Ce助剂对V/SiO<sub>2</sub>催化CO<sub>2</sub>氧化乙苯脱氢性能的影响

引用本文: 张海新, 陈树伟, 崔杏雨, 潘大海, 秦张峰, 王建国. Ce助剂对V/SiO₂催化CO₂氧化乙苯脱氢性能的影响[J]. 物理化学学报, 2014, 30(2): 351-358. doi: 10.3866/PKU.WHXB201312021 shu

Citation: ZHANG Hai-Xin, CHEN Shu-Wei, CUI Xing-Yu, PAN Da-Hai, QIN Zhang-Feng, WANG Jian-Guo. Effect of Ce Promoter on Catalytic Performance of V/SiO₂ in Oxidative Dehydrogenation of Ethylbenzene with Carbon Dioxide[J]. Acta Physico-Chimica Sinica, 2014, 30(2): 351-358. doi: 10.3866/PKU.WHXB201312021 shu

Ce助剂对V/SiO₂催化CO₂氧化乙苯脱氢性能的影响

基金项目:
国家自然科学基金(51172154)，山西省科技攻关项目(20130313001-3)，煤转化国家重点实验室开放课题基金(J12-13-603) (51172154)，山西省科技攻关项目(20130313001-3)，煤转化国家重点实验室开放课题基金(J12-13-603)

山西省自然科学(青年)基金(2012021006-2)资助 (青年)基金(2012021006-2)

摘要:

通过N₂吸附、X射线衍射(XRD)、X射线光电子能谱(XPS)、H₂程序升温还原(H₂-TPR)、CO₂程序升温脱附(CO₂-TPD)和热重分析(TGA)等多种表征手段和催化反应性能评价，研究了铈助剂的添加对V/SiO₂催化CO₂氧化乙苯脱氢性能的影响. 结果表明，Ce助剂不仅提高了催化剂活性组分分散性和氧化还原性能，抑制了钒物种的深度还原，而且增强了催化剂碱性和CO₂吸附能力，减缓了积炭生成，从而显著提高了V-Ce/SiO₂对CO₂氧化乙苯脱氢反应的催化活性和稳定性. 在本实验中，V(0.8)-Ce(0.25)/SiO₂催化剂表现出最佳的催化性能，苯乙烯(ST)收率可达55.6%，选择性为98.5%，反应12 h 后，催化剂活性基本不变，与惰性N₂气氛比较，CO₂明显促进了乙苯脱氢反应，归因于CO₂能保持催化剂表面钒物种的高价态.

关键词:

English

Effect of Ce Promoter on Catalytic Performance of V/SiO₂ in Oxidative Dehydrogenation of Ethylbenzene with Carbon Dioxide

1.
1 College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, P. R. China;
2 State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, P. R. China;
3 Institute of Special Chemicals, Taiyuan University of Technology, Taiyuan 030024, P. R. China
Received Date: 06 August 2013
Available Online: 23 January 2014
Fund Project:
国家自然科学基金(51172154)，山西省科技攻关项目(20130313001-3)，煤转化国家重点实验室开放课题基金(J12-13-603)

山西省自然科学(青年)基金(2012021006-2)资助

Abstract:

The effect of a Ce promoter on the catalytic properties of V/SiO₂ was investigated for the oxidative dehydrogenation of ethylbenzene (EB) to styrene (ST) with CO₂ (CO₂-ODEB). The catalysts were characterized by nitrogen adsorption, X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), H₂ temperature-programmed reduction (H₂-TPR), CO₂ temperature-programmed desorption (CO₂-TPD), and thermogravimetric analyses (TGA). It was found that incorporation of Ce into V/SiO₂ increased the dispersion of active V species, enhanced the redox properties of the system, and inhibited deep V reduction of V⁵⁺ to V³⁺ . The Ce promoter also improves the basicity of V/SiO₂ and CO₂ adsorption on the catalyst, and suppresses coke formation. The addition of a Ce promoter greatly improves the catalytic activity and stability of V/SiO₂ towards CO₂-ODEB. The ST yield and selectivity reach 55.6% and 98.5%, respectively, for CO₂-ODEB over the most efficient catalyst, V(0.8)Ce(0.25)/SiO₂, at 550℃, and a CO₂/EB molar ratio of 20. Moreover, after reaction for 12 h, the V(0.8)Ce(0.25)/SiO₂ still shows stable catalytic activity. The ST yield in CO₂ is higher than that in an inert N₂ atmosphere, showing the significant promoting effect of CO₂ on EB dehydrogenation; this is because CO₂ is a soft oxidant and can effectively keep/regain the high valence of V for high activity with CO₂-ODEB.

Key words:

1. [1]
  
  (1) Lee, E. H. Catal. Rev. 1973, 8, 285.
  (1) Lee, E. H. Catal. Rev. 1973, 8, 285.
2. [2]
  (2) Rossetti, I.; Bencini, E.; Trentini, L.; Forni, L. Appl. Catal. A2005, 92, 118.(2) Rossetti, I.; Bencini, E.; Trentini, L.; Forni, L. Appl. Catal. A2005, 92, 118.
3. [3]
  (3) Cavani, F.; Trifiro, F. Appl. Catal. A 1995, 133, 219. doi: 10.1016/0926-860X(95)00218-9(3) Cavani, F.; Trifiro, F. Appl. Catal. A 1995, 133, 219. doi: 10.1016/0926-860X(95)00218-9
4. [4]
  (4) Xu, J.; Xue, B.; Liu, Y. M.; Li, Y. X.; Cao, Y.; Fan, K. N. Appl. Catal. A 2011, 405, 142. doi: 10.1016/j.apcata.2011.08.001(4) Xu, J.; Xue, B.; Liu, Y. M.; Li, Y. X.; Cao, Y.; Fan, K. N. Appl. Catal. A 2011, 405, 142. doi: 10.1016/j.apcata.2011.08.001
5. [5]
  (5) Martyn, P.; Michael, F.; Trevor, R. F.; Paul, T. A. Science 2002,297, 807. doi: 10.1126/science.297.5582.807(5) Martyn, P.; Michael, F.; Trevor, R. F.; Paul, T. A. Science 2002,297, 807. doi: 10.1126/science.297.5582.807
6. [6]
  (6) Mimura, N.; Takahara, I.; Saito, M.; Hattori, T.; Ohkuma, K.;Ando, M. Catal. Today 1998, 45, 6l.(6) Mimura, N.; Takahara, I.; Saito, M.; Hattori, T.; Ohkuma, K.;Ando, M. Catal. Today 1998, 45, 6l.
7. [7]
  (7) Sun, A. L.; Qin, Z. F.; Chen, S.W.;Wang, J. G. Catal. Today2004, 93-95, 273.(7) Sun, A. L.; Qin, Z. F.; Chen, S.W.;Wang, J. G. Catal. Today2004, 93-95, 273.
8. [8]
  (8) Chen, S.W.; Qin, Z. F.; Xu, X. F.;Wang, J. G. Appl. Catal. A2006, 302, 185. doi: 10.1016/j.apcata.2006.01.003(8) Chen, S.W.; Qin, Z. F.; Xu, X. F.;Wang, J. G. Appl. Catal. A2006, 302, 185. doi: 10.1016/j.apcata.2006.01.003
9. [9]
  (9) Chen, S.W.; Qin, Z. F.;Wang, G. F.; Dong, M.;Wang, J. G.Fuel 2013, 109, 43. doi: 10.1016/j.fuel.2012.06.004(9) Chen, S.W.; Qin, Z. F.;Wang, G. F.; Dong, M.;Wang, J. G.Fuel 2013, 109, 43. doi: 10.1016/j.fuel.2012.06.004
10. [10]
  (10) Sakurai, Y.; Suzaki, T.; Nakagawa, K.; Ikenaga, N.; Aota, H.;Suzuki, T. J. Catal. 2002, 209, 16. doi: 10.1006/jcat.2002.3593(10) Sakurai, Y.; Suzaki, T.; Nakagawa, K.; Ikenaga, N.; Aota, H.;Suzuki, T. J. Catal. 2002, 209, 16. doi: 10.1006/jcat.2002.3593
11. [11]
  (11) Chang, J. S.; Vislovskiy, V. P.; Park, M. S.; Hong, D. Y.; Yoo, J.S.; Park, S. E. Green Chem. 2003, 5, 587. doi: 10.1039/b304825j(11) Chang, J. S.; Vislovskiy, V. P.; Park, M. S.; Hong, D. Y.; Yoo, J.S.; Park, S. E. Green Chem. 2003, 5, 587. doi: 10.1039/b304825j
12. [12]
  (12) Liu, B. S.; Rui, G.; Chang, R. Z.; Au, C. T. Appl. Catal. A 2008,335, 88. doi: 10.1016/j.apcata.2007.11.013(12) Liu, B. S.; Rui, G.; Chang, R. Z.; Au, C. T. Appl. Catal. A 2008,335, 88. doi: 10.1016/j.apcata.2007.11.013
13. [13]
  (13) Qiao, Y. Y.; Miao, C. X.; Yue, Y. H.; Xie, Z. K.; Yang,W. M.;Hua,W. M.; Gao, Z. Microporous Mesoporous Mat. 2009, 119,150. doi: 10.1016/j.micromeso.2008.10.010(13) Qiao, Y. Y.; Miao, C. X.; Yue, Y. H.; Xie, Z. K.; Yang,W. M.;Hua,W. M.; Gao, Z. Microporous Mesoporous Mat. 2009, 119,150. doi: 10.1016/j.micromeso.2008.10.010
14. [14]
  (14) Reddy, B. M.; Lee, S.; Han, D.; Park, S. Appl. Catal. B 2009,87, 230. doi: 10.1016/j.apcatb.2008.08.026(14) Reddy, B. M.; Lee, S.; Han, D.; Park, S. Appl. Catal. B 2009,87, 230. doi: 10.1016/j.apcatb.2008.08.026
15. [15]
  (15) Saito, K.; Okuda, K.; Ikenaga, N.; Miyake, T.; Suzuki, T.J. Phys. Chem. A 2010, 114, 3845. doi: 10.1021/jp906166u(15) Saito, K.; Okuda, K.; Ikenaga, N.; Miyake, T.; Suzuki, T.J. Phys. Chem. A 2010, 114, 3845. doi: 10.1021/jp906166u
16. [16]
  (16) Liu, Z.W.;Wang, C.; Fan,W. B.; Liu, Z. T.; Hao, Q. Q.; Long,X.; Lu, J.;Wang, J. G.; Qin, Z. F.; Su, D. S. ChemSusChem2011, 4, 341. doi: 10.1002/cssc.v4.3(16) Liu, Z.W.;Wang, C.; Fan,W. B.; Liu, Z. T.; Hao, Q. Q.; Long,X.; Lu, J.;Wang, J. G.; Qin, Z. F.; Su, D. S. ChemSusChem2011, 4, 341. doi: 10.1002/cssc.v4.3
17. [17]
  (17) Nederlof, C.; Kapteijn, F.; Makkee, M. Appl. Catal. A 2012,417-418, 163.(17) Nederlof, C.; Kapteijn, F.; Makkee, M. Appl. Catal. A 2012,417-418, 163.
18. [18]
  (18) Zhang, S. J.; Li, X. H.; Jing, J. Y.; Fan, H. X.;Wang, Q.; Li,W.Y. Catal. Commun. 2013, 34, 5. doi: 10.1016/j.catcom.2013.01.003(18) Zhang, S. J.; Li, X. H.; Jing, J. Y.; Fan, H. X.;Wang, Q.; Li,W.Y. Catal. Commun. 2013, 34, 5. doi: 10.1016/j.catcom.2013.01.003
19. [19]
  (19) Ji, M.; Chen, G.;Wang, J.;Wang, X.; Zhang, T. Catal. Today2010, 158, 464. doi: 10.1016/j.cattod.2010.07.014(19) Ji, M.; Chen, G.;Wang, J.;Wang, X.; Zhang, T. Catal. Today2010, 158, 464. doi: 10.1016/j.cattod.2010.07.014
20. [20]
  (20) Sun, A. L.; Qin, Z. F.; Chen, S.W.;Wang, J. G. J. Mol. Catal. A2004, 210, 189. doi: 10.1016/j.molcata.2003.09.016(20) Sun, A. L.; Qin, Z. F.; Chen, S.W.;Wang, J. G. J. Mol. Catal. A2004, 210, 189. doi: 10.1016/j.molcata.2003.09.016
21. [21]
  (21) Castro, A. J. R.; Marques, S. P. D.; Soares, J. M.; Filho, J. M.;Saraiva, G. D.; Oliveira, A. C. Chem. Eng. J. 2012, 209,345. doi: 10.1016/j.cej.2012.07.094(21) Castro, A. J. R.; Marques, S. P. D.; Soares, J. M.; Filho, J. M.;Saraiva, G. D.; Oliveira, A. C. Chem. Eng. J. 2012, 209,345. doi: 10.1016/j.cej.2012.07.094
22. [22]
  (22) Ye, X.; Yue, Y.; Miao, C.; Xie, Z.; Hua,W.; Gao, Z. Green Chem. 2005, 7, 524. doi: 10.1039/b505781g(22) Ye, X.; Yue, Y.; Miao, C.; Xie, Z.; Hua,W.; Gao, Z. Green Chem. 2005, 7, 524. doi: 10.1039/b505781g
23. [23]
  (23) Chen, Y. D.;Wang, L.; Guan, X. X.; Liu, Y. B.; ng, M. C.;Chen, Y. Q. Acta Phys. -Chim. Sin. 2013, 29, 1048. [陈永东,王磊, 关小旭, 刘永兵, 龚茂初, 陈耀强. 物理化学学报,2013, 29, 1048.] doi: 10.3866/PKU.WHXB201303051(23) Chen, Y. D.;Wang, L.; Guan, X. X.; Liu, Y. B.; ng, M. C.;Chen, Y. Q. Acta Phys. -Chim. Sin. 2013, 29, 1048. [陈永东,王磊, 关小旭, 刘永兵, 龚茂初, 陈耀强. 物理化学学报,2013, 29, 1048.] doi: 10.3866/PKU.WHXB201303051
24. [24]
  (24) Blank, J. H.; Bechers, J.; Collignon, P. F.; Clerc, F.; Rothenberg,G. Chem. Eur. J. 2007, 13, 5121.(24) Blank, J. H.; Bechers, J.; Collignon, P. F.; Clerc, F.; Rothenberg,G. Chem. Eur. J. 2007, 13, 5121.
25. [25]
  (25) Wei, Z.; Li, H.; Zhang, X.; Yan, S.; Lv, Z.; Chen, Y.; ng, M.J. Alloy. Compd. 2008, 455, 322. doi: 10.1016/j.jallcom.2007.01.060(25) Wei, Z.; Li, H.; Zhang, X.; Yan, S.; Lv, Z.; Chen, Y.; ng, M.J. Alloy. Compd. 2008, 455, 322. doi: 10.1016/j.jallcom.2007.01.060
26. [26]
  (26) Murugan, B.; Ramaswamy, A. V. J. Am. Chem. Soc. 2007, 129,3062. doi: 10.1021/ja066834k(26) Murugan, B.; Ramaswamy, A. V. J. Am. Chem. Soc. 2007, 129,3062. doi: 10.1021/ja066834k
27. [27]
  (27) Rao, R.; Zhang, Q.; Liu, H.; Yang, H.; Ling, Q.; Yang, M.;Zhang, A.; Chen,W. J. Mol. Catal. A 2012, 363-364, 283.(27) Rao, R.; Zhang, Q.; Liu, H.; Yang, H.; Ling, Q.; Yang, M.;Zhang, A.; Chen,W. J. Mol. Catal. A 2012, 363-364, 283.
28. [28]
  (28) Chueh,W. C.; Falter, C.; Abbott, M.; Scipio, D.; Furler, P.;Haile, S. M.; Steinfeld, A. Science 2010, 330, 1797. doi: 10.1126/science.1197834(28) Chueh,W. C.; Falter, C.; Abbott, M.; Scipio, D.; Furler, P.;Haile, S. M.; Steinfeld, A. Science 2010, 330, 1797. doi: 10.1126/science.1197834
29. [29]
  (29) Staudt, T.; Lykhach, Y.; Tsud, N.; Skala, T.; Prince, K. C.;Matolin, V.; Libuda, J. J. Catal. 2010, 275, 181. doi: 10.1016/j.jcat.2010.07.032(29) Staudt, T.; Lykhach, Y.; Tsud, N.; Skala, T.; Prince, K. C.;Matolin, V.; Libuda, J. J. Catal. 2010, 275, 181. doi: 10.1016/j.jcat.2010.07.032
30. [30]
  (30) Qin, Z. F.; Liu, J. G,; Sun, A. L.;Wang, J. G. Ind. Eng. Chem. Res. 2003, 42, 1329. doi: 10.1021/ie020762y(30) Qin, Z. F.; Liu, J. G,; Sun, A. L.;Wang, J. G. Ind. Eng. Chem. Res. 2003, 42, 1329. doi: 10.1021/ie020762y
31. [31]
  (31) Park, M. S.; Vislovskiy, V. P.; Chang, J. S.; Shul, Y. G.; Yoo, J.S.; Park, S. E. Catal. Today 2003, 87, 205. doi: 10.1016/j.cattod.2003.10.015(31) Park, M. S.; Vislovskiy, V. P.; Chang, J. S.; Shul, Y. G.; Yoo, J.S.; Park, S. E. Catal. Today 2003, 87, 205. doi: 10.1016/j.cattod.2003.10.015
32. [32]
  (32) Kobayashi, M.; Kuma, R.; Masaki, S.; Sugishima, N. Appl. Catal. B 2005, 60, 173. doi: 10.1016/j.apcatb.2005.02.030(32) Kobayashi, M.; Kuma, R.; Masaki, S.; Sugishima, N. Appl. Catal. B 2005, 60, 173. doi: 10.1016/j.apcatb.2005.02.030
33. [33]
  (33) Rao, K. N.; Reddy, B. M.; Abhishek, B.; Seo, Y. H.; Jiang, N.;Park, S. E. Appl. Catal. B 2009, 91, 649. doi: 10.1016/j.apcatb.2009.07.003(33) Rao, K. N.; Reddy, B. M.; Abhishek, B.; Seo, Y. H.; Jiang, N.;Park, S. E. Appl. Catal. B 2009, 91, 649. doi: 10.1016/j.apcatb.2009.07.003
34. [34]
  (34) Reddy, B. M.; Bharali, P.; Saikia, P.; Khan, A.; Loridant, S.;Muhler, M.; Grunert,W. J. Phys. Chem. C 2007, 111, 10478.(34) Reddy, B. M.; Bharali, P.; Saikia, P.; Khan, A.; Loridant, S.;Muhler, M.; Grunert,W. J. Phys. Chem. C 2007, 111, 10478.
35. [35]
  (35) Shen, B. X.; Liu, T. Acta Phys. -Chim. Sin. 2010, 26, 3009.[沈伯雄, 刘亭. 物理化学学报, 2010, 26, 3009.] doi: 10.3866/PKU.WHXB20101120(35) Shen, B. X.; Liu, T. Acta Phys. -Chim. Sin. 2010, 26, 3009.[沈伯雄, 刘亭. 物理化学学报, 2010, 26, 3009.] doi: 10.3866/PKU.WHXB20101120
36. [36]
  (36) Reddy, E.; Varma, R. J. Catal. 2004, 221, 93. doi: 10.1016/j.jcat.2003.07.011(36) Reddy, E.; Varma, R. J. Catal. 2004, 221, 93. doi: 10.1016/j.jcat.2003.07.011
37. [37]
  (37) Liu, Y. M.; Cao, Y.; Yi, N.; Feng,W. L.; Dai,W. L.; Yan, S. R.J. Catal. 2004, 224, 417. doi: 10.1016/j.jcat.2004.03.010(37) Liu, Y. M.; Cao, Y.; Yi, N.; Feng,W. L.; Dai,W. L.; Yan, S. R.J. Catal. 2004, 224, 417. doi: 10.1016/j.jcat.2004.03.010
38. [38]
  (38) Takehira, K.; Ohishi, Y.; Shishido, T.; Kawabata, T.; Takaki, K.;Zhang, Q.;Wang, Y. J. Catal. 2004, 224, 404. doi: 10.1016/j.jcat.2004.03.014(38) Takehira, K.; Ohishi, Y.; Shishido, T.; Kawabata, T.; Takaki, K.;Zhang, Q.;Wang, Y. J. Catal. 2004, 224, 404. doi: 10.1016/j.jcat.2004.03.014
39. [39]
  (39) Nie, J. F.; Liu, H. C. Pure Appl. Chem. 2012, 84, 765. doi: 10.1351/PAC-CON-11-07-02
  (39) Nie, J. F.; Liu, H. C. Pure Appl. Chem. 2012, 84, 765. doi: 10.1351/PAC-CON-11-07-02

扫一扫看文章

计量

PDF下载量: 605
文章访问数: 1224
HTML全文浏览量: 11

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

Ce助剂对V/SiO₂催化CO₂氧化乙苯脱氢性能的影响

English

Effect of Ce Promoter on Catalytic Performance of V/SiO₂ in Oxidative Dehydrogenation of Ethylbenzene with Carbon Dioxide

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

Ce助剂对V/SiO2催化CO2氧化乙苯脱氢性能的影响

English

Effect of Ce Promoter on Catalytic Performance of V/SiO2 in Oxidative Dehydrogenation of Ethylbenzene with Carbon Dioxide

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

Ce助剂对V/SiO₂催化CO₂氧化乙苯脱氢性能的影响

Effect of Ce Promoter on Catalytic Performance of V/SiO₂ in Oxidative Dehydrogenation of Ethylbenzene with Carbon Dioxide

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs