scholarly journals Exploring catalyst passivation with NMR relaxation

2017 ◽  
Vol 204 ◽  
pp. 439-452 ◽  
Author(s):  
Neil Robinson ◽  
Lynn F. Gladden ◽  
Carmine D’Agostino
Keyword(s):  
Liquid Phase ◽  
Complex Analysis ◽  
Nmr Relaxation ◽  
Lattice Relaxation ◽  
Spin Lattice Relaxation ◽  
Bulk Liquid ◽  
Hydroxyl Groups ◽  
Surface Dynamics ◽  
Spin Lattice ◽  
Non Invasive

NMR relaxation has recently emerged as a novel and non-invasive tool for probing the surface dynamics of adsorbate molecules within liquid-saturated mesoporous catalysts. The elucidation of such dynamics is of particular relevance to the study and development of solvated green catalytic processes, such as the production of chemicals and fuels from bio-resources. In this paper we develop and implement a protocol using high field 1H NMR spin–lattice relaxation as a probe of the reorientational dynamics of liquids imbibed within mesoporous oxide materials. The observed relaxation of liquids within mesoporous materials is highly sensitive to the adsorbed surface layer, giving insight into tumbling behaviour of spin-bearing chemical environments at the pore surface. As a prototypical example of relevance to liquid-phase catalytic systems, we examine the mobility of liquid methanol within a range of common catalyst supports. In particular, through the calculation and comparison of a suitable interaction parameter, we assess and quantify changes to these surface dynamics upon replacing surface hydroxyl groups with hydrophobic alkyl chains. Our results indicate that the molecular tumbling of adsorbed methanol is enhanced upon surface passivation due to the suppression of surface-adsorbate hydrogen bonding interactions, and tends towards that of the unrestricted bulk liquid. A complex analysis in which we account for the influence of changing pore structure and surface chemistry upon passivation is discussed. The results presented highlight the use of NMR spin–lattice relaxation measurements as a non-invasive probe of molecular dynamics at surfaces of interest to liquid-phase heterogeneous catalysis.

1HNMR Study on the Motion of NH4+ in Ferroelectric NH4H(ClH2CCOO)2 and Mixed (NH4)1-xRbxH(ClH2CCOO)2 (x = 0.15)

2002 ◽  
Vol 57 (11) ◽  
pp. 883-887 ◽  
Author(s):  
M. Zdanowska-Fra̡czek ◽  
A. Kozaka ◽  
R. Jakubasb ◽  
J. Wa̡sickia ◽  
R. Utrechta
Keyword(s):  
Relaxation Time ◽  
Group Dynamics ◽  
Nmr Relaxation ◽  
Activation Parameters ◽  
Lattice Relaxation ◽  
Relaxation Mechanism ◽  
Lattice Relaxation Time ◽  
Spin Lattice Relaxation ◽  
Temperature Dependent ◽  
Spin Lattice

Temperature-dependent proton NMR relaxation time measurements have been performed at 60 MHz in order to study the NH4+ dynamics in ferroelectric NH4H(ClH2CCOO)2 and mixed Rbx(NH4)1-x(ClH2CCOO)2, where x = 0.15. The data indicate that the dominant relaxation mechanism for the NMR spin-lattice relaxation time T 1 in both crystals involves simultaneous NH4 group reorientation about their C2 and C3 symmetry axis in the paraelectric phase. Details of the NH4+reorientation have been inferred from analysis of temperature dependence of T1 assuming the Watton model. The activation parameters of the motionshave been determined.It has been found that the substitution of Rb does not change the activation parameters of the NH4 group dynamics.

scholarly journals Methyl Group Rotation and Tunnellingin Crystals of 5-Membered Ring Molecules

1988 ◽  
Vol 43 (1) ◽  
pp. 35-42 ◽  
Author(s):  
A.-S. Montjoie ◽  
W. Müller-Warmuth ◽  
Hildegard Stiller ◽  
J. Stanislawski
Keyword(s):  
Elevated Temperatures ◽  
Inelastic Neutron Scattering ◽  
Relaxation Times ◽  
Nmr Relaxation ◽  
Lattice Relaxation ◽  
Inelastic Neutron ◽  
Spin Lattice Relaxation ◽  
Relaxation Rates ◽  
Quantum Tunnelling ◽  
Spin Lattice

Abstract1H NMR spin-lattice relaxation times T1 and -if accessible -level-crossing peaks and inelastic neutron scattering spectra have been measured for solid 2-and 3-methylfuran, 2-and 3-methylthiophene, 3-and 4-methylpyrazole, 1-methylimidazole, and 5-methylisoxazole. From the tunnel splittings, the torsional excitations and the NMR relaxation rates, the molecular dynamics of the methyl rotators has been evaluated between the limits of quantum tunnelling at low temperatures and thermally activated random reorientation at elevated temperatures.

Ionic mobility in Nasicon-type LiMIV2(PO4)3 materials followed by 7Li NMR spectroscopy.

2011 ◽  
Vol 1313 ◽  
Author(s):  
K. Arbi ◽  
I. Sobrados ◽  
M. Hoelzel ◽  
A. Kuhn ◽  
F. Garcia-Alvarado ◽  
...  
Keyword(s):  
Nmr Spectroscopy ◽  
Impedance Spectroscopy ◽  
Nmr Relaxation ◽  
Lattice Relaxation ◽  
Ionic Mobility ◽  
Spin Lattice Relaxation ◽  
Pulse Field ◽  
Relaxation Rates ◽  
Arrhenius Behavior ◽  
Spin Lattice

AbstractLithium mobility in LiM2(PO4)3 compounds, with M= Ge, Ti, Sn, Zr and Hf, has been investigated by 7Li Nuclear Magnetic Resonance (NMR) spectroscopy in the temperature range 100-500 K. From the analysis of 7Li NMR quadrupole interactions (CQ and η parameters), Li sites occupancy and exchange processes between structural sites have been studied. Below 250K, Li ions are preferentially located at M1 sites in rhombohedral phases, but occupy M12 sites in triclinic ones. At increasing temperatures, Li mobility has been deduced from spin-spin () and spin-lattice relaxation () rates. In this analysis, the presence of two relaxation mechanisms in plots has been associated with departures of conductivity from the Arrhenius behavior. At high temperatures, residence times at M12−T11−T11−T1 and M12 sites become similar and conductivity significantly increase. This superionic state can be achieved by enlarged order-disorder transformations in rhombohedral phases, or by sharp first order transitions in triclinic ones. Results described in the LiTi2(PO4)3 sample have been compared with those obtained in rhombohedral Li1+xTi2-xAlx(PO4)3 and LiTi2-xZrx(PO4)3 series showing respectively higher and lower conductivities. In the case of Li1.2Ti1.8Al0.2(PO4)3, displaying the highest reported conductivity, NMR results are discussed in relation with those obtained by Neutron Diffraction (ND) and Impedance Spectroscopy (IS). Diffusion coefficients determined by NMR Pulse Field Gradient (PFG) technique are similar to those deduced from Impedance Spectroscopy and NMR relaxation data.

Spin–lattice relaxation and hydrodynamical rotation of triphenylene

1977 ◽  
Vol 55 (20) ◽  
pp. 3602-3608 ◽  
Author(s):  
Roderick E. Wasylishen ◽  
Brian A. Pettitt ◽  
Werner Danchura
Keyword(s):  
Nmr Relaxation ◽  
Lattice Relaxation ◽  
Spin Lattice Relaxation ◽  
Relaxation Rates ◽  
Hindered Rotation ◽  
Spin Lattice ◽  
Slip Boundary ◽  
The Times ◽  
Dynamic Rotation ◽  
C Nmr

The viscosity and temperature dependence of 1H, 2H, and 13C nmr relaxation rates of triphenylene were investigated. The observed η/T dependence of the reorientation correlation time, τc, is compared with that derived from the work of Hu and Zwanzig based on hydro–dynamic rotation with 'stick' and 'slip' boundary conditions. In the hydrodynamic regime,τ = Cη/T. The observed slope, Cexperimental, is 6.2 ± 2 ns K/cP and the calculated values are Cslip = 4.1 ± 0.6 ns K/cP and Cstick = 31.0 ± 3.1 ns K/cP. These data imply that the reorientation of triphenylene obeys a near-slip condition. That is, rotation in the plane of the molecule encounters little resistance, but rotation of the plane of the molecule is resisted by shear forces in the solvent displaced during rotation. Expressions are given for Boltzmann-averaged free rotation times and comparisons are made with the η = 0 intercept and the times for slightly hindered rotation.

scholarly journals Analysis of water state adsorbed by cellulose fibers

2019 ◽  
Vol 58 (5) ◽  
pp. 24-31
Author(s):  
Daria S. Masas ◽  
◽  
Maria S. Ivanova ◽  
Gocha Sh. Gogelashvili ◽  
Alexander S. Maslennikov ◽  
...  
Keyword(s):  
Adsorbed Water ◽  
Lattice Relaxation ◽  
Spin Lattice Relaxation ◽  
Water Molecules ◽  
Hydroxyl Groups ◽  
Active Centers ◽  
Surface Hydroxyl ◽  
Spin Lattice ◽  
Donor Acceptor ◽  
Elementary Fibrils

Modernized model of microfibril cellulose layered structure is proposed. This model considers presence of slit-shaped micropores in space between elementary fibrils and cellulose microfibrils. It’s discussed the nature of donor-acceptor hydrogen bonds formation: intra-, intermolecular, and interlayer bonds inherent in each glucopyranous cellulose link. It’s described the mechanism of water molecules specific adsorption interactions in a monolayer with active centers located on the hydrophilic surfaces of elementary fibrils. Dipole-dipole energy transition into energy of hydrogen bond is discussed during adsorption process between active centers of cellulose and water adsorptive molecules. Analysis of water molecules dipole-dipole interactions with surface hydroxyl groups of cellulose showed that at distance of 2.5-3 Å energy of this interaction transforms into energy of hydrogen bond. It is discussed the formation mechanism of water molecules donor-acceptor bonds with cellulose surface hydroxyl groups. Thermodynamic parameters characterizing adsorbate state the in these layers are determined by proton magnetic relaxation and sorption measurements. It’s established the possibility of determining adsorption net heat in bilayer considering Arrhenius nature of adsorbate thermal molecular motions correlation times. Increase in entropy of adsorbed water during adsorption process is revealed basis on Vant Hoff equation and certain adsorption equilibrium constant. The calculation established that distance between nearest active centers of cellulose is 6.5 Å. This leads to disunity of adsorbed water molecules and allows application of Langmuir and BET adsorption theory. Analysis of spin-lattice relaxation times dependence on cellulose moisture content made it possible to establish the cause of its crystallite wedging from adsorbed water molecules at adsorption initial stages. Decline of the spin-lattice relaxation unambiguously indicates the process of cellulose dispersion into its structural elements. It was established that during adsorption a part of the internal regions of crystallites passes to their surface with participation of cellulose hydroxyl groups. During desorption reverse process is observed.

scholarly journals Possibilities of proton magnetic resonance in determination the cellulose crystallinity

2019 ◽  
Vol 59 (8) ◽  
pp. 116-123
Author(s):  
Yury B. Grunin ◽  
◽  
Maria S. Ivanova ◽  
Keyword(s):  
Relaxation Time ◽  
Relaxation Times ◽  
Nmr Relaxation ◽  
Lattice Relaxation ◽  
Active Surface ◽  
Lattice Relaxation Time ◽  
Spin Lattice Relaxation ◽  
Cellulose Crystallinity ◽  
Spin Lattice ◽  
Free Induction

A layered model of the structural organization of macrofibrils of native cellulose, consisting of microfibrils, which include elementary fibrils, has been developed. A feature of the proposed model is the presence of slit-like pores between the crystalline elements of cellulose. It was found that, on average, each water molecule interacts with one glucose residue of the surface chains of cellulose with the formation of hydrogen bonds in the framework of monolayer adsorption. This allows to establish a correlation between the cellulose crystallinity and the capacity of the adsorption water monolayer on its active surface. Based on the condition of rapid molecular exchange between the adsorption water layers in the framework of the Bloembergen-Purcell-Pound theory, an approach is proposed for determination the capacity of water monolayer. The obtained values are consistent with the results of solving the Brunauer-Emmett-Teller equation for the adsorption isotherm of water on the active surface of cellulose. The Fourier transform of the free induction decay signal of cellulose allows to estimate its crystallinity at various moisture contents. Methods have been developed for assessing the crystallinity of different types of dry cellulose based on NMR relaxation parameters — spin-lattice relaxation time and spin-spin relaxation time. Using the method of deuteration of cellulose, the relaxation times of its crystalline regions were determined. The results of preliminary studies showed that the crystallinity of cotton cellulose is higher in comparison with the same parameter of woody types of cellulose. A comparison of the literature and the data we obtained using 1H-NMR relaxation confirmed the possibility of utilizing the developed methods to solve the tasks of scientific research and conducting quality control of cellulosic materials at specialized enterprises.

Ionic Dynamics in Plastic Crystal KNO2 Studied by 39K and 15N NMR

1994 ◽  
Vol 49 (1-2) ◽  
pp. 247-252 ◽  
Author(s):  
Motoko Kenmotsu ◽  
Hisashi Honda ◽  
Hiroshi Ohki ◽  
Ryuichi Ikeda ◽  
Tomoki Erata ◽  
...  
Keyword(s):  
Intermediate Phase ◽  
Relaxation Times ◽  
Nmr Relaxation ◽  
Lattice Relaxation ◽  
Lattice Relaxation Time ◽  
Spin Lattice Relaxation ◽  
15N Nmr ◽  
Temperature Phase ◽  
Self Diffusion ◽  
Spin Lattice

AbstractThe spin-lattice relaxation time of 39K NMR observed in the low-temperature phase (T<264.1 K) of KNO2 is explained by the quadrupole mechanism contributed from a newly found NO2- motion. The in-plane C3 reorientation and the overvall NO2 rotation as well as the self-diffusion were shown in the intermediate phase (T ≤ 314.7 K) and the high-temperature plastic phase (T < melting point: 710 K), respectively, by observing 39K and 15N NMR relaxation times and 15N lineshapes.

scholarly journals Permeation of small molecules into the cavity of ferritin as revealed by proton nuclear magnetic resonance relaxation

1995 ◽  
Vol 307 (1) ◽  
pp. 253-256 ◽  
Author(s):  
D Yang ◽  
K Nagayama
Keyword(s):  
Relaxation Times ◽  
Nmr Relaxation ◽  
Maximum Size ◽  
Lattice Relaxation ◽  
Spin Lattice Relaxation ◽  
Proton Nuclear Magnetic Resonance ◽  
Ferric Ions ◽  
Spin Lattice ◽  
Resonance Relaxation ◽  
Pass Through

The NMR relaxation technique was used to investigate the permeation of molecules into the cavity of ferritin. Spin-lattice relaxation times in the rotating frame of various probe molecules were measured for solutions of recombinant horse L-apoferritin without iron and horse spleen apoferritin with very small amounts of ferric ions. The results show that molecules larger than the size of the ferritin channels can pass through the channels into the ferritin interior, and that the maximum size of molecules for the permeation is smaller than maltotriose.

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