水促进Co/Mo/Al<sub>2</sub>O<sub>3</sub>催化剂上碳纳米管的生长

引用本文: 崔超婕, 骞伟中, 魏飞. 水促进Co/Mo/Al₂O₃催化剂上碳纳米管的生长[J]. 物理化学学报, 2011, 27(10): 2462-2468. doi: 10.3866/PKU.WHXB20111007 shu

Citation: CUI Chao-Jie, QIAN Wei-Zhong, WEI Fei. Water-Assisted Growth of Carbon Nanotubes over Co/Mo/Al₂O₃ Catalyst[J]. Acta Physico-Chimica Sinica, 2011, 27(10): 2462-2468. doi: 10.3866/PKU.WHXB20111007 shu

水促进Co/Mo/Al₂O₃催化剂上碳纳米管的生长

基金项目:
国家重点基础研究发展规划项目(973) (2011CB932602) (973) (2011CB932602)

国家自然科学重点基金(20736007, 20736004)资助 (20736007, 20736004)

摘要: 对水促进Co/Mo/Al₂O₃催化剂裂解乙烯生长碳纳米管(CNTs)的研究发现, 通入体积分数(φ)为0.6%的水蒸汽在1 h 内可将CNTs 的生长倍率从3.7 g·g^-1提高至70 g·g^-1. 水的作用在于恢复被无定形碳包覆的催化剂颗粒的活性, 水的加入量由于其积碳(促进固体碳生成)和消碳(去除固体碳)的竞争作用而存在最佳值. 不同反应时间下乙烯的转化率与有效催化剂含量的分析表明, 在CNTs 生长后期, 水的催化促进作用减弱. 将催化剂的相对活性与CNT聚团的相对密度关联发现, 反应后期的CNTs 主要在聚团内部缠绕生长, 催化剂被包覆失活. 拉曼测试与差热热重分析表明, 生长阻力导致所得CNTs 缺陷增多, CNT 聚团密度变化与CNT缺陷间存在对应关系. 聚团内外CNTs 的生长阻力不同, 生长倍率不同, 导致产品纯度不均匀.

关键词:

English

Water-Assisted Growth of Carbon Nanotubes over Co/Mo/Al₂O₃ Catalyst

1.
Beijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing 100084, P. R. China
Received Date: 13 May 2011
Available Online: 27 September 2011
Fund Project:
国家重点基础研究发展规划项目(973) (2011CB932602)

国家自然科学重点基金(20736007, 20736004)资助

Abstract: We studied the growth of carbon nanotubes (CNTs) over a Co/Mo/Al₂O₃ catalyst by decomposing ethylene with or without the assistance of water. The optimal amount of water was determined to be 0.6% (φ) since excess water removed the amorphous carbon around the catalysts and also directly etched the CNTs at high temperature. Under this condition, the yield of CNTs can be increased from 3.7 g·g^-1, based on the mass of catalyst, to 70 g·g^-1 within 1 h. The time-dependent online conversion of ethylene and the ratio of effective catalysts suggested that the effect of water is insignificant in the final growth period of the CNTs compared to that at the beginning. The correlation between the relative activity of the catalyst and the relative density of the CNT agglomerate suggests that the lack of growth volume inside the CNT agglomerate results in a gradual deactivation of the catalyst in the final CNT growth period. Raman characterization suggests that the degree of CNT defects increases with the bulk density of the CNT agglomerates since the mechanical resistance that is exposed on CNTs inside the agglomerate increases with reaction time. Thermal-gravimetric analysis indicates that the purity of CNTs ranges from 95.0% to 99.9% for a product with average purity of 99.2%. The non-uniform purity of the CNTs is due to the difference in mechanical resistance inside and outside the CNT agglomerate. The growth of CNTs outside the agglomerate is nearly free of mechanical resistance compared to that inside the agglomerate and, consequently, results in a high yield and high purity for the CNTs. These results suggest that it is necessary to control the agglomerate size and the structure, and to use a reactor with a large reactor volume for the growth of CNTs with low resistance and with high yield.

Key words:

1. [1]
  (1) Iijima, S. Nature 1991, 354, 56. (1) Iijima, S. Nature 1991, 354, 56.
2. [2]
  (2) Zhou,W. Y.; Bai, X. D.;Wang, E. G.; Xie, S. S. Adv. Mater. 2009, 21, 4565. (2) Zhou,W. Y.; Bai, X. D.;Wang, E. G.; Xie, S. S. Adv. Mater. 2009, 21, 4565.
3. [3]
  (3) Su, D. S.; Schlogl, R. ChemSusChem 2010, 3, 136. (3) Su, D. S.; Schlogl, R. ChemSusChem 2010, 3, 136.
4. [4]
  (4) Liu, C.; Li, F.; Ma, L. P.; Cheng, H. M. Adv. Mater. 2010, 22, E28.(4) Liu, C.; Li, F.; Ma, L. P.; Cheng, H. M. Adv. Mater. 2010, 22, E28.
5. [5]
  (5) Wei, F.; Zhang, Q.; Qian,W. Z.; Yu, H.;Wang, Y.; Luo, G. H.; Xu, G. H.;Wang, D. Z. Powder Technol. 2008, 183, 10. (5) Wei, F.; Zhang, Q.; Qian,W. Z.; Yu, H.;Wang, Y.; Luo, G. H.; Xu, G. H.;Wang, D. Z. Powder Technol. 2008, 183, 10.
6. [6]
  (6) Wang, M. Z.; Li, F.; Yang, Q. H.; Cheng, H. M. New Carbon Mater. 2003, 18, 250.(6) Wang, M. Z.; Li, F.; Yang, Q. H.; Cheng, H. M. New Carbon Mater. 2003, 18, 250.
7. [7]
  [王茂章, 李峰, 杨全红, 成会明. 新型碳材料, 2003, 18, 250.][王茂章, 李峰, 杨全红, 成会明. 新型碳材料, 2003, 18, 250.]
8. [8]
  (7) Li, Y.; Zhang, X. Q.; Xu, J. M.; Tao, X. Y.; Chen, F.; Liu, F. J. Inorg. Mater. 2005, 20, 71.(7) Li, Y.; Zhang, X. Q.; Xu, J. M.; Tao, X. Y.; Chen, F.; Liu, F. J. Inorg. Mater. 2005, 20, 71.
9. [9]
  [李昱, 张孝彬, 徐军明, 陶新永, 陈飞, 刘芙. 无机材料学报, 2005, 20, 71.][李昱, 张孝彬, 徐军明, 陶新永, 陈飞, 刘芙. 无机材料学报, 2005, 20, 71.]
10. [10]
  (8) Qian,W. Z.; Tian, T.; Guo, C. Y.;Wen, Q.; Li, K. J.; Zhang, H. B.; Shi, H. B.;Wang, D. Z.; Liu, Y.; Zhang, Q.; Zhang, Y. X.; Wei, F.;Wang, Z.W.; Li, X. D.; Li, Y. D. J. Phys. Chem. C 2008, 112, 7588. (8) Qian,W. Z.; Tian, T.; Guo, C. Y.;Wen, Q.; Li, K. J.; Zhang, H. B.; Shi, H. B.;Wang, D. Z.; Liu, Y.; Zhang, Q.; Zhang, Y. X.; Wei, F.;Wang, Z.W.; Li, X. D.; Li, Y. D. J. Phys. Chem. C 2008, 112, 7588.
11. [11]
  (9) Patil, K. N.; Solanki, C. S. J. Nano Res. 2009, 6, 75. (9) Patil, K. N.; Solanki, C. S. J. Nano Res. 2009, 6, 75.
12. [12]
  (10) Rashidi, A. M.; Akbarnejad, M. M.; Khodadadi, A. A.; Mortazavi, Y.; Ahmadpourd, A. Nanotechnology 2007, 18, 315605. (10) Rashidi, A. M.; Akbarnejad, M. M.; Khodadadi, A. A.; Mortazavi, Y.; Ahmadpourd, A. Nanotechnology 2007, 18, 315605.
13. [13]
  (11) Xu, C. B.; Zhu, J. Nanotechnology 2004, 15, 1671. (11) Xu, C. B.; Zhu, J. Nanotechnology 2004, 15, 1671.
14. [14]
  (12) Lim, S.; Li, N.; Fang, F.; Pinault, M.; Zoican, C.;Wang, C.; Fadel, T.; Pfefferle, L. D.; Haller, G. L. J. Phys. Chem. C 2008, 112, 12442. (12) Lim, S.; Li, N.; Fang, F.; Pinault, M.; Zoican, C.;Wang, C.; Fadel, T.; Pfefferle, L. D.; Haller, G. L. J. Phys. Chem. C 2008, 112, 12442.
15. [15]
  (13) Zhou, Q. M.;Wang, Y.; Tang, P. P.;Wu, X. M.; Lin, G. D.; Zhang, H. B. Chin. J. Appl. Chem. 2005, 22, 118.(13) Zhou, Q. M.;Wang, Y.; Tang, P. P.;Wu, X. M.; Lin, G. D.; Zhang, H. B. Chin. J. Appl. Chem. 2005, 22, 118.
16. [16]
  [周金梅, 王毅, 汤培平, 武小满, 林国栋, 张鸿斌. 应用化学, 2005, 22, 118.][周金梅, 王毅, 汤培平, 武小满, 林国栋, 张鸿斌. 应用化学, 2005, 22, 118.]
17. [17]
  (14) Liu, J. X.; Xie, Y. C. Acta Phys. -Chim. Sin. 2003, 22, 1093.(14) Liu, J. X.; Xie, Y. C. Acta Phys. -Chim. Sin. 2003, 22, 1093.
18. [18]
  [刘霁欣, 谢有畅. 物理化学学报, 2003, 22, 1093.][刘霁欣, 谢有畅. 物理化学学报, 2003, 22, 1093.]
19. [19]
  (15) Li, Y. D.; Li, D. X.;Wang, G.W. Catal. Today 2011, 162, 1. (15) Li, Y. D.; Li, D. X.;Wang, G.W. Catal. Today 2011, 162, 1.
20. [20]
  (16) Duan, X. J.; He, M. S.;Wang, X.; Zhang, J.; Liu, Z. F. Chin. Sci. Bull. 2004, 49, 377.(16) Duan, X. J.; He, M. S.;Wang, X.; Zhang, J.; Liu, Z. F. Chin. Sci. Bull. 2004, 49, 377.
21. [21]
  [段小洁, 何茂帅, 王璇, 张锦, 刘忠范. 科学通报, 2004, 49, 377.][段小洁, 何茂帅, 王璇, 张锦, 刘忠范. 科学通报, 2004, 49, 377.]
22. [22]
  (17) Amelinckx, S.; Zhang, X. B.; Bernaerts, D.; Zhang, X. F.; Ivanov, V.; Nagy, J. B. Science 1994, 265, 635. (17) Amelinckx, S.; Zhang, X. B.; Bernaerts, D.; Zhang, X. F.; Ivanov, V.; Nagy, J. B. Science 1994, 265, 635.
23. [23]
  (18) Hata, K.; Futaba, D. N.; Mizuno, K.; Namai, T.; Yumura, M.; Iijima, S. Science 2004, 306, 1362. (18) Hata, K.; Futaba, D. N.; Mizuno, K.; Namai, T.; Yumura, M.; Iijima, S. Science 2004, 306, 1362.
24. [24]
  (19) Wen, Q.; Qian,W. Z.;Wei, F.; Liu, Y.; Ning, G. Q.; Zhang, Q. Chem. Mater. 2007, 19, 1226. (19) Wen, Q.; Qian,W. Z.;Wei, F.; Liu, Y.; Ning, G. Q.; Zhang, Q. Chem. Mater. 2007, 19, 1226.
25. [25]
  (20) Wen, Q.; Zhang, R. F.; Qian,W. Z.;Wang, Y. R.; Tan, P. H.; Nie, J. Q.;Wei, F. Chem. Mater. 2010, 22, 1294. (20) Wen, Q.; Zhang, R. F.; Qian,W. Z.;Wang, Y. R.; Tan, P. H.; Nie, J. Q.;Wei, F. Chem. Mater. 2010, 22, 1294.
26. [26]
  (21) Qian,W. Z.; Yu, H.;Wei, F.; Zhang, Q. F.;Wang, Z.W. Carbon 2002, 40, 2968. (21) Qian,W. Z.; Yu, H.;Wei, F.; Zhang, Q. F.;Wang, Z.W. Carbon 2002, 40, 2968.
27. [27]
  (22) Avdeeva, L. B.; ncharova, O. V.; Kochubey, D. I.; Zaikovskii, V. I.; Plyasova, L. M.; Nov rodov, B. N.; Shaikhutdinov, S. K. Appl. Catal. A-Gen. 1996, 141, 117. (22) Avdeeva, L. B.; ncharova, O. V.; Kochubey, D. I.; Zaikovskii, V. I.; Plyasova, L. M.; Nov rodov, B. N.; Shaikhutdinov, S. K. Appl. Catal. A-Gen. 1996, 141, 117.
28. [28]
  (23) Feng, C. Q.; Yao, Y. G.; Zhang, J.; Liu, Z. F. Nano Res. 2009, 2, 768.(23) Feng, C. Q.; Yao, Y. G.; Zhang, J.; Liu, Z. F. Nano Res. 2009, 2, 768.
29. [29]
  (24) Cheng, H. M.; Li, F.; Sun, X.; Brown, S.; Pimenta, M. A.; Marucci, A.; Dresselhaus, G.; Dresselhaus, M. S. Chem. Phys. Lett. 1998, 289, 602. (24) Cheng, H. M.; Li, F.; Sun, X.; Brown, S.; Pimenta, M. A.; Marucci, A.; Dresselhaus, G.; Dresselhaus, M. S. Chem. Phys. Lett. 1998, 289, 602.
30. [30]
  (25) Li,W. Z.; Xie, S. S.; Qian, L. X.; Chang, B. H.; Zou, B. S.; Zhou,W. Y.; Zhao, R. A.;Wang, G. Science 1996, 274, 1701. (25) Li,W. Z.; Xie, S. S.; Qian, L. X.; Chang, B. H.; Zou, B. S.; Zhou,W. Y.; Zhao, R. A.;Wang, G. Science 1996, 274, 1701.

扫一扫看文章

计量

PDF下载量: 1230
文章访问数: 4110
HTML全文浏览量: 125

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

水促进Co/Mo/Al₂O₃催化剂上碳纳米管的生长

English

Water-Assisted Growth of Carbon Nanotubes over Co/Mo/Al₂O₃ Catalyst

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？

计量

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

水促进Co/Mo/Al2O3催化剂上碳纳米管的生长

English

Water-Assisted Growth of Carbon Nanotubes over Co/Mo/Al2O3 Catalyst

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？

计量

文章相关

通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

水促进Co/Mo/Al₂O₃催化剂上碳纳米管的生长

Water-Assisted Growth of Carbon Nanotubes over Co/Mo/Al₂O₃ Catalyst

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs