Surface Interactions and Nanoconfinement of Methane and Methane plus CO2 Revealed by High-Pressure Magic Angle Spinning NMR Spectroscopy and Molecular Dynamics.

This study explores the fundamental, molecular- to microscopic-level behavior of methane gas confined into nanoporous silica proxies with different pore diameters and surface-to-volume (S/V) ratios. Surfaces and pore walls of nanoporous silica matrices are decorated with hydroxyl (-OH) groups, resembling natural heterogeneity. High-pressure MAS NMR was utilized to characterize the interactions between methane and the engineered nanoporous silica proxies under various temperature and pressure regimes. There was a change in the chemical shift position of confined methane slightly in the mixtures with nanoporous silica up to 393 K, as shown by high-pressure 13C-NMR. The 13C-NMR chemical shift of methane was changed by pressure, explained by the densification of methane inside the nanoporous silica materials. The influence of pore diameter and S/V of the nanoporous silica materials on the behaviors and dynamics of methane were studied. The presence of CO2 in mixtures of silica and methane needs analysis with caution because CO2 in a supercritical state and gaseous CO2 change the original structure of nanoporous silica and change surface area and pore volume. According to simulation, the picosecond scale dynamics of methane confined in larger pores of amorphous silica is faster. In the 4 nm pore, the diffusivity obtained from MD simulations in the pore with a higher S/V ratio is slower due to the trapping of methane molecules in adsorbed layers close to the corrugated pore surface. In contrast, relaxation measured with NMR for smaller pores (higher S/V) exhibits larger T1, indicating slower relaxation.

Fluid Behavior in Nanoporous Silica.

We investigate dynamics of water (H2O) and methanol (CH3OH and CH3OD) inside mesoporous silica materials with pore diameters of 4.0, 2.5, and 1.5 nm using low-field (LF) nuclear magnetic resonance (NMR) relaxometry. Experiments were conducted to test the effects of pore size, pore volume, type of fluid, fluid/solid ratio, and temperature on fluid dynamics. Longitudinal relaxation times (T1) and transverse relaxation times (T2) were obtained for the above systems. We observe an increasing deviation in confined fluid behavior compared to that of bulk fluid with decreasing fluid-to-solid ratio. Our results show that the surface area-to-volume ratio is a critical parameter compared to pore diameter in the relaxation dynamics of confined water. An increase in temperature for the range between 25 and 50°C studied did not influence T2 times of confined water significantly. However, when the temperature was increased, T1 times of water confined in both silica-2.5 nm and silica-1.5 nm increased, while those of water in silica-4.0 nm did not change. Reductions in both T1 and T2 values as a function of fluid-to-solid ratio were independent of confined fluid species studied here. The parameter T1/T2 indicates that H2O interacts more strongly with the pore walls of silica-4.0 nm than CH3OH and CH3OD.

Density of hydrophobically confined deeply cooled water investigated by small angle X-ray scattering.

Water's behavior near hydrophobic surfaces has attracted great attention due to chemical and geological applications. Here, we report small angle X-ray scattering (SAXS) studies of water confined in the hydrophobic nanoporous carbon material, CMK-1-14, from ambient to deeply cooled temperatures. By monitoring the scattering intensity of the first Bragg peak, which is directly related to the scattering length density contrast between the carbon matrix and the confined water, the average density of the hydrophobically confined water was determined from 300 K to 150 K at ambient pressure. Furthermore, differential scanning calorimetry and X-ray diffraction measurements showed that the majority of such hydrophobically confined water did not crystallize in the investigated temperature range. By exploiting the fast speed of SAXS measurements and the continuous temperature ramping, the average density profile and the deduced thermal expansion coefficient (αp) were obtained. We found that the well-known density maximum of water at 277 K downshifted to 260 K, and the density minimum which has been observed in hydrophilic confinement disappeared. In addition, the previously measured large density decreasing of 18% at low temperature was recalibrated to a more reasonable 10% instead. Consequently, the recalculated αp peak was found to be quite similar to that of the water confined in hydrophilic MCM-41-S-15 suggesting an intrinsic property of water, which does not sensitively depend on the confinement surface.

Pore-size dependent THz absorption of nano-confined water.

We performed a THz absorption spectroscopy study on liquid water confined in mesoporous silica materials, MCM-41-S-18 and MCM-41-S-21, of two different pore sizes at room temperatures. We found that stronger confinement with a smaller pore size causes reduced THz absorption, indicating reduced water mobility due to confinement. Combined with recent theoretical studies showing that the microscopic structure of water inside the nanopores can be separated into a core water region and an interfacial water region, our spectroscopy analysis further reveals a bulk-water-like THz absorption behavior in the core water region and a solid-like THz absorption behavior in the interfacial water region.

Evidence of the existence of the high-density and low-density phases in deeply-cooled confined heavy water under high pressures.

The average density of D2O confined in a nanoporous silica matrix (MCM-41-S) is studied with neutron scattering. We find that below ~210 K, the pressure-temperature plane of the system can be divided into two regions. The average density of the confined D2O in the higher-pressure region is about 16% larger than that in the lower-pressure region. These two regions could represent the so-called "low-density liquid" and "high-density liquid" phases. The dividing line of these two regions, which could represent the associated 1st order liquid-liquid transition line, is also determined.

Boson peak in deeply cooled confined water: a possible way to explore the existence of the liquid-to-liquid transition in water.

The boson peak in deeply cooled water confined in nanopores is studied with inelastic neutron scattering. We show that in the (P, T) plane, the locus of the emergence of the boson peak is nearly parallel to the Widom line below ∼ 1600 bar. Above 1600 bar, the situation is different and from this difference the end pressure of the Widom line is estimated. The frequency and width of the boson peak correlate with the density of water, which suggests a method to distinguish the hypothetical "low-density liquid" and "high-density liquid" phases in deeply cooled water.

Density and anomalous thermal expansion of deeply cooled water confined in mesoporous silica investigated by synchrotron X-ray diffraction.

A synchrotron X-ray diffraction method was used to measure the average density of water (H2O) confined in mesoporous silica materials MCM-41-S-15 and MCM-41-S-24. The average density versus temperature at atmospheric pressure of deeply cooled water is obtained by monitoring the intensity change of the MCM-41-S Bragg peaks, which is directly related to the scattering length density contrast between the silica matrix and the confined water. Within MCM-41-S-15, the pore size is small enough to prevent the crystallization at least down to 130 K. Besides the well-known density maximum at 277 K, a density minimum is observed at 200 K for the confined water, below which a regular thermal expansion behavior is restored. Within MCM-41-S-24 of larger pore size, water freezes at 220.5 K. The average water/ice density measurement in MCM-41-S-24 validated the diffraction method. The anomalous thermal expansion coefficient (αp) is calculated. The temperature at which the αp reaches maximum is found to be pore size independent, but the peak height of the αp maximum is linearly dependent on the pore size. The obtained data are critical to verify available theoretical and computational models of water.

Temperature dependence of structure and density for D2O confined in MCM-41-S.

Using neutron diffraction, we have tracked the temperature dependence of structural properties for heavy water confined in the nanoporous silica matrix MCM-41-S. By observing the correlation peak corresponding to the pore-pore distance, which is determined by the scattering contrast between the silica and the water, we monitored the density of the confined water. Concurrently, we studied the prominent first diffraction peak of D(2)O at ≈ 1.8 Å(-1), which furnishes information on the microscopic arrangement of the water molecules. The data show the presence of a density maximum at ≈ 275 K (± 10 K), a property similar to bulk water, and the occurrence of a density minimum at ≈ 180 K (± 10 K). The prominent diffraction peak of D(2)O is found to shift and sharpen over a wide T range from 200 to 270 K, reflecting structural changes that are strongly correlated with the changes in density. We also observe the continuous formation of external ice, arising from water expelled from the pores while expansion takes place within the pores. An efficient method for monitoring the density of the confined D(2)O using a triple-axis spectrometer is demonstrated.

Density hysteresis of heavy water confined in a nanoporous silica matrix.

A neutron scattering technique was developed to measure the density of heavy water confined in a nanoporous silica matrix in a temperature-pressure range, from 300 to 130 K and from 1 to 2,900 bars, where bulk water will crystalize. We observed a prominent hysteresis phenomenon in the measured density profiles between warming and cooling scans above 1,000 bars. We interpret this hysteresis phenomenon as support (although not a proof) of the hypothetical existence of a first-order liquid-liquid phase transition of water that would exist in the macroscopic system if crystallization could be avoided in the relevant phase region. Moreover, the density data we obtained for the confined heavy water under these conditions are valuable to large communities in biology and earth and planetary sciences interested in phenomena in which nanometer-sized water layers are involved.

Low-temperature dynamics of water confined in a hydrophobic mesoporous material.

Quasielastic neutron scattering was used to study the dynamics of three-dimensional confined water in a hydrophobic mesoporous material designated as CMK-1 in the temperature range from 250 to 170 K. We observe a crossover phenomenon at temperature T(L) . We find that T(L) of water confined in CMK-1 occurs in between previous observations of one-dimensional confined water in materials with different hydrophilicities. This provides the first evidence that besides the obvious surface effect brought about by the hydrophobic confinements, T(L) is also dependent on the dimensionality of the geometry of the confinement.

Single particle dynamics of water confined in a hydrophobically modified MCM-41-S nanoporous matrix.

The single particle dynamics of water confined in a hydrophobically modified MCM-41-S sample has been studied using three high resolution quasielastic neutron scattering spectrometers in the temperature range from 300 to 210 K. A careful modeling of the dynamics allowed us to obtain good agreement among the results obtained with the three instruments, which have very different energy resolutions. The picture arising from the data is that, because of the heterogenous environment experienced by the water molecules, the dynamics show a broad distribution of relaxation times. However, the Fickian diffusive behavior is retained. In the investigated temperature range we found no evidence of the dynamic crossover, from a non-Arrhenius to an Arrhenius behavior, which was detected for water confined in hydrophilic MCM-41-S. This finding is in agreement with what was reported by Chu et al. [Phys. Rev. E 76, 021505 (2007)] for water confined in other hydrophobic confining media that the dynamic crossover takes place at a much lower temperature. The results reported in the paper help clarify the role that the chemical interaction between the water molecules and the walls of the confining host plays in determining the characteristics of the water dynamics, as compared to purely geometric constraints such as the size and shape of the pores.

Absence of the density minimum of supercooled water in hydrophobic confinement.

The surface effect on the peculiar dynamic and thermodynamic properties of supercooled water, such as the density, has been puzzling the scientific community for years. Recently, using the small angle neutron scattering method, we were able to measure the density of H(2)O confined in the hydrophobic mesoporous material CMK-1-14 from room temperature down to the deeply supercooled temperature 130 K at ambient pressure. We found that the well-known density maximum of water is shifted 17 K lower and, more interestingly, that the previously observed density minimum in hydrophilic confinement disappears. Furthermore, the deduced thermal expansion coefficient shows a much broader peak spanning from 240 to 180 K in comparison with the sharp peak at 230 K in hydrophilic confinement. These present results may help in the understanding of the effect of hydrophobic/hydrophilic interfaces on the properties of supercooled confined water.