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Crystallography 2018 Structural Chemistry & Crystallography Communication
ISSN: 2470-9905 Page 27
June 04-05, 2018
London, UK
3rd Edition of International Conference on
Advanced Spectroscopy,
Crystallography and Applications
in Modern Chemistry
NMR crystallography combines state-of-the-art high-
resolution solid-state NMR experiments with state-of-the-
art quantum chemistry calculations thus allowing determining
structural and dynamic characteristics in a variety of systems.
In this work, we are going to demonstrate different steps of
NMR crystallography approaches with an example of supported
oxide catalysts. The recent advances in NMR of oxide-based
systems are primarily associated with the achievements in
NMR spectroscopy of quadrupolar nuclei since the majority
of NMR-observable isotopes of elements composing oxide
systems possess quadrupole moments. Ultra-high magnetic
fields (up to 23.5 T), ultra-high sample spinning (~ 100 kHz),
as well as modern electronic components and devices together
with a number of software programs allowing researchers to
extract parameters of chemical shift and nuclear quadrupole
interaction tensors, as well as their mutual orientation.
The first step of the study was to test NMR crystallography
approach on individual compounds. After, experimental NMR
parameters of real catalysts were determined. Based on
values obtained, several sets of models were proposed. For
suggested models, NMR parameters were calculated by DFT.
When a good matching between experimental and calculated
NMR parameters was achieved, it was concluded that the 3D
structure of surface sites is identified. It is very important that
NMR crystallography in application to catalysts could serve not
only for characterization of structure of surface sites, but also
for characterization of their catalytic activity, for this we have
to check catalytic activity of different sites by probe molecules
(both experimentally and theoretically). The next step was
connected with adsorption of test molecules (H2O, CO2,
CH3OH, etc.) on real catalysts (experimental part) and onmodel
surface sites (theoretical part). At this stage, it is reasonable to
use additional experimental techniques (for instance, FTIR). In
case of good agreement between experimantal and theoretical
parameters, it is possible to determine 3D structures of active
sites.
Acknowledgements: Authors thank funding provided via RFBR
projects № 17-03-00531.
Recent Publications
1. O.B. Lapina, V.V. Terskikh (2012) Quadrupolar Metal
NMR of Oxide Materials Including Catalysts’ Chapter
27, in NMR of Quadrupolar Nuclei in Solid Materials.
Wasylishen, R.E., Ashbrook, S.E. and Wimperis, S.
(eds). John Wiley & Sons Ltd, Chichester, UK, pp 467-
494.
2. O.B. Lapina, (2017), Modern ssNMR for heterogeneous
catalysis, Catal. Today, 285, 179.
3. E. Papulovskiy, D.F. Khabibulin, V.V. Terskikh, E.A.
Paukshtis, V. M. Bondareva, A.A. Shubin, A.S. Andreev,
and O.Lapina, (2015) Effect of Impregnation on
the Structure of Niobium Oxide/Alumina Catalysts
Studied by Multinuclear Solid-State NMR, FTIR, and
Quantum Chemical Calculations, J. Phys. Chem.C,
119, 10400−10411.
4. A.S. Andreev , N.V. Bulina, M.V. Chaikina,
Prosanov, V.V. Terskikh, O.B. Lapina, (2017) Solid-
state NMR and computational insights into the
crystal structure of silicocarnotite-based bioceramic
materials synthesized mechanochemically, Solid
State Nuclear Magnetic Resonance 84, 151–157.
5. A.S. Andreev, М.A. Kazakova, A.V. Ishchenko, A.G.
Selyutin, O.B. Lapina, V.L. Kuznetsov, J.-B.d’Espinose
de Lacaillerie, (2017) Magnetic and dielectric
properties of carbon nanotubes with embedded cobalt
nanoparticles, Carbon, 114, 39-49
6. I.V. Yakovlev, A.M. Volodin, E.S. Papulovskiy, A.S.
Andreev, O.B. Lapina, (2017) Structure of Carbon-
Coated C12A7 Electride via Solid-State NMR and DFT
Calculations, J.Phys.Chem.C 121, 22268.
7. A.S. Andreev, D.V. Krasnikov, V.I. Zaikovskii, S.V.
Cherepanova, M.A. Kazakova, O.B. Lapina, V.L.
NMR CRYSTALLOGRAPHY AS A TOOL FOR CHARACTERIZATION OF ACTIVE
SITES OF SOLID CATALYSTS
Olga B. Lapina1,2, A.A. Shubin1,2 and E. Papulovsky1
1Boreskov Institute of catalysis, Russia
2Novosibirsk State University, Russia
Olga B. Lapina et al., Struct Chem Crystallogr Commun 2018, Volume 4
DOI: 10.21767/2470-9905-C1-005