Abstract
2H solid-state NMR represents a reliable method for probing the dynamics of the molecules in confined geometries, including microporous and mesoporous materials such as zeolites or metal–organic frameworks (MOFs). Dynamic characteristics derived from analyses of 2H NMR line shape and spin relaxation for adsorbed deuterated molecules can be related with translational motions along the porous framework. This opens up the possibility to use 2H NMR for probing self-diffusion within porous materials. Herein we discuss the basic principles and approaches that can be used to derive the information on diffusion coefficients based on analysis of the dynamics of confined molecules by 2H NMR. We discuss the corresponding possibilities and limitations of 2H NMR compared to other experimental methods, such QENS and PFG NMR. Several examples for estimation of diffusion coefficients by 2H NMR for alkanes, olefins, alcohol, benzene, pyridine in zeolites and MOFs are provided.
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Abbreviations
- T 1 :
-
Spin–lattice relaxation time
- T 2 :
-
Spin–spin relaxation time
- Q 0 :
-
Quadrupole coupling constant of deuterium nucleus in C–2H bond of a hydrocarbon molecule
- Q eff :
-
Effective quadrupole coupling constant
- D :
-
Diffusion coefficient
- D NMR :
-
Diffusion coefficient determined by NMR
- D QENS :
-
Diffusion coefficient determined by QENS
- D 0 self :
-
Self-diffusion coefficient of benzene in ZIF-8
- D i,MS :
-
Diffusion coefficient derived from membrane permeation or sorption uptake studies
- D iso :
-
Diffusion coefficient for benzene in UiO-66
- D anis :
-
Diffusion coefficient for benzene in UiO-66 estimated provided that anisotropic motion of benzene was taken into account
- D i (i = 1–3):
-
Diffusion coefficients for olefins in NaX, NaY and AgNaX zeolites
- < l 2 > :
-
Mean square displacement of the molecule in the pores
- τ :
-
Diffusion time in Eq. (1), Einstein equation
- τ c :
-
2H NMR reorientational correlation time
- τ D :
-
Characteristic time for one translational jump
- τ ci :
-
Characteristic time for conformational isomerization
- τ R :
-
Characteristic time for reorientational motion by random collision with the cage walls
- τ i ( i = 1–3):
-
Diffusion correlation times for olefins in NaX, NaY and AgNaX zeolites
- τ QENS :
-
Characteristic time of diffusional jump determined by QENS
- τ ex :
-
Characteristic time of molecule exchange between the cages
- τ Diso :
-
Correlation time for isotropic motion of benzene in UiO-66
- τ Danis :
-
Correlation time for anisotropic motion of benzene in UiO-66
- τ iso :
-
Correlation time for isotropic motion of benzene in MIL-100
- E ci :
-
Activation energy for conformational isomerization
- E D :
-
Activation energy for diffusion
- E R :
-
Activation energy for reorientational motion by random collision with the cage walls
- E QENS :
-
Activation energy for diffusion derived by QENS
- E iso :
-
Activation energy for isotropic motion of benzene in UiO-66 or pyridine in MIL-53
- E i :
-
Activation energy for diffusion of olefins in NaX and AgNaX zeolites
- E Danis :
-
Activation energy for anisotropic motion of benzene in UiO-66
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Acknowledgements
This work was supported by Russian Foundation for Basic Research (Grants No. 18-29-04009) and also in part by the Ministry of Science and High Education of the Russian Federation (budget Project No. AAAA-A17-117041710084-2 for Boreskov Institute of Catalysis).
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Kolokolov, D.I., Freude, D. & Stepanov, A.G. Dynamics in nanoporous materials probed by 2H solid state NMR: estimation of self-diffusion coefficients. Adsorption 27, 841–855 (2021). https://doi.org/10.1007/s10450-020-00256-x
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DOI: https://doi.org/10.1007/s10450-020-00256-x