Hydraulic Transport Across Hydrophilic and Hydrophobic Nanopores: Flow Experiments with Water and n-Hexane

We experimentally explore pressure-driven flow of water and n-hexane across nanoporous silica (Vycor glass monoliths with 7 or 10 nm pore diameters, respectively) as a function of temperature and surface functionalization (native and silanized glass surfaces). Hydraulic flow rates are measured by applying hydrostatic pressures via inert gases (argon and helium, pressurized up to 70 bar) on the upstream side in a capacitor-based membrane permeability setup. For the native, hydrophilic silica walls, the measured hydraulic permeabilities can be quantitatively accounted for by bulk fluidity provided we assume a sticking boundary layer, i.e. a negative velocity slip length of molecular dimensions. The thickness of this boundary layer is discussed with regard to previous capillarity-driven flow experiments (spontaneous imbibition) and with regard to velocity slippage at the pore walls resulting from dissolved gas. Water flow across the silanized, hydrophobic nanopores is blocked up to a hydrostatic pressure of at least 70 bar. The absence of a sticking boundary layer quantitatively accounts for an enhanced n-hexane permeability in the hydrophobic compared to the hydrophilic nanopores.Comment: 15 pages, 7 figures, in press, Physical Review E 201

Capillary rise of water in hydrophilic nanopores

We report on the capillary rise of water in three-dimensional networks of hydrophilic silica pores with 3.5nm and 5nm mean radii, respectively (porous Vycor monoliths). We find classical square root of time Lucas-Washburn laws for the imbibition dynamics over the entire capillary rise times of up to 16h investigated. Provided we assume two preadsorbed strongly bound layers of water molecules resting at the silica walls, which corresponds to a negative velocity slip length of -0.5nm for water flow in silica nanopores, we can describe the filling process by a retained fluidity and capillarity of water in the pore center. This anticipated partitioning in two dynamic components reflects the structural-thermodynamic partitioning in strongly silica bound water layers and capillary condensed water in the pore center which is documented by sorption isotherm measurements.Comment: 4 pages, 3 figure

Molecular dynamics of n-hexane: A quasi-elastic neutron scattering study on the bulk and spatially nanochannel-confined liquid

We present incoherent quasi-elastic neutron scattering measurements in a wavevector transfer range from 0.4 AA^{-1} to 1.6AA^{-1} on liquid n-hexane confined in cylindrical, parallel-aligned nanochannels of 6 nm mean diameter and 260 micrometer length in monolithic, mesoporous silicon. They are complemented with, and compared to, measurements on the bulk system in a temperature range from 50K to 250K. The time-of-flight spectra of the bulk liquid can be modeled by microscopic translational as well as fast localized rotational, thermally-excited, stochastic motions of the molecules. In the nano-confined state of the liquid, which was prepared by vapor condensation, we find two molecular populations with distinct dynamics, a fraction which is immobile on the time scale of 1ps to 100ps probed in our experiments and a second component with a self-diffusion dynamics slightly slower than observed for the bulk liquid. No hints of an anisotropy of the translational diffusion with regard to the orientation of the channels' long axes have been found. The immobile fraction amounts to about 5% at 250K, gradually increases upon cooling and exhibits an abrupt increase at 160K (20K below bulk crystallization), which indicates pore freezingComment: 10 pages, 7 figure

Melting and freezing of argon in a granular packing of linear mesopore arrays

Freezing and melting of Ar condensed in a granular packing of template-grown arrays of linear mesopores (SBA-15, mean pore diameter 8 nanometer) has been studied by specific heat measurements C as a function of fractional filling of the pores. While interfacial melting leads to a single melting peak in C, homogeneous and heterogeneous freezing along with a delayering transition for partial fillings of the pores result in a complex freezing mechanism explainable only by a consideration of regular adsorption sites (in the cylindrical mesopores) and irregular adsorption sites (in niches of the rough external surfaces of the grains, and at points of mutual contact of the powder grains). The tensile pressure release upon reaching bulk liquid/vapor coexistence quantitatively accounts for an upward shift of the melting/freeezing temperature observed while overfilling the mesopores.Comment: 4 pages, 4 figures, to appear as a Letter in Physical Review Letter

Neutron diffraction on methane and hydrogen hydrates under high pressure

Gas hydrates are crystalline solids composed of water and gas. They have attracted considerable attention over the past decade both for their geophysical relevancy [1] and for their possible application to gas storage [2]. Pressure is a key parameter in the study of these systems as gas hydrates are believed to exist at pressure in nature and the gas content is found to increase in gas hydrates as their crystalline structure rearranges upon compression. In addition, high-pressure studies on gas hydrates offer new possibilities to explore water-gas interactions. We will present recent work on methane and hydrogen hydrates at high pressure performed by neutron diffraction in the GPa range [3]. Several issues including the gas content in the different high-pressure structures will be discussed

Effects of Cr Doping and Water Content on the Crystal Structure Transitions of Ba₂In₂O₅

Temperature-dependent crystal structure alterations in the brownmillerite-type material Ba₂In₂O₅ play a fundamental role in its applications: (i) photocatalytic CO₂ conversion; (ii) oxygen transport membranes; and (iii) proton conduction. This is connected to a reversible uptake of up an equimolar amount of water. In this study, in situ X-ray and neutron diffraction were combined with Raman spectroscopy and solid-state nuclear magnetic resonance experiments to unravel the effects of Cr doping and water content on the crystal structure transitions of Ba₂In₂O₅(H₂O)x over a wide temperature range (10 K ≤ T ≤ 1573 K, x < 1). A mixture of isolated and correlated protons was identified, leading to a highly dynamic situation for the protons. Hence, localisation of the protons by diffraction techniques was not possible. Cr doping led to an overall higher degree of disorder and stabilisation of the tetragonal polymorph, even at 10 K. In contrast, a further disordering at high temperatures, leading to a cubic polymorph, was found at 1123 K. Cr doping in Ba₂In₂O₅ resulted in severe structural changes and provides a powerful way to adjust its physical properties to the respective application

Illuminating solid gas storage in confined spaces – methane hydrate formation in porous model carbons

Methane hydrate nucleation and growth in porous model carbon materials illuminates the way towards the design of an optimized solid-based methane storage technology. High-pressure methane adsorption studies on pre-humidified carbons with well-defined and uniform porosity show that methane hydrate formation in confined nanospace can take place at relatively low pressures, even below 3 MPa CH4, depending on the pore size and the adsorption temperature. The methane hydrate nucleation and growth is highly promoted at temperatures below the water freezing point, due to the lower activation energy in ice vs. liquid water. The methane storage capacity via hydrate formation increases with an increase in the pore size up to an optimum value for the 25 nm pore size model-carbon, with a 173% improvement in the adsorption capacity as compared to the dry sample. Synchrotron X-ray powder diffraction measurements (SXRPD) confirm the formation of methane hydrates with a sI structure, in close agreement with natural hydrates. Furthermore, SXRPD data anticipate a certain contraction of the unit cell parameter for methane hydrates grown in small pores.L. B. gratefully acknowledges the Federal Ministry of Education and Research (Bundesministerium für Bildung und Forschung, BMBF) for support of the Mechanocarb project (award number 03SF0498). J. S. A. acknowledges financial support from MINECO (project MAT-2013-45008-p) and Generalitat Valenciana (PROMETEOII/2014/004). V. B. thanks the Federal Ministry of Education and Research (Bundesministerium für Bildung und Forschung, BMBF) for financial support (project No. 05K13OD3)

Cooperative light-induced breathing of soft porous crystals via azobenzene buckling

Although light is a prominent stimulus for smart materials, the application of photoswitches as light-responsive triggers for phase transitions of porous materials remains poorly explored. Here we incorporate an azobenzene photoswitch in the backbone of a metal-organic framework producing light-induced structural contraction of the porous network in parallel to gas adsorption. Light-stimulation enables non-invasive spatiotemporal control over the mechanical properties of the framework, which ultimately leads to pore contraction and subsequent guest release via negative gas adsorption. The complex mechanism of light-gated breathing is established by a series of in situ diffraction and spectroscopic experiments, supported by quantum mechanical and molecular dynamic simulations. Unexpectedly, this study identifies a novel light-induced deformation mechanism of constrained azobenzene photoswitches relevant to the future design of light-responsive materials

CO2 Adsorption Enhanced by Tuning the Layer Charge in a Clay Mineral

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