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Title: Operando Solid-State NMR Observation of Solvent-Mediated Adsorption-Reaction of Carbohydrates in Zeolites

Abstract

Liquid-phase processing of molecules using heterogeneous catalysts – an important strategy for obtaining renewable chemicals sustainably from biomass – involves reactions that occur at solid-liquid interfaces. In glucose isomerization catalyzed by basic faujasite zeolites, the catalytic activity depends strongly on the solvent composition: initially, it declines precipitously when water is mixed with a small amount of the organic co-solvent γ-valerolactone (GVL), then recovers as the GVL content increases. Using solid-state 13C NMR spectroscopy, we observed glucose isomers located inside the zeolite pores directly, and followed their transformations into fructose and mannose in real time. At low GVL concentrations, glucose is depleted in the zeolite pores relative to the liquid phase, while higher GVL concentrations in solution drive glucose inside the pores, resulting in up to a 32 enhancement in the local glucose concentration. Although their populations exchange rapidly, molecules present at the reactive interface experience a significantly different environment from the bulk solution.

Authors:
;  [1]; ;  [2];  [2];  [2];  [2]; ORCiD logo [2]; ORCiD logo; ORCiD logo [1]; ORCiD logo
  1. Department of Chemical and Biological Engineering, University of Wisconsin, Madison, Wisconsin 53706, United States
  2. Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, Washington 99354, United States
Publication Date:
Research Org.:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US), Environmental Molecular Sciences Laboratory (EMSL)
Sponsoring Org.:
USDOE
OSTI Identifier:
1422335
Report Number(s):
PNNL-SA-119548
Journal ID: ISSN 2155-5435; 48898; KP1704020
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Resource Relation:
Journal Name: ACS Catalysis; Journal Volume: 7; Journal Issue: 5
Country of Publication:
United States
Language:
English
Subject:
interfacial reaction; operando spectroscopy; solid-state NMR; carbohydrate isomerization; selective adsorption; Environmental Molecular Sciences Laboratory

Citation Formats

Qi, Long, Alamillo, Ricardo, Elliott, William A., Andersen, Amity, Hoyt, David W., Walter, Eric D., Han, Kee Sung, Washton, Nancy M., Rioux, Robert M., Dumesic, James A., and Scott, Susannah L.. Operando Solid-State NMR Observation of Solvent-Mediated Adsorption-Reaction of Carbohydrates in Zeolites. United States: N. p., 2017. Web. doi:10.1021/acscatal.7b01045.
Qi, Long, Alamillo, Ricardo, Elliott, William A., Andersen, Amity, Hoyt, David W., Walter, Eric D., Han, Kee Sung, Washton, Nancy M., Rioux, Robert M., Dumesic, James A., & Scott, Susannah L.. Operando Solid-State NMR Observation of Solvent-Mediated Adsorption-Reaction of Carbohydrates in Zeolites. United States. doi:10.1021/acscatal.7b01045.
Qi, Long, Alamillo, Ricardo, Elliott, William A., Andersen, Amity, Hoyt, David W., Walter, Eric D., Han, Kee Sung, Washton, Nancy M., Rioux, Robert M., Dumesic, James A., and Scott, Susannah L.. Tue . "Operando Solid-State NMR Observation of Solvent-Mediated Adsorption-Reaction of Carbohydrates in Zeolites". United States. doi:10.1021/acscatal.7b01045.
@article{osti_1422335,
title = {Operando Solid-State NMR Observation of Solvent-Mediated Adsorption-Reaction of Carbohydrates in Zeolites},
author = {Qi, Long and Alamillo, Ricardo and Elliott, William A. and Andersen, Amity and Hoyt, David W. and Walter, Eric D. and Han, Kee Sung and Washton, Nancy M. and Rioux, Robert M. and Dumesic, James A. and Scott, Susannah L.},
abstractNote = {Liquid-phase processing of molecules using heterogeneous catalysts – an important strategy for obtaining renewable chemicals sustainably from biomass – involves reactions that occur at solid-liquid interfaces. In glucose isomerization catalyzed by basic faujasite zeolites, the catalytic activity depends strongly on the solvent composition: initially, it declines precipitously when water is mixed with a small amount of the organic co-solvent γ-valerolactone (GVL), then recovers as the GVL content increases. Using solid-state 13C NMR spectroscopy, we observed glucose isomers located inside the zeolite pores directly, and followed their transformations into fructose and mannose in real time. At low GVL concentrations, glucose is depleted in the zeolite pores relative to the liquid phase, while higher GVL concentrations in solution drive glucose inside the pores, resulting in up to a 32 enhancement in the local glucose concentration. Although their populations exchange rapidly, molecules present at the reactive interface experience a significantly different environment from the bulk solution.},
doi = {10.1021/acscatal.7b01045},
journal = {ACS Catalysis},
number = 5,
volume = 7,
place = {United States},
year = {Tue Apr 18 00:00:00 EDT 2017},
month = {Tue Apr 18 00:00:00 EDT 2017}
}