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Title: Transition state stabilization depends on solvent identity, pore size, and hydrophilicity for epoxidations in zeolites

Abstract

Ti-silicates activate H2O2 to form Ti-hydroperoxo and Ti-peroxo intermediates that can react with alkenes to form epoxide products. Comparisons of kinetics for 1-octene epoxidation with H2O2 on Ti-BEA and Ti-MFI catalysts with different hydrophilicities in methanol (CH3OH) or acetonitrile (CH3CN) solvents show the significance of the solvent for stabilizing catalytically-relevant species and the complex interdependencies between solvent, catalyst topology, and hydrophilicity. Epoxidation turnover rates are higher in CH3CN than CH3OH for Ti-BEA, but the opposite trend is observed for Ti-MFI. Ti-silicates with greater silanol densities, however, give greater epoxidation turnover rates than their hydrophobic counterparts in both solvents. Kinetic, spectroscopic, and thermodynamic analyses show that differences in turnover rates mainly arise from changes in the stabilization of reactive surface species by solvent mediated interactions, because the mechanism of the reaction and stability of the fluid-phase reactants remain similar in CH3CN and CH3OH. Specifically, apparent activation free energy values ($$ΔG^{‡}_{App}$$) indicate that surface intermediates responsible for alkene epoxidation are stabilized to a greater extent in CH3CN on Ti-BEA and in CH3OH on Ti-MFI. Hydrophilic Ti-silicates present lower ($$ΔG^{‡}_{App}$$) values regardless of solvent identity, which suggests that these differences correspond to the number of hydrogen-bonding solvent molecules found near reactive species bound to Ti active sites. Finally, taken together, these findings demonstrate the role of solvent molecules in allowing reactive intermediates to recognize the properties of active sites beyond the length-scale of covalent bonds, which carry implications for epoxidation but also other reactions within solvent-filled pores of microporous materials.

Authors:
 [1]; ORCiD logo [1];  [1]; ORCiD logo [1]
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  1. Univ. of Illinois at Urbana-Champaign, IL (United States)
Publication Date:
Research Org.:
Univ. of Illinois at Urbana-Champaign, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC); National Science Foundation (NSF)
OSTI Identifier:
1977251
Grant/Contract Number:  
SC0020224; DGE-1746047
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Catalysis
Additional Journal Information:
Journal Volume: 405; Journal Issue: C; Journal ID: ISSN 0021-9517
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Solvent effects; Hydrophobicity; Transition state theory; Solvent structure; Excess free energies

Citation Formats

Tan, Jun Zhi, Bregante, Daniel T., Torres, Chris, and Flaherty, David W. Transition state stabilization depends on solvent identity, pore size, and hydrophilicity for epoxidations in zeolites. United States: N. p., 2021. Web. doi:10.1016/j.jcat.2021.11.029.
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Tan, Jun Zhi, Bregante, Daniel T., Torres, Chris, & Flaherty, David W. Transition state stabilization depends on solvent identity, pore size, and hydrophilicity for epoxidations in zeolites. United States. https://doi.org/10.1016/j.jcat.2021.11.029
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Tan, Jun Zhi, Bregante, Daniel T., Torres, Chris, and Flaherty, David W. Fri . "Transition state stabilization depends on solvent identity, pore size, and hydrophilicity for epoxidations in zeolites". United States. https://doi.org/10.1016/j.jcat.2021.11.029. https://www.osti.gov/servlets/purl/1977251.
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@article{osti_1977251,
title = {Transition state stabilization depends on solvent identity, pore size, and hydrophilicity for epoxidations in zeolites},
author = {Tan, Jun Zhi and Bregante, Daniel T. and Torres, Chris and Flaherty, David W.},
abstractNote = {Ti-silicates activate H2O2 to form Ti-hydroperoxo and Ti-peroxo intermediates that can react with alkenes to form epoxide products. Comparisons of kinetics for 1-octene epoxidation with H2O2 on Ti-BEA and Ti-MFI catalysts with different hydrophilicities in methanol (CH3OH) or acetonitrile (CH3CN) solvents show the significance of the solvent for stabilizing catalytically-relevant species and the complex interdependencies between solvent, catalyst topology, and hydrophilicity. Epoxidation turnover rates are higher in CH3CN than CH3OH for Ti-BEA, but the opposite trend is observed for Ti-MFI. Ti-silicates with greater silanol densities, however, give greater epoxidation turnover rates than their hydrophobic counterparts in both solvents. Kinetic, spectroscopic, and thermodynamic analyses show that differences in turnover rates mainly arise from changes in the stabilization of reactive surface species by solvent mediated interactions, because the mechanism of the reaction and stability of the fluid-phase reactants remain similar in CH3CN and CH3OH. Specifically, apparent activation free energy values ($ΔG^{‡}_{App}$) indicate that surface intermediates responsible for alkene epoxidation are stabilized to a greater extent in CH3CN on Ti-BEA and in CH3OH on Ti-MFI. Hydrophilic Ti-silicates present lower ($ΔG^{‡}_{App}$) values regardless of solvent identity, which suggests that these differences correspond to the number of hydrogen-bonding solvent molecules found near reactive species bound to Ti active sites. Finally, taken together, these findings demonstrate the role of solvent molecules in allowing reactive intermediates to recognize the properties of active sites beyond the length-scale of covalent bonds, which carry implications for epoxidation but also other reactions within solvent-filled pores of microporous materials.},
doi = {10.1016/j.jcat.2021.11.029},
journal = {Journal of Catalysis},
number = C,
volume = 405,
place = {United States},
year = {Fri Nov 26 00:00:00 EST 2021},
month = {Fri Nov 26 00:00:00 EST 2021}
}
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Works referenced in this record:

Is 1-hexene epoxidation in TS-1 diffusion limited in different solvents?
journal, December 2006

Two Kinds of Framework Al Sites Studied in BEA Zeolite by X-ray Diffraction, Fourier Transform Infrared Spectroscopy, NMR Techniques, and V Probe
journal, November 2008

  • Hajjar, Redouane; Millot, Yannick; Man, Pascal P.
  • The Journal of Physical Chemistry C, Vol. 112, Issue 51
  • DOI: 10.1021/jp808356q

UV−Visible Diffuse Reflectance Spectroscopy of Zeolite-Hosted Mononuclear Titanium Oxide Species
journal, February 1997

  • Klaas, Joachim; Schulz-Ekloff, Günter; Jaeger, Nils I.
  • The Journal of Physical Chemistry B, Vol. 101, Issue 8
  • DOI: 10.1021/jp9627133

Influence of Hydrophilicity on the Snβ-Catalyzed Baeyer-Villiger Oxidation of Cyclohexanone with Aqueous Hydrogen Peroxide
journal, December 2016

Development of transition-state theory
journal, July 1983

  • Laidler, Keith J.; King, M. Christine
  • The Journal of Physical Chemistry, Vol. 87, Issue 15
  • DOI: 10.1021/j100238a002

Engineering of Transition Metal Catalysts Confined in Zeolites
journal, May 2018

Ti-Peroxo Species in the TS-1/H 2 O 2 /H 2 O System
journal, March 2004

  • Bonino, Francesca; Damin, Alessandro; Ricchiardi, Gabriele
  • The Journal of Physical Chemistry B, Vol. 108, Issue 11
  • DOI: 10.1021/jp036166e

Effect of the Confinement and Presence of Cations on Hydrogen Bonding of Water in LTA-Type Zeolite
journal, April 2014

  • Calero, S.; Gómez-Álvarez, P.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 17
  • DOI: 10.1021/jp5014847

In Situ UV Raman Spectroscopic Study on the Reaction Intermediates for Propylene Epoxidation on TS-1
journal, April 2012

  • Wang, Longlong; Xiong, Guang; Su, Ji
  • The Journal of Physical Chemistry C, Vol. 116, Issue 16
  • DOI: 10.1021/jp3017425

Dominant Role of Entropy in Stabilizing Sugar Isomerization Transition States within Hydrophobic Zeolite Pores
journal, September 2018

  • Cordon, Michael J.; Harris, James W.; Vega-Vila, Juan Carlos
  • Journal of the American Chemical Society, Vol. 140, Issue 43
  • DOI: 10.1021/jacs.8b08336

The shape of water in zeolites and its impact on epoxidation catalysis
journal, September 2021

Epoxidation of Lower Olefins with Hydrogen Peroxide and Titanium Silicalite
journal, March 1993

Shape Selective Epoxidation of Alkenes Catalyzed by Titanosilicate
journal, February 1990

  • Tatsumi, Takashi; Nakamura, Makoto; Yuasa, Kensei
  • Chemistry Letters, Vol. 19, Issue 2
  • DOI: 10.1246/cl.1990.297

Quantification of Intraporous Hydrophilic Binding Sites in Lewis Acid Zeolites and Consequences for Sugar Isomerization Catalysis
journal, September 2020

Factors that Determine Zeolite Stability in Hot Liquid Water
journal, September 2015

  • Zhang, Lu; Chen, Kuizhi; Chen, Banghao
  • Journal of the American Chemical Society, Vol. 137, Issue 36
  • DOI: 10.1021/jacs.5b07398

Reactivity of Surface Species in Heterogeneous Catalysts Probed by In Situ X-ray Absorption Techniques
journal, February 2013

  • Bordiga, Silvia; Groppo, Elena; Agostini, Giovanni
  • Chemical Reviews, Vol. 113, Issue 3
  • DOI: 10.1021/cr2000898

Effects of Si/Al Ratio on the Distribution of Framework Al and on the Rates of Alkane Monomolecular Cracking and Dehydrogenation in H-MFI
journal, December 2013

  • Janda, Amber; Bell, Alexis T.
  • Journal of the American Chemical Society, Vol. 135, Issue 51
  • DOI: 10.1021/ja4081937

The roles of different titanium species in TS-1 zeolite in propylene epoxidation studied by in situ UV Raman spectroscopy
journal, January 2016

  • Xiong, Guang; Cao, Yuanyuan; Guo, Zhendong
  • Physical Chemistry Chemical Physics, Vol. 18, Issue 1
  • DOI: 10.1039/C5CP05268H

Comparative Study of the Effect of Defects on Selective Adsorption of Butanol from Butanol/Water Binary Vapor Mixtures in Silicalite-1 Films
journal, August 2017

Vibrational Structure of Titanium Silicate Catalysts. A Spectroscopic and Theoretical Study
journal, November 2001

  • Ricchiardi, Gabriele; Damin, Alessandro; Bordiga, Silvia
  • Journal of the American Chemical Society, Vol. 123, Issue 46
  • DOI: 10.1021/ja010607v

The Nature and Catalytic Function of Cation Sites in Zeolites: a Computational Perspective
journal, October 2018

Lewis Acids as Catalysts in Oxidation Reactions:  From Homogeneous to Heterogeneous Systems
journal, October 2002

  • Corma, Avelino; García, Hermenegildo
  • Chemical Reviews, Vol. 102, Issue 10
  • DOI: 10.1021/cr010333u

Probing zeolites by vibrational spectroscopies
journal, January 2015

  • Bordiga, Silvia; Lamberti, Carlo; Bonino, Francesca
  • Chemical Society Reviews, Vol. 44, Issue 20
  • DOI: 10.1039/C5CS00396B

Structure and solvation of confined water and water–ethanol clusters within microporous Brønsted acids and their effects on ethanol dehydration catalysis
journal, January 2020

  • Bates, Jason S.; Bukowski, Brandon C.; Greeley, Jeffrey
  • Chemical Science, Vol. 11, Issue 27
  • DOI: 10.1039/D0SC02589E

Defect‐Mediated Ordering of Condensed Water Structures in Microporous Zeolites
journal, November 2019

  • Bukowski, Brandon C.; Bates, Jason S.; Gounder, Rajamani
  • Angewandte Chemie International Edition, Vol. 58, Issue 46
  • DOI: 10.1002/anie.201908151

Fluid catalytic cracking: recent developments on the grand old lady of zeolite catalysis
journal, January 2015

  • Vogt, E. T. C.; Weckhuysen, B. M.
  • Chemical Society Reviews, Vol. 44, Issue 20
  • DOI: 10.1039/C5CS00376H

Breaking Linear Scaling Relationships with Secondary Interactions in Confined Space: A Case Study of Methane Oxidation by Fe/ZSM-5 Zeolite
journal, September 2019

  • Szécsényi, Ágnes; Khramenkova, Elena; Chernyshov, Ivan Yu.
  • ACS Catalysis, Vol. 9, Issue 10
  • DOI: 10.1021/acscatal.9b01914

Cooperative Effects between Hydrophilic Pores and Solvents: Catalytic Consequences of Hydrogen Bonding on Alkene Epoxidation in Zeolites
journal, January 2019

  • Bregante, Daniel T.; Johnson, Alayna M.; Patel, Ami Y.
  • Journal of the American Chemical Society, Vol. 141, Issue 18
  • DOI: 10.1021/jacs.8b12861

Outer-Sphere Control of Catalysis on Surfaces: A Comparative Study of Ti(IV) Single-Sites Grafted on Amorphous versus Crystalline Silicates for Alkene Epoxidation
journal, March 2018

  • Grosso-Giordano, Nicolás A.; Schroeder, Christian; Okrut, Alexander
  • Journal of the American Chemical Society, Vol. 140, Issue 15
  • DOI: 10.1021/jacs.7b11467

Quantitative Sorption Experiments on Ti-Zeolites and Relation with α-Olefin Oxidation by H2O2
journal, October 1999

  • Langhendries, Gunther; De Vos, Dirk E.; Baron, Gino V.
  • Journal of Catalysis, Vol. 187, Issue 2
  • DOI: 10.1006/jcat.1999.2608

Zeolite titanium beta: A versatile epoxidation catalyst. Solvent effects
journal, October 1997

Effect of solvents on propylene epoxidation over TS-1 catalyst
journal, January 2008

Effect of temperature and branching on the nature and stability of alkene cracking intermediates in H-ZSM-5
journal, January 2017

Influence of Hydronium Ions in Zeolites on Sorption
journal, March 2019

  • Eckstein, Sebastian; Hintermeier, Peter H.; Zhao, Ruixue
  • Angewandte Chemie International Edition, Vol. 58, Issue 11
  • DOI: 10.1002/anie.201812184

Carbonylation of Dimethyl Ether to Methyl Acetate over SSZ-13
journal, December 2019

Hydrogen bonding of water confined in zeolites and their zeolitic imidazolate framework counterparts
journal, January 2014

Enhancing the catalytic activity of hydronium ions through constrained environments
journal, March 2017

  • Liu, Yuanshuai; Vjunov, Aleksei; Shi, Hui
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/ncomms14113

Nature of hydroxy groups in MCM-41
journal, January 1996

  • Jentys, Andreas; Pham, Ngan H.; Vinek, Hannelore
  • Journal of the Chemical Society, Faraday Transactions, Vol. 92, Issue 17
  • DOI: 10.1039/ft9969203287

Periodic Trends in Olefin Epoxidation over Group IV and V Framework-Substituted Zeolite Catalysts: A Kinetic and Spectroscopic Study
journal, May 2017

  • Bregante, Daniel T.; Flaherty, David W.
  • Journal of the American Chemical Society, Vol. 139, Issue 20
  • DOI: 10.1021/jacs.7b01422

Tuning the Adsorption Properties of Zeolites as Adsorbents for CO 2 Separation: Best Compromise between the Working Capacity and Selectivity
journal, May 2014

  • García, Edder J.; Pérez-Pellitero, Javier; Pirngruber, Gerhard D.
  • Industrial & Engineering Chemistry Research, Vol. 53, Issue 23
  • DOI: 10.1021/ie500207s

Catalytic Consequences of Oxidant, Alkene, and Pore Structures on Alkene Epoxidations within Titanium Silicates
journal, August 2020

Consequences of Confinement for Alkene Epoxidation with Hydrogen Peroxide on Highly Dispersed Group 4 and 5 Metal Oxide Catalysts
journal, February 2018

  • Bregante, Daniel T.; Thornburg, Nicholas E.; Notestein, Justin M.
  • ACS Catalysis, Vol. 8, Issue 4
  • DOI: 10.1021/acscatal.7b03986

Hydrophobic Zeolites for Biofuel Upgrading Reactions at the Liquid–Liquid Interface in Water/Oil Emulsions
journal, May 2012

  • Zapata, Paula A.; Faria, Jimmy; Ruiz, M. Pilar
  • Journal of the American Chemical Society, Vol. 134, Issue 20
  • DOI: 10.1021/ja3015082

Direct Synthesis and Characterization of Hydrophobic Aluminum-Free Ti−Beta Zeolite
journal, January 1998

  • Blasco, T.; Camblor, M. A.; Corma, A.
  • The Journal of Physical Chemistry B, Vol. 102, Issue 1
  • DOI: 10.1021/jp973288w

Catalytic epoxidation of alkenes with hydrogen peroxide over first mesoporous titanium-containing zeolite
journal, January 2000

  • Schmidt, Iver; Krogh, Anne; Wienberg, Katrine
  • Chemical Communications, Issue 21
  • DOI: 10.1039/b006460m

Hydrophobicity and catalytic properties of Ti-MFI zeolites synthesized by microwave and conventional heating
journal, February 2006

Kinetic and spectroscopic evidence for reaction pathways and intermediates for olefin epoxidation on Nb in *BEA
journal, April 2017

Water-Mediated Heterogeneously Catalyzed Reactions
journal, December 2019

Ordered Hydrogen-Bonded Alcohol Networks Confined in Lewis Acid Zeolites Accelerate Transfer Hydrogenation Turnover Rates
journal, October 2020

  • Di Iorio, John R.; Johnson, Blake A.; Román-Leshkov, Yuriy
  • Journal of the American Chemical Society, Vol. 142, Issue 45
  • DOI: 10.1021/jacs.0c09825

Titration and quantification of open and closed Lewis acid sites in Sn-Beta zeolites that catalyze glucose isomerization
journal, March 2016

Effects of Zeolite Structural Confinement on Adsorption Thermodynamics and Reaction Kinetics for Monomolecular Cracking and Dehydrogenation of n -Butane
journal, March 2016

  • Janda, Amber; Vlaisavljevich, Bess; Lin, Li-Chiang
  • Journal of the American Chemical Society, Vol. 138, Issue 14
  • DOI: 10.1021/jacs.5b11355

Solvent effects in the epoxidation reaction of 1-hexene with titanium silicalite-1 catalyst
journal, January 2008

Photocatalytic Reduction of CO 2 with H 2 O on Ti−β Zeolite Photocatalysts:  Effect of the Hydrophobic and Hydrophilic Properties
journal, September 2001

  • Ikeue, Keita; Yamashita, Hiromi; Anpo, Masakazu
  • The Journal of Physical Chemistry B, Vol. 105, Issue 35
  • DOI: 10.1021/jp010885g

Kinetics of Heterogeneous Catalytic Epoxidation of Propene with Hydrogen Peroxide over Titanium Silicalite (TS-1)
journal, September 2010

  • Shin, Sang Baek; Chadwick, David
  • Industrial & Engineering Chemistry Research, Vol. 49, Issue 17
  • DOI: 10.1021/ie100083u

Implications of Transition State Confinement within Small Voids for Acid Catalysis
journal, July 2014

  • Jones, Andrew J.; Zones, Stacey I.; Iglesia, Enrique
  • The Journal of Physical Chemistry C, Vol. 118, Issue 31
  • DOI: 10.1021/jp5050095

E factors, green chemistry and catalysis: an odyssey
journal, January 2008

Effect of solvent on the propylene epoxidation over TS-1 catalyst
journal, September 2004

Role of silanol groups in the incorporation of V in β zeolite
journal, April 2000

  • Dzwigaj, Stanislaw; Massiani, Pascale; Davidson, Anne
  • Journal of Molecular Catalysis A: Chemical, Vol. 155, Issue 1-2
  • DOI: 10.1016/S1381-1169(99)00332-5

The Roles of Entropy and Enthalpy in Stabilizing Ion-Pairs at Transition States in Zeolite Acid Catalysis
journal, August 2011

  • Gounder, Rajamani; Iglesia, Enrique
  • Accounts of Chemical Research, Vol. 45, Issue 2
  • DOI: 10.1021/ar200138n

Enthalpy and Entropy Barriers Explain the Effects of Topology on the Kinetics of Zeolite-Catalyzed Reactions
journal, July 2013

  • Van der Mynsbrugge, Jeroen; De Ridder, Jeroen; Hemelsoet, Karen
  • Chemistry - A European Journal, Vol. 19, Issue 35
  • DOI: 10.1002/chem.201301272

Adsorption properties of Fe-containing dealuminated BEA zeolites as revealed by FTIR spectroscopy
journal, June 2010

  • Hadjiivanov, Konstantin; Ivanova, Elena; Kefirov, Radoslav
  • Microporous and Mesoporous Materials, Vol. 131, Issue 1-3
  • DOI: 10.1016/j.micromeso.2009.11.034
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