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:
-
- 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.
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
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.
@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}
}
Works referenced in this record:
Sensitivity Enhancement in Solid State 15N NMR by Indirect Detection with High-Speed Magic Angle Spinning
journal, January 2000
- Ishii, Yoshitaka; Tycko, Robert
- Journal of Magnetic Resonance, Vol. 142, Issue 1
Dynamic Nuclear Polarization of 17 O: Direct Polarization
journal, November 2013
- Michaelis, Vladimir K.; Corzilius, Björn; Smith, Albert A.
- The Journal of Physical Chemistry B, Vol. 117, Issue 48
Dynamic Nuclear Polarization Enhanced Solid-State NMR Spectroscopy of Functionalized Metal-Organic Frameworks
journal, November 2011
- Rossini, Aaron J.; Zagdoun, Alexandre; Lelli, Moreno
- Angewandte Chemie International Edition, Vol. 51, Issue 1
Bond length-bond angle correlation in densified silica—Results from 17 O NMR spectroscopy
journal, May 2017
- Trease, Nicole M.; Clark, Ted M.; Grandinetti, Philip J.
- The Journal of Chemical Physics, Vol. 146, Issue 18
Proton-Selective 17 O− 1 H Distance Measurements in Fast Magic-Angle-Spinning Solid-State NMR Spectroscopy for the Determination of Hydrogen Bond Lengths
journal, November 2006
- Brinkmann, Andreas; Kentgens, Arno P. M.
- Journal of the American Chemical Society, Vol. 128, Issue 46
Mechanism of Solid-State Thermolysis of Ammonia Borane: A 15 N NMR Study Using Fast Magic-Angle Spinning and Dynamic Nuclear Polarization
journal, August 2014
- Kobayashi, Takeshi; Gupta, Shalabh; Caporini, Marc A.
- The Journal of Physical Chemistry C, Vol. 118, Issue 34
BDPA-Nitroxide Biradicals Tailored for Efficient Dynamic Nuclear Polarization Enhanced Solid-State NMR at Magnetic Fields up to 21.1 T
journal, September 2018
- Wisser, Dorothea; Karthikeyan, Ganesan; Lund, Alicia
- Journal of the American Chemical Society, Vol. 140, Issue 41
Insights into the Catalytic Activity of Nitridated Fibrous Silica (KCC-1) Nanocatalysts from 15 N and 29 Si NMR Spectroscopy Enhanced by Dynamic Nuclear Polarization
journal, December 2014
- Lilly Thankamony, Aany Sofia; Lion, Cédric; Pourpoint, Frédérique
- Angewandte Chemie International Edition, Vol. 54, Issue 7
Materials Characterization by Dynamic Nuclear Polarization-Enhanced Solid-State NMR Spectroscopy
journal, August 2018
- Rossini, Aaron J.
- The Journal of Physical Chemistry Letters, Vol. 9, Issue 17
Enabling Natural Abundance 17 O Solid-State NMR by Direct Polarization from Paramagnetic Metal Ions
journal, June 2020
- Jardón-Álvarez, Daniel; Reuveni, Guy; Harchol, Adi
- The Journal of Physical Chemistry Letters, Vol. 11, Issue 14
Recoupling of heteronuclear dipolar interactions in solid state magic-angle spinning NMR by simultaneous frequency and amplitude modulation
journal, July 1997
- Fu, Riqiang; Smith, Scott A.; Bodenhausen, Geoffrey
- Chemical Physics Letters, Vol. 272, Issue 5-6
Chemoselective Hydrogenation with Supported Organoplatinum(IV) Catalyst on Zn(II)-Modified Silica
journal, February 2018
- Camacho-Bunquin, Jeffrey; Ferrandon, Magali; Sohn, Hyuntae
- Journal of the American Chemical Society, Vol. 140, Issue 11
Endogenous Dynamic Nuclear Polarization for Natural Abundance 17 O and Lithium NMR in the Bulk of Inorganic Solids
journal, November 2018
- Wolf, Tamar; Kumar, Sandeep; Singh, Harishchandra
- Journal of the American Chemical Society, Vol. 141, Issue 1
Surface-selective direct 17 O DNP NMR of CeO 2 nanoparticles
journal, January 2017
- Hope, Michael A.; Halat, David M.; Magusin, Pieter C. M. M.
- Chemical Communications, Vol. 53, Issue 13
Dynamic Nuclear Polarization Enhanced Solid-State NMR Spectroscopy of Functionalized Metal-Organic Frameworks
journal, November 2011
- Rossini, Aaron J.; Zagdoun, Alexandre; Lelli, Moreno
- Angewandte Chemie, Vol. 124, Issue 1
Selective Host-Guest Interaction between Metal Ions and Metal-Organic Frameworks Using Dynamic Nuclear Polarization Enhanced Solid-State NMR Spectroscopy
journal, October 2014
- Guo, Zhiyong; Kobayashi, Takeshi; Wang, Lin-Lin
- Chemistry - A European Journal, Vol. 20, Issue 49
Large Molecular Weight Nitroxide Biradicals Providing Efficient Dynamic Nuclear Polarization at Temperatures up to 200 K
journal, August 2013
- Zagdoun, Alexandre; Casano, Gilles; Ouari, Olivier
- Journal of the American Chemical Society, Vol. 135, Issue 34
Microstructure of silica monolayer solid acid catalysts determined by 29Si NMR spectroscopy
journal, May 1998
- Katada, Naonobu; Niwa, Miki
- Research on Chemical Intermediates, Vol. 24, Issue 5
Dynamic Nuclear Polarization Enhanced Natural Abundance 17 O Spectroscopy
journal, February 2013
- Blanc, Frédéric; Sperrin, Luke; Jefferson, David A.
- Journal of the American Chemical Society, Vol. 135, Issue 8
Studies of Organically Functionalized Mesoporous Silicas Using Heteronuclear Solid-State Correlation NMR Spectroscopy under Fast Magic Angle Spinning
journal, May 2005
- Trebosc, Julien; Wiench, Jerzy W.; Huh, Seong
- Journal of the American Chemical Society, Vol. 127, Issue 20
Detection of Brønsted acid sites in zeolite HY with high-field 17O-MAS-NMR techniques
journal, February 2005
- Peng, Luming; Liu, Yun; Kim, Namjun
- Nature Materials, Vol. 4, Issue 3
Natural Abundance 15 N NMR by Dynamic Nuclear Polarization: Fast Analysis of Binding Sites of a Novel Amine-Carboxyl-Linked Immobilized Dirhodium Catalyst
journal, January 2015
- Gutmann, Torsten; Liu, Jiquan; Rothermel, Niels
- Chemistry - A European Journal, Vol. 21, Issue 9
DNP by Thermal Mixing under Optimized Conditions Yields >60 000-fold Enhancement of 89 Y NMR Signal
journal, June 2011
- Lumata, Lloyd; Jindal, Ashish K.; Merritt, Matthew E.
- Journal of the American Chemical Society, Vol. 133, Issue 22
Atomic Description of the Interface between Silica and Alumina in Aluminosilicates through Dynamic Nuclear Polarization Surface-Enhanced NMR Spectroscopy and First-Principles Calculations
journal, August 2015
- Valla, Maxence; Rossini, Aaron J.; Caillot, Maxime
- Journal of the American Chemical Society, Vol. 137, Issue 33
Rapid acquisition of wideline MAS solid-state NMR spectra with fast MAS, proton detection, and dipolar HMQC pulse sequences
journal, January 2016
- Rossini, Aaron J.; Hanrahan, Michael P.; Thuo, Martin
- Physical Chemistry Chemical Physics, Vol. 18, Issue 36
A Slowly Relaxing Rigid Biradical for Efficient Dynamic Nuclear Polarization Surface-Enhanced NMR Spectroscopy: Expeditious Characterization of Functional Group Manipulation in Hybrid Materials
journal, January 2012
- Zagdoun, Alexandre; Casano, Gilles; Ouari, Olivier
- Journal of the American Chemical Society, Vol. 134, Issue 4
Well-Defined Silanols in the Structure of the Calcined High-Silica Zeolite SSZ-70: New Understanding of a Successful Catalytic Material
journal, November 2017
- Smeets, Stef; Berkson, Zachariah J.; Xie, Dan
- Journal of the American Chemical Society, Vol. 139, Issue 46
Dynamic Nuclear Polarization NMR of Low-γ Nuclei: Structural Insights into Hydrated Yttrium-Doped BaZrO 3
journal, June 2014
- Blanc, Frédéric; Sperrin, Luke; Lee, Daniel
- The Journal of Physical Chemistry Letters, Vol. 5, Issue 14
Oxygen-17 dynamic nuclear polarisation enhanced solid-state NMR spectroscopy at 18.8 T
journal, January 2017
- Brownbill, Nick J.; Gajan, David; Lesage, Anne
- Chemical Communications, Vol. 53, Issue 17
Non-Topotactic Transformation of Silicate Nanolayers into Mesostructured MFI Zeolite Frameworks During Crystallization
journal, April 2017
- Berkson, Zachariah J.; Messinger, Robert J.; Na, Kyungsu
- Angewandte Chemie, Vol. 129, Issue 19
Natural Abundance 17 O DNP Two-Dimensional and Surface-Enhanced NMR Spectroscopy
journal, June 2015
- Perras, Frédéric A.; Kobayashi, Takeshi; Pruski, Marek
- Journal of the American Chemical Society, Vol. 137, Issue 26
Probing O–H Bonding through Proton Detected 1 H– 17 O Double Resonance Solid-State NMR Spectroscopy
journal, November 2018
- Carnahan, Scott L.; Lampkin, Bryan J.; Naik, Pranjali
- Journal of the American Chemical Society, Vol. 141, Issue 1
Insights into the Catalytic Activity of Nitridated Fibrous Silica (KCC-1) Nanocatalysts from 15 N and 29 Si NMR Spectroscopy Enhanced by Dynamic Nuclear Polarization
journal, December 2014
- Lilly Thankamony, Aany Sofia; Lion, Cédric; Pourpoint, Frédérique
- Angewandte Chemie, Vol. 127, Issue 7
The Role of Ligands in the Chemical Synthesis and Applications of Inorganic Nanoparticles
journal, March 2019
- Heuer-Jungemann, Amelie; Feliu, Neus; Bakaimi, Ioanna
- Chemical Reviews, Vol. 119, Issue 8
Natural Abundance 17 O DNP NMR Provides Precise O−H Distances and Insights into the Brønsted Acidity of Heterogeneous Catalysts
journal, June 2017
- Perras, Frédéric A.; Wang, Zhuoran; Naik, Pranjali
- Angewandte Chemie International Edition, Vol. 56, Issue 31
Silica Gel Surface: Molecular Dynamics of Surface Silanols
journal, February 2008
- Kobayashi, Takeshi; DiVerdi, Joseph A.; Maciel, Gary E.
- The Journal of Physical Chemistry C, Vol. 112, Issue 11
Ab initio Calculation of the 17 O and 1 H NMR Parameters for Various OH Groups: Implications to the Speciation and Dynamics of Dissolved Water in Silicate Glasses
journal, May 2001
- Xue, Xianyu; Kanzaki, Masami
- The Journal of Physical Chemistry B, Vol. 105, Issue 17
Combining fast magic angle spinning dynamic nuclear polarization with indirect detection to further enhance the sensitivity of solid-state NMR spectroscopy
journal, October 2020
- Wang, Zhuoran; Hanrahan, Michael P.; Kobayashi, Takeshi
- Solid State Nuclear Magnetic Resonance, Vol. 109
Surface enhanced dynamic nuclear polarization solid-state NMR spectroscopy sheds light on Brønsted–Lewis acid synergy during the zeolite catalyzed methanol-to-hydrocarbon process
journal, January 2019
- Dutta Chowdhury, Abhishek; Yarulina, Irina; Abou-Hamad, Edy
- Chemical Science, Vol. 10, Issue 39
A 29Si NMR investigation of the structure of amorphous silica—alumina supports
journal, January 1989
- McMillan, M.; Brinen, J. S.; Carruthers, J. D.
- Colloids and Surfaces, Vol. 38, Issue 1
Magic angle spinning oxygen-17 NMR of aluminum oxides and hydroxides
journal, September 1989
- Walter, Thomas H.; Oldfield, Eric
- The Journal of Physical Chemistry, Vol. 93, Issue 18
Non-Topotactic Transformation of Silicate Nanolayers into Mesostructured MFI Zeolite Frameworks During Crystallization
journal, April 2017
- Berkson, Zachariah J.; Messinger, Robert J.; Na, Kyungsu
- Angewandte Chemie International Edition, Vol. 56, Issue 19
Correlated structural distributions in silica glass
journal, August 2004
- Clark, Ted M.; Grandinetti, Philip J.; Florian, Pierre
- Physical Review B, Vol. 70, Issue 6
Observation of Low-γ Quadrupolar Nuclei by Surface-Enhanced NMR Spectroscopy
journal, May 2020
- Nagashima, Hiroki; Trébosc, Julien; Kon, Yoshihiro
- Journal of the American Chemical Society, Vol. 142, Issue 24
Interfacial Ca2+ environments in nanocrystalline apatites revealed by dynamic nuclear polarization enhanced 43Ca NMR spectroscopy
journal, January 2017
- Lee, Daniel; Leroy, César; Crevant, Charlène
- Nature Communications, Vol. 8, Issue 1
Probing Surface Hydrogen Bonding and Dynamics by Natural Abundance, Multidimensional, 17 O DNP-NMR Spectroscopy
journal, May 2016
- Perras, Frédéric A.; Chaudhary, Umesh; Slowing, Igor I.
- The Journal of Physical Chemistry C, Vol. 120, Issue 21
Determinations of structure and bonding in amorphous SiO2 using 17O NMR
journal, January 1983
- Geissberger, A. E.; Bray, P. J.
- Journal of Non-Crystalline Solids, Vol. 54, Issue 1-2
Natural Abundance 17 O DNP NMR Provides Precise O−H Distances and Insights into the Brønsted Acidity of Heterogeneous Catalysts
journal, June 2017
- Perras, Frédéric A.; Wang, Zhuoran; Naik, Pranjali
- Angewandte Chemie, Vol. 129, Issue 31