CaltechAUTHORS
  A Caltech Library Service

Monosaccharide and disaccharide isomerization over Lewis acid sites in hydrophobic and hydrophilic molecular sieves

Gounder, Rajamani and Davis, Mark E. (2013) Monosaccharide and disaccharide isomerization over Lewis acid sites in hydrophobic and hydrophilic molecular sieves. Journal of Catalysis, 308 . pp. 176-188. ISSN 0021-9517. doi:10.1016/j.jcat.2013.06.016. https://resolver.caltech.edu/CaltechAUTHORS:20140220-100357901

[img] MS Word (Supplementary Data) - Supplemental Material
See Usage Policy.

627kB

Use this Persistent URL to link to this item: https://resolver.caltech.edu/CaltechAUTHORS:20140220-100357901

Abstract

Lewis acid sites isolated within low-defect, hydrophobic molecular sieves (Sn-Beta-F, Ti-Beta-F) catalyze monosaccharide (glucose–fructose) and disaccharide (lactose–lactulose) aldose–ketose isomerization reactions in liquid water at initial turnover rates (per total metal atom; 373 K) that are, respectively, ∼10–30 and ∼10^3–10^4 factors higher than sites isolated within highly defective, hydrophilic molecular sieves (Ti-Beta-OH) or amorphous co-precipitated oxides (TiO_(2)–SiO_(2)). Glucose-H2/glucose-D2 kinetic isotope effects of ∼2 (at 373 K) for intramolecular C2–C1 hydride shift isomerization to fructose indicate that glucose transport to active sites within Ti-Beta-F or Ti-Beta-OH does not limit turnover rates in liquid water or methanol, in spite of dramatic differences in the volumetric occupation of hydrophobic and hydrophilic void spaces by physisorbed solvent molecules. Glucose isomerization turnover rates (per total Ti; 373 K) in liquid water are first-order in aqueous glucose concentration (at least up to 1.5% (w/w)). The mechanistic interpretation of measured first-order isomerization rate constants indicates that they reflect free energies of kinetically relevant isomerization transition states relative to two bound solvent molecules, which adsorb competitively with sugars at Lewis acid sites and are the most abundant surface intermediates during steady-state catalysis. The lower isomerization rate constants on Ti centers in highly defective environments, in part, reflect stronger coordination of solvent molecules to Ti centers via additional hydrogen bonding interactions with proximal surface hydroxyl groups. The direct measurement of glucose isomerization rate constants in the liquid phase provides a rigorous and quantitative description of the catalytic differences prevalent among Lewis acidic silica-based solids with hydrophobic or hydrophilic properties, and their interpretation using a mechanism-based rate equation provides further clarity into the inhibition of catalytic turnovers at Lewis acid sites by solvent coordination.


Item Type:Article
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1016/j.jcat.2013.06.016DOIArticle
http://www.sciencedirect.com/science/article/pii/S0021951713002327PublisherArticle
ORCID:
AuthorORCID
Gounder, Rajamani0000-0003-1347-534X
Davis, Mark E.0000-0001-8294-1477
Additional Information:© 2013 Elsevier Inc. Received 28 February 2013; Revised 20 May 2013; Accepted 19 June 2013; Available online 20 July 2013. This work was financially supported as part of the Catalysis Center for Energy Innovation, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE-SC0001004. We thank Ricardo Bermejo-Deval for synthesis of the Ti-Beta-OH sample, Carly Bond for experimental assistance, and Joshua Pacheco, Yashodhan Bhawe and Marat Orazov for helpful technical discussions.
Funders:
Funding AgencyGrant Number
Department of Energy (DOE) Office of Science, Office of Basic Energy SciencesDE-SC0001004
Subject Keywords:Sugar Isomerization; Hydrophilic; Hydrophobic; Lewis Acid; Zeolites
DOI:10.1016/j.jcat.2013.06.016
Record Number:CaltechAUTHORS:20140220-100357901
Persistent URL:https://resolver.caltech.edu/CaltechAUTHORS:20140220-100357901
Official Citation:Gounder, R., & Davis, M. E. (2013). Monosaccharide and disaccharide isomerization over Lewis acid sites in hydrophobic and hydrophilic molecular sieves. Journal of Catalysis, 308(0), 176-188. doi: http://dx.doi.org/10.1016/j.jcat.2013.06.016
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:43889
Collection:CaltechAUTHORS
Deposited By: Jason Perez
Deposited On:20 Feb 2014 22:00
Last Modified:10 Nov 2021 16:44

Repository Staff Only: item control page