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

Journal Article · Wed Nov 01 00:00:00 EDT 2017 · Journal of Catalysis

DOI:https://doi.org/10.1016/j.jcat.2017.09.001· OSTI ID:1463646

Li, Sha ^[1]; Josephson, Tyler ^[1]; Vlachos, Dionisios G. ^[1]; Caratzoulas, Stavros ^[2]

University of Delaware, Newark, DE (United States). Catalysis Center for Energy Innovation; University of Delaware, Newark, DE (United States). Department of Chemical and Biomolecular Engineering
University of Delaware, Newark, DE (United States). Catalysis Center for Energy Innovation

We investigate the isomerization and epimerization of glucose to fructose and mannose in Sn-BEA andNa-exchanged Sn-BEA using density-functional theory calculations on periodic BEA crystals. We comparereaction pathways both in the absence and presence of water molecules in the vicinity of the active siteand find that water effectively determines the selectivity in Na-Sn-BEA. We identify two competingepimerization pathways, one involving direct 1,2-carbon shift and the other involving 1,2-hydride shiftvia fructose. In Sn-BEA, the isomerization to fructose is the kinetically dominant pathway, while mannoseis formed via the indirect 1,2-hydride shift epimerization pathway. In Na-Sn-BEA, the kinetically domi-nant 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 preferredin the absence of water. We argue that polar water molecules that coordinate around the Na cation screenstrong electrostatic interactions between Na+and the glucose backbone that are responsible for thestrong inhibition of the 1,2-carbon shift mechanism in the absence of water. In Sn-BEA, the presenceof water does not influence the selectivity. Our calculations resolve for the first time the role of waterand Na cations in the catalytic activity of Sn-BEA, and rationalize the experimental data.

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Research Organization:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Energy Frontier Research Centers (EFRC) (United States). Catalysis Center for Energy Innovation (CCEI)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR)

DOE Contract Number:: SC0001004; AC02-05CH11231

OSTI ID:: 1463646

Journal Information:: Journal of Catalysis, Vol. 355, Issue C; ISSN 0021-9517

Publisher:: Elsevier

Country of Publication:: United States

Language:: English

References (51)

Connecting Biomass and Petroleum Processing with a Chemical Bridge Bozell, Joseph J. Science, Vol. 329, Issue 5991, p. 522-523 https://doi.org/10.1126/science.1191662	journal	July 2010
Catalytic conversion of lignocellulosic biomass to fine chemicals and fuels Zhou, Chun-Hui; Xia, Xi; Lin, Chun-Xiang Chemical Society Reviews, Vol. 40, Issue 11 https://doi.org/10.1039/c1cs15124j	journal	January 2011
Production of Lactic Acid/Lactates from Biomass and Their Catalytic Transformations to Commodities Mäki-Arvela, Päivi; Simakova, Irina L.; Salmi, Tapio Chemical Reviews, Vol. 114, Issue 3 https://doi.org/10.1021/cr400203v	journal	November 2013
Towards the conversion of carbohydrate biomass feedstocks to biofuels via hydroxylmethylfurfural James, Olusola O.; Maity, Sudip; Usman, Lamidi Ajao Energy & Environmental Science, Vol. 3, Issue 12 https://doi.org/10.1039/b925869h	journal	January 2010
Hydroxymethylfurfural, A Versatile Platform Chemical Made from Renewable Resources van Putten, Robert-Jan; van der Waal, Jan C.; de Jong, Ed Chemical Reviews, Vol. 113, Issue 3 https://doi.org/10.1021/cr300182k	journal	February 2013
Kinetics of Homogeneous Brønsted Acid Catalyzed Fructose Dehydration and 5-Hydroxymethyl Furfural Rehydration: A Combined Experimental and Computational Study Swift, T. Dallas; Bagia, Christina; Choudhary, Vinit ACS Catalysis, Vol. 4, Issue 1 https://doi.org/10.1021/cs4009495	journal	December 2013
Efficient conversion of glucose into 5-hydroxymethylfurfural catalyzed by a common Lewis acid SnCl4 in an ionic liquid Hu, Suqin; Zhang, Zhaofu; Song, Jinliang Green Chemistry, Vol. 11, Issue 11 https://doi.org/10.1039/b914601f	journal	January 2009
Efficient process for conversion of fructose to 5-hydroxymethylfurfural with ionic liquids Qi, Xinhua; Watanabe, Masaru; Aida, Taku M. Green Chemistry, Vol. 11, Issue 9 https://doi.org/10.1039/b905975j	journal	January 2009
Sn-zeolite beta as a heterogeneous chemoselective catalyst for Baeyer–Villiger oxidations Corma, Avelino; Nemeth, Laszlo T.; Renz, Michael Nature, Vol. 412, Issue 6845 https://doi.org/10.1038/35086546	journal	July 2001
Selective and Shape-Selective Baeyer–Villiger Oxidations of Aromatic Aldehydes and Cyclic Ketones with Sn-Beta Zeolites and H2O2 Renz, Michael; Blasco, Teresa; Corma, Avelino Chemistry - A European Journal, Vol. 8, Issue 20 https://doi.org/10.1002/1521-3765(20021018)8:20<4708::AID-CHEM4708>3.0.CO;2-U	journal	October 2002
Al-Free Sn-Beta Zeolite as a Catalyst for the Selective Reduction of Carbonyl Compounds (Meerwein−Ponndorf−Verley Reaction) Corma, Avelino; Domine, Marcelo E.; Nemeth, Laszlo Journal of the American Chemical Society, Vol. 124, Issue 13, p. 3194-3195 https://doi.org/10.1021/ja012297m	journal	April 2002
Water-resistant solid Lewis acid catalysts: Meerwein–Ponndorf–Verley and Oppenauer reactions catalyzed by tin-beta zeolite Corma, A. Journal of Catalysis, Vol. 215, Issue 2 https://doi.org/10.1016/S0021-9517(03)00014-9	journal	April 2003
Solid Lewis Acids Catalyze the Carbon–Carbon Coupling between Carbohydrates and Formaldehyde Van de Vyver, Stijn; Odermatt, Caroline; Romero, Kevin ACS Catalysis, Vol. 5, Issue 2 https://doi.org/10.1021/cs5015964	journal	January 2015
Synthesis of terephthalic acid via Diels-Alder reactions with ethylene and oxidized variants of 5-hydroxymethylfurfural Pacheco, J. J.; Davis, M. E. Proceedings of the National Academy of Sciences, Vol. 111, Issue 23 https://doi.org/10.1073/pnas.1408345111	journal	May 2014
Tin-containing zeolites are highly active catalysts for the isomerization of glucose in water Moliner, M.; Roman-Leshkov, Y.; Davis, M. E. Proceedings of the National Academy of Sciences, Vol. 107, Issue 14, p. 6164-6168 https://doi.org/10.1073/pnas.1002358107	journal	March 2010
Framework and Extraframework Tin Sites in Zeolite Beta React Glucose Differently Bermejo-Deval, Ricardo; Gounder, Rajamani; Davis, Mark E. ACS Catalysis, Vol. 2, Issue 12 https://doi.org/10.1021/cs300474x	journal	November 2012
Metalloenzyme-like catalyzed isomerizations of sugars by Lewis acid zeolites Bermejo-Deval, R.; Assary, R. S.; Nikolla, E. Proceedings of the National Academy of Sciences, Vol. 109, Issue 25 https://doi.org/10.1073/pnas.1206708109	journal	June 2012
Active Sites in Sn-Beta for Glucose Isomerization to Fructose and Epimerization to Mannose Bermejo-Deval, Ricardo; Orazov, Marat; Gounder, Rajamani ACS Catalysis, Vol. 4, Issue 7, p. 2288-2297 https://doi.org/10.1021/cs500466j	journal	May 2014
Tin-containing zeolite for the isomerization of cellulosic sugars Lew, Christopher M.; Rajabbeigi, Nafiseh; Tsapatsis, Michael Microporous and Mesoporous Materials, Vol. 153, p. 55-58 https://doi.org/10.1016/j.micromeso.2011.12.020	journal	May 2012
“One-Pot” Synthesis of 5-(Hydroxymethyl)furfural from Carbohydrates using Tin-Beta Zeolite Nikolla, Eranda; Román-Leshkov, Yuriy; Moliner, Manuel ACS Catalysis, Vol. 1, Issue 4, p. 408-410 https://doi.org/10.1021/cs2000544	journal	April 2011
Tin Silsesquioxanes as Models for the “Open” Site in Tin-Containing Zeolite Beta Brand, Stephen K.; Labinger, Jay A.; Davis, Mark E. ChemCatChem, Vol. 8, Issue 1 https://doi.org/10.1002/cctc.201501067	journal	November 2015
Titration and quantification of open and closed Lewis acid sites in Sn-Beta zeolites that catalyze glucose isomerization Harris, James W.; Cordon, Michael J.; Di Iorio, John R. Journal of Catalysis, Vol. 335 https://doi.org/10.1016/j.jcat.2015.12.024	journal	March 2016
Correlating Synthetic Methods, Morphology, Atomic-Level Structure, and Catalytic Activity of Sn-β Catalysts Wolf, Patrick; Valla, Maxence; Núñez-Zarur, Francisco ACS Catalysis, Vol. 6, Issue 7 https://doi.org/10.1021/acscatal.6b00114	journal	May 2016
Computational Insight into the Effect of Sn-Beta Na Exchange and Solvent on Glucose Isomerization and Epimerization Christianson, Jeffrey R.; Caratzoulas, Stavros; Vlachos, Dionisios G. ACS Catalysis, Vol. 5, Issue 9 https://doi.org/10.1021/acscatal.5b01258	journal	August 2015
Role of Silanol Group in Sn-Beta Zeolite for Glucose Isomerization and Epimerization Reactions Rai, Neeraj; Caratzoulas, Stavros; Vlachos, Dionisios G. ACS Catalysis, Vol. 3, Issue 10 https://doi.org/10.1021/cs400476n	journal	September 2013
The Mechanism of Glucose Isomerization to Fructose over Sn-BEA Zeolite: A Periodic Density Functional Theory Study Yang, Gang; Pidko, Evgeny A.; Hensen, Emiel J. M. ChemSusChem, Vol. 6, Issue 9 https://doi.org/10.1002/cssc.201300342	journal	August 2013
Analysis of the Reaction Mechanism and Catalytic Activity of Metal-Substituted Beta Zeolite for the Isomerization of Glucose to Fructose Li, Yi-Pei; Head-Gordon, Martin; Bell, Alexis T. ACS Catalysis, Vol. 4, Issue 5 https://doi.org/10.1021/cs401054f	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 Li, Guanna; Pidko, Evgeny A.; Hensen, Emiel J. M. Catal. Sci. Technol., Vol. 4, Issue 8 https://doi.org/10.1039/C4CY00186A	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 Boronat, M.; Concepcion, P.; Corma, A. Journal of Catalysis, Vol. 234, Issue 1 https://doi.org/10.1016/j.jcat.2005.05.023	journal	August 2005
Effect of water treatment on Sn-BEA zeolite: Origin of 960 cm−1 FTIR peak Courtney, Timothy D.; Chang, Chun-Chih; Gorte, Raymond J. Microporous and Mesoporous Materials, Vol. 210 https://doi.org/10.1016/j.micromeso.2015.02.012	journal	July 2015
Comparison of Homogeneous and Heterogeneous Catalysts for Glucose-to-Fructose Isomerization in Aqueous Media Choudhary, Vinit; Pinar, Ana B.; Lobo, Raul F. ChemSusChem, Vol. 6, Issue 12 https://doi.org/10.1002/cssc.201300328	journal	September 2013
Mechanism of Glucose Isomerization Using a Solid Lewis Acid Catalyst in Water Román-Leshkov, Yuriy; Moliner, Manuel; Labinger, Jay A. Angewandte Chemie International Edition, Vol. 49, Issue 47, p. 8954-8957 https://doi.org/10.1002/anie.201004689	journal	October 2010
Distribution of open sites in Sn-Beta zeolite Josephson, Tyler R.; Jenness, Glen R.; Vlachos, Dionisios G. Microporous and Mesoporous Materials, Vol. 245 https://doi.org/10.1016/j.micromeso.2017.02.065	journal	June 2017
Beyond shape selective catalysis with zeolites: Hydrophobic void spaces in zeolites enable catalysis in liquid water Gounder, Rajamani; Davis, Mark E. AIChE Journal, Vol. 59, Issue 9, p. 3349-3358 https://doi.org/10.1002/aic.14016	journal	January 2013
Monosaccharide and disaccharide isomerization over Lewis acid sites in hydrophobic and hydrophilic molecular sieves Gounder, Rajamani; Davis, Mark E. Journal of Catalysis, Vol. 308 https://doi.org/10.1016/j.jcat.2013.06.016	journal	December 2013
Solid State NMR Characterization of Sn-Beta Zeolites that Catalyze Glucose Isomerization and Epimerization Hwang, Son-Jong; Gounder, Rajamani; Bhawe, Yashodhan Topics in Catalysis, Vol. 58, Issue 7-9 https://doi.org/10.1007/s11244-015-0388-7	journal	March 2015
An Inner-/Outer-Sphere Stabilized Sn Active Site in β-Zeolite: Spectroscopic Evidence and Kinetic Consequences Dijkmans, Jan; Dusselier, Michiel; Janssens, Wout ACS Catalysis, Vol. 6, Issue 1 https://doi.org/10.1021/acscatal.5b01822	journal	November 2015
NMR Signatures of the Active Sites in Sn-β Zeolite Wolf, Patrick; Valla, Maxence; Rossini, Aaron J. Angewandte Chemie International Edition, Vol. 53, Issue 38 https://doi.org/10.1002/anie.201403905	journal	July 2014
Competitive Adsorption of Substrate and Solvent in Sn-Beta Zeolite During Sugar Isomerization van der Graaff, William N. P.; Tempelman, Christiaan H. L.; Li, Guanna ChemSusChem, Vol. 9, Issue 22 https://doi.org/10.1002/cssc.201600800	journal	October 2016
Quantitative NMR Approach to Optimize the Formation of Chemical Building Blocks from Abundant Carbohydrates Elliot, Samuel G.; Tolborg, Søren; Sádaba, Irantzu ChemSusChem, Vol. 10, Issue 14 https://doi.org/10.1002/cssc.201700587	journal	July 2017
From ultrasoft pseudopotentials to the projector augmented-wave method Kresse, G.; Joubert, D. Physical Review B, Vol. 59, Issue 3, p. 1758-1775 https://doi.org/10.1103/PhysRevB.59.1758	journal	January 1999
Projector augmented-wave method Blöchl, P. E. Physical Review B, Vol. 50, Issue 24, p. 17953-17979 https://doi.org/10.1103/PhysRevB.50.17953	journal	December 1994
Effect of the damping function in dispersion corrected density functional theory Grimme, Stefan; Ehrlich, Stephan; Goerigk, Lars Journal of Computational Chemistry, Vol. 32, Issue 7 https://doi.org/10.1002/jcc.21759	journal	March 2011
A climbing image nudged elastic band method for finding saddle points and minimum energy paths Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904 https://doi.org/10.1063/1.1329672	journal	December 2000
Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points Henkelman, Graeme; Jónsson, Hannes The Journal of Chemical Physics, Vol. 113, Issue 22 https://doi.org/10.1063/1.1323224	journal	December 2000
Structural, Electronic, and Bonding Properties of Zeolite Sn-Beta: A Periodic Density Functional Theory Study Shetty, Sharan; Pal, Sourav; Kanhere, Dilip G. Chemistry - A European Journal, Vol. 12, Issue 2 https://doi.org/10.1002/chem.200500487	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 Yang, Gang; Pidko, Evgeny A.; Hensen, Emiel J. M. The Journal of Physical Chemistry C, Vol. 117, Issue 8 https://doi.org/10.1021/jp310433r	journal	February 2013
Identifying Sn Site Heterogeneities Prevalent Among Sn-Beta Zeolites Wolf, Patrick; Liao, Wei-Chih; Ong, Ta-Chung Helvetica Chimica Acta, Vol. 99, Issue 12 https://doi.org/10.1002/hlca.201600234	journal	November 2016
Structural Characterization of Zeolite Beta Newsam, J. M.; Treacy, M. M. J.; Koetsier, W. T. Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 420, Issue 1859 https://doi.org/10.1098/rspa.1988.0131	journal	December 1988
Modification of Sn-Beta zeolite: characterization of acidic/basic properties and catalytic performance in Baeyer–Villiger oxidation Otomo, Ryoichi; Kosugi, Ryota; Kamiya, Yuichi Catalysis Science & Technology, Vol. 6, Issue 8 https://doi.org/10.1039/C6CY00532B	journal	January 2016
Insights into the isomerization of xylose to xylulose and lyxose by a Lewis acid catalyst Choudhary, Vinit; Caratzoulas, Stavros; Vlachos, Dionisios G. Carbohydrate Research, Vol. 368 https://doi.org/10.1016/j.carres.2012.12.019	journal	March 2013

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