掺杂Fe作为第二种金属组分的V-HMS催化剂的苯羟基化反应

引用本文: heyonghe@fudan.edu.cn, 岳斌, 汪玉, 叶林, 贺鹤勇. 掺杂Fe作为第二种金属组分的V-HMS催化剂的苯羟基化反应[J]. 物理化学学报, 2011, 27(12): 2881-2886. doi: 10.3866/PKU.WHXB20112881 shu

Citation: FENG Su-Jiao, YUE Bin, WANG Yu, YE Lin, HE He-Yong. Hydroxylation of Benzene over V-HMS Catalysts with the Addition of Fe as the Second Metal Component[J]. Acta Physico-Chimica Sinica, 2011, 27(12): 2881-2886. doi: 10.3866/PKU.WHXB20112881 shu

掺杂Fe作为第二种金属组分的V-HMS催化剂的苯羟基化反应

基金项目:
国家重点基础研究发展规划项目(973) (2009CB623506) (973) (2009CB623506)

国家高技术研究发展计划(863) (2009AA033701) (863) (2009AA033701)

上海市优秀学科带头人计划(10XD1400300) (10XD1400300)

上海市重点学科建设项目(B108)资助 (B108)

摘要: 采用浸渍法在V-HMS中引入第二种金属组分(Fe、Al、Cu、Ni、Co、Mo、Cr)以提高催化剂在H₂O₂为氧化剂的苯羟基化反应中的催化性能. 筛选发现, Fe在所研究的金属组分中最为有效. 进一步采用共合成法制备了一系列Fe_xV_y-HMS催化剂. 采用粉末X射线衍射、N₂物理吸附、透射电子显微镜、NH₃程序升温脱附、H₂程序升温还原等手段对催化剂的结构和性质进行表征, 结果表明, HMS仍保持介孔结构, Fe的加入在催化剂中产生了新的酸性位和更强的氧化还原性. 在苯羟基化反应中, 钒物种是反应活性物种, 铁物种起助剂作用, 其中Fe_0.04V_0.06-HMS具有最高的催化活性, 苯酚收率由不含Fe的Fe_0.00V_0.06-HMS的13.1%提高到18.1%. 提出了Fe、V参与反应过程的可能机理.

关键词:

铁
/ 钒
/ 介孔硅
/ 苯
/ 羟基化
/ 苯酚

English

Hydroxylation of Benzene over V-HMS Catalysts with the Addition of Fe as the Second Metal Component

1.
Department of Chemistry, Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, Fudan University,Shanghai 200433, P. R. China
Received Date: 15 July 2011
Available Online: 25 November 2011
Fund Project:
国家重点基础研究发展规划项目(973) (2009CB623506)

国家高技术研究发展计划(863) (2009AA033701)

上海市优秀学科带头人计划(10XD1400300)

上海市重点学科建设项目(B108)资助

Abstract: Second metals (Fe, Al, Cu, Ni, Co, Mo, Cr) were incorporated into V-HMS catalyst by impregnation to enhance the catalytic activity for the hydroxylation of benzene with hydrogen peroxide as the oxidant. Among the studied second metals, Fe was found to be effective in improving the catalytic performance. Therefore, we synthesized a series of Fe_xV_y-HMS catalysts containing different amounts of Fe and V by the co-synthesis method. The catalysts were characterized by powder X-ray diffraction (XRD), N₂ physisorption, transmission electron microscopy (TEM), NH₃ temperature-programmed desorption (NH₃- TPD), and H₂ temperature-programmed reduction (H₂-TPR). The characterization results show that the mesoporous structure of HMS is maintained and the addition of Fe creates new acid sites and a stronger redox ability. Catalytic tests show that vanadium species are the active species and that the iron species promote the reaction. Under optimal reaction conditions, the Fe_0.04V_0.06-HMS catalyst gives the best catalytic performance with a highest phenol yield of 18.1% by comparison with 13.1% over the Fe-free catalyst Fe_0.00V_0.06-HMS. We propose a possible mechanism involving the Fe and V species for the hydroxylation of benzene with H₂O₂ as the oxidant.

Key words:

1. [1]
  (1) Niwa, S.; Eswaramoorthy, M.; Nair, J.; Raj, A.; Itoh, N.; Shoji, H.; Namba, T.; Mizukami, F. Science 2002, 295, 105.(1) Niwa, S.; Eswaramoorthy, M.; Nair, J.; Raj, A.; Itoh, N.; Shoji, H.; Namba, T.; Mizukami, F. Science 2002, 295, 105.
2. [2]
  (2) Li, Y.; Xia, H. A.; Fan, F. T.; Feng, Z. C.; van Santen, R. A.; Hensen, E. J. M.; Li, C. Chem. Commun. 2008, No. 6, 774.(2) Li, Y.; Xia, H. A.; Fan, F. T.; Feng, Z. C.; van Santen, R. A.; Hensen, E. J. M.; Li, C. Chem. Commun. 2008, No. 6, 774.
3. [3]
  (3) Balducci, L.; Bianchi, D.; Bortolo, R.; D'Aloisio, R.; Ricci, M.; Tassinari, R.; Ungarelli, R. Angew. Chem. Int. Edit. 2003, 42, 4937. (3) Balducci, L.; Bianchi, D.; Bortolo, R.; D'Aloisio, R.; Ricci, M.; Tassinari, R.; Ungarelli, R. Angew. Chem. Int. Edit. 2003, 42, 4937.
4. [4]
  (4) Bhaumik, A.; Mukherjee, P.; Kumar, R. J. Catal. 1998, 178, 101. (4) Bhaumik, A.; Mukherjee, P.; Kumar, R. J. Catal. 1998, 178, 101.
5. [5]
  (5) Choi, J. S.; Kim, T. H.; Choo, K. Y.; Sung, J. S.; Saidutta, M. B.; Ryu, S. O.; Song, S. D.; Ramachandra, B.; Rhee, Y.W. Appl. Catal. A-Gen. 2005, 290, 1. (5) Choi, J. S.; Kim, T. H.; Choo, K. Y.; Sung, J. S.; Saidutta, M. B.; Ryu, S. O.; Song, S. D.; Ramachandra, B.; Rhee, Y.W. Appl. Catal. A-Gen. 2005, 290, 1.
6. [6]
  (6) Monfared, H. H.; Amouei, Z. J. Mol. Catal. A-Chem. 2004, 217, 161. (6) Monfared, H. H.; Amouei, Z. J. Mol. Catal. A-Chem. 2004, 217, 161.
7. [7]
  (7) Tanarungsun, G.; Kiatkittipong,W.; Praserthdam, P.; Yamada, H.; Tagawa, T.; Assabumrungrat, S. Catal. Commun. 2008, 9, 1886. (7) Tanarungsun, G.; Kiatkittipong,W.; Praserthdam, P.; Yamada, H.; Tagawa, T.; Assabumrungrat, S. Catal. Commun. 2008, 9, 1886.
8. [8]
  (8) Tani, M.; Sakamoto, T.; Mita, S.; Sakaguchi, S.; Ishii, Y. Angew. Chem. Int. Edit. 2005, 44, 2586. (8) Tani, M.; Sakamoto, T.; Mita, S.; Sakaguchi, S.; Ishii, Y. Angew. Chem. Int. Edit. 2005, 44, 2586.
9. [9]
  (9) Barbera, D.; Cavani, F.; D'Alessandro, T.; Fornasari, G.; Guidetti, S.; Aloise, A.; Giordano, G.; Piumetti, M.; Bonelli, B.; Zanzottera, C. J. Catal. 2010, 275, 158. (9) Barbera, D.; Cavani, F.; D'Alessandro, T.; Fornasari, G.; Guidetti, S.; Aloise, A.; Giordano, G.; Piumetti, M.; Bonelli, B.; Zanzottera, C. J. Catal. 2010, 275, 158.
10. [10]
  (10) Kubacka, A.;Wang, Z. L.; Sulikowski, B.; Corberan, V. C. J. Catal. 2007, 250, 184. (10) Kubacka, A.;Wang, Z. L.; Sulikowski, B.; Corberan, V. C. J. Catal. 2007, 250, 184.
11. [11]
  (11) Bal, R.; Tada, M.; Sasaki, T.; Iwasawa, Y. Angew. Chem. Int. Edit. 2006, 45, 448. (11) Bal, R.; Tada, M.; Sasaki, T.; Iwasawa, Y. Angew. Chem. Int. Edit. 2006, 45, 448.
12. [12]
  (12) Ribera, A.; Arends, I.W. C. E.; de Vries, S.; Perez-Ramirez, J.; Sheldon, R. A. J. Catal. 2000, 195, 287. (12) Ribera, A.; Arends, I.W. C. E.; de Vries, S.; Perez-Ramirez, J.; Sheldon, R. A. J. Catal. 2000, 195, 287.
13. [13]
  (13) Panov, G. I.; Uriarte, A. K.; Rodkin, M. A.; Sobolev, V. I. Catal. Today 1998, 41, 365. (13) Panov, G. I.; Uriarte, A. K.; Rodkin, M. A.; Sobolev, V. I. Catal. Today 1998, 41, 365.
14. [14]
  (14) Joseph, J. K.; Singhal, S.; Jain, S. L.; Sivakumaran, R.; Kumar, B.; Sain, B. Catal. Today 2009, 141, 211. (14) Joseph, J. K.; Singhal, S.; Jain, S. L.; Sivakumaran, R.; Kumar, B.; Sain, B. Catal. Today 2009, 141, 211.
15. [15]
  (15) Renuka, N. K. J. Mol. Catal. A-Chem. 2010, 316, 126. (15) Renuka, N. K. J. Mol. Catal. A-Chem. 2010, 316, 126.
16. [16]
  (16) Miyahara, T.; Kanzaki, H.; Hamada, R.; Kuroiwa, S.; Nishiyama, S.; Tsuruya, S. J. Mol. Catal. A-Chem. 2001, 176, 141. (16) Miyahara, T.; Kanzaki, H.; Hamada, R.; Kuroiwa, S.; Nishiyama, S.; Tsuruya, S. J. Mol. Catal. A-Chem. 2001, 176, 141.
17. [17]
  (17) Panov, G. I.; Kharitonov, A. S.; Sobolev, V. I. Appl. Catal. A-Gen. 1993, 98, 1. (17) Panov, G. I.; Kharitonov, A. S.; Sobolev, V. I. Appl. Catal. A-Gen. 1993, 98, 1.
18. [18]
  (18) Neidig, M. L.; Hirsekorn, K. F. Catal. Commun. 2011, 12, 480. (18) Neidig, M. L.; Hirsekorn, K. F. Catal. Commun. 2011, 12, 480.
19. [19]
  (19) Tanev, P. T.; Chibwe, M.; Pinnavaia, T. J. Nature 1994, 368, 321. (19) Tanev, P. T.; Chibwe, M.; Pinnavaia, T. J. Nature 1994, 368, 321.
20. [20]
  (20) Williams, T.; Beltramini, J.; Lu, G. Q. Microporous Mesoporous Mat. 2006, 88, 91. (20) Williams, T.; Beltramini, J.; Lu, G. Q. Microporous Mesoporous Mat. 2006, 88, 91.
21. [21]
  (21) Zhang,W. Z.;Wang, J. L.; Tanev, P. T.; Pinnavaia, T. J. Chem. Commun. 1996, No. 8, 979.(21) Zhang,W. Z.;Wang, J. L.; Tanev, P. T.; Pinnavaia, T. J. Chem. Commun. 1996, No. 8, 979.
22. [22]
  (22) George, J.; Shylesh, S.; Singh, A. P. Appl. Catal. A-Gen. 2005, 290, 148. (22) George, J.; Shylesh, S.; Singh, A. P. Appl. Catal. A-Gen. 2005, 290, 148.
23. [23]
  (23) Shiraishi, Y.; Morishita, M.; Teshima, Y.; Hirai, T. J. Phys. Chem. B 2006, 110, 6587. (23) Shiraishi, Y.; Morishita, M.; Teshima, Y.; Hirai, T. J. Phys. Chem. B 2006, 110, 6587.
24. [24]
  (24) Zhu, Y. J.; Dong, Y. L.; Zhao, L. N.; Yuan, F. L. J. Mol. Catal. A-Chem. 2010, 315, 205. (24) Zhu, Y. J.; Dong, Y. L.; Zhao, L. N.; Yuan, F. L. J. Mol. Catal. A-Chem. 2010, 315, 205.
25. [25]
  (25) Liu, Y. Y.; Murata, K.; Inaba, M.; Mimura, N. Catal. Lett. 2003, 89, 49. (25) Liu, Y. Y.; Murata, K.; Inaba, M.; Mimura, N. Catal. Lett. 2003, 89, 49.
26. [26]
  (26) Knotek, P.; Capek, L.; Bulanek, R.; Adam, J. Top. Catal. 2007, 45, 51. (26) Knotek, P.; Capek, L.; Bulanek, R.; Adam, J. Top. Catal. 2007, 45, 51.
27. [27]
  (27) Parvulescu, V.; Tablet, C.; Anastasescu, C.; Su, B. L. Catal. Today 2004, 93-5, 307.(27) Parvulescu, V.; Tablet, C.; Anastasescu, C.; Su, B. L. Catal. Today 2004, 93-5, 307.
28. [28]
  (28) Parvulescu, V.; Anastasescu, C.; Su, B. L. J. Mol. Catal. AChem. 2004, 211, 143. (28) Parvulescu, V.; Anastasescu, C.; Su, B. L. J. Mol. Catal. AChem. 2004, 211, 143.
29. [29]
  (29) Gutierrez, O. Y.; Fuentes, G. A.; Salcedo, C.; Klimova, T. Catal. Today 2006, 116, 485. (29) Gutierrez, O. Y.; Fuentes, G. A.; Salcedo, C.; Klimova, T. Catal. Today 2006, 116, 485.
30. [30]
  (30) Zhang, Y. H.; Gao, F.;Wan, H. Q.;Wu, C.; Kong, Y.;Wu, X. C.; Zhao, B.; Dong, L.; Chen, Y. Microporous Mesoporous Mat. 2008, 113, 393. (30) Zhang, Y. H.; Gao, F.;Wan, H. Q.;Wu, C.; Kong, Y.;Wu, X. C.; Zhao, B.; Dong, L.; Chen, Y. Microporous Mesoporous Mat. 2008, 113, 393.
31. [31]
  (31) Kong, Y.; Xu, X. J.;Wu, Y.; Zhang, R.;Wang, J. Chin. J. Catal. 2008, 29, 385. [孔岩, 徐鑫杰, 吴勇, 张瑞, 王军. 催化学报, 2008, 29, 385.] (31) Kong, Y.; Xu, X. J.;Wu, Y.; Zhang, R.;Wang, J. Chin. J. Catal. 2008, 29, 385. [孔岩, 徐鑫杰, 吴勇, 张瑞, 王军. 催化学报, 2008, 29, 385.]
32. [32]
  (32) Tanarungsun, G.; Kiatkittipong,W.; Praserthdam, P.; Yamada, H.; Tagawa, T.; Assabumrungrat, S. J. Ind. Eng. Chem. 2008, 14, 596. (32) Tanarungsun, G.; Kiatkittipong,W.; Praserthdam, P.; Yamada, H.; Tagawa, T.; Assabumrungrat, S. J. Ind. Eng. Chem. 2008, 14, 596.
33. [33]
  (33) Gu, Y. Y.; Li, J.; Zhao, X. H.;Wang, L. P.; Shan, Y. K. Acta Chim. Sin. 2007, 65, 2423. [顾颖颖, 李疆, 赵新华, 王莉萍, 单永奎. 化学学报, 2007, 65, 2423.](33) Gu, Y. Y.; Li, J.; Zhao, X. H.;Wang, L. P.; Shan, Y. K. Acta Chim. Sin. 2007, 65, 2423. [顾颖颖, 李疆, 赵新华, 王莉萍, 单永奎. 化学学报, 2007, 65, 2423.]
34. [34]
  (34) Feng, S. J.; Pei, S. P.; Yue, B.; Ye, L.; Qian, L. P.; He, H. Y. Catal. Lett. 2009, 131, 458. (34) Feng, S. J.; Pei, S. P.; Yue, B.; Ye, L.; Qian, L. P.; He, H. Y. Catal. Lett. 2009, 131, 458.
35. [35]
  (35) Fornes, V.; Lopez, C.; Lopez, H. H.; Martinez, A. Appl. Catal. A-Gen. 2003, 249, 345. (35) Fornes, V.; Lopez, C.; Lopez, H. H.; Martinez, A. Appl. Catal. A-Gen. 2003, 249, 345.
36. [36]
  (36) Braganca, L. F. F. P. G.; Avilez, R. R.; de Silva, M. I. Colloid Surface A 2010, 358, 79. (36) Braganca, L. F. F. P. G.; Avilez, R. R.; de Silva, M. I. Colloid Surface A 2010, 358, 79.
37. [37]
  (37) Lemke, K.; Ehrich, H.; Lohse, U.; Berndt, H.; Jahnisch, K. Appl. Catal. A-Gen. 2003, 243, 41. (37) Lemke, K.; Ehrich, H.; Lohse, U.; Berndt, H.; Jahnisch, K. Appl. Catal. A-Gen. 2003, 243, 41.
38. [38]
  (38) Arichi, J.; Eternot, M.; Louis, B. Catal. Today 2008, 138, 117. (38) Arichi, J.; Eternot, M.; Louis, B. Catal. Today 2008, 138, 117.
39. [39]
  (39) Seo, Y. J.; Mukai, Y.; Tagawa, T.; to, S. J. Mol. Catal. A-Chem. 1997, 120, 149. (39) Seo, Y. J.; Mukai, Y.; Tagawa, T.; to, S. J. Mol. Catal. A-Chem. 1997, 120, 149.

扫一扫看文章

计量

PDF下载量: 868
文章访问数: 4129
HTML全文浏览量: 51

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

掺杂Fe作为第二种金属组分的V-HMS催化剂的苯羟基化反应

English

Hydroxylation of Benzene over V-HMS Catalysts with the Addition of Fe as the Second Metal Component

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

掺杂Fe作为第二种金属组分的V-HMS催化剂的苯羟基化反应

English

Hydroxylation of Benzene over V-HMS Catalysts with the Addition of Fe as the Second Metal Component

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

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs