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Title: Indirectly Detected DNP-Enhanced 17O NMR Spectroscopy: Observation of Non-Protonated Near-Surface Oxygen at Naturally Abundant Silica and Silica-Alumina

Abstract

Abstract Recent studies have shown that dynamic nuclear polarization (DNP) can be used to detect 17 O solid‐state NMR spectra of naturally abundant samples within a reasonable experimental time. Observations using indirect DNP, which relies on 1 H mediation in transferring electron hyperpolarization to 17 O, are currently limited mostly to hydroxyls. Direct DNP schemes can hyperpolarize non‐protonated oxygen near the radicals; however, they generally offer much lower signal enhancements. In this study, we demonstrate the detection of signals from non‐protonated 17 O in materials containing silicon. The sensitivity boost that made the experiment possible originates from three sources: indirect DNP excitation of 29 Si via protons, indirect detection of 17 O through 29 Si nuclei using two‐dimensional 29 Si{ 17 O} D ‐HMQC, and Carr‐Purcell‐Meiboom‐Gill refocusing of 29 Si magnetization during acquisition. This 29 Si‐detected scheme enabled, for the first time, 2D 17 O− 29 Si heteronuclear correlation spectroscopy in mesoporous silica and silica‐alumina surfaces at natural abundance. In contrast to the silanols showing motion‐averaged 17 O signals, the framework oxygens exhibit unperturbed powder patterns as unambiguous fingerprints of surface sites. Along with hydroxyl oxygens, detection of these moieties will help in gaining more atomistic‐scale insights into surface chemistry.

Authors:
ORCiD logo [1]; ORCiD logo [1]
+ Show Author Affiliations
  1. Ames Lab., and Iowa State Univ., Ames, IA (United States)
Publication Date:
Research Org.:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; USDOE
OSTI Identifier:
1797583
Alternate Identifier(s):
OSTI ID: 1787409
Report Number(s):
IS-J-10,499
Journal ID: ISSN 1439-4235
Grant/Contract Number:  
AC02-07CH11358
Resource Type:
Accepted Manuscript
Journal Name:
ChemPhysChem
Additional Journal Information:
Journal Volume: 22; Journal Issue: 14; Journal ID: ISSN 1439-4235
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Kobayashi, Takeshi, and Pruski, Marek. Indirectly Detected DNP-Enhanced 17O NMR Spectroscopy: Observation of Non-Protonated Near-Surface Oxygen at Naturally Abundant Silica and Silica-Alumina. United States: N. p., 2021. Web. doi:10.1002/cphc.202100290.
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Kobayashi, Takeshi, & Pruski, Marek. Indirectly Detected DNP-Enhanced 17O NMR Spectroscopy: Observation of Non-Protonated Near-Surface Oxygen at Naturally Abundant Silica and Silica-Alumina. United States. https://doi.org/10.1002/cphc.202100290
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Kobayashi, Takeshi, and Pruski, Marek. Fri . "Indirectly Detected DNP-Enhanced 17O NMR Spectroscopy: Observation of Non-Protonated Near-Surface Oxygen at Naturally Abundant Silica and Silica-Alumina". United States. https://doi.org/10.1002/cphc.202100290. https://www.osti.gov/servlets/purl/1797583.
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@article{osti_1797583,
title = {Indirectly Detected DNP-Enhanced 17O NMR Spectroscopy: Observation of Non-Protonated Near-Surface Oxygen at Naturally Abundant Silica and Silica-Alumina},
author = {Kobayashi, Takeshi and Pruski, Marek},
abstractNote = {Abstract Recent studies have shown that dynamic nuclear polarization (DNP) can be used to detect 17 O solid‐state NMR spectra of naturally abundant samples within a reasonable experimental time. Observations using indirect DNP, which relies on 1 H mediation in transferring electron hyperpolarization to 17 O, are currently limited mostly to hydroxyls. Direct DNP schemes can hyperpolarize non‐protonated oxygen near the radicals; however, they generally offer much lower signal enhancements. In this study, we demonstrate the detection of signals from non‐protonated 17 O in materials containing silicon. The sensitivity boost that made the experiment possible originates from three sources: indirect DNP excitation of 29 Si via protons, indirect detection of 17 O through 29 Si nuclei using two‐dimensional 29 Si{ 17 O} D ‐HMQC, and Carr‐Purcell‐Meiboom‐Gill refocusing of 29 Si magnetization during acquisition. This 29 Si‐detected scheme enabled, for the first time, 2D 17 O− 29 Si heteronuclear correlation spectroscopy in mesoporous silica and silica‐alumina surfaces at natural abundance. In contrast to the silanols showing motion‐averaged 17 O signals, the framework oxygens exhibit unperturbed powder patterns as unambiguous fingerprints of surface sites. Along with hydroxyl oxygens, detection of these moieties will help in gaining more atomistic‐scale insights into surface chemistry.},
doi = {10.1002/cphc.202100290},
journal = {ChemPhysChem},
number = 14,
volume = 22,
place = {United States},
year = {Fri May 21 00:00:00 EDT 2021},
month = {Fri May 21 00:00:00 EDT 2021}
}
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https://doi.org/10.1002/cphc.202100290
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