H-ZSM-5分子筛上环己烯芳构化反应历程的理论研究

催化学报 , 2012, 33(8): 1367-1373. doi: 10.3724/SP.J.1088.2012.20346

H-ZSM-5分子筛上环己烯芳构化反应历程的理论研究

左士颖 ^1, , 周丹红 ^2, , 任珏 ^3, , 王凤娇 ^4,

1.辽宁师范大学化学化工学院功能材料化学研究所,辽宁大连116029

2.辽宁师范大学化学化工学院功能材料化学研究所,辽宁大连116029

3.辽宁师范大学化学化工学院功能材料化学研究所,辽宁大连116029

4.辽宁师范大学化学化工学院功能材料化学研究所,辽宁大连116029

基金项目: 国家自然科学基金(20073058)

关键词： H-ZSM-5分子筛 , 环己烯 , 芳构化 , 脱氢 , 量子力学/分子力学

Theoretical Study of Reaction Mechanism of Cyclohexene Aromatization over H-ZSM-5 Zeolite

基于76T簇模型,采用量子力学和分子力学联合的ONIOM2 (B3LYP/6-31G(d,p):UFF)方法研究了H-ZSM-5分子筛上环己烯芳构化反应历程.结果表明,环己烯首先吸附在分子筛酸性位上,与酸性质子共同脱除一个H2分子后,在分子筛骨架氧上生成烷氧配合物中间体；然后再脱质子得到环己二烯,同时酸性位复原；再经历脱氢和脱质子历程,最后得到产物苯,并吸附在复原的分子筛酸性位上.计算得到脱氢的活化能依次为279.64和260.21kJ/mol,脱质子的活化能依次为74.64和59.14kJ/mol.所有脱氢反应都是吸热过程,生成表面烷氧活性中间体,随后的脱质子反应能垒较低,而且是放热过程.此外,比较了环己烯在分子筛酸性位上的三个竞争反应,即脱氢、质子化和氢交换反应的活化能垒,证明环己烯优先发生脱氢反应.

参考文献

[1]	Corma A .[J].Chemical Reviews,1995,95:559.
[2]	Tukur N M;Al-Khattaf S .[J].Chemical Engineering Progress,2005,44:1257.
[3]	Xu Y D;Shu Y Y;Liu S T;Huang J S Guo X X .[J].Catalysis Letters,1995,35:233.
[4]	Solymosi F;Erd(o)helyi A;Sz(o)ke A .[J].Catalysis Letters,1995,32:43.
[5]	邢双英,周丹红,曹亮,李新.Mo/ZSM-5分子筛碳化钼活性中心结构及甲烷活化机理的密度泛函理论研究[J].催化学报,2010(04):415-422.
[6]	张佳,周丹红,倪丹.H-ZSM-5分子筛上的乙烯二聚反应机理的理论计算研究[J].催化学报,2008(08):715-719.
[7]	曹亮,周丹红,邢双英,李新.HZSM-5分子筛上乙烯芳构化过程中C4至C6中间体的反应机理[J].催化学报,2010(06):645-650.
[8]	Derouane E G;Fripiat J G .[J].Journal of Physical Chemistry,1987,91:145.
[9]	Fripiat J G;Berger-Andre F;Andre J M;Deroane E G .[J].Zeolites,1983,3:306.
[10]	Rozanska X;van Santen R A;Hutschka F .[J].Journal of Physical Chemistry B,2002,106:4652.
[11]	Chatterjee A;Bhattacharya D;Chatterjee M;Iwasaki T .[J].Microporous and Mesoporous Materials,1999,32:189.
[12]	Chu Y Y;Han B;Fang H J;Zheng A M Deng F .[J].Microporous and Mesoporous Materials,2012,151:241.
[13]	Zheng A M;Deng F;Liu Sh B .[J].Catalysis Today,2011,164:40.
[14]	Vreven T;Byun K S;Komáromi I;Dapprich S Montgomery J A Jr Morokuma K Frisch M J .[J].JOURNAL OF CHEMICAL THEORY AND COMPUTATION,2006,2:815.
[15]	Maseras F.;Morokuma K. .IMOMM - A NEW INTEGRATED AB INITIO PLUS MOLECULAR MECHANICS GEOMETRY OPTIMIZATION SCHEME OF EQUILIBRIUM STRUCTURES AND TRANSITION STATES[J].Journal of Computational Chemistry: Organic, Inorganic, Physical, Biological,1995(9):1170-1179.
[16]	Humbel S.;Morokuma K.;Sieber S. .THE IMOMO METHOD - INTEGRATION OF DIFFERENT LEVELS OF MOLECULAR ORBITAL APPROXIMATIONS FOR GEOMETRY OPTIMIZATION OF LARGE SYSTEMS - TEST FOR N-BUTANE CONFORMATION AND S(N)2 REACTION - RCL+CL-[J].The Journal of Chemical Physics,1996(5):1959-1967.
[17]	Vreven T.;Morokuma K. .On the application of the IMOMO (integrated molecular orbital plus molecular orbital) method[J].Journal of Computational Chemistry: Organic, Inorganic, Physical, Biological,2000(16):1419-1432.
[18]	Boronat M;Viruela P M;Corma A .[J].Journal of the American Chemical Society,2004,126:3300.
[19]	Joshi Y V;Thomson K T .[J].Journal of Catalysis,2005,230:440.
[20]	Jansang B;Nanok T;Limtrakul J .[J].Journal of Physical Chemistry B,2006,110:12626.
[21]	Rungsirisakun R;Jansang B;Pantu P;Limtrakul J .The adsorption of benzene on industrially important nanostructured catalysts (H-BEA, H-ZSM-5, and H-FAU): confinement effects[J].Journal of Molecular Structure,2005(1/3):239-246.
[22]	李惊鸿,周丹红,任珏.Ga/HZSM-5分子筛上乙烯二聚反应的理论研究[J].物理化学学报,2011(06):1393-1399.
[23]	Sun Y X;Yang J;Zhao L F;Dai J X Sun H .[J].Journal of Physical Chemistry C,2010,114:5975.
[24]	Derouane E G;Chang C D .[J].Microporous and Mesoporous Materials,2000,35-36:425.
[25]	Derouane EG. .Zeolites as solid solvents[J].Journal of molecular catalysis, A. Chemical,1998(1/3):29-45.
[26]	Kasuriya S;Namuangruk S;Treesukol P;Tirtowidjojo M Limtrakul J .[J].Journal of Catalysis,2003,219:320.
[27]	Namuangruk S;Pantu P;Limtrakul J .Investigation of ethylene dimerization over faujasite zeolite by the ONIOM method[J].Chemphyschem: A European journal of chemical physics and physical chemistry,2005(7):1333-1339.
[28]	Derouane E G;Fripiat J G .[J].Zeolites,1985,5:165.
[29]	Lonsinger S R;Chakraborty A K;Theodorou D N;Bell A T .[J].Catalysis Letters,1991,11:209.
[30]	Zheng X B;Blowers P .[J].Journal of Physical Chemistry A,2006,110:2455.
[31]	Kazansky V B .[J].Catalysis Today,1999,51:419.
[32]	Chatterjee A;Vetrivel R .[J].Microporous and Mesoporous Materials,1994,3:211.
[33]	Van Koningveld H;Van Bekkum H;Jansen J C .[J].Acta Crystallographica Section B:Structural Science,1987,43:127.
[34]	Frisch M J;Trucks G W;Schlegel H B;Scuseria G E,Robb M A,Cheeseman J R,Montgomery J A Jr,Vreven T,KudinK N,Burant J C.Gaussian 03,Revision C.02 Ed[M].Wallingford,CT:Gaussian,Inc,2004
[35]	Panjan W.;Limtrakul J. .The influence of the framework on adsorption properties of ethylene/H-ZSM-5 system: an ONIOM study[J].Journal of Molecular Structure,2003(1/3):35-45.
[36]	Correa R J;Mota C J A .[J].Physical Chemistry Chemical Physics,2002,4:375.
[37]	Cuán A;Martínez-Magadán J M;García-Cruz I;Galván M .[J].Journal of Molecular Catalysis A:Chemical,2005,236:194.
[38]	Furtado EA.;Lins JOMDA.;Nascimento MAC.;Milas I. .The dehydrogenation reaction of light alkanes catalyzed by zeolites[J].Physica Status Solidi, A. Applied Research,2001(1):275-288.
[39]	Gounder, R;Iglesia, E .Catalytic Consequences of Spatial Constraints and Acid Site Location for Monomolecular Alkane Activation on Zeolites[J].Journal of the American Chemical Society,2009(5):1958-1971.

上一张下一张

计量

下载量()
访问量()

作者相关

文章评分

您的评分：
1

0%
2

0%
3

0%
4

0%
5

0%

材料期刊网