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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}
}
  • Operando pair distribution function (PDF) analysis and ex situ Na-23 magic-angle spinning solid-state nuclear magnetic resonance (MAS ssNMR) spectroscopy are used to gain insight into the alloying mechanism of high-capacity antimony anodes for sodium-ion batteries. Subtraction of the PDF of crystalline NaxSb phases from the total PDF, an approach constrained by chemical phase information gained from Na-23 ssNMR in reference to relevant model compounds, identifies two previously uncharacterized intermediate species formed electro-chemically; a-Na3-xSb (x approximate to 0.4-0.5), a structure locally similar to crystalline Na3Sb (c-Na3Sb) but with significant numbers of sodium vacancies and a limited correlation length, and a-Na1.7Sb, amore » highly amorphous structure featuring some Sb-Sb bonding. The first sodiation breaks down the crystalline antimony to form first a-Na3-xSb and, finally, crystalline Na3Sb. Desodiation results in the formation of an electrode formed of a composite of crystalline and amorphous antimony networks. We link the different reactivity of these networks to a series of sequential sodiation reactions manifesting as a cascade of processes observed in the electrochemical profile of subsequent cycles. The amorphofis network reacts at higher voltages reforming a-Na1.7Sb, then a-Na3-xSb, whereas lower potentials are required for the sodiation of crystalline antimony, which reacts to form a-Na3-xSb without the formation of a-Na3-xSb. a-Na3-xSb is converted to crystalline Na3Sb at the end of the second discharge. We find no evidence of formation of NaSb. Variable temperature Na-23 NMR experiments reveal significant sodium mobility within c-Na3Sb; this is a possible contributing factor to the excellent rate performance of Sb anodes.« less
  • We use operando pair distribution function (PDF) analysis and ex situ 23Na magic-angle spinning solid-state nuclear magnetic resonance (MAS ssNMR) spectroscopy to gain insight into the alloying mechanism of high-capacity antimony anodes for sodium-ion batteries. Subtraction of the PDF of crystalline Na xSb phases from the total PDF, an approach constrained by chemical phase information gained from 23Na ssNMR in reference to relevant model compounds, identifies two previously uncharacterized intermediate species formed electrochemically; a-Na 3–xSb (x ≈ 0.4–0.5), a structure locally similar to crystalline Na 3Sb (c-Na 3Sb) but with significant numbers of sodium vacancies and a limited correlation length,more » and a-Na1.7Sb, a highly amorphous structure featuring some Sb–Sb bonding. The first sodiation breaks down the crystalline antimony to form first a-Na 3–xSb and, finally, crystalline Na 3Sb. Desodiation results in the formation of an electrode formed of a composite of crystalline and amorphous antimony networks. We link the different reactivity of these networks to a series of sequential sodiation reactions manifesting as a cascade of processes observed in the electrochemical profile of subsequent cycles. The amorphous network reacts at higher voltages reforming a-Na 1.7Sb, then a-Na 3–xSb, whereas lower potentials are required for the sodiation of crystalline antimony, which reacts to form a-Na 3–xSb without the formation of a-Na 1.7Sb. a-Na 3–xSb is converted to crystalline Na 3Sb at the end of the second discharge. In the end, we find no evidence of formation of NaSb. Variable temperature 23Na NMR experiments reveal significant sodium mobility within c-Na 3Sb; this is a possible contributing factor to the excellent rate performance of Sb anodes.« less
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  • We use operando pair distribution function (PDF) analysis and ex situ 23Na magic-angle spinning solid-state nuclear magnetic resonance (MAS ssNMR) spectroscopy to gain insight into the alloying mechanism of high-capacity antimony anodes for sodium-ion batteries. Subtraction of the PDF of crystalline Na xSb phases from the total PDF, an approach constrained by chemical phase information gained from 23Na ssNMR in reference to relevant model compounds, identifies two previously uncharacterized intermediate species formed electrochemically; a-Na 3–xSb (x ≈ 0.4–0.5), a structure locally similar to crystalline Na 3Sb (c-Na 3Sb) but with significant numbers of sodium vacancies and a limited correlation length,more » and a-Na1.7Sb, a highly amorphous structure featuring some Sb–Sb bonding. The first sodiation breaks down the crystalline antimony to form first a-Na 3–xSb and, finally, crystalline Na 3Sb. Desodiation results in the formation of an electrode formed of a composite of crystalline and amorphous antimony networks. We link the different reactivity of these networks to a series of sequential sodiation reactions manifesting as a cascade of processes observed in the electrochemical profile of subsequent cycles. The amorphous network reacts at higher voltages reforming a-Na 1.7Sb, then a-Na 3–xSb, whereas lower potentials are required for the sodiation of crystalline antimony, which reacts to form a-Na 3–xSb without the formation of a-Na 1.7Sb. a-Na 3–xSb is converted to crystalline Na 3Sb at the end of the second discharge. In the end, we find no evidence of formation of NaSb. Variable temperature 23Na NMR experiments reveal significant sodium mobility within c-Na 3Sb; this is a possible contributing factor to the excellent rate performance of Sb anodes.« less
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  • No abstract prepared.