Ce助剂对V/SiO2催化CO2氧化乙苯脱氢性能的影响

doi:10.3866/PKU.WHXB201312021

物理化学学报 >> 2014, Vol. 30 >> Issue (2): 351-358.doi: 10.3866/PKU.WHXB201312021

Ce助剂对V/SiO₂催化CO₂氧化乙苯脱氢性能的影响

张海新¹, 陈树伟^1,2, 崔杏雨³, 潘大海¹, 秦张峰², 王建国²

1 太原理工大学化学化工学院, 太原030024;
2 中国科学院山西煤炭化学研究所, 煤转化国家重点实验室, 太原030001;
3 太原理工大学精细化工研究所, 太原030024

收稿日期:2013-08-06 修回日期:2013-11-29 发布日期:2014-01-23
通讯作者: 陈树伟，崔杏雨 E-mail:csw603@163.com；cuixingyu@tyut.edu.cn
基金资助:
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)及山西省自然科学(青年)基金(2012021006-2)资助

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

ZHANG Hai-Xin¹, CHEN Shu-Wei^1,2, CUI Xing-Yu³, PAN Da-Hai¹, QIN Zhang-Feng², WANG Jian-Guo²

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:2013-08-06 Revised:2013-11-29 Published:2014-01-23
Contact: CHEN Shu-Wei, CUI Xing-Yu E-mail:csw603@163.com；cuixingyu@tyut.edu.cn
Supported by:
The project was supported by the National Natural Science Foundation of China (51172154), Science and Technology Project of Shanxi Province, China (20130313001-3), Foundation of State Key Laboratory of Coal Conversion, China (J12-13-603), and Shanxi Province Science Foundation for Youths, China (2012021006-2).

摘要/Abstract

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: 氧化铈, 负载型钒催化剂, 二氧化碳, 乙苯脱氢, 苯乙烯

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: Cerium oxide, Supported vanadium oxide catalyst, Carbon dioxide, Ethylbenzene dehydrogenation, Styrene

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

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 Phys. -Chim. Sin. 2014, 30(2), 351-358. doi: 10.3866/PKU.WHXB201312021

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201312021

https://www.whxb.pku.edu.cn/CN/Y2014/V30/I2/351

参考文献

(1) Lee, E. H. Catal. Rev. 1973, 8, 285.
(2) Rossetti, I.; Bencini, E.; Trentini, L.; Forni, L. Appl. Catal. A2005, 92, 118.
(3) Cavani, F.; Trifiro, F. Appl. Catal. A 1995, 133, 219. doi: 10.1016/0926-860X(95)00218-9
(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) Martyn, P.; Michael, F.; Trevor, R. F.; Paul, T. A. Science 2002,297, 807. doi: 10.1126/science.297.5582.807
(6) Mimura, N.; Takahara, I.; Saito, M.; Hattori, T.; Ohkuma, K.;Ando, M. Catal. Today 1998, 45, 6l.
(7) Sun, A. L.; Qin, Z. F.; Chen, S.W.;Wang, J. G. Catal. Today2004, 93-95, 273.
(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) 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) Sakurai, Y.; Suzaki, T.; Nakagawa, K.; Ikenaga, N.; Aota, H.;Suzuki, T. J. Catal. 2002, 209, 16. doi: 10.1006/jcat.2002.3593
(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) 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) 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) Reddy, B. M.; Lee, S.; Han, D.; Park, S. Appl. Catal. B 2009,87, 230. doi: 10.1016/j.apcatb.2008.08.026
(15) Saito, K.; Okuda, K.; Ikenaga, N.; Miyake, T.; Suzuki, T.J. Phys. Chem. A 2010, 114, 3845. doi: 10.1021/jp906166u
(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) Nederlof, C.; Kapteijn, F.; Makkee, M. Appl. Catal. A 2012,417-418, 163.
(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) Ji, M.; Chen, G.;Wang, J.;Wang, X.; Zhang, T. Catal. Today2010, 158, 464. doi: 10.1016/j.cattod.2010.07.014
(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) 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) Ye, X.; Yue, Y.; Miao, C.; Xie, Z.; Hua,W.; Gao, Z. Green Chem. 2005, 7, 524. doi: 10.1039/b505781g
(23) Chen, Y. D.;Wang, L.; Guan, X. X.; Liu, Y. B.; Gong, 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) Blank, J. H.; Bechers, J.; Collignon, P. F.; Clerc, F.; Rothenberg,G. Chem. Eur. J. 2007, 13, 5121.
(25) Wei, Z.; Li, H.; Zhang, X.; Yan, S.; Lv, Z.; Chen, Y.; Gong, M.J. Alloy. Compd. 2008, 455, 322. doi: 10.1016/j.jallcom.2007.01.060
(26) Murugan, B.; Ramaswamy, A. V. J. Am. Chem. Soc. 2007, 129,3062. doi: 10.1021/ja066834k
(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) 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) 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) Qin, Z. F.; Liu, J. G,; Sun, A. L.;Wang, J. G. Ind. Eng. Chem. Res. 2003, 42, 1329. doi: 10.1021/ie020762y
(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) Kobayashi, M.; Kuma, R.; Masaki, S.; Sugishima, N. Appl. Catal. B 2005, 60, 173. doi: 10.1016/j.apcatb.2005.02.030
(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) Reddy, B. M.; Bharali, P.; Saikia, P.; Khan, A.; Loridant, S.;Muhler, M.; Grunert,W. J. Phys. Chem. C 2007, 111, 10478.
(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) Reddy, E.; Varma, R. J. Catal. 2004, 221, 93. doi: 10.1016/j.jcat.2003.07.011
(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) 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) Nie, J. F.; Liu, H. C. Pure Appl. Chem. 2012, 84, 765. doi: 10.1351/PAC-CON-11-07-02

[1]	曹玥晗, 郭瑞, 马敏智, 黄泽皑, 周莹. 活性位点电子密度变化对光催化CO₂活化和选择转化的影响[J]. 物理化学学报, 2024, 40(1): 2303029 - .
[2]	陈瑶, 陈存, 曹雪松, 王震宇, 张楠, 刘天西. CO₂和N₂电还原中缺陷及界面工程的最新进展[J]. 物理化学学报, 2023, 39(8): 2212053 -0 .
[3]	韦天然, 张书胜, 刘倩, 邱园, 罗俊, 刘熙俊. 富氧空位的非晶氧化铜高选择性电催化还原CO₂制乙烯[J]. 物理化学学报, 2023, 39(2): 2207026 -0 .
[4]	李景学, 于跃, 徐斯然, 闫文付, 木士春, 张佳楠. 电子自旋效应在电催化剂中的作用[J]. 物理化学学报, 2023, 39(12): 2302049 - .
[5]	彭芦苇, 张杨, 何瑞楠, 徐能能, 乔锦丽. 电催化二氧化碳还原催化剂、电解液、反应器和隔膜研究进展[J]. 物理化学学报, 2023, 39(12): 2302037 - .
[6]	董金涛, 季赛楠, 张屹, 季梦夏, 王彬, 李英杰, 陈志刚, 夏杰祥, 李华明. 构筑Z型MnO₂/BiOBr异质结用于光催化环丙沙星去除和CO₂还原[J]. 物理化学学报, 2023, 39(11): 2212011 - .
[7]	王天杰, 王耀伟, 陈宇辉, 刘建鹏, 史会兵, 郭丽敏, 赵志伟, 刘春太, 彭章泉. 锂-空气电池的实用化之路：规避二氧化碳负面效应[J]. 物理化学学报, 2022, 38(8): 2009071 - .
[8]	朱弼辰, 洪小洋, 唐丽永, 刘芹芹, 唐华. 二维/一维BiOBr_0.5Cl_0.5/WO₃ S型异质结助力光催化CO₂还原[J]. 物理化学学报, 2022, 38(7): 2111008 - .
[9]	宋雨珂, 谢文富, 邵明飞. 一体化电极电催化二氧化碳还原研究进展[J]. 物理化学学报, 2022, 38(6): 2101028 - .
[10]	杜亚东, 孟祥桐, 汪珍, 赵鑫, 邱介山. 石墨烯基二氧化碳电化学还原催化剂的研究进展[J]. 物理化学学报, 2022, 38(2): 2101009 - .
[11]	黄小雄, 马英杰, 智林杰. 超薄氮掺杂碳纳米片负载单原子镍用于高效电催化还原二氧化碳[J]. 物理化学学报, 2022, 38(2): 2011050 - .
[12]	陈宇新, 王丽君, 姚志波, 郝磊端, 谭心怡, Masa Justus, Robertson Alex W., 孙振宇. 单原子配位结构及与载体相互作用的调控用于二氧化碳电催化还原[J]. 物理化学学报, 2022, 38(11): 2207024 -0 .
[13]	郝磊端, 孙振宇. 基于金属氧化物材料的二氧化碳电催化还原[J]. 物理化学学报, 2021, 37(7): 2009033 - .
[14]	高增强, 王聪勇, 李俊俊, 朱亚廷, 张志成, 胡文平. 导电金属有机框架材料在电催化中的成就，挑战和机遇[J]. 物理化学学报, 2021, 37(7): 2010025 - .
[15]	王则鉴, 洪佳佳, Ng Sue-Faye, 刘雯, 黄俊杰, 陈鹏飞, Ong Wee-Jun. 氧化物钙钛矿的光催化研究进展：CO₂还原、水裂解、固氮[J]. 物理化学学报, 2021, 37(6): 2011033 - .

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

PDF

赞

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

Metrics

推荐阅读 0