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

Kobayashi, Takeshi; Pruski, Marek

doi:10.1002/cphc.202100290

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

Journal Article · Fri May 21 00:00:00 EDT 2021 · ChemPhysChem

DOI:https://doi.org/10.1002/cphc.202100290· OSTI ID:1797583

^[1];

^[1]

Ames Lab., and Iowa State Univ., Ames, IA (United States)

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.

View Accepted Manuscript (DOE)

View Accepted Manuscript (Publisher)

Cite

Export

Save

Research Organization:: Ames Laboratory (AMES), Ames, IA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division; USDOE

Grant/Contract Number:: AC02-07CH11358

OSTI ID:: 1797583

Alternate ID(s):: OSTI ID: 1787409

Report Number(s):: IS-J-10,499

Journal Information:: ChemPhysChem, Vol. 22, Issue 14; ISSN 1439-4235

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

References (48)

Sensitivity Enhancement in Solid State 15N NMR by Indirect Detection with High-Speed Magic Angle Spinning Ishii, Yoshitaka; Tycko, Robert Journal of Magnetic Resonance, Vol. 142, Issue 1 https://doi.org/10.1006/jmre.1999.1976	journal	January 2000
Dynamic Nuclear Polarization of ¹⁷ O: Direct Polarization Michaelis, Vladimir K.; Corzilius, Björn; Smith, Albert A. The Journal of Physical Chemistry B, Vol. 117, Issue 48 https://doi.org/10.1021/jp408440z	journal	November 2013
Dynamic Nuclear Polarization Enhanced Solid-State NMR Spectroscopy of Functionalized Metal-Organic Frameworks Rossini, Aaron J.; Zagdoun, Alexandre; Lelli, Moreno Angewandte Chemie International Edition, Vol. 51, Issue 1 https://doi.org/10.1002/anie.201106030	journal	November 2011
Bond length-bond angle correlation in densified silica—Results from ¹⁷ O NMR spectroscopy Trease, Nicole M.; Clark, Ted M.; Grandinetti, Philip J. The Journal of Chemical Physics, Vol. 146, Issue 18 https://doi.org/10.1063/1.4983041	journal	May 2017
Proton-Selective ¹⁷ O− ¹ H Distance Measurements in Fast Magic-Angle-Spinning Solid-State NMR Spectroscopy for the Determination of Hydrogen Bond Lengths Brinkmann, Andreas; Kentgens, Arno P. M. Journal of the American Chemical Society, Vol. 128, Issue 46 https://doi.org/10.1021/ja065415k	journal	November 2006
Mechanism of Solid-State Thermolysis of Ammonia Borane: A ¹⁵ N NMR Study Using Fast Magic-Angle Spinning and Dynamic Nuclear Polarization Kobayashi, Takeshi; Gupta, Shalabh; Caporini, Marc A. The Journal of Physical Chemistry C, Vol. 118, Issue 34 https://doi.org/10.1021/jp504328x	journal	August 2014
BDPA-Nitroxide Biradicals Tailored for Efficient Dynamic Nuclear Polarization Enhanced Solid-State NMR at Magnetic Fields up to 21.1 T Wisser, Dorothea; Karthikeyan, Ganesan; Lund, Alicia Journal of the American Chemical Society, Vol. 140, Issue 41 https://doi.org/10.1021/jacs.8b08081	journal	September 2018
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 Lilly Thankamony, Aany Sofia; Lion, Cédric; Pourpoint, Frédérique Angewandte Chemie International Edition, Vol. 54, Issue 7 https://doi.org/10.1002/anie.201406463	journal	December 2014
Materials Characterization by Dynamic Nuclear Polarization-Enhanced Solid-State NMR Spectroscopy Rossini, Aaron J. The Journal of Physical Chemistry Letters, Vol. 9, Issue 17 https://doi.org/10.1021/acs.jpclett.8b01891	journal	August 2018
Enabling Natural Abundance ¹⁷ O Solid-State NMR by Direct Polarization from Paramagnetic Metal Ions Jardón-Álvarez, Daniel; Reuveni, Guy; Harchol, Adi The Journal of Physical Chemistry Letters, Vol. 11, Issue 14 https://doi.org/10.1021/acs.jpclett.0c01527	journal	June 2020
Recoupling of heteronuclear dipolar interactions in solid state magic-angle spinning NMR by simultaneous frequency and amplitude modulation Fu, Riqiang; Smith, Scott A.; Bodenhausen, Geoffrey Chemical Physics Letters, Vol. 272, Issue 5-6 https://doi.org/10.1016/S0009-2614(97)00537-X	journal	July 1997
Chemoselective Hydrogenation with Supported Organoplatinum(IV) Catalyst on Zn(II)-Modified Silica Camacho-Bunquin, Jeffrey; Ferrandon, Magali; Sohn, Hyuntae Journal of the American Chemical Society, Vol. 140, Issue 11 https://doi.org/10.1021/jacs.7b11981	journal	February 2018
Endogenous Dynamic Nuclear Polarization for Natural Abundance ¹⁷ O and Lithium NMR in the Bulk of Inorganic Solids Wolf, Tamar; Kumar, Sandeep; Singh, Harishchandra Journal of the American Chemical Society, Vol. 141, Issue 1 https://doi.org/10.1021/jacs.8b11015	journal	November 2018
Surface-selective direct ¹⁷ O DNP NMR of CeO ₂ nanoparticles Hope, Michael A.; Halat, David M.; Magusin, Pieter C. M. M. Chemical Communications, Vol. 53, Issue 13 https://doi.org/10.1039/C6CC10145C	journal	January 2017
Dynamic Nuclear Polarization Enhanced Solid-State NMR Spectroscopy of Functionalized Metal-Organic Frameworks Rossini, Aaron J.; Zagdoun, Alexandre; Lelli, Moreno Angewandte Chemie, Vol. 124, Issue 1 https://doi.org/10.1002/ange.201106030	journal	November 2011
Selective Host-Guest Interaction between Metal Ions and Metal-Organic Frameworks Using Dynamic Nuclear Polarization Enhanced Solid-State NMR Spectroscopy Guo, Zhiyong; Kobayashi, Takeshi; Wang, Lin-Lin Chemistry - A European Journal, Vol. 20, Issue 49 https://doi.org/10.1002/chem.201403884	journal	October 2014
Large Molecular Weight Nitroxide Biradicals Providing Efficient Dynamic Nuclear Polarization at Temperatures up to 200 K Zagdoun, Alexandre; Casano, Gilles; Ouari, Olivier Journal of the American Chemical Society, Vol. 135, Issue 34 https://doi.org/10.1021/ja405813t	journal	August 2013
Microstructure of silica monolayer solid acid catalysts determined by 29Si NMR spectroscopy Katada, Naonobu; Niwa, Miki Research on Chemical Intermediates, Vol. 24, Issue 5 https://doi.org/10.1163/156856798X00014	journal	May 1998
Dynamic Nuclear Polarization Enhanced Natural Abundance ¹⁷ O Spectroscopy Blanc, Frédéric; Sperrin, Luke; Jefferson, David A. Journal of the American Chemical Society, Vol. 135, Issue 8 https://doi.org/10.1021/ja4004377	journal	February 2013
Studies of Organically Functionalized Mesoporous Silicas Using Heteronuclear Solid-State Correlation NMR Spectroscopy under Fast Magic Angle Spinning Trebosc, Julien; Wiench, Jerzy W.; Huh, Seong Journal of the American Chemical Society, Vol. 127, Issue 20 https://doi.org/10.1021/ja0509127	journal	May 2005
Detection of Brønsted acid sites in zeolite HY with high-field 17O-MAS-NMR techniques Peng, Luming; Liu, Yun; Kim, Namjun Nature Materials, Vol. 4, Issue 3 https://doi.org/10.1038/nmat1332	journal	February 2005
Natural Abundance ¹⁵ N NMR by Dynamic Nuclear Polarization: Fast Analysis of Binding Sites of a Novel Amine-Carboxyl-Linked Immobilized Dirhodium Catalyst Gutmann, Torsten; Liu, Jiquan; Rothermel, Niels Chemistry - A European Journal, Vol. 21, Issue 9 https://doi.org/10.1002/chem.201405043	journal	January 2015
DNP by Thermal Mixing under Optimized Conditions Yields >60 000-fold Enhancement of ⁸⁹ Y NMR Signal Lumata, Lloyd; Jindal, Ashish K.; Merritt, Matthew E. Journal of the American Chemical Society, Vol. 133, Issue 22 https://doi.org/10.1021/ja201880y	journal	June 2011
Atomic Description of the Interface between Silica and Alumina in Aluminosilicates through Dynamic Nuclear Polarization Surface-Enhanced NMR Spectroscopy and First-Principles Calculations Valla, Maxence; Rossini, Aaron J.; Caillot, Maxime Journal of the American Chemical Society, Vol. 137, Issue 33 https://doi.org/10.1021/jacs.5b06134	journal	August 2015
Rapid acquisition of wideline MAS solid-state NMR spectra with fast MAS, proton detection, and dipolar HMQC pulse sequences Rossini, Aaron J.; Hanrahan, Michael P.; Thuo, Martin Physical Chemistry Chemical Physics, Vol. 18, Issue 36 https://doi.org/10.1039/C6CP04279A	journal	January 2016
A Slowly Relaxing Rigid Biradical for Efficient Dynamic Nuclear Polarization Surface-Enhanced NMR Spectroscopy: Expeditious Characterization of Functional Group Manipulation in Hybrid Materials Zagdoun, Alexandre; Casano, Gilles; Ouari, Olivier Journal of the American Chemical Society, Vol. 134, Issue 4 https://doi.org/10.1021/ja210177v	journal	January 2012
Well-Defined Silanols in the Structure of the Calcined High-Silica Zeolite SSZ-70: New Understanding of a Successful Catalytic Material Smeets, Stef; Berkson, Zachariah J.; Xie, Dan Journal of the American Chemical Society, Vol. 139, Issue 46 https://doi.org/10.1021/jacs.7b08810	journal	November 2017
Dynamic Nuclear Polarization NMR of Low-γ Nuclei: Structural Insights into Hydrated Yttrium-Doped BaZrO ₃ Blanc, Frédéric; Sperrin, Luke; Lee, Daniel The Journal of Physical Chemistry Letters, Vol. 5, Issue 14 https://doi.org/10.1021/jz5007669	journal	June 2014
Oxygen-17 dynamic nuclear polarisation enhanced solid-state NMR spectroscopy at 18.8 T Brownbill, Nick J.; Gajan, David; Lesage, Anne Chemical Communications, Vol. 53, Issue 17 https://doi.org/10.1039/C6CC09743J	journal	January 2017
Non-Topotactic Transformation of Silicate Nanolayers into Mesostructured MFI Zeolite Frameworks During Crystallization Berkson, Zachariah J.; Messinger, Robert J.; Na, Kyungsu Angewandte Chemie, Vol. 129, Issue 19 https://doi.org/10.1002/ange.201609983	journal	April 2017
Natural Abundance ¹⁷ O DNP Two-Dimensional and Surface-Enhanced NMR Spectroscopy Perras, Frédéric A.; Kobayashi, Takeshi; Pruski, Marek Journal of the American Chemical Society, Vol. 137, Issue 26 https://doi.org/10.1021/jacs.5b03905	journal	June 2015
Probing O–H Bonding through Proton Detected ¹ H– ¹⁷ O Double Resonance Solid-State NMR Spectroscopy Carnahan, Scott L.; Lampkin, Bryan J.; Naik, Pranjali Journal of the American Chemical Society, Vol. 141, Issue 1 https://doi.org/10.1021/jacs.8b10878	journal	November 2018
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 Lilly Thankamony, Aany Sofia; Lion, Cédric; Pourpoint, Frédérique Angewandte Chemie, Vol. 127, Issue 7 https://doi.org/10.1002/ange.201406463	journal	December 2014
The Role of Ligands in the Chemical Synthesis and Applications of Inorganic Nanoparticles Heuer-Jungemann, Amelie; Feliu, Neus; Bakaimi, Ioanna Chemical Reviews, Vol. 119, Issue 8 https://doi.org/10.1021/acs.chemrev.8b00733	journal	March 2019
Natural Abundance ¹⁷ O DNP NMR Provides Precise O−H Distances and Insights into the Brønsted Acidity of Heterogeneous Catalysts Perras, Frédéric A.; Wang, Zhuoran; Naik, Pranjali Angewandte Chemie International Edition, Vol. 56, Issue 31 https://doi.org/10.1002/anie.201704032	journal	June 2017
Silica Gel Surface: Molecular Dynamics of Surface Silanols Kobayashi, Takeshi; DiVerdi, Joseph A.; Maciel, Gary E. The Journal of Physical Chemistry C, Vol. 112, Issue 11 https://doi.org/10.1021/jp709759e	journal	February 2008
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 Xue, Xianyu; Kanzaki, Masami The Journal of Physical Chemistry B, Vol. 105, Issue 17 https://doi.org/10.1021/jp0040751	journal	May 2001
Combining fast magic angle spinning dynamic nuclear polarization with indirect detection to further enhance the sensitivity of solid-state NMR spectroscopy Wang, Zhuoran; Hanrahan, Michael P.; Kobayashi, Takeshi Solid State Nuclear Magnetic Resonance, Vol. 109 https://doi.org/10.1016/j.ssnmr.2020.101685	journal	October 2020
Surface enhanced dynamic nuclear polarization solid-state NMR spectroscopy sheds light on Brønsted–Lewis acid synergy during the zeolite catalyzed methanol-to-hydrocarbon process Dutta Chowdhury, Abhishek; Yarulina, Irina; Abou-Hamad, Edy Chemical Science, Vol. 10, Issue 39 https://doi.org/10.1039/C9SC02215E	journal	January 2019
A 29Si NMR investigation of the structure of amorphous silica—alumina supports McMillan, M.; Brinen, J. S.; Carruthers, J. D. Colloids and Surfaces, Vol. 38, Issue 1 https://doi.org/10.1016/0166-6622(89)80150-7	journal	January 1989
Magic angle spinning oxygen-17 NMR of aluminum oxides and hydroxides Walter, Thomas H.; Oldfield, Eric The Journal of Physical Chemistry, Vol. 93, Issue 18 https://doi.org/10.1021/j100355a034	journal	September 1989
Non-Topotactic Transformation of Silicate Nanolayers into Mesostructured MFI Zeolite Frameworks During Crystallization Berkson, Zachariah J.; Messinger, Robert J.; Na, Kyungsu Angewandte Chemie International Edition, Vol. 56, Issue 19 https://doi.org/10.1002/anie.201609983	journal	April 2017
Correlated structural distributions in silica glass Clark, Ted M.; Grandinetti, Philip J.; Florian, Pierre Physical Review B, Vol. 70, Issue 6 https://doi.org/10.1103/PhysRevB.70.064202	journal	August 2004
Observation of Low-γ Quadrupolar Nuclei by Surface-Enhanced NMR Spectroscopy Nagashima, Hiroki; Trébosc, Julien; Kon, Yoshihiro Journal of the American Chemical Society, Vol. 142, Issue 24 https://doi.org/10.1021/jacs.9b13838	journal	May 2020
Interfacial Ca2+ environments in nanocrystalline apatites revealed by dynamic nuclear polarization enhanced 43Ca NMR spectroscopy Lee, Daniel; Leroy, César; Crevant, Charlène Nature Communications, Vol. 8, Issue 1 https://doi.org/10.1038/ncomms14104	journal	January 2017
Probing Surface Hydrogen Bonding and Dynamics by Natural Abundance, Multidimensional, ¹⁷ O DNP-NMR Spectroscopy Perras, Frédéric A.; Chaudhary, Umesh; Slowing, Igor I. The Journal of Physical Chemistry C, Vol. 120, Issue 21 https://doi.org/10.1021/acs.jpcc.6b02579	journal	May 2016
Determinations of structure and bonding in amorphous SiO2 using 17O NMR Geissberger, A. E.; Bray, P. J. Journal of Non-Crystalline Solids, Vol. 54, Issue 1-2 https://doi.org/10.1016/0022-3093(83)90087-X	journal	January 1983
Natural Abundance ¹⁷ O DNP NMR Provides Precise O−H Distances and Insights into the Brønsted Acidity of Heterogeneous Catalysts Perras, Frédéric A.; Wang, Zhuoran; Naik, Pranjali Angewandte Chemie, Vol. 129, Issue 31 https://doi.org/10.1002/ange.201704032	journal	June 2017

Similar Records

Indirectly detected chemical shift correlation NMR spectroscopy in solids under fast magic angle spinning

Thesis/Dissertation · Sat Jan 01 00:00:00 EST 2011 · OSTI ID:1797583

Mao, Kanmi

Natural abundance ¹⁷O DNP two-dimensional and surface-enhanced NMR spectroscopy

Journal Article · Mon Jun 22 00:00:00 EDT 2015 · Journal of the American Chemical Society · OSTI ID:1797583

Perras, Frédéric A.; Kobayashi, Takeshi; Pruski, Marek

Characterization of nanostructured organic-inorganic hybrid materials using advanced solid-state NMR spectroscopy

Journal Article · Fri May 01 00:00:00 EDT 2009 · Materials Research Society Symposia Proceedings · OSTI ID:1797583

Mao, Kanmi; Rapp, Jennifer L; Wiench, Jerzy W; +1 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

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

Citation Formats

References (48)

Similar Records

Related Subjects

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