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Title: Interrogating the Lewis Acidity of Metal Sites in Beta Zeolites with 15N Pyridine Adsorption Coupled with MAS NMR Spectroscopy

Journal Article · · Journal of Physical Chemistry. C
 [1];  [2];  [3];  [4]
  1. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Chemical Engineering; ExxonMobil Research and Engineering Co., Annandale, NJ (United States)
  2. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Chemical Engineering. Dept. of Chemistry and Francis Bitter Magnet Lab.; Univ. of Alberta, Edmonton, AB (Canada). Dept. of Chemistry
  3. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Chemical Engineering. Dept. of Chemistry and Francis Bitter Magnet Lab.
  4. Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States). Dept. of Chemical Engineering
+ Show Author Affiliations

Here, the Lewis acidity of isolated framework metal sites in Beta zeolites was characterized with 15N isotopically labeled pyridine adsorption coupled with magic-angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy. The 15N chemical shift of adsorbed pyridine was found to scale with the acid character of both Lewis (Ti, Hf, Zr, Nb, Ta, and Sn) and Brønsted (B, Ga, and Al) acidic heteroatoms. The 15N chemical shift showed a linear correlation with Mulliken electronegativity of the metal center in the order Ti < Hf < Zr < Nb < Ta < Sn < H+. Theoretical calculations using density functional theory (DFT) showed a strong correlation between experimental 15N chemical shift and the calculated metal–nitrogen bond dissociation energy, and revealed the importance of active site reorganization when determining adsorption strength. The relationships found between 15N pyridine chemical shift and intrinsic chemical descriptors of metal framework sites complement adsorption equilibrium data and provide a robust method to characterize, and ultimately optimize, metal-reactant binding and activation for Lewis acid zeolites. Direct 15N MAS NMR detection protocols applied to the Lewis acid–base adducts allowed the differentiation and quantification of framework metal sites in the presence of extraframework oxides, including highly quadrupolar nuclei that are not amenable for quantification with conventional NMR methods.

Research Organization:
Massachusetts Inst. of Technology (MIT), Cambridge, MA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; National Institutes of Health (NIH); Natural Sciences and Engineering Research Council of Canada (NSERC)
Grant/Contract Number:
SC0016214; EB-002026
OSTI ID:
1462348
Journal Information:
Journal of Physical Chemistry. C, Vol. 120, Issue 50; ISSN 1932-7447
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 83 works
Citation information provided by
Web of Science

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Silica‐Supported Mn II Sites as Efficient Catalysts for Carbonyl Hydroboration, Hydrosilylation, and Transesterification journal October 2012
The Nature and Catalytic Function of Cation Sites in Zeolites: a Computational Perspective journal October 2018
Tungsten Catalyst Incorporating a Well‐Defined Tetracoordinated Aluminum Surface Ligand for Selective Metathesis of Propane, [(≡Si−O−Si≡)(≡Si−O−) 2 Al−O−W(≡C t Bu) (H) 2 ] journal October 2018
Formation and Rearrangement of Reduced Diiminepyridine Complexes of Zr and Hf: Formation and Rearrangement of Reduced Diiminepyridine Complexes of Zr and Hf journal November 2018
Formation and Rearrangement of Reduced Diiminepyridine Complexes of Zr and Hf journal November 2018

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