Citation: YANG Han-Pei, ZHANG Ying-Chao, FU Xiao-Fei, SONG Shuang-Shuang, WU Jun-Ming. Surface Modification of CNTs and Improved Photocatalytic Activity of TiO₂-CNTs Heterojunction[J]. Acta Physico-Chimica Sinica, ;2013, 29(06): 1327-1335. doi: 10.3866/PKU.WHXB201303212 shu

Surface Modification of CNTs and Improved Photocatalytic Activity of TiO₂-CNTs Heterojunction

1.
Key Laboratory of Integrated Regulation and Resource Development on Shallow Lakes, Ministry of Education, College of Environment, Hohai University, Nanjing 210098, P.R.China

Received Date: 25 January 2013
Available Online: 21 March 2013
Fund Project: 教育部留学归国人员基金(20071256)资助项目 (20071256)

Carbon nanotubes (CNTs) have been ultrasonically treated with the mixed acid (H₂SO₄/HNO₃, 3:1, volume ratio), embedding the active －COOH groups onto the surface of the CNTs. As a result, the acid-treated CNTs serve as chemical reactors for subsequent grafting of L-lysine or octadecylamine (ODA). It was revealed that L-lysine and ODA covalently bond to the surface of the oxidized CNTs through amidation of carboxylic acid groups (CNTs-COOH) and lysine or ODA via intermediate acyl chlorides (CNTs-COCl). The hydrophilic and lipophilic CNTs have high aquatic and ethanol solubility, and the solubility of the surface modified CNTs in water and ethanol were measured to be as high as 6.85 and 10.15 mg·mL^-1, respectively. The surface nature of modified CNTs and the properties of TiO₂-CNTs composite photocatalysts, which were prepared through sol-gel or low temperature hydrothermal synthesis, were investigated by Fourier transform infrared (FTIR), laser Raman, X-ray diffraction (XRD), Brunauer-Emmett-Teller N2 adsorption, transmission electron microscopy (TEM), and X-ray photoelectron spectrum (XPS). Improved photocatalytic performance was observed for TiO₂ coupled by hydrophilic or lipophilic CNT, which were obtained by low temperature hydrothermal and sol-gel synthesis, respectively, and it was revealed that there is an affinity between the photocatalytic performance of TiO₂-CNTs hybrids and the dispersibility of CNTs. It is proposed that the improved photocatalytic activity of CNT-TiO₂ compared with pure TiO₂ photocatalysts can be mainly attributed to the homogeneous and dense dispersion of TiO₂ on the modified CNTs and the intimate contact between TiO₂ and CNTs, which results in dense heterojunctions at the interface of TiO₂ and CNTs through the Ti－O－C structure.
- Carbon nanotubes,
- Surface modification,
- Solubility,
- TiO₂,
- Photocatalytic degradation
1. [1]
  
  (1) Hu, L. B.; Hecht, D. S.; Gruner, G. Chem. Rev. 2010, 110, 5790.doi: 10.1021/cr9002962
2. [2]
  (2) Wu, Y. C.; Liu, X. L.; Ye, M.; Xie, T.; Huang, X. M. Acta Phys. - Chim. Sin. 2008, 24, 97. [吴玉程, 刘晓璐, 叶敏, 解挺,黄新民. 物理化学学报, 2008, 24, 97.] doi: 10.3866/PKU.WHXB20080117
3. [3]
  (3) Zhang, K.; Zhang, F.; Chen, M.; Oh,W. Ultrason. Sonochem.2011, 18, 765. doi: 10.1016/j.ultsonch.2010.11.008
4. [4]
  (4) Barkauskasa, J.; Stankeviciene, I.; Selskis, A. Sep. Purif. Technol. 2010, 71, 331. doi: 10.1016/j.seppur.2009.12.019
5. [5]
  (5) Stobinski, L.; Lesiak, B.; Kövér, L. J. Alloy. Compd. 2010, 501,77. doi: 10.1016/j.jallcom.2010.04.032
6. [6]
  (6) Tian, R.;Wang, X.; Li, M.; Hu, H. Appl. Surf. Sci. 2008, 255,3294. doi: 10.1016/j.apsusc.2008.09.040
7. [7]
  (7) Dyke, C. A.; Stewart, M. P.; Tour, J. M. J. Am. Chem. Soc. 2005,127, 4497. doi: 10.21/ja042828h
8. [8]
  (8) Zeng, L.; Zhang, L.; Barron, A. R. Nano Lett. 2005, 5, 2001.doi: 10.1021/nl0514994
9. [9]
  (9) Balasubramanian, K.; Burghard, M. Small 2005, 1, 180.
10. [10]
  (10) Ye, Q.; Zhang, Y.; Li, M.; Shi, Y. Acta Phys. -Chim. Sin. 2012,28, 1223. [叶青, 张瑜, 李茗, 施耀. 物理化学学报,2012, 28, 1223.] doi: 10.3866/PKU.WHXB201202234
11. [11]
  (11) Mugadza, T.; Nyokong, T. Electrochim. Acta 2010, 55, 2606.doi: 10.1016/j.electacta.2009.12.051
12. [12]
  (12) Mugadza, T.; Nyokong, T. Synth. Met. 2010, 160, 2089.doi: 10.1016/j.synthmet.2010.07.036
13. [13]
  (13) Wei, T.; Fan, Z.; Luo, G.;Wei, F. Mater. Lett. 2008, 62, 64.
14. [14]
  (14) Chen, Y.; Zhang, Y. Q.; Zhang, T. H. Carbon 2006, 44, 37.doi: 10.1016/j.carbon.2005.07.011
15. [15]
  (15) Mills, A.; Hunte, S. L. J. Photochem. Photobiol. A: Chem. 1997,108, l.
16. [16]
  (16) Qiu,W.; Ren, C. J.; ng, M. C.; Hou, Y. Z.; Chen, Y. Q. Acta Phys. -Chim. Sin. 2011, 27, 1487. [仇伟, 任成军, 龚茂初,侯云泽, 陈耀强. 物理化学学报, 2011, 27, 1487.] doi: 10.3866/PKU.WHXB20110621
17. [17]
  (17) Wang, H.;Wang, H. L.; Jiang,W. F.; Li, Z. Q. Water Res. 2009,43, 204. doi: 10.1016/j.watres.2008.10.003
18. [18]
  (18) Wang,W.; Serp, P.; Kalck, P.; Faria, J. L. Appl. Catal. B: Environ. 2005, 56, 305. doi: 10.1016/j.apcatb.2004.09.018
19. [19]
  (19) Suzuki, Y.; Yoshikawa, S. J. Mater. Res. 2004, 19, 982.doi: 10.1557/JMR.2004.0128
20. [20]
  (20) Yang, H. P.; Shi, Z. M.; Dai, K. J.; Duan, Y. P.;Wu, J. M. Acta Chim. Sin. 2011, 69, 536. [杨汉培, 石泽敏, 戴开静, 段云平,吴俊明. 化学学报, 2011, 69, 536.]
21. [21]
  (21) Sun, J. H.; Qiao, L. P.; Sun, S. P.;Wang, G. L. J. Hazard Mater.2008, 155, 312. doi: 10.1016/j.jhazmat.2007.11.062
22. [22]
  (22) Maiyalagan, T.; Viswanathan, B. Mater. Chem. Phys. 2005, 93,291. doi: 10.1016/j.matchemphys.2005.03.039
23. [23]
  (23) Kim, S. D.; Kim, J.W.; Im, J. S. J. Fluorine Chem. 2007, 128,60. doi: 10.1016/j.jfluchem.2006.10.010
24. [24]
  (24) Osorio, A. G.; Silveira, I. C. L.; Bueno, V. L. Appl. Surf. Sci.2008, 255, 2485. doi: 10.1016/j.apsusc.2008.07.144
25. [25]
  (25) Yang, Y. S.; Qi, G. R.; Qian, J.W.; Yang, S. L. J. Appl. Polym. Sci. 1998, 68, 665.
26. [26]
  (26) Hannus, I.; Kollár, T.; Kónya, Z.; Kiricsi, I. Vib. Spectrosc.2000, 22, 29. doi: 10.1016/S0924-2031(99)00059-4
27. [27]
  (27) Ba, C. Y.; Economy, J. J. Memb. Sci. 2010, 363, 140.doi: 10.1016/j.memsci.2010.07.019
28. [28]
  (28) Peter, J.; Khalyavina, A.; Kǐí?, J.; Bleha, M. Eur. Polym. J.2009, 45, 1716. doi: 10.1016/j.eurpolymj.2009.03.003
29. [29]
  (29) Svatos, A.; Attygalle, A. B. Anal. Chem. 1997, 69, 1827.doi: 10.1021/ac960890u
30. [30]
  (30) Xu, M.; Huang, Q.; Chen, Q.; Guo, P.; Sun, Z. Chem. Phys. Lett.2003, 375, 598. doi: 10.1016/S0009-2614(03)00923-0
31. [31]
  (31) Okabayashi, H.; Etori, H.; Yamada, Y.; Taga, K.; Yoshida, T.Vib. Spectrosc. 1996, 13, 51. doi: 10.1016/0924-2031(96)00034-3
32. [32]
  (32) Venkataraman, N. V.; Barman, S.; Vasudevan, S.; Seshadri, R.Chem. Phys. Lett. 2002, 358, 139. doi: 10.1016/S0009-2614(02)00604-8
33. [33]
  (33) Georgiev, A.; Karamancheva, I.; Dimov, D. J. Mol. Struct. 2008,888, 214. doi: 10.1016/j.molstruc.2007.12.006
34. [34]
  (34) Zhao, X. A.; Ong, C.W.; Tsang, Y. C. Appl. Phys. Lett. 1995,66, 2652. doi: 10.1063/1.113114
35. [35]
  (35) Choi, S.; Park, K. H.; Lee, S.; Koh, K. H. J. Appl. Phys. 2002,92, 4007. doi: 10.1063/1.1499233
36. [36]
  (36) Hou, P. X.; Liu, C.; Cheng, H. M. Carbon 2008, 46, 2003.doi: 10.1016/j.carbon.2008.09.009
37. [37]
  (37) Fernando, K. A. S.; Lin, Y.; Sun, Y. P. Langmuir 2004, 20, 4777.doi: 10.1021/la036217z
38. [38]
  (38) Wang,W. D.; Serp, P.; Kalck, P.; Faria, J. L. J. Molec. Catal. A2005, 235, 194. doi: 10.1016/j.molcata.2005.02.027
39. [39]
  (39) Klug, H. P.; Alexander, L. E. X-ray Diffraction Procedures;Academic Press: New York, 1967; pp 132-136.
40. [40]
  (40) Lee, S.W.; Sigmund,W. M. Chem. Commun. 2003, 6, 780.
41. [41]
  (41) Yu, Y.; Yu, J. C.; Yu, J. G.; Kwok, Y. C.; Che, Y. K.; Zhao, J. C.;Ding, L.; Ge,W. K.;Wong, P. K. Appl. Catal. A: Gen. 2005,289, 186. doi: 10.1016/j.apcata.2005.04.057
42. [42]
  (42) Yu, H.; Quan, X.; Chen, S.; Zhao, H. J. Phys. Chem. C 2007,111, 12987. doi: 10.1021/jp0728454
43. [43]
  (43) Akhavan, O.; Abdolahad, M.; Abdi, Y.; Mohajerzadeh, S.Carbon 2009, 47, 3280. doi: 10.1016/j.carbon.2009.07.046
44. [44]
  (44) Tian, L. H.; Ye, L. Q.; Deng, K. J.; Zan, J. Solid State Chem.2011, 184, 1465. doi: 10.1016/j.jssc.2011.04.014
45. [45]
  (45) Chen, L. C.; Ho, Y. C.; Guo,W. S.; Huang, C. M.; Pan, T. C.Electrochimica Acta 2009, 54, 3884. doi: 10.1016/j.electacta.2009.02.001
46. [46]
  (46) Nahar, M. S.; Zhang, J.; Hasegawa, K. Mater. Sci. Semicond. Process 2009, 12, 168. doi: 10.1016/j.mssp.2009.09.011
47. [47]
  (47) Yang, J.; Bai, H.; Tan, X.; Lian, J. Appl. Sur. Sci. 2006, 253,1988. doi: 10.1016/j.apsusc.2006.03.078
48. [48]
  (48) Song, Z.; Hrbek, J.; Os od, R. Nano Lett. 2005, 5, 1327.doi: 10.1021/nl0505703
49. [49]
  (49) Jitianu, A.; Cacciaguerra, T.; Benoit, R.; Delpeux, S.; Beguin,F.; Bonnamy S. Carbon 2004, 42, 1147.
50. [50]
  (50) Shanmugharaj, A. M.; Bae, J. H.; Lee, K. Y.; Noh,W. H.Compos. Sci. Technol. 2007, 67, 1813. doi: 10.1016/j.compscitech.2006.10.021
51. [51]
  (51) Kim, S. D.; Kim, J.W.; Im, J. S.; Kim, Y. H.; Lee, Y. S.J. Fluorine Chem. 2007, 128, 60. doi: 10.1016/j.jfluchem.2006.10.010
1. [1]
  Xiaoyao YIN , Wenhao ZHU , Puyao SHI , Zongsheng LI , Yichao WANG , Nengmin ZHU , Yang WANG , Weihai SUN . Fabrication of all-inorganic CsPbBr₃ perovskite solar cells with SnCl₂ interface modification. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 469-479. doi: 10.11862/CJIC.20240309
2. [2]
  Hailang JIA , Hongcheng LI , Pengcheng JI , Yang TENG , Mingyun GUAN . Preparation and performance of N-doped carbon nanotubes composite Co₃O₄ as oxygen reduction reaction electrocatalysts. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 693-700. doi: 10.11862/CJIC.20230402
3. [3]
  Haihua Yang , Minjie Zhou , Binhong He , Wenyuan Xu , Bing Chen , Enxiang Liang . Synthesis and Electrocatalytic Performance of Iron Phosphide@Carbon Nanotubes as Cathode Material for Zinc-Air Battery: a Comprehensive Undergraduate Chemical Experiment. University Chemistry, 2024, 39(10): 426-432. doi: 10.12461/PKU.DXHX202405100
4. [4]
  Guangming YIN , Huaiyao WANG , Jianhua ZHENG , Xinyue DONG , Jian LI , Yi'nan SUN , Yiming GAO , Bingbing WANG . Preparation and photocatalytic degradation performance of Ag/protonated g-C₃N₄ nanorod materials. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1491-1500. doi: 10.11862/CJIC.20240086
5. [5]
  Hongye Bai , Lihao Yu , Jinfu Xu , Xuliang Pang , Yajie Bai , Jianguo Cui , Weiqiang Fan . Controllable Decoration of Ni-MOF on TiO2: Understanding the Role of Coordination State on Photoelectrochemical Performance. Chinese Journal of Structural Chemistry, 2023, 42(10): 100096-100096. doi: 10.1016/j.cjsc.2023.100096
6. [6]
  Zhiqiang Wang , Yajie Gao , Tianjun Wang , Wei Chen , Zefeng Ren , Xueming Yang , Chuanyao Zhou . Photocatalyzed oxidation of water on oxygen pretreated rutile TiO₂(110). Chinese Chemical Letters, 2025, 36(4): 110602-. doi: 10.1016/j.cclet.2024.110602
7. [7]
  Jiatong Li , Linlin Zhang , Peng Huang , Chengjun Ge . Carbon bridge effects regulate TiO₂–acrylate fluoroboron coatings for efficient marine antifouling. Chinese Chemical Letters, 2025, 36(2): 109970-. doi: 10.1016/j.cclet.2024.109970
8. [8]
  Cailiang Yue , Nan Sun , Yixing Qiu , Linlin Zhu , Zhiling Du , Fuqiang Liu . A direct Z-scheme 0D α-Fe₂O₃/TiO₂ heterojunction for enhanced photo-Fenton activity with low H₂O₂ consumption. Chinese Chemical Letters, 2024, 35(12): 109698-. doi: 10.1016/j.cclet.2024.109698
9. [9]
  Maosen Xu , Pengfei Zhu , Qinghong Cai , Meichun Bu , Chenghua Zhang , Hong Wu , Youzhou He , Min Fu , Siqi Li , Xingyan Liu . In-situ fabrication of TiO₂/NH₂−MIL-125(Ti) via MOF-driven strategy to promote efficient interfacial effects for enhancing photocatalytic NO removal activity. Chinese Chemical Letters, 2024, 35(10): 109524-. doi: 10.1016/j.cclet.2024.109524
10. [10]
  Bing LIU , Huang ZHANG , Hongliang HAN , Changwen HU , Yinglei ZHANG . Visible light degradation of methylene blue from water by triangle Au@TiO₂ mesoporous catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 941-952. doi: 10.11862/CJIC.20230398
11. [11]
  Xinzhe HUANG , Lihui XU , Yue YANG , Liming WANG , Zhangyong LIU , Zhongjian WANG . Preparation and visible light responsive photocatalytic properties of BiSbO₄/BiOBr. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 284-292. doi: 10.11862/CJIC.20240212
12. [12]
  Xiufang Wang , Donglin Zhao , Kehua Zhang , Xiaojie Song . “Preparation of Carbon Nanotube/SnS₂ Photoanode Materials”: A Comprehensive University Chemistry Experiment. University Chemistry, 2024, 39(4): 157-162. doi: 10.3866/PKU.DXHX202308025
13. [13]
  Hongbo Zhang , Yihong Tang , Suxia Zhang , Yuanting Li . Electrochemical Monitoring of Photocatalytic Degradation of Phenol Pollutants: A Recommended Comprehensive Analytical Chemistry Experiment. University Chemistry, 2024, 39(6): 326-333. doi: 10.3866/PKU.DXHX202310013
14. [14]
  Qiang ZHAO , Zhinan GUO , Shuying LI , Junli WANG , Zuopeng LI , Zhifang JIA , Kewei WANG , Yong GUO . Cu₂O/Bi₂MoO₆ Z-type heterojunction: Construction and photocatalytic degradation properties. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 885-894. doi: 10.11862/CJIC.20230435
15. [15]
  Bowen Yang , Rui Wang , Benjian Xin , Lili Liu , Zhiqiang Niu . C-SnO₂/MWCNTs Composite with Stable Conductive Network for Lithium-based Semi-Solid Flow Batteries. Acta Physico-Chimica Sinica, 2025, 41(2): 100015-. doi: 10.3866/PKU.WHXB202310024
16. [16]
  Zhinan GUO , Junli WANG , Qiang ZHAO , Zhifang JIA , Zuopeng LI , Kewei WANG , Yong GUO . Cu₂O/Bi₂CrO₆ Z-scheme heterojunction: Construction and photocatalytic degradation properties for tetracycline. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 741-752. doi: 10.11862/CJIC.20240403
17. [17]
  Qingwang LIU . MoS₂/Ag/g-C₃N₄ Z-scheme heterojunction: Preparation and photocatalytic performance. Chinese Journal of Inorganic Chemistry, 2025, 41(4): 821-832. doi: 10.11862/CJIC.20240148
18. [18]
  Zhuoyan Lv , Yangming Ding , Leilei Kang , Lin Li , Xiao Yan Liu , Aiqin Wang , Tao Zhang . Light-Enhanced Direct Epoxidation of Propylene by Molecular Oxygen over CuO_x/TiO₂ Catalyst. Acta Physico-Chimica Sinica, 2025, 41(4): 100038-. doi: 10.3866/PKU.WHXB202408015
19. [19]
  Yaping ZHANG , Tongchen WU , Yun ZHENG , Bizhou LIN . Z-scheme heterojunction β-Bi₂O₃ pillared CoAl layered double hydroxide nanohybrid: Fabrication and photocatalytic degradation property. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 531-539. doi: 10.11862/CJIC.20240256
20. [20]
  Peng YUE , Liyao SHI , Jinglei CUI , Huirong ZHANG , Yanxia GUO . Effects of Ce and Mn promoters on the selective oxidation of ammonia over V₂O₅/TiO₂ catalyst. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 293-307. doi: 10.11862/CJIC.20240210

Get Citation

PDF

XML

Metrics

PDF Downloads(1035)
Abstract views(1258)
HTML views(27)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Surface Modification of CNTs and Improved Photocatalytic Activity of TiO2-CNTs Heterojunction

Metrics

通讯作者: 陈斌, bchen63@163.com

Surface Modification of CNTs and Improved Photocatalytic Activity of TiO₂-CNTs Heterojunction