skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Natural abundance 17O DNP NMR provides precise O–H distances and insights into the Brønsted acidity of heterogeneous catalysts

Journal Article · · Angewandte Chemie (International Edition)
 [1];  [1];  [1];  [1];  [1]
  1. Ames Lab. and Iowa State Univ., Ames, IA (United States)
+ Show Author Affiliations

Abstract Heterogeneous Brønsted acid catalysts are tremendously important in industry, particularly in catalytic cracking processes. Here we show that these Brønsted acid sites can be directly observed at natural abundance by 17 O DNP surface‐enhanced NMR spectroscopy (SENS). We additionally show that the O−H bond length in these catalysts can be measured with sub‐picometer precision, to enable a direct structural gauge of the lability of protons in a given material, which is correlated with the pH of the zero point of charge of the material. Experiments performed on materials impregnated with pyridine also allow for the direct detection of intermolecular hydrogen bonding interactions through the lengthening of O−H bonds.

Research Organization:
Ames Laboratory (AMES), Ames, IA (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
AC02-07CH11358; FY2015-MPRU-0812
OSTI ID:
1363633
Alternate ID(s):
OSTI ID: 1374912
Report Number(s):
IS-J-9274
Journal Information:
Angewandte Chemie (International Edition), Vol. 56, Issue 31; ISSN 1433-7851
Publisher:
WileyCopyright Statement
Country of Publication:
United States
Language:
English

References (48)

Improving dipolar recoupling for site-specific structural and dynamics studies in biosolids NMR: windowed RN-symmetry sequences journal January 2016
Heteronuclear NMR Spectroscopy as a Surface-Selective Technique: A Unique Look at the Hydroxyl Groups of γ-Alumina. journal March 2014
Evaluation of Cross-Correlation Effects and Measurement of One-Bond Couplings in Proteins with Short Transverse Relaxation Times journal March 2000
Solid-state nuclear magnetic resonance investigations of the nature, property, and activity of acid sites on solid catalysts journal May 2011
Solid-State QCPMG NMR of Low-γ Quadrupolar Metal Nuclei in Natural Abundance journal July 2000
Phosphate modified ceria as a Brønsted acidic/redox multifunctional catalyst journal January 2017
1H/15N NMR chemical shielding, dipolar15N,2H coupling and hydrogen bond geometry correlations in a novel series of hydrogen-bonded acid-base complexes of collidine with carboxylic acids journal January 2001
Windowed R-PDLF recoupling: A flexible and reliable tool to characterize molecular dynamics journal September 2013
Highly Dispersed SiO x /Al 2 O 3 Catalysts Illuminate the Reactivity of Isolated Silanol Sites journal September 2015
The Point of Zero Charge of CeO2 journal October 1994
17 O Magic Angle Spinning NMR Studies of Brønsted Acid Sites in Zeolites HY and HZSM-5 journal January 2007
Enhanced symmetry-based dipolar recoupling in solid-state NMR journal August 2003
Surface-selective direct 17 O DNP NMR of CeO 2 nanoparticles journal January 2017
Dynamic nuclear polarization at high magnetic fields journal February 2008
Large Molecular Weight Nitroxide Biradicals Providing Efficient Dynamic Nuclear Polarization at Temperatures up to 200 K journal August 2013
The zero point of charge of silica—alumina oxide suspensions journal January 1984
NMR Determination of Amide N−H Equilibrium Bond Length from Concerted Dipolar Coupling Measurements journal December 2008
Dynamic Nuclear Polarization Enhanced Natural Abundance 17 O Spectroscopy journal February 2013
Detection of Brønsted acid sites in zeolite HY with high-field 17O-MAS-NMR techniques journal February 2005
Surface Enhanced NMR Spectroscopy by Dynamic Nuclear Polarization journal November 2010
Oxide/water interfaces: how the surface chemistry modifies interfacial water properties journal March 2012
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
Measurement of NH Bond Lengths by Fast Magic-Angle Spinning Solid-State NMR Spectroscopy:  A New Method for the Quantification of Hydrogen Bonds journal November 2001
Measuring Brønsted Acid Site O−H Distances in Zeolites HY and HZSM-5 with Low-Temperature 17 O− 1 H Double Resonance MAS NMR Spectroscopy journal December 2010
Oxygen-17 dynamic nuclear polarisation enhanced solid-state NMR spectroscopy at 18.8 T journal January 2017
Dynamic Nuclear Polarization Surface Enhanced NMR Spectroscopy journal March 2013
Natural Abundance 17 O DNP Two-Dimensional and Surface-Enhanced NMR Spectroscopy journal June 2015
A Model for the Surface of γ-Alumina 1 journal January 1965
Pyridine- 15 N A Mobile NMR Sensor for Surface Acidity and Surface Defects of Mesoporous Silica journal October 2003
Structure of alumina surfaces journal January 1996
17 O NMR Gives Unprecedented Insights into the Structure of Supported Catalysts and Their Interaction with the Silica Carrier journal May 2012
Measurements of motionally averaged heteronuclear dipolar couplings in MAS NMR using R-type recoupling journal June 2004
Dynamic Nuclear Polarization of Oxygen-17 journal July 2012
Heteronuclear polarization transfer by symmetry-based recoupling sequences in solid-state NMR journal September 2004
17O MQMAS NMR studies of Na-A and Ca-AElectronic supplementary information (ESI) available: Fig. S1: schematic structure of zeolite A. Fig. S2: 17O 1-pulse spectra. Fig. S3: 17O MQMAS NMR spectra. Comparison of hydrated and dehydrated Na-A. See http://www.rsc.org/suppdata/cc/b2/b208356f/ journal October 2002
Inorganic Solid Acids and Their Use in Acid-Catalyzed Hydrocarbon Reactions journal May 1995
Zero-point-of-charge prediction from crystal chemistry and solvation theory journal July 1994
Infrared spectroscopic study of hydroxyl group acid strength of silica, alumina, and magnesia mixed oxides journal September 1982
Coking and deactivation of zeolites journal September 1989
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
Theoretical prediction of single-site surface-protonation equilibrium constants for oxides and silicates in water journal October 1996
Magic angle spinning oxygen-17 NMR of aluminum oxides and hydroxides journal September 1989
Mutable Lewis and Brønsted Acidity of Aluminated SBA-15 as Revealed by NMR of Adsorbed Pyridine- 15 N journal October 2011
Probing Surface Hydrogen Bonding and Dynamics by Natural Abundance, Multidimensional, 17 O DNP-NMR Spectroscopy journal May 2016
Highly Dispersed SiO x /Al 2 O 3 Catalysts Illuminate the Reactivity of Isolated Silanol Sites journal September 2015
Dynamic Nuclear Polarization Solid-State NMR in Heterogeneous Catalysis Research journal October 2015
Br⊘nsted Acid Sites in Zeolites Characterized by Multinuclear Solid-State NMR Spectroscopy journal November 1997
Dynamic Nuclear Polarization of 17 O: Direct Polarization journal November 2013

Cited By (5)

Mimicking Base Interaction with Acidic Sites [Si-O( H )-Al] of Zeolites in Molecular Models : Mimicking Base Interaction with Acidic Sites [Si-O( journal October 2017
Fast detection and structural identification of carbocations on zeolites by dynamic nuclear polarization enhanced solid-state NMR journal January 2018
DNP NMR spectroscopy reveals new structures, residues and interactions in wild spider silks journal January 2019
Shedding light on the atomic-scale structure of amorphous silica-alumina and its Brønsted acid sites text January 2019
Determining the Surface Structure of Silicated Alumina Catalysts via Isotopic Enrichment and Dynamic Nuclear Polarization Surface-Enhanced NMR Spectroscopy journal October 2017

Similar Records

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY