Adsorption in slit pores and pore-size distribution: A molecular layer structure theory

A new approach is developed to analyze the thermodynamic properties of a sub-critical fluid adsorbed in a slit pore of activated carbon. The approach is based on a representation that an adsorbed fluid forms an ordered structure close to a smoothed solid surface. This ordered structure is modelled as a collection of parallel molecular layers. Such a structure allows us to express the Helmholtz free energy of a molecular layer as the sum of the intrinsic Helmholtz free energy specific to that layer and the potential energy of interaction of that layer with all other layers and the solid surface. The intrinsic Helmholtz free energy of a molecular layer is a function (at given temperature) of its two-dimensional density and it can be readily obtained from bulk-phase properties, while the interlayer potential energy interaction is determined by using the 10-4 Lennard-Jones potential. The positions of all layers close to the graphite surface or in a slit pore are considered to correspond to the minimum of the potential energy of the system. This model has led to accurate predictions of nitrogen and argon adsorption on carbon black at their normal boiling points. In the case of adsorption in slit pores, local isotherms are determined from the minimization of the grand potential. The model provides a reasonable description of the 0-1 monolayer transition, phase transition and packing effect. The adsorption of nitrogen at 77.35 K and argon at 87.29 K on activated carbons is analyzed to illustrate the potential of this theory, and the derived pore-size distribution is compared favourably with that obtained by the Density Functional Theory (DFT). The model is less time-consuming than methods such as the DFT and Monte-Carlo simulation, and most importantly it can be readily extended to the adsorption of mixtures and capillary condensation phenomena.

The effects of energy sites on adsorption of Lennard–Jones fluids and phase transition in carbon slit pore of finite length a computer simulation study

A Monte Carlo simulation method is Used 10 study the effects of adsorption strength and topology of sites on adsorption of simple Lennard-Jones fluids in a carbon slit pore of finite length. Argon is used as a model adsorbate, while the adsorbent is modeled as a finite carbon slit pore whose two walls composed of three graphene layers with carbon atoms arranged in a hexagonal pattern. Impurities having well depth of interaction greater than that of carbon atom are assumed to be grafted onto the surface. Different topologies of the impurities; corner, centre, shelf and random topologies are studied. Adsorption isotherms of argon at 87.3 K are obtained for pore having widths of 1, 1.5 and 3 11111 using a Grand Canonical Monte Carlo simulation (GCMC). These results are compared with isotherms obtained for infinite pores. It is shown that the Surface heterogeneity affects significantly the overall adsorption isotherm, particularly the phase transition. Basically it shifts the onset of adsorption to lower pressure and the adsorption isotherms for these four impurity models are generally greater than that for finite pore. The positions of impurities on solid Surface also affect the shape of the adsorption isotherm and the phase transition. We have found that the impurities allocated at the centre of pore walls provide the greatest isotherm at low pressures. However when the pressure increases the impurities allocated along the edges of the graphene layers show the most significant effect on the adsorption isotherm. We have investigated the effect of surface heterogeneity on adsorption hysteresis loops of three models of impurity topology, it shows that the adsorption branches of these isotherms are different, while the desorption branches are quite close to each other. This suggests that the desorption branch is either the thermodynamic equilibrium branch or closer to it than the adsorption branch. (c) 2005 Elsevier Inc. All rights reserved.

Pore size distribution analysis of activated carbons: Application of density functional theory using nongraphitized carbon black as a reference system

The application of nonlocal density functional theory (NLDFT) to determine pore size distribution (PSD) of activated carbons using a nongraphitized carbon black, instead of graphitized thermal carbon black, as a reference system is explored. We show that in this case nitrogen and argon adsorption isotherms in activated carbons are precisely correlated by the theory, and such an excellent correlation would never be possible if the pore wall surface was assumed to be identical to that of graphitized carbon black. It suggests that pore wall surfaces of activated carbon are closer to that of amorphous solids because of defects of crystalline lattice, finite pore length, and the presence of active centers.. etc. Application of the NLDFT adapted to amorphous solids resulted in quantitative description of N-2 and Ar adsorption isotherms on nongraphitized carbon black BP280 at their respective boiling points. In the present paper we determined solid-fluid potentials from experimental adsorption isotherms on nongraphitized carbon black and subsequently used those potentials to model adsorption in slit pores and generate a corresponding set of local isotherms, which we used to determine the PSD functions of different activated carbons. (c) 2005 Elsevier Ltd. All rights reserved.

Biocompatible properties of surgical mesh using an animal model

To study the biocompatibility of surgical meshes for use in pelvic reconstructive surgery using an animal model. Eight different types of mesh: Atrium, Dexon, Gynemesh, IVS tape, Prolene, SPARC tape, TVT tape and Vypro II, were implanted into the abdominal walls of rats for 3 months' duration. Explanted meshes were assessed, using light microscopy, for parameters of rejection and incorporation. Type 1 (Atrium, Gynemesh, Prolene, SPARC and TVT) and type 3 (Vypro II, Dexon and IVS) meshes demonstrated different biocompatible properties. Inflammatory cellular response and fibrosis at the interface of mesh and host tissue was most marked with Vypro II and IVS. All type 1 meshes displayed similar cellular responses despite markedly different mesh architecture. The inflammatory response and fibrous reaction in the non-absorbable type 3 meshes tested (IVS and Vypro II) was more marked than the type 1 meshes. The increased inflammatory and fibrotic response may be because of the multifilamentous polypropylene components of these meshes. Material and filament composition of mesh is the main factor in determining cellular response.

Mechanisms influencing levitation and the scaling laws in nanopores: Oscillator model theory

We provide here a detailed theoretical explanation of the floating molecule or levitation effect, for molecules diffusing through nanopores, using the oscillator model theory (Phys. Rev. Lett. 2003, 91, 126102) recently developed in this laboratory. It is shown that on reduction of pore size the effect occurs due to decrease in frequency of wall collision of diffusing particles at a critical pore size. This effect is, however, absent at high temperatures where the ratio of kinetic energy to the solid-fluid interaction strength is sufficiently large. It is shown that the transport diffusivities scale with this ratio. Scaling of transport diffusivities with respect to mass is also observed, even in the presence of interactions.

Analysis of the pore of the unusual major intrinsic protein channel, yeast Fps1p

Fps1p is a glycerol efflux channel from Saccharomyces cerevisiae. In this atypical major intrinsic protein neither of the signature NPA motifs of the family, which are part of the pore, is preserved. To understand the functional consequences of this feature, we analyzed the pseudo-NPA motifs of Fps1p by site-directed mutagenesis and assayed the resultant mutant proteins in vivo. In addition, we took advantage of the fact that the closest bacterial homolog of Fps1p, Escherichia coli GlpF, can be functionally expressed in yeast, thus enabling the analysis in yeast cells of mutations that make this typical major intrinsic protein more similar to Fps1p. We observed that mutations made in Fps1p to "restore" the signature NPA motifs did not substantially affect channel function. In contrast, when GlpF was mutated to resemble Fps1p, all mutants had reduced activity compared with wild type. We rationalized these data by constructing models of one GlpF mutant and of the transmembrane core of Fps1p. Our model predicts that the pore of Fps1p is more flexible than that of GlpF. We discuss the fact that this may accommodate the divergent NPA motifs of Fps1p and that the different pore structures of Fps1p and GlpF may reflect the physiological roles of the two glycerol facilitators.

Pd/C catalysts based on synthetic carbons with bi- and tri-modal pore-size distribution:applications in flow chemistry

Two new types of phenolic resin-derived synthetic carbons with bi-modal and tri-modal pore-size distributions were used as supports for Pd catalysts. The catalysts were tested in chemoselective hydrogenation and hydrodehalogenation reactions in a compact multichannel flow reactor. Bi-modal and tri-modal micro-mesoporous structures of the synthetic carbons were characterised by N2 adsorption. HR-TEM, PXRD and XPS analyses were performed for characterising the synthesised catalysts. N2 adsorption revealed that tri-modal synthetic carbon possesses a well-developed hierarchical mesoporous structure (with 6.5 nm and 42 nm pores), contributing to a larger mesopore volume than the bi-modal carbon (1.57 cm3 g-1versus 1.23 cm3 g-1). It was found that the tri-modal carbon promotes a better size distribution of Pd nanoparticles than the bi-modal carbon due to presence of hierarchical mesopore limitting the growth of Pd nanoparticles. For all the model reactions investigated, the Pd catalyst based on tri-modal synthetic carbon (Pd/triC) show high activity as well as high stability and reproducibility. The trend in reactivities of different functional groups over the Pd/triC catalyst follows a general order alkyne ≫ nitro > bromo ≫ aldehyde.

Nutrients of pore water in sediments of the central equatorial Pacific

Shipboard whole-core squeezing was used to measure pore water concentration vs depth profiles of [NO3]-, O2 and SiO2 at 12 stations in the equatorial Pacific along a transect from 15°S to 11°N at 135°W. The [NO3]- and SiO2 profiles were combined with fine-scale resistivity and porosity measurements to calculate benthic fluxes. After using O2 profiles, coupled with the [NO3]- profiles, to constrain the C:N of the degrading organic matter, the [NO3]- fluxes were converted to benthic organic carbon degradation rates. The range in benthic organic carbon degradation rates is 7-30 ?mol cm**-2 y**-1, with maximum values at the equator and minimum values at the southern end of the transect. The zonal trend of benthic degradation rates, with its equatorial maximum and with elevated values skewed to the north of the equator, is similar to the pattern of primary production observed in the region. Benthic organic carbon degradation is 1-2% of primary production. The range of benthic biogenic silica dissolution rates is 6.9-20 µmol cm**-2 y**-1, representing 2.5-5% of silicon fixation in the surface ocean of the region. Its zonal pattern is distinctly different from that of organic carbon degradation: the range in the ratio of silica dissolution to carbon degradation along the transect is 0.44-1.7 mol Si mol C**-1, with maximum values occurring between 12°S and 2°S, and with fairly constant values of 0.5-0.7 north of the equator. A box model calculation of the average lifetime of the organic carbon in the upper 1 cm of the sediments, where 80 +/- 11% of benthic organic carbon degradation occurs, indicates that it is short: from 3.1 years at high flux stations to 11 years at low flux stations. The reactive component of the organic matter must have a shorter lifetime than this average value. In contrast, the average lifetime of biogenic silica in the upper centimeter of these sediments is 55 +/- 28 years, and shows no systematic variations with benthic flux.

Sulfate and methane concentrations measured in pore water of sediment core GeoB13809-1 and GeoB13849-1

Several previous studies have shown that submarine mass-movements can profoundly impact the shape of pore water profiles. Therefore, pore water geochemistry and diffusion models were proposed as tools for identifying and dating recent (max. several thousands of years old) mass-transport deposits (MTDs). In particular, sulfate profiles evidentially indicate transient pore water conditions generated by submarine landslides. After mass-movements that result in the deposition of sediment packages with distinct pore water signatures, the sulfate profiles can be kink-shaped and evolve into the concave and linear shape with time due to molecular diffusion. Here we present data from the RV METEOR cruise M78/3 along the continental margin off Uruguay and Argentina. Sulfate profiles of 15 gravity cores are compared with the respective acoustic facies recorded by a sediment echosounder system. Our results show that in this very dynamic depositional setting, non-steady state profiles occur often, but are not exclusively associated with mass-movements. Three sites that show acoustic indications for recent MTDs are presented in detail. Where recent MTDs are identified, a geochemical transport/reaction model is used to estimate the time that has elapsed since the perturbation of the pore water system and, thus, the timing of the MTD emplacement. We conclude that geochemical analyses are a powerful complementary tool in the identification of recent MTDs and provide a simple and accurate way of dating such deposits.

Pore water and solid-phase measurements on sediment cores from the Black Sea

The surface sediments in the Black Sea are underlain by extensive deposits of iron (Fe) oxide-rich lake sediments that were deposited prior to the inflow of marine Mediterranean Sea waters ca. 9000 years ago. The subsequent downward diffusion of marine sulfate into the methane-bearing lake sediments has led to a multitude of diagenetic reactions in the sulfate-methane transition zone (SMTZ), including anaerobic oxidation of methane (AOM) with sulfate. While the sedimentary cycles of sulfur (S), methane and Fe in the SMTZ have been extensively studied, relatively little is known about the diagenetic alterations of the sediment record occurring below the SMTZ. Here we combine detailed geochemical analyses of the sediment and pore water with multicomponent diagenetic modeling to study the diagenetic alterations below the SMTZ at two sites in the western Black Sea. We focus on the dynamics of Fe, S and phosphorus (P) and demonstrate that diagenesis has strongly overprinted the sedimentary burial records of these elements. Our results show that sulfate-mediated AOM substantially enhances the downward diffusive flux of sulfide into the deep limnic deposits. During this downward sulfidization, Fe oxides, Fe carbonates and Fe phosphates (e.g. vivianite) are converted to sulfide phases, leading to an enrichment in solid phase S and the release of phosphate to the pore water. Below the sulfidization front, high concentrations of dissolved ferrous Fe (Fe2+) lead to sequestration of downward diffusing phosphate as authigenic vivianite, resulting in a transient accumulation of total P directly below the sulfidization front. Our model results further demonstrate that downward migrating sulfide becomes partly re-oxidized to sulfate due to reactions with oxidized Fe minerals, fueling a cryptic S cycle and thus stimulating slow rates of sulfate-driven AOM (~ 1-100 pmol/cm**3/d) in the sulfate-depleted limnic deposits. However, this process is unlikely to explain the observed release of dissolved Fe2+ below the SMTZ. Instead, we suggest that besides organoclastic Fe oxide reduction, AOM coupled to the reduction of Fe oxides may also provide a possible mechanism for the high concentrations of Fe2+ in the pore water at depth. Our results reveal that methane plays a key role in the diagenetic alterations of Fe, S and P records in Black Sea sediments. The downward sulfidization into the limnic deposits is enhanced through sulfate-driven AOM with sulfate and AOM with Fe oxides may provide a deep source of dissolved Fe2+ that drives the sequestration of P in vivianite below the sulfidization front.

Mechanism that dictates pore width and <111>a pore propagation in InP

We report a mechanism for pore growth and propagation based on a three-step charge transfer model. The study is supported by electron microscopy analysis of highly doped n-InP samples anodised in aqueous KOH. The model and experimental data are used to explain propagation of pores of characteristic diameter preferentially along the <111>A directions. We also show evidence for deviation of pore growth from the <111>A directions and explain why such deviations should occur. The model is self-consistent and predicts how carrier concentration affects the internal dimensions of the porous structures.

(Table 1) Chemical and isotopic composition of pore fluids in cores TGC-1 and TGC-6

The role of sediment diagenesis in the marine cycles of Li and B is poorly understood. Because Li and B are easily mobilized during burial and are consumed in authigenic clay mineral formation, their abundance in marine pore waters varies considerably. Exchange with the overlying ocean through diffusive fluxes should thus be common. Nevertheless, only a minor Li sink associated with the low-temperature alteration of volcanic ash has been observed. We describe a low-temperature diagenetic environment in the Black Sea dominated by the alteration of detrital plagioclase feldspars. Fluids expelled from the Odessa mud volcano in the Sorokin Trough originate from shallow (~100-400 m deep) sediments which are poor in volcanic materials but rich in anorthite. These fluids are depleted in Na+, K+, Li+, B, and 18O and enriched in Ca2+ and Sr2+, indicating that anorthite is dissolving and authigenic clays are forming. Using a simple chemical model, we calculate the pH and the partial pressure of CO2 (PCO2) in fluids associated with this alteration process. Our results show that the pH of these fluids is up to 1.5 pH units lower than in most deep marine sediments and that PCO2 levels are up to several hundred times higher than in the atmosphere. These conditions are similar to those which favor the weathering of silicate minerals in subaerial soil environments. We propose that in Black Sea sediments enhanced organic matter preservation favors CO2 production through methanogenesis and results in a low pore water pH, compared to most deep sea sediments. As a result, silicate mineral weathering, which is a sluggish process in most marine diagenetic environments, proceeds rapidly in Black Sea sediments. There is a potential for organic matter-rich continental shelf environments to host this type of diagenesis. Should such environments be widespread, this new Li and B sink could help balance the marine Li and Li isotope budgets but would imply an apparent imbalance in the B cycle.