The origin of selectivity in the conversion of glucose to fructose and mannose in Sn-BEA and Na-exchanged Sn-BEA zeolites

Li, Sha; Josephson, Tyler; Vlachos, Dionisios G; Caratzoulas, Stavros

doi:10.1016/j.jcat.2017.09.001

Title: The origin of selectivity in the conversion of glucose to fructose and mannose in Sn-BEA and Na-exchanged Sn-BEA zeolites

Abstract

Here, we investigate the isomerization and epimerization of glucose to fructose and mannose in Sn-BEA and Na-exchanged Sn-BEA using density-functional theory calculations on periodic BEA crystals. We compare reaction pathways both in the absence and presence of water molecules in the vicinity of the active site and find that water effectively determines the selectivity in Na-Sn-BEA. We identify two competing epimerization pathways, one involving direct 1,2-carbon shift and the other involving 1,2-hydride shift via fructose. In Sn-BEA, the isomerization to fructose is the kinetically dominant pathway, while mannose is formed via the indirect 1,2-hydride shift epimerization pathway. In Na-Sn-BEA, the kinetically dominant pathway is epimerization to mannose via the direct 1,2-carbon shift pathway (Bilik mechanism) only in the presence of water solvent in the vicinity of the active site, whereas isomerization is preferred in the absence of water. We argue that polar water molecules that coordinate around the Na cation screen strong electrostatic interactions between Na+ and the glucose backbone that are responsible for the strong inhibition of the 1,2-carbon shift mechanism in the absence of water. In Sn-BEA, the presence of water does not influence the selectivity. Our calculations resolve for the first time the role of water andmore »« less

Authors:

Li, Sha ^[1]; Josephson, Tyler ^[1]; Vlachos, Dionisios G ^[1]; Caratzoulas, Stavros ^[1]

Energy Frontier Research Centers (EFRC) (United States). Catalysis Center for Energy Innovation (CCEI); Univ. of Delaware, Newark, DE (United States)

Publication Date:: Thu Sep 21 00:00:00 EDT 2017

Research Org.:: Energy Frontier Research Centers (EFRC) (United States). Catalysis Center for Energy Innovation (CCEI); Univ. of Delaware, Newark, DE (United States); Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

OSTI Identifier:: 1662010

Alternate Identifier(s):: OSTI ID: 1549216

Grant/Contract Number:: SC0001004; AC02-05CH11231

Resource Type:: Accepted Manuscript

Journal Name:: Journal of Catalysis

Additional Journal Information:: Journal Volume: 355; Journal ID: ISSN 0021-9517

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Glucose isomerization; Glucose epimerization; Sn-BEA zeolite; Na-exchanged Sn-BEA zeolite; Periodic density-functional theory

Citation Formats


                    Li, Sha, Josephson, Tyler, Vlachos, Dionisios G, and Caratzoulas, Stavros. The origin of selectivity in the conversion of glucose to fructose and mannose in Sn-BEA and Na-exchanged Sn-BEA zeolites.  United States: N. p., 2017. 
Web.  doi:10.1016/j.jcat.2017.09.001.

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                    Li, Sha, Josephson, Tyler, Vlachos, Dionisios G, & Caratzoulas, Stavros. The origin of selectivity in the conversion of glucose to fructose and mannose in Sn-BEA and Na-exchanged Sn-BEA zeolites.  United States.  https://doi.org/10.1016/j.jcat.2017.09.001

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                    Li, Sha, Josephson, Tyler, Vlachos, Dionisios G, and Caratzoulas, Stavros. Thu .  
"The origin of selectivity in the conversion of glucose to fructose and mannose in Sn-BEA and Na-exchanged Sn-BEA zeolites".  United States.  https://doi.org/10.1016/j.jcat.2017.09.001.  https://www.osti.gov/servlets/purl/1662010.

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@article{osti_1662010,

  title        = {The origin of selectivity in the conversion of glucose to fructose and mannose in Sn-BEA and Na-exchanged Sn-BEA zeolites},

  author       = {Li, Sha and Josephson, Tyler and Vlachos, Dionisios G and Caratzoulas, Stavros},

  abstractNote = {Here, we investigate the isomerization and epimerization of glucose to fructose and mannose in Sn-BEA and Na-exchanged Sn-BEA using density-functional theory calculations on periodic BEA crystals. We compare reaction pathways both in the absence and presence of water molecules in the vicinity of the active site and find that water effectively determines the selectivity in Na-Sn-BEA. We identify two competing epimerization pathways, one involving direct 1,2-carbon shift and the other involving 1,2-hydride shift via fructose. In Sn-BEA, the isomerization to fructose is the kinetically dominant pathway, while mannose is formed via the indirect 1,2-hydride shift epimerization pathway. In Na-Sn-BEA, the kinetically dominant pathway is epimerization to mannose via the direct 1,2-carbon shift pathway (Bilik mechanism) only in the presence of water solvent in the vicinity of the active site, whereas isomerization is preferred in the absence of water. We argue that polar water molecules that coordinate around the Na cation screen strong electrostatic interactions between Na+ and the glucose backbone that are responsible for the strong inhibition of the 1,2-carbon shift mechanism in the absence of water. In Sn-BEA, the presence of water does not influence the selectivity. Our calculations resolve for the first time the role of water and Na cations in the catalytic activity of Sn-BEA, and rationalize the experimental data.},

  doi          = {10.1016/j.jcat.2017.09.001},

  journal      = {Journal of Catalysis},

  number       = ,

  volume       = 355,

  place        = {United States},

  year         = {Thu Sep 21 00:00:00 EDT 2017},

  month        = {Thu Sep 21 00:00:00 EDT 2017}

}

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Title: The origin of selectivity in the conversion of glucose to fructose and mannose in Sn-BEA and Na-exchanged Sn-BEA zeolites

Abstract

Citation Formats

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Selective and Shape-Selective Baeyer–Villiger Oxidations of Aromatic Aldehydes and Cyclic Ketones with Sn-Beta Zeolites and H2O2 journal, October 2002

Al-Free Sn-Beta Zeolite as a Catalyst for the Selective Reduction of Carbonyl Compounds (Meerwein−Ponndorf−Verley Reaction) journal, April 2002

Water-resistant solid Lewis acid catalysts: Meerwein–Ponndorf–Verley and Oppenauer reactions catalyzed by tin-beta zeolite journal, April 2003

Solid Lewis Acids Catalyze the Carbon–Carbon Coupling between Carbohydrates and Formaldehyde journal, January 2015

Synthesis of terephthalic acid via Diels-Alder reactions with ethylene and oxidized variants of 5-hydroxymethylfurfural journal, May 2014

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

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

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

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

Tin-containing zeolite for the isomerization of cellulosic sugars journal, May 2012

“One-Pot” Synthesis of 5-(Hydroxymethyl)furfural from Carbohydrates using Tin-Beta Zeolite journal, April 2011

Tin Silsesquioxanes as Models for the “Open” Site in Tin-Containing Zeolite Beta journal, November 2015

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

Correlating Synthetic Methods, Morphology, Atomic-Level Structure, and Catalytic Activity of Sn-β Catalysts journal, May 2016

Computational Insight into the Effect of Sn-Beta Na Exchange and Solvent on Glucose Isomerization and Epimerization journal, August 2015

Role of Silanol Group in Sn-Beta Zeolite for Glucose Isomerization and Epimerization Reactions journal, September 2013

The Mechanism of Glucose Isomerization to Fructose over Sn-BEA Zeolite: A Periodic Density Functional Theory Study journal, August 2013

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

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

Determination of the catalytically active oxidation Lewis acid sites in Sn-beta zeolites, and their optimisation by the combination of theoretical and experimental studies journal, August 2005

Effect of water treatment on Sn-BEA zeolite: Origin of 960 cm−1 FTIR peak journal, July 2015

Comparison of Homogeneous and Heterogeneous Catalysts for Glucose-to-Fructose Isomerization in Aqueous Media journal, September 2013

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

Distribution of open sites in Sn-Beta zeolite journal, June 2017

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

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

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

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

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

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

Quantitative NMR Approach to Optimize the Formation of Chemical Building Blocks from Abundant Carbohydrates journal, July 2017

From ultrasoft pseudopotentials to the projector augmented-wave method journal, January 1999

Projector augmented-wave method journal, December 1994

Effect of the damping function in dispersion corrected density functional theory journal, March 2011

A climbing image nudged elastic band method for finding saddle points and minimum energy paths journal, December 2000

Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points journal, December 2000

Structural, Electronic, and Bonding Properties of Zeolite Sn-Beta: A Periodic Density Functional Theory Study journal, January 2006

Structure, Stability, and Lewis Acidity of Mono and Double Ti, Zr, and Sn Framework Substitutions in BEA Zeolites: A Periodic Density Functional Theory Study journal, February 2013

Identifying Sn Site Heterogeneities Prevalent Among Sn-Beta Zeolites journal, November 2016

Structural Characterization of Zeolite Beta journal, December 1988

Modification of Sn-Beta zeolite: characterization of acidic/basic properties and catalytic performance in Baeyer–Villiger oxidation journal, January 2016

Insights into the isomerization of xylose to xylulose and lyxose by a Lewis acid catalyst journal, March 2013

Effects of Alkali-Metal Ions and Counter Ions in Sn-Beta-Catalyzed Carbohydrate Conversion journal, March 2018

Efficient Epimerization of Glucose to Mannose over Molybdenum‐Based Catalyst in Aqueous Media journal, February 2020

Kinetic analysis of hexose conversion to methyl lactate by Sn-Beta: effects of substrate masking and of water journal, January 2018

Expeditious isomerization of glucose to fructose in aqueous media over sodium titanate nanotubes journal, January 2018

Tin modified Nb 2 O 5 as an efficient solid acid catalyst for the catalytic conversion of triose sugars to lactic acid journal, January 2019

Stoichiometric active site modification observed by alkali ion titrations of Sn-Beta journal, January 2019

Sn–Al-USY for the valorization of glucose to methyl lactate: switching from hydrolytic to retro-aldol activity by alkaline ion exchange journal, January 2019

Connecting Biomass and Petroleum Processing with a Chemical Bridge
journal, July 2010

Catalytic conversion of lignocellulosic biomass to fine chemicals and fuels
journal, January 2011

Production of Lactic Acid/Lactates from Biomass and Their Catalytic Transformations to Commodities
journal, November 2013

Towards the conversion of carbohydrate biomass feedstocks to biofuels via hydroxylmethylfurfural
journal, January 2010

Hydroxymethylfurfural, A Versatile Platform Chemical Made from Renewable Resources
journal, February 2013

Kinetics of Homogeneous Brønsted Acid Catalyzed Fructose Dehydration and 5-Hydroxymethyl Furfural Rehydration: A Combined Experimental and Computational Study
journal, December 2013

Efficient conversion of glucose into 5-hydroxymethylfurfural catalyzed by a common Lewis acid SnCl4 in an ionic liquid
journal, January 2009

Efficient process for conversion of fructose to 5-hydroxymethylfurfural with ionic liquids
journal, January 2009

Sn-zeolite beta as a heterogeneous chemoselective catalyst for Baeyer–Villiger oxidations
journal, July 2001

Selective and Shape-Selective Baeyer–Villiger Oxidations of Aromatic Aldehydes and Cyclic Ketones with Sn-Beta Zeolites and H2O2
journal, October 2002

Al-Free Sn-Beta Zeolite as a Catalyst for the Selective Reduction of Carbonyl Compounds (Meerwein−Ponndorf−Verley Reaction)
journal, April 2002

Water-resistant solid Lewis acid catalysts: Meerwein–Ponndorf–Verley and Oppenauer reactions catalyzed by tin-beta zeolite
journal, April 2003

Solid Lewis Acids Catalyze the Carbon–Carbon Coupling between Carbohydrates and Formaldehyde
journal, January 2015

Synthesis of terephthalic acid via Diels-Alder reactions with ethylene and oxidized variants of 5-hydroxymethylfurfural
journal, May 2014

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

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

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

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

Tin-containing zeolite for the isomerization of cellulosic sugars
journal, May 2012

“One-Pot” Synthesis of 5-(Hydroxymethyl)furfural from Carbohydrates using Tin-Beta Zeolite
journal, April 2011

Tin Silsesquioxanes as Models for the “Open” Site in Tin-Containing Zeolite Beta
journal, November 2015

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

Correlating Synthetic Methods, Morphology, Atomic-Level Structure, and Catalytic Activity of Sn-β Catalysts
journal, May 2016

Computational Insight into the Effect of Sn-Beta Na Exchange and Solvent on Glucose Isomerization and Epimerization
journal, August 2015

Role of Silanol Group in Sn-Beta Zeolite for Glucose Isomerization and Epimerization Reactions
journal, September 2013

The Mechanism of Glucose Isomerization to Fructose over Sn-BEA Zeolite: A Periodic Density Functional Theory Study
journal, August 2013

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

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

Determination of the catalytically active oxidation Lewis acid sites in Sn-beta zeolites, and their optimisation by the combination of theoretical and experimental studies
journal, August 2005

Effect of water treatment on Sn-BEA zeolite: Origin of 960 cm−1 FTIR peak
journal, July 2015

Comparison of Homogeneous and Heterogeneous Catalysts for Glucose-to-Fructose Isomerization in Aqueous Media
journal, September 2013

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

Distribution of open sites in Sn-Beta zeolite
journal, June 2017

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

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

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

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

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

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

Quantitative NMR Approach to Optimize the Formation of Chemical Building Blocks from Abundant Carbohydrates
journal, July 2017

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999

Projector augmented-wave method
journal, December 1994

Effect of the damping function in dispersion corrected density functional theory
journal, March 2011

A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000

Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points
journal, December 2000

Structural, Electronic, and Bonding Properties of Zeolite Sn-Beta: A Periodic Density Functional Theory Study
journal, January 2006

Structure, Stability, and Lewis Acidity of Mono and Double Ti, Zr, and Sn Framework Substitutions in BEA Zeolites: A Periodic Density Functional Theory Study
journal, February 2013

Identifying Sn Site Heterogeneities Prevalent Among Sn-Beta Zeolites
journal, November 2016

Structural Characterization of Zeolite Beta
journal, December 1988

Modification of Sn-Beta zeolite: characterization of acidic/basic properties and catalytic performance in Baeyer–Villiger oxidation
journal, January 2016

Insights into the isomerization of xylose to xylulose and lyxose by a Lewis acid catalyst
journal, March 2013

Effects of Alkali-Metal Ions and Counter Ions in Sn-Beta-Catalyzed Carbohydrate Conversion
journal, March 2018

Efficient Epimerization of Glucose to Mannose over Molybdenum‐Based Catalyst in Aqueous Media
journal, February 2020

Kinetic analysis of hexose conversion to methyl lactate by Sn-Beta: effects of substrate masking and of water
journal, January 2018

Expeditious isomerization of glucose to fructose in aqueous media over sodium titanate nanotubes
journal, January 2018

Tin modified Nb ₂ O ₅ as an efficient solid acid catalyst for the catalytic conversion of triose sugars to lactic acid
journal, January 2019

Stoichiometric active site modification observed by alkali ion titrations of Sn-Beta
journal, January 2019

Sn–Al-USY for the valorization of glucose to methyl lactate: switching from hydrolytic to retro-aldol activity by alkaline ion exchange
journal, January 2019