skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Deactivation of Sn-Beta zeolites caused by structural transformation of hydrophobic to hydrophilic micropores during aqueous-phase glucose isomerization

Abstract

The structural changes underlying the deactivation of Sn-Beta zeolites under aqueous-phase reaction conditions at elevated temperatures (373 K) are investigated using spectroscopic characterization and site titration techniques together with turnover rates for glucose isomerization, a well-understood probe reaction for which changes in measured rates can be ascribed to specific changes in catalyst structure. In the case of hydrophobic, low-defect Sn-Beta zeolites (Sn-Beta-F), treatment in hot liquid water (373 K) for short times (<1 h) prior to reaction causes glucose–fructose isomerization turnover rates (per open Sn site, 373 K) to increase, while longer-term exposure (>3 h) to hot liquid water causes turnover rates to decrease and approach values characteristic of hydrophilic, defect-rich Sn-Beta zeolites (Sn-Beta-OH). However, turnover rates on hydrophilic Sn-Beta-OH zeolites are insensitive to the duration of hot liquid water exposure prior to reaction. Activation and deactivation phenomena on Sn-Beta-F zeolites occur concomitantly with the formation of silanol defects (by ~2–10×) with increasing durations (0–24 h) of hot water treatment, despite negligible differences in open and closed Sn site speciation as quantified ex situ by CD3CN IR spectra. Mechanistic interpretations of these phenomena suggest that silanol groups present at low densities serve as binding sites for water molecules and clusters,more » which confer enthalpic stability to kinetically-relevant hydride-shift transition states and increase turnover rates, while silanol groups present in higher densities stabilize extended hydrogen-bonded water networks, which entropically destabilize kinetically-relevant transition states and decrease turnover rates. Intraporous voids within hydrophobic Sn-Beta-F zeolites become increasingly hydrophilic as silanol groups are formed by hydrolysis of framework siloxane bridges with increasing durations of water treatment, thereby decreasing aqueous-phase glucose isomerization turnover rates (per open Sn site). These findings imply design strategies that suppress framework hydrolysis would attenuate the deactivation of Lewis acid zeolites in aqueous media.« less

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Purdue Univ., West Lafayette, IN (United States)
  2. California Inst. of Technology (CalTech), Pasadena, CA (United States)
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Sponsoring Org.:
USDOE Office of Science (SC); National Science Foundation (NSF)
OSTI Identifier:
1505311
Grant/Contract Number:  
AC05-00OR22725
Resource Type:
Accepted Manuscript
Journal Name:
Catalysis Science and Technology
Additional Journal Information:
Journal Volume: 9; Journal Issue: 7; Journal ID: ISSN 2044-4753
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Cordon, Michael J., Hall, Jacklyn N., Harris, James W., Bates, Jason S., Hwang, Son-Jong, and Gounder, Rajamani. Deactivation of Sn-Beta zeolites caused by structural transformation of hydrophobic to hydrophilic micropores during aqueous-phase glucose isomerization. United States: N. p., 2019. Web. doi:10.1039/c8cy02589d.
Cordon, Michael J., Hall, Jacklyn N., Harris, James W., Bates, Jason S., Hwang, Son-Jong, & Gounder, Rajamani. Deactivation of Sn-Beta zeolites caused by structural transformation of hydrophobic to hydrophilic micropores during aqueous-phase glucose isomerization. United States. doi:10.1039/c8cy02589d.
Cordon, Michael J., Hall, Jacklyn N., Harris, James W., Bates, Jason S., Hwang, Son-Jong, and Gounder, Rajamani. Tue . "Deactivation of Sn-Beta zeolites caused by structural transformation of hydrophobic to hydrophilic micropores during aqueous-phase glucose isomerization". United States. doi:10.1039/c8cy02589d. https://www.osti.gov/servlets/purl/1505311.
@article{osti_1505311,
title = {Deactivation of Sn-Beta zeolites caused by structural transformation of hydrophobic to hydrophilic micropores during aqueous-phase glucose isomerization},
author = {Cordon, Michael J. and Hall, Jacklyn N. and Harris, James W. and Bates, Jason S. and Hwang, Son-Jong and Gounder, Rajamani},
abstractNote = {The structural changes underlying the deactivation of Sn-Beta zeolites under aqueous-phase reaction conditions at elevated temperatures (373 K) are investigated using spectroscopic characterization and site titration techniques together with turnover rates for glucose isomerization, a well-understood probe reaction for which changes in measured rates can be ascribed to specific changes in catalyst structure. In the case of hydrophobic, low-defect Sn-Beta zeolites (Sn-Beta-F), treatment in hot liquid water (373 K) for short times (<1 h) prior to reaction causes glucose–fructose isomerization turnover rates (per open Sn site, 373 K) to increase, while longer-term exposure (>3 h) to hot liquid water causes turnover rates to decrease and approach values characteristic of hydrophilic, defect-rich Sn-Beta zeolites (Sn-Beta-OH). However, turnover rates on hydrophilic Sn-Beta-OH zeolites are insensitive to the duration of hot liquid water exposure prior to reaction. Activation and deactivation phenomena on Sn-Beta-F zeolites occur concomitantly with the formation of silanol defects (by ~2–10×) with increasing durations (0–24 h) of hot water treatment, despite negligible differences in open and closed Sn site speciation as quantified ex situ by CD3CN IR spectra. Mechanistic interpretations of these phenomena suggest that silanol groups present at low densities serve as binding sites for water molecules and clusters, which confer enthalpic stability to kinetically-relevant hydride-shift transition states and increase turnover rates, while silanol groups present in higher densities stabilize extended hydrogen-bonded water networks, which entropically destabilize kinetically-relevant transition states and decrease turnover rates. Intraporous voids within hydrophobic Sn-Beta-F zeolites become increasingly hydrophilic as silanol groups are formed by hydrolysis of framework siloxane bridges with increasing durations of water treatment, thereby decreasing aqueous-phase glucose isomerization turnover rates (per open Sn site). These findings imply design strategies that suppress framework hydrolysis would attenuate the deactivation of Lewis acid zeolites in aqueous media.},
doi = {10.1039/c8cy02589d},
journal = {Catalysis Science and Technology},
number = 7,
volume = 9,
place = {United States},
year = {2019},
month = {3}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 4 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

First principles, microkinetic, and experimental analysis of Lewis acid site speciation during ethanol dehydration on Sn-Beta zeolites
journal, September 2018


Overcoming catalyst deactivation during the continuous conversion of sugars to chemicals: maximising the performance of Sn-Beta with a little drop of water
journal, January 2018

  • Padovan, Daniele; Tolborg, Søren; Botti, Luca
  • Reaction Chemistry & Engineering, Vol. 3, Issue 2
  • DOI: 10.1039/C7RE00180K

Solvent Effects in Acid-Catalyzed Biomass Conversion Reactions
journal, September 2014

  • Mellmer, Max A.; Sener, Canan; Gallo, Jean Marcel R.
  • Angewandte Chemie International Edition, Vol. 53, Issue 44
  • DOI: 10.1002/anie.201408359

Beyond shape selective catalysis with zeolites: Hydrophobic void spaces in zeolites enable catalysis in liquid water
journal, January 2013

  • Gounder, Rajamani; Davis, Mark E.
  • AIChE Journal, Vol. 59, Issue 9, p. 3349-3358
  • DOI: 10.1002/aic.14016

Hydration Behavior under Confinement by Nanoscale Surfaces with Patterned Hydrophobicity and Hydrophilicity
journal, December 2006

  • Giovambattista, Nicolas; Debenedetti, Pablo G.; Rossky, Peter J.
  • The Journal of Physical Chemistry C, Vol. 111, Issue 3
  • DOI: 10.1021/jp065419b

Influence of confining environment polarity on ethanol dehydration catalysis by Lewis acid zeolites
journal, September 2018


Competitive Adsorption of Substrate and Solvent in Sn-Beta Zeolite During Sugar Isomerization
journal, October 2016

  • van der Graaff, William N. P.; Tempelman, Christiaan H. L.; Li, Guanna
  • ChemSusChem, Vol. 9, Issue 22
  • DOI: 10.1002/cssc.201600800

Rapid synthesis of Sn-Beta for the isomerization of cellulosic sugars
journal, January 2012

  • Chang, Chun-Chih; Wang, Zhuopeng; Dornath, Paul
  • RSC Advances, Vol. 2, Issue 28
  • DOI: 10.1039/c2ra21381h

Deactivation of solid catalysts in liquid media: the case of leaching of active sites in biomass conversion reactions
journal, January 2015

  • Sádaba, Irantzu; López Granados, Manuel; Riisager, Anders
  • Green Chemistry, Vol. 17, Issue 8
  • DOI: 10.1039/C5GC00804B

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

Metal Ion Roles and the Movement of Hydrogen during Reaction Catalyzed by D-Xylose Isomerase: A Joint X-Ray and Neutron Diffraction Study
journal, June 2010


Framework and Extraframework Tin Sites in Zeolite Beta React Glucose Differently
journal, November 2012

  • Bermejo-Deval, Ricardo; Gounder, Rajamani; Davis, Mark E.
  • ACS Catalysis, Vol. 2, Issue 12
  • DOI: 10.1021/cs300474x

Probing Lewis Acid Sites in Sn-Beta Zeolite
journal, February 2013

  • Roy, Sounak; Bakhmutsky, Kevin; Mahmoud, Eyas
  • ACS Catalysis, Vol. 3, Issue 4
  • DOI: 10.1021/cs300599z

A transmission infrared cell design for temperature-controlled adsorption and reactivity studies on heterogeneous catalysts
journal, October 2016

  • Cybulskis, Viktor J.; Harris, James W.; Zvinevich, Yury
  • Review of Scientific Instruments, Vol. 87, Issue 10
  • DOI: 10.1063/1.4963665

Controlled insertion of tin atoms into zeolite framework vacancies and consequences for glucose isomerization catalysis
journal, December 2016


High silica zeolites with three-dimensional systems of large pore channels
journal, November 2001

  • Camblor, Miguel A.; Barrett, Philip A.; Dı́az-Cabañas, Marı́a-José
  • Microporous and Mesoporous Materials, Vol. 48, Issue 1-3
  • DOI: 10.1016/S1387-1811(01)00325-0

Active Site Hydration Governs the Stability of Sn-Beta during Continuous Glucose Conversion
journal, June 2018


Monosaccharide and disaccharide isomerization over Lewis acid sites in hydrophobic and hydrophilic molecular sieves
journal, December 2013


Hierarchical Sn-MFI zeolites prepared by facile top-down methods for sugar isomerisation
journal, January 2014

  • Dapsens, Pierre Y.; Mondelli, Cecilia; Jagielski, Jakub
  • Catalysis Science & Technology, Vol. 4, Issue 8
  • DOI: 10.1039/c4cy00172a

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

Synthesis and luminescence properties of SnO2 nanoparticles
journal, April 2003


Influence of Fluorine on the Catalytic Performance of Ti−Beta Zeolite
journal, April 2004

  • Goa, Yasuhide; Wu, Peng; Tatsumi, Takashi
  • The Journal of Physical Chemistry B, Vol. 108, Issue 14
  • DOI: 10.1021/jp049505s

NMR Signatures of the Active Sites in Sn-β Zeolite
journal, July 2014

  • Wolf, Patrick; Valla, Maxence; Rossini, Aaron J.
  • Angewandte Chemie International Edition, Vol. 53, Issue 38
  • DOI: 10.1002/anie.201403905

Sn-MFI molecular sieves: synthesis methods, 29Si liquid and solid MAS-NMR, 119Sn static and MAS NMR studies
journal, December 1997


Stability of Zeolites in Aqueous Phase Reactions
journal, August 2017


Synthesis of Hierarchical Sn-MFI as Lewis Acid Catalysts for Isomerization of Cellulosic Sugars
journal, April 2014

  • Cho, Hong Je; Dornath, Paul; Fan, Wei
  • ACS Catalysis, Vol. 4, Issue 6
  • DOI: 10.1021/cs500295u

A Continuous Flow Strategy for the Coupled Transfer Hydrogenation and Etherification of 5-(Hydroxymethyl)furfural using Lewis Acid Zeolites
journal, July 2014

  • Lewis, Jennifer D.; Van de Vyver, Stijn; Crisci, Anthony J.
  • ChemSusChem, Vol. 7, Issue 8
  • DOI: 10.1002/cssc.201402100

Influence of Composition and Preparation Method on the Continuous Performance of Sn-Beta for Glucose-Fructose Isomerisation
journal, November 2018


Intensification and deactivation of Sn-beta investigated in the continuous regime
journal, January 2016

  • Padovan, Daniele; Parsons, Charlie; Simplicio Grasina, Manuel
  • Green Chemistry, Vol. 18, Issue 18
  • DOI: 10.1039/C6GC01288D

Sustainable Solvent Systems for Use in Tandem Carbohydrate Dehydration Hydrogenation
journal, March 2013

  • Tucker, Mark H.; Alamillo, Ricardo; Crisci, Anthony J.
  • ACS Sustainable Chemistry & Engineering, Vol. 1, Issue 5
  • DOI: 10.1021/sc400044d

Silylated hydrophobic zeolites with enhanced tolerance to hot liquid water
journal, December 2013


Synthesis of Sn-Beta with Exclusive and High Framework Sn Content
journal, February 2015

  • van der Graaff, William N. P.; Li, Guanna; Mezari, Brahim
  • ChemCatChem, Vol. 7, Issue 7
  • DOI: 10.1002/cctc.201403050

Analysis of the Reaction Mechanism and Catalytic Activity of Metal-Substituted Beta Zeolite for the Isomerization of Glucose to Fructose
journal, April 2014

  • Li, Yi-Pei; Head-Gordon, Martin; Bell, Alexis T.
  • ACS Catalysis, Vol. 4, Issue 5
  • DOI: 10.1021/cs401054f

Uniform Catalytic Site in Sn-β-Zeolite Determined Using X-ray Absorption Fine Structure
journal, September 2005

  • Bare, Simon R.; Kelly, Shelly D.; Sinkler, Wharton
  • Journal of the American Chemical Society, Vol. 127, Issue 37
  • DOI: 10.1021/ja052543k

Active Sites in Sn-Beta for Glucose Isomerization to Fructose and Epimerization to Mannose
journal, May 2014

  • Bermejo-Deval, Ricardo; Orazov, Marat; Gounder, Rajamani
  • ACS Catalysis, Vol. 4, Issue 7, p. 2288-2297
  • DOI: 10.1021/cs500466j

Deactivation of Sn-Beta during carbohydrate conversion
journal, August 2018

  • van der Graaff, William N. P.; Tempelman, Christiaan H. L.; Hendriks, Frank C.
  • Applied Catalysis A: General, Vol. 564
  • DOI: 10.1016/j.apcata.2018.07.023

Elucidation of Anchoring and Restructuring Steps during Synthesis of Silica-Supported Vanadium Oxide Catalysts
journal, June 2016


An Inner-/Outer-Sphere Stabilized Sn Active Site in β-Zeolite: Spectroscopic Evidence and Kinetic Consequences
journal, November 2015


Spontaneous nucleation and growth of pure silica zeolite-? free of connectivity defects
journal, January 1996

  • Camblor, Miguel A.; Corma, Avelino; Valencia, Susana
  • Chemical Communications, Issue 20
  • DOI: 10.1039/cc9960002365

119 Sn MAS NMR Study of the Interaction of Probe Molecules with Sn-BEA: The Origin of Penta- and Hexacoordinated Tin Formation
journal, December 2016

  • Yakimov, Alexander V.; Kolyagin, Yury G.; Tolborg, Søren
  • The Journal of Physical Chemistry C, Vol. 120, Issue 49
  • DOI: 10.1021/acs.jpcc.6b09999

Scaling Relationships for Molecular Adsorption and Dissociation in Lewis Acid Zeolites
journal, March 2016

  • Bukowski, Brandon C.; Greeley, Jeffrey
  • The Journal of Physical Chemistry C, Vol. 120, Issue 12
  • DOI: 10.1021/acs.jpcc.6b01157

Water Interactions in Zeolite Catalysts and Their Hydrophobically Modified Analogues
journal, November 2015


Synergy between Lewis acid sites and hydroxyl groups for the isomerization of glucose to fructose over Sn-containing zeolites: a theoretical perspective
journal, January 2014

  • Li, Guanna; Pidko, Evgeny A.; Hensen, Emiel J. M.
  • Catal. Sci. Technol., Vol. 4, Issue 8
  • DOI: 10.1039/C4CY00186A

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

Impact of structural defects and hydronium ion concentration on the stability of zeolite BEA in aqueous phase
journal, December 2018


Metalloenzyme-like catalyzed isomerizations of sugars by Lewis acid zeolites
journal, June 2012

  • Bermejo-Deval, R.; Assary, R. S.; Nikolla, E.
  • Proceedings of the National Academy of Sciences, Vol. 109, Issue 25
  • DOI: 10.1073/pnas.1206708109

Deactivation mechanisms of tin-zeolites in biomass conversions
journal, January 2016

  • Lari, G. M.; Dapsens, P. Y.; Scholz, D.
  • Green Chemistry, Vol. 18, Issue 5
  • DOI: 10.1039/C5GC02147B

Hydrophobic properties of zeolites
journal, January 1976


Impact of Zeolite Aging in Hot Liquid Water on Activity for Acid-Catalyzed Dehydration of Alcohols
journal, August 2015

  • Vjunov, Aleksei; Derewinski, Miroslaw A.; Fulton, John L.
  • Journal of the American Chemical Society, Vol. 137, Issue 32
  • DOI: 10.1021/jacs.5b06169

Stability of Zeolites in Hot Liquid Water
journal, November 2010

  • Ravenelle, Ryan M.; Schüβler, Florian; D’Amico, Andrew
  • The Journal of Physical Chemistry C, Vol. 114, Issue 46
  • DOI: 10.1021/jp104639e

Heterogeneous Catalysis for the Conversion of Sugars into Polymers
journal, April 2015


Solid State NMR Characterization of Sn-Beta Zeolites that Catalyze Glucose Isomerization and Epimerization
journal, March 2015

  • Hwang, Son-Jong; Gounder, Rajamani; Bhawe, Yashodhan
  • Topics in Catalysis, Vol. 58, Issue 7-9
  • DOI: 10.1007/s11244-015-0388-7

Molecular Structure and Confining Environment of Sn Sites in Single-Site Chabazite Zeolites
journal, October 2017


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


Tin-containing zeolites are highly active catalysts for the isomerization of glucose in water
journal, March 2010

  • Moliner, M.; Roman-Leshkov, Y.; Davis, M. E.
  • Proceedings of the National Academy of Sciences, Vol. 107, Issue 14, p. 6164-6168
  • DOI: 10.1073/pnas.1002358107

Operando Solid-State NMR Observation of Solvent-Mediated Adsorption-Reaction of Carbohydrates in Zeolites
journal, April 2017


Periodic Trends in Highly Dispersed Groups IV and V Supported Metal Oxide Catalysts for Alkene Epoxidation with H 2 O 2
journal, August 2015

  • Thornburg, Nicholas E.; Thompson, Anthony B.; Notestein, Justin M.
  • ACS Catalysis, Vol. 5, Issue 9
  • DOI: 10.1021/acscatal.5b01105

Solvent-enabled control of reactivity for liquid-phase reactions of biomass-derived compounds
journal, February 2018

  • Mellmer, Max A.; Sanpitakseree, Chotitath; Demir, Benginur
  • Nature Catalysis, Vol. 1, Issue 3
  • DOI: 10.1038/s41929-018-0027-3

Mechanism of Glucose Isomerization Using a Solid Lewis Acid Catalyst in Water
journal, October 2010

  • Román-Leshkov, Yuriy; Moliner, Manuel; Labinger, Jay A.
  • Angewandte Chemie International Edition, Vol. 49, Issue 47, p. 8954-8957
  • DOI: 10.1002/anie.201004689

Revisiting Acidity of SnBEA Catalysts by Combined Application of FTIR Spectroscopy of Different Probe Molecules
journal, May 2017

  • Sushkevich, Vitaly L.; Ivanova, Irina I.; Yakimov, Alexander V.
  • The Journal of Physical Chemistry C, Vol. 121, Issue 21
  • DOI: 10.1021/acs.jpcc.7b02206