Tighter Confinement Increases Selectivity of d-Glucose Isomerization Toward l-Sorbose in Titanium Zeolites

Cordon, Michael J.; Vega‐Vila, Juan Carlos; Casper, Alyssa; Huang, Zige; Gounder, Rajamani

doi:10.1002/anie.202005207

Tighter Confinement Increases Selectivity of d-Glucose Isomerization Toward l-Sorbose in Titanium Zeolites

Journal Article · Tue Jun 30 00:00:00 EDT 2020 · Angewandte Chemie (International Edition)

DOI:https://doi.org/10.1002/anie.202005207· OSTI ID:1651330

^[1]; Vega‐Vila, Juan Carlos ^[2]; Casper, Alyssa ^[2]; Huang, Zige ^[2]; ^[2]

Purdue Univ., West Lafayette, IN (United States); Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
Purdue Univ., West Lafayette, IN (United States)

Aqueous-phase isomerization of D-glucose to D-fructose and L-sorbose is catalyzed in parallel by Lewis acidic Ti sites in siliceous frameworks. Glucose isomerization rates (per Ti, 373 K) are undetectable when Ti sites are confined within mesoporous voids (Ti-MCM-41, TiO₂-SiO₂) and increase to detectable values when Ti sites are confined within the smaller 12-membered ring (12-MR) micropores of Ti-Beta. Furthermore, isomerization rates decrease to lower values (by ≈20×) with further decreases in micropore size as Ti sites are confined within 10-MR pores (Ti-MFI, Ti-CON), likely because of intrapore reactant diffusion restrictions, and reach undetectable values within the 8-MR pores of Ti-CHA as size exclusion prevents glucose from accessing active sites. Remarkably, the selectivity toward l-sorbose over d-fructose increases systematically as spatial constraints around Ti sites become tighter, and is >10 on Ti-MFI. These findings demonstrate the marked influence of confinement around Ti active sites on the selectivity between parallel stereoselective sugar isomerization pathways.

View Accepted Manuscript (DOE)

Research Organization:: Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)

Sponsoring Organization:: USDOE

Grant/Contract Number:: AC05-00OR22725

OSTI ID:: 1651330

Journal Information:: Angewandte Chemie (International Edition), Journal Name: Angewandte Chemie (International Edition) Journal Issue: 7 Vol. 59; ISSN 1433-7851

Publisher:: WileyCopyright Statement

Country of Publication:: United States

Language:: English

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