SiO<sub>2</sub>气凝胶负载的Ni催化剂在甲烷部分氧化制合成气反应中的催化性能及稳定性

引用本文: 李琪, 侯玉慧, 董玲玉, 黄铭湘, 翁维正, 夏文生, 万惠霖. SiO₂气凝胶负载的Ni催化剂在甲烷部分氧化制合成气反应中的催化性能及稳定性[J]. 物理化学学报, 2013, 29(10): 2245-2254. doi: 10.3866/PKU.WHXB201308201 shu

Citation: LI Qi, HOU Yu-Hui, DONG Ling-Yu, HUANG Ming-Xiang, WENG Wei-Zheng, XIA Wen-Sheng, WAN Hui-Lin. Catalytic Behaviors and Stability of Aerogel Silica-Supported Ni Catalysts for the Partial Oxidation of Methane into Synthesis Gas[J]. Acta Physico-Chimica Sinica, 2013, 29(10): 2245-2254. doi: 10.3866/PKU.WHXB201308201 shu

SiO₂气凝胶负载的Ni催化剂在甲烷部分氧化制合成气反应中的催化性能及稳定性

基金项目:
国家重点基础研究发展计划(973) (2010CB732303) (973) (2010CB732303)

国家自然科学基金(21033006, 21373169) (21033006, 21373169)

长江学者和创新团队发展计划(IRT1036)资助 (IRT1036)

摘要:

以常压有机溶剂置换(A)和溶剂置换-表面改性(B)方式制备的两种SiO₂气凝胶(SiO₂-A(或B)型气凝胶,记为SiO₂-A(or B)G)为载体, 采用常规浸渍法和聚乙烯吡咯烷酮(PVP)添加浸渍法合成不同SiO₂气凝胶负载的Ni/SiO₂催化剂, 并考察其催化的甲烷部分氧化(POM)制合成气的反应性能. 结果表明, 各催化剂的初始反应性能相近, 但Ni/SiO₂-BG的POM稳定性明显较Ni/SiO₂-AG的差, 而PVP添加制备的催化剂稳定性则获明显改善, Ni/SiO₂-AG-PVP、Ni/SiO₂-BG-PVP上POM稳定性相近. 结合X射线衍射(XRD)、程序升温还原反应(H₂-TPR)、高分辨透射电镜(TEM)和Brunauer-Emmett-Teller (BET)等表征结果的分析发现: (1) SiO₂-AG表面上存在一定量的羟基, 可促进亲水性金属物种与其的相互作用, 而SiO₂-BG表面上基本为有机基团, 与亲水性金属物种几乎无作用; (2) PVP的存在可使金属物种进入亲/疏水载体孔道深处, 抑制焙烧中载体骨架的收缩和金属颗粒的生长, 进而促进金属-载体的相互作用. 这二者均能有效地提高催化剂的POM反应稳定性.

关键词:

SiO₂
/ 气凝胶
/ 甲烷部分氧化
/ 羟基
/ PVP
/ 稳定性

English

Catalytic Behaviors and Stability of Aerogel Silica-Supported Ni Catalysts for the Partial Oxidation of Methane into Synthesis Gas

1.
State Key Laboratory of Physical Chemistry of Solid State Surfaces, National Engineering Laboratory for Green Chemical Productions of Alcohols-Ethers-Esters, Fujian Province Key Laboratory of Theoretical and Computational Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian Province, P. R. China
Received Date: 07 June 2013
Available Online: 26 September 2013
Fund Project:
国家重点基础研究发展计划(973) (2010CB732303)

国家自然科学基金(21033006, 21373169)

长江学者和创新团队发展计划(IRT1036)资助

Abstract:

Two types of aerogel silica, denoted as SiO₂-A(or B)G are synthesized with either solvent substitution (A) or solvent substitution-surface modification (B) under atmospheric conditions. Aerogel silicasupported Ni catalysts are then prepared via impregnated (IM) and polyvinylpyrrolidone (PVP)-added IM methods, and their performances for the partial oxidation of methane (POM) are investigated. The similar initial catalytic performances (activity and selectivity) are observed over the different Ni/SiO₂ catalysts. With respect to POMstability, Ni/SiO₂-BG is significantly worse than Ni/SiO₂-AG, while catalysts with PVP addition (during preparation) exhibit a significant improvement. In this case, Ni/SiO₂-BG-PVPis comparable to Ni/SiO₂-AG-PVP. We characterize the catalysts with X-ray diffraction (XRD), temperature-programmed hydrogen reduction (H₂-TPR), transmission electron microscopy (TEM), and Brunauer-Emmett-Teller (BET) analysis. We find that there are hydroxyls on the SiO₂-AG surface that favor their interaction with hydrophilic metal species, while on the SiO₂-BGsurface there are organic groups that do not interact with hydrophilic metal species. In addition, with the help of PVP, metal species can access the deep pores of hydrophilic/hydrophobic silica gels. Then, the contraction of the silica framework and the growth of metal particles are inhibited during calcinations, enhancing interactions between Ni and the silica gels. These (benefits fromsurface hydroxyls and PVP) result in significant improvements in the catalysts with respect to POMstability.

Key words:

SiO₂
/ Aerogel
/ POM
/ Hydroxyl
/ PVP
/ Stability

1. [1]
  
  (1) Zhang, Y. W.; Liu, J.; Ding, W. Z.; Lu, X. G. Fuel 2011, 90,324. doi: 10.1016/j.fuel.2010.08.027
  (1) Zhang, Y. W.; Liu, J.; Ding, W. Z.; Lu, X. G. Fuel 2011, 90,324. doi: 10.1016/j.fuel.2010.08.027
2. [2]
  (2) Mudu, F.; Arstad, B.; Bakken, E.; Fjellvåg, H.; Olsbye, U.Journal of Catalysis 2010, 275, 25. doi: 10.1016/j.jcat.2010.07.004(2) Mudu, F.; Arstad, B.; Bakken, E.; Fjellvåg, H.; Olsbye, U.Journal of Catalysis 2010, 275, 25. doi: 10.1016/j.jcat.2010.07.004
3. [3]
  (3) Christian, E. B.; Lødeng, R.; Holmen, A. Applied Catalysis A: General 2008, 346, 1. doi: 10.1016/j.apcata.2008.05.018(3) Christian, E. B.; Lødeng, R.; Holmen, A. Applied Catalysis A: General 2008, 346, 1. doi: 10.1016/j.apcata.2008.05.018
4. [4]
  (4) Nematollahi, B.; Rezaei, M.; Khajenoori, M. International Journal of Hydrogen Energy 2011, 36, 2969. doi: 10.1016/j.ijhydene.2010.12.007(4) Nematollahi, B.; Rezaei, M.; Khajenoori, M. International Journal of Hydrogen Energy 2011, 36, 2969. doi: 10.1016/j.ijhydene.2010.12.007
5. [5]
  (5) Yang, S. W.; Kondo, J. N.; Hayashi, K.; Hirano, M.; Domen, K.;Hosono, H. Applied Catalysis A: General 2004, 277, 239. doi: 10.1016/j.apcata.2004.09.030(5) Yang, S. W.; Kondo, J. N.; Hayashi, K.; Hirano, M.; Domen, K.;Hosono, H. Applied Catalysis A: General 2004, 277, 239. doi: 10.1016/j.apcata.2004.09.030
6. [6]
  (6) Weng, W. Z.; Pei, X. Q.; Li, J. M.; Luo, C. R.; Liu, Y.; Lin, H.Q.; Huang, C. J.; Wan, H. L. Catalysis Today 2006, 117, 53. doi: 10.1016/j.cattod.2006.05.011(6) Weng, W. Z.; Pei, X. Q.; Li, J. M.; Luo, C. R.; Liu, Y.; Lin, H.Q.; Huang, C. J.; Wan, H. L. Catalysis Today 2006, 117, 53. doi: 10.1016/j.cattod.2006.05.011
7. [7]
  (7) Li, J. M.; Huang, F. Y.; Weng, W. Z.; Pei, X. Q.; Luo, C. R.; Lin,H. Q.; Huang, C. J.;Wan, H. L. Catalysis Today 2008, 131, 179.doi: 10.1016/j.cattod.2007.10.040(7) Li, J. M.; Huang, F. Y.; Weng, W. Z.; Pei, X. Q.; Luo, C. R.; Lin,H. Q.; Huang, C. J.;Wan, H. L. Catalysis Today 2008, 131, 179.doi: 10.1016/j.cattod.2007.10.040
8. [8]
  (8) He, S. F.;Wu, H. M.; Yu, W. J.; Mo, L. Y.; Lou, H.; Zheng, X.M. International Journal of Hydrogen Energy 2009, 34, 839.doi: 10.1016/j.ijhydene.2008.10.072(8) He, S. F.;Wu, H. M.; Yu, W. J.; Mo, L. Y.; Lou, H.; Zheng, X.M. International Journal of Hydrogen Energy 2009, 34, 839.doi: 10.1016/j.ijhydene.2008.10.072
9. [9]
  (9) Özdemir, H.; Faruk Öksüzömer, M. A.; Ali Gürkaynak, M.International Journal of Hydrogen Energy 2010, 35, 12147. doi: 10.1016/j.ijhydene.2010.08.091(9) Özdemir, H.; Faruk Öksüzömer, M. A.; Ali Gürkaynak, M.International Journal of Hydrogen Energy 2010, 35, 12147. doi: 10.1016/j.ijhydene.2010.08.091
10. [10]
  (10) Jing, Q.; Lou, H.; Fei, J.; Hou, Z.; Zheng, X. International Journal of Hydrogen Energy 2004, 29, 1245. doi: 10.1016/j.ijhydene.2004.01.012(10) Jing, Q.; Lou, H.; Fei, J.; Hou, Z.; Zheng, X. International Journal of Hydrogen Energy 2004, 29, 1245. doi: 10.1016/j.ijhydene.2004.01.012
11. [11]
  (11) Takenaka, S.; Umebayashi, H.; Tanabe, E.; Matsune, H.;Kishida, M. Journal of Catalysis 2007, 245, 392. doi: 10.1016/j.jcat.2006.11.005(11) Takenaka, S.; Umebayashi, H.; Tanabe, E.; Matsune, H.;Kishida, M. Journal of Catalysis 2007, 245, 392. doi: 10.1016/j.jcat.2006.11.005
12. [12]
  (12) He, S. F.; Wu, H. M.; Yu, W. J.; Mo, L. Y.; Lou, H.; Zheng, X.M. Catalysis Today 2009, 148, 130. doi: 10.1016/j.cattod.2009.03.009(12) He, S. F.; Wu, H. M.; Yu, W. J.; Mo, L. Y.; Lou, H.; Zheng, X.M. Catalysis Today 2009, 148, 130. doi: 10.1016/j.cattod.2009.03.009
13. [13]
  (13) Li, L.; He, S. C.; Song, Y. Y.; Zhao, J.; Ji, W. J.; Au, C. T.Journal of Catalysis 2012, 288, 54. doi: 10.1016/j.jcat.2012.01.004(13) Li, L.; He, S. C.; Song, Y. Y.; Zhao, J.; Ji, W. J.; Au, C. T.Journal of Catalysis 2012, 288, 54. doi: 10.1016/j.jcat.2012.01.004
14. [14]
  (14) Choudhary, V. R.; Mamman, A. S. Applied Energy 2000, 66,161. doi: 10.1016/S0306-2619(99)00039-2(14) Choudhary, V. R.; Mamman, A. S. Applied Energy 2000, 66,161. doi: 10.1016/S0306-2619(99)00039-2
15. [15]
  (15) Requies, J.; Cabrero, M. A.; Barrio, V. L.; Güemez, M. B.;Cambra, J. F.; Arias, P. L.; Pérez-Alonso, F. J.; Ojeda, M.; Peña,M. A.; Fierro, J. L. G. Applied Catalysis A: General 2005, 289,214. doi: 10.1016/j.apcata.2005.05.002(15) Requies, J.; Cabrero, M. A.; Barrio, V. L.; Güemez, M. B.;Cambra, J. F.; Arias, P. L.; Pérez-Alonso, F. J.; Ojeda, M.; Peña,M. A.; Fierro, J. L. G. Applied Catalysis A: General 2005, 289,214. doi: 10.1016/j.apcata.2005.05.002
16. [16]
  (16) Li, B. T.; Xu, X. J.; Zhang, S. Y. International Journal of Hydrogen Energy 2013, 38, 890.(16) Li, B. T.; Xu, X. J.; Zhang, S. Y. International Journal of Hydrogen Energy 2013, 38, 890.
17. [17]
  (17) Chen, L.; Zhu, Q. S.;Wu, R. F. International Journal of Hydrogen Energy 2011, 36, 2128. doi: 10.1016/j.ijhydene.2010.11.042(17) Chen, L.; Zhu, Q. S.;Wu, R. F. International Journal of Hydrogen Energy 2011, 36, 2128. doi: 10.1016/j.ijhydene.2010.11.042
18. [18]
  (18) Xia, W. S.; Hou, Y. H.; Chang, G.; Weng, W. Z.; Han, G. B.;Wan, H. L. International Journal of Hydrogen Energy 2012, 37,8343. doi: 10.1016/j.ijhydene.2012.02.141(18) Xia, W. S.; Hou, Y. H.; Chang, G.; Weng, W. Z.; Han, G. B.;Wan, H. L. International Journal of Hydrogen Energy 2012, 37,8343. doi: 10.1016/j.ijhydene.2012.02.141
19. [19]
  (19) Guan, L. X.; Zhang, L. W.; Qu, Y. X. Fine Chemical 2010, 27,738. [关鲁雄, 张利伟, 区叶秀. 精细化工2010, 27, 738.](19) Guan, L. X.; Zhang, L. W.; Qu, Y. X. Fine Chemical 2010, 27,738. [关鲁雄, 张利伟, 区叶秀. 精细化工2010, 27, 738.]
20. [20]
  (20) Zhu, H. F. Supports of Catalyst; Chemical Industy Press:Beijing, 1980; p 473. [朱洪法. 催化剂载体. 北京:化学工业出版社, 1980: 473.](20) Zhu, H. F. Supports of Catalyst; Chemical Industy Press:Beijing, 1980; p 473. [朱洪法. 催化剂载体. 北京:化学工业出版社, 1980: 473.]
21. [21]
  (21) Jiang, J. T.; Wei, X. J.; Xu, C. Y.; Zhou, Z. X.; Zhen, L. Journal of Magnetism and Magnetic Materials 2013, 334, 111. doi: 10.1016/j.jmmm.2012.12.036(21) Jiang, J. T.; Wei, X. J.; Xu, C. Y.; Zhou, Z. X.; Zhen, L. Journal of Magnetism and Magnetic Materials 2013, 334, 111. doi: 10.1016/j.jmmm.2012.12.036
22. [22]
  (22) Dissanayake, D.; Rosynek, M. P.; Lunsford, J. H. Journal of Physical Chemistry 1993, 97, 3644. doi: 10.1021/j100117a002(22) Dissanayake, D.; Rosynek, M. P.; Lunsford, J. H. Journal of Physical Chemistry 1993, 97, 3644. doi: 10.1021/j100117a002
23. [23]
  (23) Song, Y. Q.; Liu, H. M.; Liu, S. Q.; He, D. H. Energy& Fuels2009, 23, 1925. doi: 10.1021/ef800954a(23) Song, Y. Q.; Liu, H. M.; Liu, S. Q.; He, D. H. Energy& Fuels2009, 23, 1925. doi: 10.1021/ef800954a
24. [24]
  (24) Li, B.; Weng, W. Z.; Zhang, Q.; Wang, Z. W.; Wan, H. L.ChemCatChem 2011, 3, 1277. doi: 10.1002/cctc.v3.8(24) Li, B.; Weng, W. Z.; Zhang, Q.; Wang, Z. W.; Wan, H. L.ChemCatChem 2011, 3, 1277. doi: 10.1002/cctc.v3.8
25. [25]
  (25) Lin, J. B.; Chen, H. J.; Yao, L. C. Applied Surface Science 2010,256, 5978. doi: 10.1016/j.apsusc.2010.03.105(25) Lin, J. B.; Chen, H. J.; Yao, L. C. Applied Surface Science 2010,256, 5978. doi: 10.1016/j.apsusc.2010.03.105
26. [26]
  (26) Hegde, N. D.; Hirashima, H.; Venkateswara Rao, A. Journal of Porous Materials 2007, 14, 165. doi: 10.1007/s10934-006-9021-2(26) Hegde, N. D.; Hirashima, H.; Venkateswara Rao, A. Journal of Porous Materials 2007, 14, 165. doi: 10.1007/s10934-006-9021-2
27. [27]
  (27) Ermakova, M. A.; Ermakov, D. Y. Catalysis Today 2002, 77,225. doi: 10.1016/S0920-5861(02)00248-1(27) Ermakova, M. A.; Ermakov, D. Y. Catalysis Today 2002, 77,225. doi: 10.1016/S0920-5861(02)00248-1
28. [28]
  (28) Gao, C. G.; Zhao, Y. X.; Liu, D. S. Catalysis Letters 2007, 118,50. doi: 10.1007/s10562-007-9135-4(28) Gao, C. G.; Zhao, Y. X.; Liu, D. S. Catalysis Letters 2007, 118,50. doi: 10.1007/s10562-007-9135-4
29. [29]
  (29) Rao, A. V.; Kulkarni, M. M.; Pajonk, G. M.; Amalnerkar, D. P.;Seth, T. Journal of Sol-Gel Science and Technology 2003, 27,103. doi: 10.1023/A:1023765030983
  (29) Rao, A. V.; Kulkarni, M. M.; Pajonk, G. M.; Amalnerkar, D. P.;Seth, T. Journal of Sol-Gel Science and Technology 2003, 27,103. doi: 10.1023/A:1023765030983

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

SiO₂气凝胶负载的Ni催化剂在甲烷部分氧化制合成气反应中的催化性能及稳定性

English

Catalytic Behaviors and Stability of Aerogel Silica-Supported Ni Catalysts for the Partial Oxidation of Methane into Synthesis Gas

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？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

SiO2气凝胶负载的Ni催化剂在甲烷部分氧化制合成气反应中的催化性能及稳定性

English

Catalytic Behaviors and Stability of Aerogel Silica-Supported Ni Catalysts for the Partial Oxidation of Methane into Synthesis Gas

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？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

SiO₂气凝胶负载的Ni催化剂在甲烷部分氧化制合成气反应中的催化性能及稳定性

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs