
Cu掺杂TiO2纳米管可见光催化矿化甲苯
采用低温水热法制备氢钛酸管, 通过吸附-煅烧法制备Cu掺杂TiO2纳米管(Cu-TNT)催化剂. 利用X射线衍射(XRD)、电感耦合等离子体-原子发射光谱(ICP-AES)、X射线光电子能谱(XPS)、透射电镜(TEM)、紫外-可见漫反射光谱(UV-Vis-DRS)和电化学测试手段对样品进行表征, 并进行平面波赝势密度泛函理论(DFT)计算. 结果表明, 样品中Cu/Ti原子比接近理论值, Cu掺杂进入TiO2晶格内部, 诱发催化剂可见光活性. 掺Cu后,Cu 3d轨道和O 2p轨道杂化形成价带顶, 价带负向偏移, 样品禁带宽度减小为2.50-2.91 eV, 具有可见光响应.以甲苯为模型污染物研究催化剂对挥发性有机化合物(VOCs)的催化去除和矿化效果. 未掺杂的TNT可见光催化活性较差; Cu掺杂量超过0.1%(Cu/Ti原子比)时, 样品催化活性也减弱; Cu掺杂量为0.1%的催化剂具有最佳可见光催化氧化能力, 7 h内甲苯的去除率达77%, 甲苯的矿化率达59%.
English
Cu-Doped Titania Nanotubes for Visible-Light Photocatalytic Mineralization of Toluene
Based on hydrogen titanate nanotubes prepared by a low-temperature hydrothermal technique, Cu-doped titania nanotube (Cu-TNT) catalysts were prepared using absorption-calcination methods. They were characterized by X-ray diffraction (XRD), inductively coupled plasma-atomic emission spectroscopy (ICP-AES), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), UV-Vis diffuse reflectance spectroscopy (UV-Vis-DRS), and electrochemical techniques. Density functional theory (DFT) was used to calculate the nanotube band structure and density of states. Cu/Ti atomic ratios in the synthesized powders were very close to the nominal values, and the Cu-doped TiO2 lattice exhibited improved visible-light absorption. This was because the valence band, formed by hybridization of O 2p states with Cu 3d states, was negatively shifted. Thus, the band gap was reduced to 2.50-2.91 eV and the samples exhibited visible-light responses. Toluene was chosen as a model pollutant to evaluate the removal capacity and the CO2 mineralization rate of volatile organic compounds under visible light. Pure TNT displayed poor visible-light activity, and the activities of samples with >0.1% Cu doping were also weak. Samples doped with 0.1% Cu exhibited optimumvisible-light photocatalytic oxidation activity, with a 77%toluene degradation efficiency and a 59%mineralization rate in 7 h.
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[1]
(1) Wu, S. X.; Ma, Z.; Qin, Y. S.; Qi, X. Z.; Liang, Z. C. Acta Phys. -Chim. Sin. 2004, 20 (2), 138. [吴树新,马智,秦永守, 齐晓周,梁珍成. 物理化学学报, 2004, 20 (2), 138.] doi: 10.3866/PKU.WHXB20040206
(1) Wu, S. X.; Ma, Z.; Qin, Y. S.; Qi, X. Z.; Liang, Z. C. Acta Phys. -Chim. Sin. 2004, 20 (2), 138. [吴树新,马智,秦永守, 齐晓周,梁珍成. 物理化学学报, 2004, 20 (2), 138.] doi: 10.3866/PKU.WHXB20040206
-
[2]
(2) Maeda, M.; Yamada, T. J. Phys.: Conf. Ser. 2007, 61, 755. doi: 10.1088/1742-6596/61/1/151(2) Maeda, M.; Yamada, T. J. Phys.: Conf. Ser. 2007, 61, 755. doi: 10.1088/1742-6596/61/1/151
-
[3]
(3) Karunakaran, C.; Abiramasundari, G.; mathisankar, P.;Manikandan, G.; Anandi, V. J. Colloid Interface Sci. 2010, 352 (1), 68. doi: 10.1016/j.jcis.2010.08.012(3) Karunakaran, C.; Abiramasundari, G.; mathisankar, P.;Manikandan, G.; Anandi, V. J. Colloid Interface Sci. 2010, 352 (1), 68. doi: 10.1016/j.jcis.2010.08.012
-
[4]
(4) Park, H. S.; Kim, D. H.; Kim, S. J.; Lee, K. S. J. Alloy. Compd.2006, 415 (1-2), 51. doi: 10.1016/j.jallcom.2005.07.055(4) Park, H. S.; Kim, D. H.; Kim, S. J.; Lee, K. S. J. Alloy. Compd.2006, 415 (1-2), 51. doi: 10.1016/j.jallcom.2005.07.055
-
[5]
(5) Choi, W.; Termin, A.; Hoffmann, M. R. J. Phys. Chem. 1994, 98 (51), 13669. doi: 10.1021/j100102a038(5) Choi, W.; Termin, A.; Hoffmann, M. R. J. Phys. Chem. 1994, 98 (51), 13669. doi: 10.1021/j100102a038
-
[6]
(6) Xu, C.; Cui, A.; Yuan, Y.; Chen, Z.; Yuan, R.; Fu, X. J. Mater. Sci. 2013, 48 (9), 3428. doi: 10.1007/s10853-012-7130-7(6) Xu, C.; Cui, A.; Yuan, Y.; Chen, Z.; Yuan, R.; Fu, X. J. Mater. Sci. 2013, 48 (9), 3428. doi: 10.1007/s10853-012-7130-7
-
[7]
(7) Deng, L.; Wang, S.; Liu, D.; Zhu, B.; Huang, W.;Wu, S.;Zhang, S. Catal. Lett. 2009, 129 (3-4), 513. doi: 10.1007/s10562-008-9834-5(7) Deng, L.; Wang, S.; Liu, D.; Zhu, B.; Huang, W.;Wu, S.;Zhang, S. Catal. Lett. 2009, 129 (3-4), 513. doi: 10.1007/s10562-008-9834-5
-
[8]
(8) Xu, S.; Du, A. J.; Liu, J.; Ng, J.; Sun, D. D. Int. J. Hydrog. Energy 2011, 36 (11), 6560. doi: 10.1016/j.ijhydene.2011.02.103(8) Xu, S.; Du, A. J.; Liu, J.; Ng, J.; Sun, D. D. Int. J. Hydrog. Energy 2011, 36 (11), 6560. doi: 10.1016/j.ijhydene.2011.02.103
-
[9]
(9) Yu, J.; Xiang, Q.; Zhou, M. Appl. Catal. B-Environ. 2009, 90 (3), 595.(9) Yu, J.; Xiang, Q.; Zhou, M. Appl. Catal. B-Environ. 2009, 90 (3), 595.
-
[10]
(10) Yousef, A.; Barakat, N. A.; Amna, T.; Al-Deyab, S. S.; Hassan,M. S.; Abdel-hay, A.; Kim, H. Y. Ceram. Int. 2012, 38 (6),4525. doi: 10.1016/j.ceramint.2012.02.029(10) Yousef, A.; Barakat, N. A.; Amna, T.; Al-Deyab, S. S.; Hassan,M. S.; Abdel-hay, A.; Kim, H. Y. Ceram. Int. 2012, 38 (6),4525. doi: 10.1016/j.ceramint.2012.02.029
-
[11]
(11) Shen, J. J.; Liu, C.; Zhu, Y. D.; Li, W.; Feng, X.; Lu, X. H. Acta Phys. -Chim. Sin. 2009, 25 (5), 1013. [沈晶晶,刘畅,朱育丹,李伟,冯新,陆小华.物理化学学报, 2009, 25 (5),1013.] doi: 10.3866/PKU.WHXB20090421(11) Shen, J. J.; Liu, C.; Zhu, Y. D.; Li, W.; Feng, X.; Lu, X. H. Acta Phys. -Chim. Sin. 2009, 25 (5), 1013. [沈晶晶,刘畅,朱育丹,李伟,冯新,陆小华.物理化学学报, 2009, 25 (5),1013.] doi: 10.3866/PKU.WHXB20090421
-
[12]
(12) You, M.; Kim, T. G.; Sung, Y. M. Cryst. Growth Des. 2009, 10 (2), 983.(12) You, M.; Kim, T. G.; Sung, Y. M. Cryst. Growth Des. 2009, 10 (2), 983.
-
[13]
(13) Nishikiori, H.; Sato, T.; Kubota, S.; Tanaka, N.; Shimizu, Y.;Fujii, T. Res. Chem. Intermed. 2012, 38 (2), 595. doi: 10.1007/s11164-011-0374-z(13) Nishikiori, H.; Sato, T.; Kubota, S.; Tanaka, N.; Shimizu, Y.;Fujii, T. Res. Chem. Intermed. 2012, 38 (2), 595. doi: 10.1007/s11164-011-0374-z
-
[14]
(14) Ou, H. H.; Lo, S. L. J. Mol. Catal. A-Chem. 2007, 275 (1-2),200. doi: 10.1016/j.molcata.2007.05.044(14) Ou, H. H.; Lo, S. L. J. Mol. Catal. A-Chem. 2007, 275 (1-2),200. doi: 10.1016/j.molcata.2007.05.044
-
[15]
(15) Wu, Q.; Su, J. F.; Sun, L.; Wang, M. Y.; Wang, Y. Y.; Lin, C. J.Acta Phys. -Chim. Sin. 2012, 28 (3), 635. [吴奇, 苏钰丰,孙岚,王梦晔,王莹莹, 林昌健.物理化学学报, 2012, 28 (3),635.] doi: 10.3866/PKU.WHXB201112231(15) Wu, Q.; Su, J. F.; Sun, L.; Wang, M. Y.; Wang, Y. Y.; Lin, C. J.Acta Phys. -Chim. Sin. 2012, 28 (3), 635. [吴奇, 苏钰丰,孙岚,王梦晔,王莹莹, 林昌健.物理化学学报, 2012, 28 (3),635.] doi: 10.3866/PKU.WHXB201112231
-
[16]
(16) Ni, M.; Leung, M. K.; Leung, D. Y.; Sumathy, K. Renewable and Sustainable Energy Reviews 2007, 11 (3), 401. doi: 10.1016/j.rser.2005.01.009(16) Ni, M.; Leung, M. K.; Leung, D. Y.; Sumathy, K. Renewable and Sustainable Energy Reviews 2007, 11 (3), 401. doi: 10.1016/j.rser.2005.01.009
-
[17]
(17) Colon, G.; Maicu, M.; Hidal , M. C.; Navio, J. A. Appl. Catal. B-Environ. 2006, 67 (1-2), 41. doi: 10.1016/j.apcatb.2006.03.019(17) Colon, G.; Maicu, M.; Hidal , M. C.; Navio, J. A. Appl. Catal. B-Environ. 2006, 67 (1-2), 41. doi: 10.1016/j.apcatb.2006.03.019
-
[18]
(18) Taveira, L. V.; Montemor, M. F.; Da Cunha Belo, M.; Ferreira,M. G.; Dick, L. F. P. Corrosion Sci. 2010, 52 (9), 2813. doi: 10.1016/j.corsci.2010.04.021(18) Taveira, L. V.; Montemor, M. F.; Da Cunha Belo, M.; Ferreira,M. G.; Dick, L. F. P. Corrosion Sci. 2010, 52 (9), 2813. doi: 10.1016/j.corsci.2010.04.021
-
[19]
(19) Cheng, X. F.; Leng, W. H.; Liu, D. P.; Zhang, J. Q.; Cao, C. N.Chemosphere 2007, 68 (10), 1976. doi: 10.1016/j.chemosphere.2007.02.010(19) Cheng, X. F.; Leng, W. H.; Liu, D. P.; Zhang, J. Q.; Cao, C. N.Chemosphere 2007, 68 (10), 1976. doi: 10.1016/j.chemosphere.2007.02.010
-
[20]
(20) Sun, L.; Li, G.; Wan, S.; An, T. Chemosphere 2010, 78 (3),313. doi: 10.1016/j.chemosphere.2009.10.032(20) Sun, L.; Li, G.; Wan, S.; An, T. Chemosphere 2010, 78 (3),313. doi: 10.1016/j.chemosphere.2009.10.032
-
[21]
(21) Guo, M.; Du, J. Physica B 2012, 407, 1003. doi: 10.1016/j.physb.2011.12.128(21) Guo, M.; Du, J. Physica B 2012, 407, 1003. doi: 10.1016/j.physb.2011.12.128
-
[22]
(22) Sopyan, I.; Watanabe, M.; Murasawa, S.; Hashimoto, K.;Fujishima, A. J. Photochem. Photobiol. A-Chem. 1996, 98 (1-2),79. doi: 10.1016/1010-6030(96)04328-6(22) Sopyan, I.; Watanabe, M.; Murasawa, S.; Hashimoto, K.;Fujishima, A. J. Photochem. Photobiol. A-Chem. 1996, 98 (1-2),79. doi: 10.1016/1010-6030(96)04328-6
-
[23]
(23) Bosc, F.; Edwards, D.; Keller, N.; Keller, V.; Ayral, A. Thin Solid Films 2006, 495 (1-2), 272. doi: 10.1016/j.tsf.2005.08.361(23) Bosc, F.; Edwards, D.; Keller, N.; Keller, V.; Ayral, A. Thin Solid Films 2006, 495 (1-2), 272. doi: 10.1016/j.tsf.2005.08.361
-
[24]
(24) Mo, J.; Zhang, Y.; Xu, Q.; Zhu, Y.; Lamson, J. J.; Zhao, R. Appl. Catal. B-Environ. 2009, 89 (3-4), 570. doi: 10.1016/j.apcatb.2009.01.015(24) Mo, J.; Zhang, Y.; Xu, Q.; Zhu, Y.; Lamson, J. J.; Zhao, R. Appl. Catal. B-Environ. 2009, 89 (3-4), 570. doi: 10.1016/j.apcatb.2009.01.015
-
[25]
(25) Mo, J.; Zhang, Y.; Xu, Q.; Lamson, J. J.; Zhao, R. Atmos. Environ. 2009, 43 (14), 2229. doi: 10.1016/j.atmosenv.2009.01.034(25) Mo, J.; Zhang, Y.; Xu, Q.; Lamson, J. J.; Zhao, R. Atmos. Environ. 2009, 43 (14), 2229. doi: 10.1016/j.atmosenv.2009.01.034
-
[26]
(26) García-Pérez, U. M.; Sepúlveda-Guzmán, S.; Martínez-de laCruz, A.; Peral, J. Int. J. Electrochem. Sci. 2012, 7, 9622.(26) García-Pérez, U. M.; Sepúlveda-Guzmán, S.; Martínez-de laCruz, A.; Peral, J. Int. J. Electrochem. Sci. 2012, 7, 9622.
-
[27]
(27) Zhou, M.; Yu, J.; Cheng, B. J. Hazard. Mater. 2006, 137 (3),1838. doi: 10.1016/j.jhazmat.2006.05.028
(27) Zhou, M.; Yu, J.; Cheng, B. J. Hazard. Mater. 2006, 137 (3),1838. doi: 10.1016/j.jhazmat.2006.05.028
-
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