Investigation of Dynamic Behavior of Confined Ionic Liquid [BMIM]+[TCM]- in Silica Material SBA-15 Using NMR.

The molecular dynamics of 1-butyl-3-methyl imidazolium tricyanomethanide ionic liquid [BMIM]+[TCM]- confined in SBA-15 mesoporous silica were examined using 1H NMR spin-lattice (T1) relaxation and diffusion measurements. An extensive temperature range (100 K-400 K) was considered in order to study both the liquid and glassy states. The hydrogen dynamics in the two states and the self-diffusion coefficients of the cation [BMIM]+ above the glass transition temperature were extracted from the experimental data. The results were then compared to the corresponding bulk substance. The effects of confinement on the dynamic properties of the ionic liquid clearly manifest themselves in both temperature regimes. In the high-temperature liquid state, the mobility of the confined cations reduces significantly compared to the bulk; interestingly, confinement drives the ionic liquid to the glassy state at a higher temperature Tg than the bulk ionic liquid, whereas an unusual T1 temperature dependence is observed in the high-temperature regime, assigned to the interaction of the ionic liquid with the silica-OH species.

Self-Diffusion in Confined Water: A Comparison between the Dynamics of Supercooled Water in Hydrophobic Carbon Nanotubes and Hydrophilic Porous Silica.

Confined liquids are model systems for the study of the metastable supercooled state, especially for bulk water, in which the onset of crystallization below 230 K hinders the application of experimental techniques. Nevertheless, in addition to suppressing crystallization, confinement at the nanoscale drastically alters the properties of water. Evidently, the behavior of confined water depends critically on the nature of the confining environment and the interactions of confined water molecules with the confining matrix. A comparative study of the dynamics of water under hydrophobic and hydrophilic confinement could therefore help to clarify the underlying interactions. As we demonstrate in this work using a few representative results from the relevant literature, the accurate assessment of the translational mobility of water molecules, especially in the supercooled state, can unmistakably distinguish between the hydrophilic and hydrophobic nature of the confining environments. Among the numerous experimental methods currently available, we selected nuclear magnetic resonance (NMR) in a field gradient, which directly measures the macroscopic translational self-diffusion coefficient, and quasi-elastic neutron scattering (QENS), which can determine the microscopic translational dynamics of the water molecules. Dielectric relaxation, which probes the re-orientational degrees of freedom, are also discussed.

Crystal and electronic facet analysis of ultrafine Ni2P particles by solid-state NMR nanocrystallography.

Structural and morphological control of crystalline nanoparticles is crucial in the field of heterogeneous catalysis and the development of "reaction specific" catalysts. To achieve this, colloidal chemistry methods are combined with ab initio calculations in order to define the reaction parameters, which drive chemical reactions to the desired crystal nucleation and growth path. Key in this procedure is the experimental verification of the predicted crystal facets and their corresponding electronic structure, which in case of nanostructured materials becomes extremely difficult. Here, by employing 31P solid-state nuclear magnetic resonance aided by advanced density functional theory calculations to obtain and assign the Knight shifts, we succeed in determining the crystal and electronic structure of the terminating surfaces of ultrafine Ni2P nanoparticles at atomic scale resolution. Our work highlights the potential of ssNMR nanocrystallography as a unique tool in the emerging field of facet-engineered nanocatalysts.

The Role of Titanium Dioxide on the Hydration of Portland Cement: A Combined NMR and Ultrasonic Study.

Titanium dioxide (TiO2) is an excellent photocatalytic material that imparts biocidal, self-cleaning and smog-abating functionalities when added to cement-based materials. The presence of TiO2 influences the hydration process of cement and the development of its internal structure. In this article, the hydration process and development of a pore network of cement pastes containing different ratios of TiO2 were studied using two noninvasive techniques (ultrasonic and NMR). Ultrasonic results show that the addition of TiO2 enhances the mechanical properties of cement paste during early-age hydration, while an opposite behavior is observed at later hydration stages. Calorimetry and NMR spin-lattice relaxation time T1 results indicated an enhancement of the early hydration reaction. Two pore size distributions were identified to evolve separately from each other during hydration: small gel pores exhibiting short T1 values and large capillary pores with long T1 values. During early hydration times, TiO2 is shown to accelerate the formation of cement gel and reduce capillary porosity. At late hydration times, TiO2 appears to hamper hydration, presumably by hindering the transfer of water molecules to access unhydrated cement grains. The percolation thresholds were calculated from both NMR and ultrasonic data with a good agreement between both results.

Resolving Dirac electrons with broadband high-resolution NMR.

Detecting the metallic Dirac electronic states on the surface of Topological Insulators (TIs) is critical for the study of important surface quantum properties (SQPs), such as Majorana zero modes, where simultaneous probing of the bulk and edge electron states is required. However, there is a particular shortage of experimental methods, showing at atomic resolution how Dirac electrons extend and interact with the bulk interior of nanoscaled TI systems. Herein, by applying advanced broadband solid-state 125Te nuclear magnetic resonance (NMR) methods on Bi2Te3 nanoplatelets, we succeeded in uncovering the hitherto invisible NMR signals with magnetic shielding that is influenced by the Dirac electrons, and we subsequently showed how the Dirac electrons spread inside the nanoplatelets. In this way, the spin and orbital magnetic susceptibilities induced by the bulk and edge electron states were simultaneously measured at atomic scale resolution, providing a pertinent experimental approach in the study of SQPs.

NMR and EPR Structural Analysis and Stability Study of Inverse Vulcanized Sulfur Copolymers.

Sulfur copolymers with high sulfur content find a broad range of applications from Li-S batteries to catalytic processes, self-healing materials, and the synthesis of nanoparticles. Synthesis of sulfur-containing polymers via the inverse vulcanization technique gained a lot of attention due to the feasibility of the reaction to produce copolymers with high sulfur content (up to 90 wt %). However, the interplay between the cross-linker and the structure of the copolymers has not yet been fully explored. In the present work, the effect of the amount of 1,3-diisopropenyl benzene (DIB) cross-linker on the structural stability of the copolymer was thoroughly investigated. Combining X-ray diffraction and differential scanning calorimetry, we demonstrated the partial depolymerization of sulfur in the copolymer containing low amount of cross-linker (<30 wt % DIB). On the other hand, by applying NMR and electron paramagnetic resonance techniques, we have shown that increasing the cross-linker content above 50 wt % leads to the formation of radicals, which may severely degrade the structural stability of the copolymer. Thus, an optimum amount of cross-linker is essential to obtain a stable copolymer. Moreover, we were able to detect the release of H2S gas during the cross-linking reaction as predicted based on the abstraction of hydrogen by the sulfur radicals and therefore we emphasize the need to take appropriate precautions while implementing the inverse vulcanization reaction.