Influence of Acid Strength and Confinement Effect on the Ethylene Dimerization Reaction over Solid Acid Catalysts: A Theoretical Calculation Study

The influence of both Bronsted acid strength and pore confinement effect on the ethylene dimerization reaction has been systematically studied by density functional theory (DFT) calculations. In the theoretical calculations, both stepwise and concerted reaction mechanisms are considered. It is demonstrated that the reactivity of the ethylene dimerization reaction can be significantly enhanced by increasing acid strength no matter which mechanism is included, while on the basis of activated barriers, the concerted mechanism is preferred on weak acids and two mechanisms are competitive when the acid strength increases to a medium strong acid. Due to the pore confinement effect that can effectively stabilize the ionic transition states of the dimerization reaction, the activity of the dimerization reaction is considerably improved inside the zeolite pore. Compared with the reaction on the isolated acid sites, the transition states of the stepwise reaction are more effectively stabilized than those of the concerted reaction inside the zeolite confined pore, resulting in the former reaction being preferred when the dimerization reaction occurs inside the zeolite confinement spaces. Additionally, on the basis of the systematic investigations on the alkene dimerization reactions over zeolites with varying pore sizes (such as ZSM-22, ZSM-S, and SSZ-13), it is demonstrated that ZSM-22 and ZSM-5 zeolites are effective catalysts for the ethylene dimerization.

[1]  V. V. Speybroeck,et al.  Efficient Approach for the Computational Study of Alcohol and Nitrile Adsorption in H-ZSM-5 , 2012 .

[2]  Han Bing,et al.  Adsorption Structure and Energy of Pyridine Confined inside Zeolite Pores , 2012 .

[3]  Weiguo Song,et al.  0.3 Å Makes the Difference: Dramatic Changes in Methanol-to-Olefin Activities between H-ZSM-12 and H-ZSM-22 Zeolites , 2011 .

[4]  Anmin Zheng,et al.  Regioselectivity of carbonium ion transition states in zeolites , 2011 .

[5]  Anmin Zheng,et al.  Theoretical Investigation of the Effects of the Zeolite Framework on the Stability of Carbenium Ions , 2011 .

[6]  A. Corma,et al.  Mechanistic differences between methanol and dimethyl ether carbonylation in side pockets and large channels of mordenite. , 2011, Physical chemistry chemical physics : PCCP.

[7]  M. Probst,et al.  Adsorption and Tautomerization Reaction of Acetone on Acidic Zeolites: The Confinement Effect in Different Types of Zeolites , 2010 .

[8]  Anmin Zheng,et al.  13C Chemical Shift of Adsorbed Acetone for Measuring the Acid Strength of Solid Acids: A Theoretical Calculation Study , 2010 .

[9]  Anmin Zheng,et al.  New Insights into the Effects of Acid Strength on the Solid Acid-Catalyzed Reaction: Theoretical Calculation Study of Olefinic Hydrocarbon Protonation Reaction , 2010 .

[10]  M. Probst,et al.  Effect of the Zeolite Nanocavity on the Reaction Mechanism of n-Hexane Cracking: A Density Functional Theory Study , 2010 .

[11]  V. V. Speybroeck,et al.  Assembly of cyclic hydrocarbons from ethene and propene in acid zeolite catalysis to produce active catalytic sites for MTO conversion , 2010 .

[12]  Y. Akacem,et al.  Theoretical Study of 4,4′-Bipyridine Adsorption on the Brønsted Acid Sites of H-ZSM-5 Zeolite , 2009 .

[13]  Jumras Limtrakul,et al.  Mechanistic Investigation on 1,5- to 2,6-Dimethylnaphthalene Isomerization Catalyzed by Acidic β Zeolite: ONIOM Study with an M06-L Functional , 2009 .

[14]  V. Van Speybroeck,et al.  Theoretical evaluation of zeolite confinement effects on the reactivity of bulky intermediates. , 2009, Physical chemistry chemical physics : PCCP.

[15]  A. Corma,et al.  The confinement effect in zeolites , 2009 .

[16]  Chaohe Yang,et al.  Effect of acid density of HZSM-5 on the oligomerization of ethylene in FCC dry gas , 2009 .

[17]  Anmin Zheng,et al.  Chemoselectivity during propene hydrogenation reaction over H-ZSM-5 zeolite: Insights from theoretical calculations , 2009 .

[18]  M. D. Foster,et al.  Packing sticky hard spheres into rigid zeolite frameworks , 2009 .

[19]  M. Neurock,et al.  Correlating Acid Properties and Catalytic Function: A First-Principles Analysis of Alcohol Dehydration Pathways on Polyoxometalates , 2009 .

[20]  Shing‐Jong Huang,et al.  31P chemical shift of adsorbed trialkylphosphine oxides for acidity characterization of solid acids catalysts. , 2008, The journal of physical chemistry. A.

[21]  D. McCann,et al.  A complete catalytic cycle for supramolecular methanol-to-olefins conversion by linking theory with experiment. , 2008, Angewandte Chemie.

[22]  Anmin Zheng,et al.  Theoretical predictions of 31p NMR chemical shift threshold of trimethylphosphine oxide absorbed on solid acid catalysts. , 2008, The journal of physical chemistry. B.

[23]  Anmin Zheng,et al.  Relationship between 1H chemical shifts of deuterated pyridinium ions and Brønsted acid strength of solid acids. , 2007, The journal of physical chemistry. B.

[24]  Stefan Grimme,et al.  Semiempirical GGA‐type density functional constructed with a long‐range dispersion correction , 2006, J. Comput. Chem..

[25]  Igor Rivin,et al.  A geometric solution to the largest-free-sphere problem in zeolite frameworks , 2006 .

[26]  Xiaobo Zheng,et al.  A computational study of methane catalytic reactions on zeolites , 2006 .

[27]  J. Sohn,et al.  Ethylene dimerization over NiSO4 supported on Fe2O3-promoted ZrO2 catalyst , 2006 .

[28]  Xiaobo Zheng,et al.  Reactivity of isobutane on zeolites: a first principles study. , 2006, The journal of physical chemistry. A.

[29]  V. Parmon,et al.  In situ (1)H and (13)C MAS NMR kinetic study of the mechanism of H/D exchange for propane on zeolite H-ZSM-5. , 2005, The journal of physical chemistry. B.

[30]  J. Limtrakul,et al.  Investigation of ethylene dimerization over faujasite zeolite by the ONIOM method. , 2005, Chemphyschem : a European journal of chemical physics and physical chemistry.

[31]  Xiaobo Zheng,et al.  An ab initio study of ethane conversion reactions on zeolites using the complete basis set composite energy method , 2005 .

[32]  S. C. Roy,et al.  Synthesis of lower olefins from methanol and subsequent conversion of ethylene to higher olefins via oligomerisation , 2004 .

[33]  Stefan Grimme,et al.  Accurate description of van der Waals complexes by density functional theory including empirical corrections , 2004, J. Comput. Chem..

[34]  O. Swang,et al.  Theoretical Investigation of the Dimerization of Linear Alkenes Catalyzed by Acidic Zeolites , 2004 .

[35]  Weiguo Song,et al.  Synthesis of the Heptamethylbenzenium Cation in Zeolite-β: in situ NMR and Theory , 2002 .

[36]  J. Sohn,et al.  Characterization and catalytic activity for ethylene dimerization of nickel sulfate supported on zirconia , 2002 .

[37]  J. Sohn,et al.  Characterization of dealuminated NiY zeolite and effect of dealumination on catalytic activity for ethylene dimerization , 2001 .

[38]  Weiguo Song,et al.  A Persistent Carbenium Ion on the Methanol-to-Olefin Catalyst HSAPO-34: Acetone Shows the Way , 2001 .

[39]  Weiguo Song,et al.  Roles for Cyclopentenyl Cations in the Synthesis of Hydrocarbons from Methanol on Zeolite Catalyst HZSM-5 , 2000 .

[40]  Michael Stöcker,et al.  Methanol-to-hydrocarbons: catalytic materials and their behavior 1 Dedicated to my wife Wencke Ophau , 1999 .

[41]  J. Sohn,et al.  High catalytic activity of NiOZrO2 modified with WO3 for ethylene dimerization , 1997 .

[42]  J. Sauer,et al.  Predicting Absolute and Site Specific Acidities for Zeolite Catalysts by a Combined Quantum Mechanics/Interatomic Potential Function Approach† , 1997 .

[43]  C. Lamberti,et al.  Propene oligomerization on H-mordenite: Hydrogen-bonding interaction, chain initiation, propagation and hydrogen transfer studied by temperature-programmed FTIR and UV-VIS spectroscopies , 1997 .

[44]  S. Blaszkowski,et al.  Activation of C-H and C-C Bonds by an Acidic Zeolite: A Density Functional Study , 1996 .

[45]  J. F. Knifton,et al.  Olefin oligomerization via zeolite catalysis , 1994 .

[46]  G. Spoto,et al.  IR study of ethene and propene oligomerization on H-ZSM-5: hydrogen-bonded precursor formation, initiation and propagation mechanisms and structure of the entrapped oligomers , 1994 .

[47]  L. Curtiss,et al.  Ab initio molecular orbital cluster studies of the zeolite ZSM-5. 1. Proton affinities , 1993 .

[48]  F. Mizukami,et al.  Shape-selective synthesis of 2,6-diisopropylnaphthalene over H-mordenite catalyst , 1991 .

[49]  J. C. Jansen,et al.  On the location and disorder of the tetrapropylammonium (TPA) ion in zeolite ZSM-5 with improved framework accuracy , 1987 .