Epoxide Alcoholysis over M-BEA Zeolites: Effects of Alcohol Chain Length on Rates and Regioselectivities

Locht, Huston; Potts, David S.; Rangoonwala, Zahra; Flaherty, David W.

doi:10.1021/acscatal.5c04379

Epoxide Alcoholysis over M-BEA Zeolites: Effects of Alcohol Chain Length on Rates and Regioselectivities

Journal Article · Thu Oct 02 00:00:00 EDT 2025 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.5c04379· OSTI ID:3000210

^[1]; ^[2]; Rangoonwala, Zahra ^[1]; ^[3]

Georgia Institute of Technology, Atlanta, GA (United States)
University of Illinois Urbana−Champaign, IL (United States)
Georgia Institute of Technology, Atlanta, GA (United States); University of Illinois Urbana−Champaign, IL (United States)

The structures of nucleophilic reactants affect their coordination behavior among solvent molecules and kinetics of reactions with surface intermediates within the confines of fluidfilled pores of zeolites and other microporous materials. Consequently, rates and regioselectivities of diverse chemistries may depend sensitively on nucleophile identity in manners not observed for classic fluid phase reactions. Here, we examine the impact of varying the primary alcohol (ROH) chain length on the kinetics of 1,2-epoxybutane (C₄H₈O) ring-opening within Brønsted (Al-BEA) and Lewis acid (Zr-BEA) zeolites. Turnover rates increase by factors of ∼6 (Al-BEA) and 4-fold (Zr-BEA) between methanol and 1-hexanol, yet the reaction mechanisms remain comparable. Despite modest rate differences, apparent activation enthalpies calculated from rates and activities of solvated reactants decrease linearly by 12 (Al-BEA) to 33 kJ mol⁻¹ (Zr- BEA) with increased proton affinity, which suggests bond formation energies for the nucleophile strongly influence rate increases. The molecular interpretation of these trends demonstrates, however, that the solvation of ring-opening transition states by zeolite pore structures and solvent molecules also governs rates. The impact of local solvating interactions appears most directly as changes in regioselectivities, which tend to enhance terminal alcohol formation with increasing ROH chain length. Regioselectivities largely do not vary with differences in fluid composition for a given ROH. The addition of H₂O increases the number of hydrogen bonds among reactive species, and trends in regioselectivities imply that the decreased hydrogen bonding ability of longer chain ROH, and not the nucleophile strength or steric bulk, determines the regioselectivities of the resulting products. This work provides direct experimental evidence that nucleophilicity and hydrogen bonding influence reaction barriers and regioselectivities in zeolitecatalyzed epoxide ring-opening, offering pathways to better control reaction kinetics.

View Accepted Manuscript (DOE)

Research Organization:: Georgia Institute of Technology, Atlanta, GA (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: SC0025362

OSTI ID:: 3000210

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 20 Vol. 15; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (53)

Directing the Rate‐Enhancement for Hydronium Ion Catalyzed Dehydration via Organization of Alkanols in Nanoscopic Confinements Shetty, Manish; Wang, Huamin; Chen, Feng Angewandte Chemie International Edition, Vol. 60, Issue 5 https://doi.org/10.1002/anie.202009835	journal	November 2020
Metal-Organic Frameworks as Efficient Heterogeneous Catalysts for the Regioselective Ring Opening of Epoxides Dhakshinamoorthy, Amarajothi; Alvaro, Mercedes; Garcia, Hermenegildo Chemistry - A European Journal, Vol. 16, Issue 28 https://doi.org/10.1002/chem.201000588	journal	June 2010
Monomolecular Conversion of Light Alkanes over H-ZSM-5 Narbeshuber, T. F.; Vinek, H.; Lercher, J. A. Journal of Catalysis, Vol. 157, Issue 2 https://doi.org/10.1006/jcat.1995.1304	journal	December 1995
Ring-opening reaction of 1,2-expoxybutane with alcohols over H-zeolites in liquid phase Ogawa, H.; Mori, M. Reaction Kinetics & Catalysis Letters, Vol. 56, Issue 2 https://doi.org/10.1007/BF02076043	journal	November 1995
Catalytic Applications of Zeolites in Chemical Industry Yilmaz, Bilge; Müller, Ulrich Topics in Catalysis, Vol. 52, Issue 6-7 https://doi.org/10.1007/s11244-009-9226-0	journal	April 2009
Mutual solubility of n-butanol + water under high pressures Aoki, Yasuhiro; Moriyoshi, Takashi The Journal of Chemical Thermodynamics, Vol. 10, Issue 12 https://doi.org/10.1016/0021-9614(78)90034-4	journal	December 1978
Stereospecific lewis acid catalyzed methanolysis of styrene oxide Moberg, Christina; Rákos, László; Tottie, Louise Tetrahedron Letters, Vol. 33, Issue 16 https://doi.org/10.1016/0040-4039(92)88174-4	journal	April 1992
Esterification of fatty acids using nylon-immobilized lipase in n-hexane: kinetic parameters and chain-length effects Zaidi, A.; Gainer, J. L.; Carta, G. Journal of Biotechnology, Vol. 93, Issue 3 https://doi.org/10.1016/S0168-1656(01)00401-1	journal	February 2002
Catalytic reaction rates in thermodynamically non-ideal systems Madon, Rostam J.; Iglesia, Enrique Journal of Molecular Catalysis A: Chemical, Vol. 163, Issue 1-2 https://doi.org/10.1016/S1381-1169(00)00386-1	journal	December 2000
Resin catalyzed alcoholysis of epoxidized fatty esters: Effect of the alcohol and the resin structures Rios, Luis A.; Weckes, Patrick P.; Schuster, Hans Applied Catalysis A: General, Vol. 284, Issue 1-2 https://doi.org/10.1016/j.apcata.2005.01.031	journal	April 2005
Synthesis and catalytic testing of Lewis acidic nano-MFI zeolites for the epoxide ring opening reaction with alcohol Parulkar, Aamena; Joshi, Rutuja; Deshpande, Nitish Applied Catalysis A: General, Vol. 566 https://doi.org/10.1016/j.apcata.2018.08.018	journal	September 2018
Synthesis and catalytic testing of Lewis acidic nano zeolite Beta for epoxide ring opening with alcohols Parulkar, Aamena; Spanos, Alexander P.; Deshpande, Nitish Applied Catalysis A: General, Vol. 577 https://doi.org/10.1016/j.apcata.2019.03.009	journal	May 2019
Investigation on the catalysis performance of metal-doped zeolites on ring-opening acidolysis reaction Huo, Fanglin; Liu, Qing; Liu, Zhendong Chemical Engineering Journal, Vol. 465 https://doi.org/10.1016/j.cej.2023.143029	journal	June 2023
Effect of carbon chain length on esterification of carboxylic acids with methanol using acid catalysis Liu, Y.; Lotero, E.; Goodwinjr, J. Journal of Catalysis, Vol. 243, Issue 2 https://doi.org/10.1016/j.jcat.2006.07.013	journal	October 2006
Entropy considerations in monomolecular cracking of alkanes on acidic zeolites Bhan, A.; Gounder, R.; Macht, J. Journal of Catalysis, Vol. 253, Issue 1 https://doi.org/10.1016/j.jcat.2007.11.003	journal	January 2008
Copper-based metal-organic framework for the facile ring-opening of epoxides Jiang, D.; Mallat, T.; Krumeich, F. Journal of Catalysis, Vol. 257, Issue 2 https://doi.org/10.1016/j.jcat.2008.05.021	journal	July 2008
Determination of the Au active site and surface active species via operando transmission FTIR and isotopic transient experiments on 2.3wt.% Au/TiO2 for the WGS reaction Wang, Jun; Kispersky, Vincent F.; Nicholas Delgass, W. Journal of Catalysis, Vol. 289 https://doi.org/10.1016/j.jcat.2012.02.008	journal	May 2012
Epoxide ring opening with alcohols using heterogeneous Lewis acid catalysts: Regioselectivity and mechanism Deshpande, Nitish; Parulkar, Aamena; Joshi, Rutuja Journal of Catalysis, Vol. 370 https://doi.org/10.1016/j.jcat.2018.11.038	journal	February 2019
Ring opening of epoxides with alcohols using Fe(Cp)2BF4 as catalyst Yadav, Geeta Devi; Singh, Surendra Tetrahedron Letters, Vol. 55, Issue 29 https://doi.org/10.1016/j.tetlet.2014.05.017	journal	July 2014
Adsorption Thermodynamics and Intrinsic Activation Parameters for Monomolecular Cracking of n -Alkanes on Brønsted Acid Sites in Zeolites Janda, Amber; Vlaisavljevich, Bess; Lin, Li-Chiang The Journal of Physical Chemistry C, Vol. 119, Issue 19 https://doi.org/10.1021/acs.jpcc.5b01715	journal	May 2015
Highly Dispersed Sn-beta Zeolites as Active Catalysts for Baeyer–Villiger Oxidation: The Role of Mobile, In Situ Sn(II)O Species in Solid-State Stannation Peeters, Elise; Pomalaza, Guillaume; Khalil, Ibrahim ACS Catalysis, Vol. 11, Issue 10 https://doi.org/10.1021/acscatal.1c00435	journal	April 2021
Effect of Interactions between Alkyl Chains and Solvent Structures on Lewis Acid Catalyzed Epoxidations Potts, David S.; Jeyaraj, Vijaya Sundar; Kwon, Ohsung ACS Catalysis, Vol. 12, Issue 21 https://doi.org/10.1021/acscatal.2c03493	journal	October 2022
Solvent Mediated Interactions on Alkene Epoxidations in Ti-MFI: Effects of Solvent Identity and Silanol Density Torres, Chris; Potts, David S.; Flaherty, David W. ACS Catalysis, Vol. 13, Issue 13 https://doi.org/10.1021/acscatal.3c01073	journal	June 2023
Understanding Rates and Regioselectivities for Epoxide Methanolysis within Zeolites: Mechanism and Roles of Covalent and Non-covalent Interactions Potts, David S.; Komar, Jessica K.; Locht, Huston ACS Catalysis, Vol. 13, Issue 22 https://doi.org/10.1021/acscatal.3c04103	journal	November 2023
Mechanism of Regioselective Ring-Opening Reactions of 1,2-Epoxyoctane Catalyzed by Tris(pentafluorophenyl)borane: A Combined Experimental, Density Functional Theory, and Microkinetic Study Yu, Ying; Zhu, Youlong; Bhagat, Mihir N. ACS Catalysis, Vol. 8, Issue 12 https://doi.org/10.1021/acscatal.8b02632	journal	October 2018
Strong Influence of the Nucleophile on the Rate and Selectivity of 1,2-Epoxyoctane Ring Opening Catalyzed by Tris(pentafluorophenyl)borane, B(C₆F₅)₃ Bennett, Charmaine K.; Bhagat, Mihir N.; Zhu, Youlong ACS Catalysis, Vol. 9, Issue 12 https://doi.org/10.1021/acscatal.9b02607	journal	October 2019
Enhancing the Regioselectivity of B(C₆F₅)₃-Catalyzed Epoxide Alcoholysis Reactions Using Hydrogen-Bond Acceptors Bhagat, Mihir N.; Bennett, Charmaine K.; Chang, Gao-Fong ACS Catalysis, Vol. 9, Issue 10 https://doi.org/10.1021/acscatal.9b03089	journal	September 2019
Impact of Specific Interactions Among Reactive Surface Intermediates and Confined Water on Epoxidation Catalysis and Adsorption in Lewis Acid Zeolites Bregante, Daniel T.; Flaherty, David W. ACS Catalysis, Vol. 9, Issue 12 https://doi.org/10.1021/acscatal.9b03323	journal	October 2019
Epoxide Ring-Opening Reactions with Mesoporous Silica-Supported Fe(III) Catalysts Das, Sayantani; Asefa, Tewodros ACS Catalysis, Vol. 1, Issue 5 https://doi.org/10.1021/cs1001256	journal	April 2011
Improved Postsynthesis Strategy to Sn-Beta Zeolites as Lewis Acid Catalysts for the Ring-Opening Hydration of Epoxides Tang, Bo; Dai, Weili; Wu, Guangjun ACS Catalysis, Vol. 4, Issue 8 https://doi.org/10.1021/cs500891s	journal	July 2014
Experimental criterion for the absence of artifacts in the measurement of rates of heterogeneous catalytic reactions Madon, Rostam J.; Boudart, Michel Industrial & Engineering Chemistry Fundamentals, Vol. 21, Issue 4, p. 438-447 https://doi.org/10.1021/i100008a022	journal	November 1982
Silicalite characterization. 2. IR spectroscopy of the interaction of carbon monoxide with internal and external hydroxyl groups Zecchina, A.; Bordiga, S.; Spoto, G. The Journal of Physical Chemistry, Vol. 96, Issue 12 https://doi.org/10.1021/j100191a048	journal	June 1992
Nucleophilic Ring Opening of Epoxides by Organolithium Compounds: Ab Initio Mechanisms Harder, Sjoerd; van Lenthe, Joop H.; van Eikema Hommes, Nicolaas J. R. Journal of the American Chemical Society, Vol. 116, Issue 6 https://doi.org/10.1021/ja00085a035	journal	March 1994
Reactivity of Nucleophilic Reagents toward Esters Jencks, William P.; Carriuolo, Joan Journal of the American Chemical Society, Vol. 82, Issue 7 https://doi.org/10.1021/ja01492a058	journal	April 1960
Consequences of Pore Polarity and Solvent Structure on Epoxide Ring-Opening in Lewis and Brønsted Acid Zeolites Potts, David S.; Komar, Jessica K.; Jacobson, Matthew A. JACS Au, Vol. 4, Issue 9 https://doi.org/10.1021/jacsau.4c00398	journal	July 2024
Mutual solubility of water and aliphatic alcohols Stephenson, Richard; Stuart, James; Tabak, Mary Journal of Chemical & Engineering Data, Vol. 29, Issue 3 https://doi.org/10.1021/je00037a019	journal	July 1984
Remarkable Effect of the Preparation Technique on the State of Cobalt Ions in BEA Zeolites Evidenced by FTIR Spectroscopy of Adsorbed CO and NO, TPR and XRD Mihaylova, Angelina; Hadjiivanov, Konstantin; Dzwigaj, Stanislaw The Journal of Physical Chemistry B, Vol. 110, Issue 39 https://doi.org/10.1021/jp0634398	journal	October 2006
Adsorption of C2−C8 n -Alkanes in Zeolites De Moor, Bart A.; Reyniers, Marie-Françoise; Gobin, Oliver C. The Journal of Physical Chemistry C, Vol. 115, Issue 4 https://doi.org/10.1021/jp106536m	journal	September 2010
Proton Affinities of Primary Alkanols: An Appraisal of the Kinetic Method Holmes, John L.; Aubry, Christiane; Mayer, Paul M. The Journal of Physical Chemistry A, Vol. 103, Issue 6 https://doi.org/10.1021/jp984094z	journal	January 1999
Copper(II) Tetrafluoroborate Catalyzed Ring-Opening Reaction of Epoxides with Alcohols at Room Temperature Barluenga, José; Vázquez-Villa, Henar; Ballesteros, Alfredo Organic Letters, Vol. 4, Issue 17 https://doi.org/10.1021/ol025997k	journal	August 2002
Cooperative Brønsted Acid-Type Organocatalysis: Alcoholysis of Styrene Oxides Weil, Torsten; Kotke, Mike; Kleiner, Christian M. Organic Letters, Vol. 10, Issue 8 https://doi.org/10.1021/ol800149y	journal	March 2008
The Model of Catalytic Reactor of Ethylene Glycol Production Shvets, V. F.; Kozlovskiy, R. A.; Kozlovskiy, I. A. Organic Process Research & Development, Vol. 9, Issue 6 https://doi.org/10.1021/op058005+	journal	November 2005
The shape of water in zeolites and its impact on epoxidation catalysis Bregante, Daniel T.; Chan, Matthew C.; Tan, Jun Zhi Nature Catalysis, Vol. 4, Issue 9 https://doi.org/10.1038/s41929-021-00672-4	journal	September 2021
Mesoporous Zr-Beta zeolites prepared by a post-synthetic strategy as a robust Lewis acid catalyst for the ring-opening aminolysis of epoxides Tang, Bo; Dai, Weili; Sun, Xiaoming Green Chemistry, Vol. 17, Issue 3 https://doi.org/10.1039/C4GC02116A	journal	January 2015
Probing the correlations between the defects in metal–organic frameworks and their catalytic activity by an epoxide ring-opening reaction Liu, Yangyang; Klet, Rachel C.; Hupp, Joseph T. Chemical Communications, Vol. 52, Issue 50 https://doi.org/10.1039/C6CC03727E	journal	January 2016
Influence of solvent structure and hydrogen bonding on catalysis at solid–liquid interfaces Potts, David S.; Bregante, Daniel T.; Adams, Jason S. Chemical Society Reviews, Vol. 50, Issue 22 https://doi.org/10.1039/D1CS00539A	journal	January 2021
Engineering intraporous solvent environments: effects of aqueous-organic solvent mixtures on competition between zeolite-catalyzed epoxidation and H₂O₂ decomposition pathways Potts, David S.; Torres, Chris; Kwon, Ohsung Chemical Science, Vol. 14, Issue 12 https://doi.org/10.1039/D2SC06473A	journal	January 2023
Aluminium triflate: a remarkable Lewis acid catalyst for the ring opening of epoxides by alcohols Williams, D. Bradley G.; Lawton, Michelle Organic & Biomolecular Chemistry, Vol. 3, Issue 18 https://doi.org/10.1039/b508924g	journal	January 2005
The use of proton-exchanged X-type zeolite in catalysing ring-opening reactions of 2-substituted epoxides with nucleophiles and its effect on regioselectivity Takeuchi, Hiroshi; Kitajima, Kunio; Yamamoto, Yasuhiro Journal of the Chemical Society, Perkin Transactions 2, Issue 2 https://doi.org/10.1039/p29930000199	journal	January 1993
Evaluated Gas Phase Basicities and Proton Affinities of Molecules: An Update Hunter, Edward P. L.; Lias, Sharon G. Journal of Physical and Chemical Reference Data, Vol. 27, Issue 3 https://doi.org/10.1063/1.556018	journal	May 1998
Role of the ionic environment in enhancing the activity of reacting molecules in zeolite pores Pfriem, Niklas; Hintermeier, Peter H.; Eckstein, Sebastian Science, Vol. 372, Issue 6545 https://doi.org/10.1126/science.abh3418	journal	May 2021
Epoxide Syntheses and Ring-Opening Reactions in Drug Development Moschona, Fotini; Savvopoulou, Ioanna; Tsitopoulou, Maria Catalysts, Vol. 10, Issue 10 https://doi.org/10.3390/catal10101117	journal	September 2020
Theoretical Determination of Size Effects in Zeolite-Catalyzed Alcohol Dehydration Kunz, Larissa Y.; Bu, Lintao; Knott, Brandon C. Catalysts, Vol. 9, Issue 9 https://doi.org/10.3390/catal9090700	journal	August 2019

Similar Records

Epoxide ring opening with alcohols using heterogeneous Lewis acid catalysts: Regioselectivity and mechanism

Journal Article · Wed Dec 19 23:00:00 EST 2018 · Journal of Catalysis · OSTI ID:1543558

Aldol Condensation and Esterification over Ti-Substituted *BEA Zeolite: Mechanisms and Effects of Pore Hydrophobicity

Journal Article · Sun Jan 09 23:00:00 EST 2022 · ACS Catalysis · OSTI ID:1902709

Related Subjects

acidic zeolites
alcohols
ethers
hydrogen bonding
nucleophilicity
regioselectivity
ring opening
selectivity
solvation
solvents
zeolites

Epoxide Alcoholysis over M-BEA Zeolites: Effects of Alcohol Chain Length on Rates and Regioselectivities

Citation Formats

References (53)

Similar Records

Related Subjects