Simple model of adsorption on external surface of carbon nanotubes: a new analytical approach basing on molecular simulation data

Nitrogen adsorption on carbon nanotubes is wide- ly studied because nitrogen adsorption isotherm measurement is a standard method applied for porosity characterization. A further reason is that carbon nanotubes are potential adsorbents for separation of nitrogen from oxygen in air. The study presented here describes the results of GCMC simulations of nitrogen (three site model) adsorption on single and multi walled closed nanotubes. The results obtained are described by a new adsorption isotherm model proposed in this study. The model can be treated as the tube analogue of the GAB isotherm taking into account the lateral adsorbate-adsorbate interactions. We show that the model describes the simulated data satisfactorily. Next this new approach is applied for a description of experimental data measured on different commercially available (and characterized using HRTEM) carbon nanotubes. We show that generally a quite good fit is observed and therefore it is suggested that the observed mechanism of adsorption in the studied materials is mainly determined by adsorption on tubes separated at large distances, so the tubes behave almost independently

Folding of graphene slit like pore walls—a simple method of improving CO2 separation from mixtures with CH4 or N2

We report for the first time a detailed procedure for creating a simulation model of energetically stable, folded graphene-like pores and simulation results of CO2/CH4 and CO2/N2 separation using these structures. We show that folding of graphene structures is a very promising method to improve the separation of CO2 from mixtures with CH4 and N2. The separation properties of the analyzed materials are compared with carbon nanotubes having similar diameters or S/V ratio. The presented results have potential importance in the field of CO2 capture and sequestration

Synergetic effect of carbon nanopore size and surface oxidation on CO2 capture from CO2/CH4 mixtures

We have studied the synergetic effect of confinement (carbon nanopore size) and surface chemistry (the number of carbonyl groups) on CO2 capture from its mixtures with CH4 at typical operating conditions for industrial adsorptive separation (298 K and compressed CO2CH4 mixtures). Although both confinement and surface oxidation have an impact on the efficiency of CO2/CH4 adsorptive separation at thermodynamics equilibrium, we show that surface functionalization is the most important factor in designing an efficient adsorbent for CO2 capture. Systematic Monte Carlo simulations revealed that adsorption of CH4 either pure or mixed with CO2 on oxidized nanoporous carbons is only slightly increased by the presence of functional groups (surface dipoles). In contrast, adsorption of CO2 is very sensitive to the number of carbonyl groups, which can be examined by a strong electric quadrupolar moment of CO2. Interestingly, the adsorbed amount of CH4 is strongly affected by the presence of the co-adsorbed CO2. In contrast, the CO2 uptake does not depend on the molar ratio of CH4 in the bulk mixture. The optimal carbonaceous porous adsorbent used for CO2 capture near ambient conditions should consist of narrow carbon nanopores with oxidized pore walls. Furthermore, the equilibrium separation factor was the greatest for CO2/CH4 mixtures with a low CO2 concentration. The maximum equilibrium separation factor of CO2 over CH4 of ∼18–20 is theoretically predicted for strongly oxidized nanoporous carbons. Our findings call for a review of the standard uncharged model of carbonaceous materials used for the modeling of the adsorption separation processes of gas mixtures containing CO2 (and other molecules with strong electric quadrupolar moment or dipole moment)

The influence of the carbon surface chemical composition on Dubinin-Astakhov equation parameters calculated from SF(6) adsorption data-grand canonical Monte Carlo simulation

Using grand canonical Monte Carlo simulation we show, for the first time, the influence of the carbon porosity and surface oxidation on the parameters of the Dubinin-Astakhov (DA) adsorption isotherm equation. We conclude that upon carbon surface oxidation, the adsorption decreases for all carbons studied. Moreover, the parameters of the DA model depend on the number of surface oxygen groups. That is why in the case of carbons containing surface polar groups, SF(6) adsorption isotherm data cannot be used for characterization of the porosity

Steroid 21-hydroxylase is a major autoantigen involved in adult onset autoimmune Addison's disease

AbstractAn adrenal-specific protein reacting with autoantibodies in the sera of patients with adult onset Addison's disease has been purified from human adrenal glands. The protein, mol.wt. 55K, has the biochemical characteristics of steroid 21-hydroxylase and reacts on Western blots with rabbit antibodies to recombinant 21-hydroxylase. Absorption of the native human 55K adrenal protein with human adrenal autoantibodies prevented the subsequent reaction of the 55K protein with rabbit antibodies to 21-hydroxylase in Western blot analysis. In addition, human adrenal autoantibodies reacted with recombinant 21-hydroxylase expressed in yeast. These data indicate that the adrenal specific enzyme steroid 21-hydroxylase is a major autoantigen involved in adult onset autoimmune Addison's disease

Morphologically disordered pore model for characterization of micro-mesoporous carbons

We present a new morphologically disordered slit-shaped pore (MDSP) model for simulating gas adsorption in micro-mesoporous carbonaceous materials. The MDSP model qualitatively accounts for the inherent roughness of carbon pore walls in accord with the atomistic structural model of LMA10 reference carbon material. The MDSP model is applied to pore size distribution (PSD) calculations from nitrogen adsorption isotherms measured at 77.4 K in the range of pore widths from 0.72 to 40 nm. The MDSP model improves significantly the nitrogen adsorption porosimetry and, being fully atomistic, it is transferable to study various adsorbate-adsorbent systems. Computations of PSD functions for a series of carbonaceous materials, including activated carbon fiber, granular activated carbons, synthetic activated carbons showed that MDSP generates smooth Gaussian-type PSD functions with a well-defined average pore size. Furthermore, PSD functions computed from the MDSP model are free from the artificial gaps in the region of narrow micropores (∼1 nm and ∼2 nm) predicted from the standard slit-shaped pore models with ideal graphite-like walls. MDSP is not only a complementary model to existing approaches, such as quench-solid density functional theory method, but it paves the way to efficient atomistic simulations of various compounds within morphologically disordered carbon nanopores

Porosity of closed carbon nanotubes compressed using hydraulic pressure

Experimental data of nitrogen adsorption (T = 77.3 K) from gaseous phase measured on commercial closed carbon nanotubes are presented. Additionally, we show the results of N2 adsorption on compressed (using hydraulic press) CNTs. In order to explain the experimental observations the results of GCMC simulations of N2 adsorption on isolated or bundled multi-walled closed nanotubes (four models of bundles) are discussed. We show that the changes of the experimental adsorption isotherms are related to the compression of the investigated adsorbents. They are qualitatively similar to the theoretical observations. Taking into account all results it is concluded that in the "architecture" of nanotubes very important role has been played by isolated nanotubes

Super-sieving effect in phenol adsorption from aqueous solutions on nanoporous carbon beads

Removal of aromatic contaminants, like phenol, from water can be efficiently achieved by preferential adsorption on porous carbons which exhibit molecular sieving properties. Here, we present nanoporous carbon beads exhibiting an outstanding sieving effect in phenol adsorption from aqueous solution at neutral pH, which is evidenced experimentally and theoretically. The molecular sieving with pure phenol adsorbed phase is achieved by tuning the pore size and surface chemistry of the adsorbent. This study elucidates the essential role of hydrophobic interactions in narrow carbon micropores in removal and clean-up of water from organic pollutants. Furthermore, we suggest a new theoretical approach for evaluation of phenol adsorption capacity that is based on the Monte Carlo simulation of phenol adsorption with the relevance to the pore size distribution function determined by the density functional theory method from low temperature nitrogen adsorption

To what extent can mutual shifting of folded carbonaceous walls in slit-like pores affect their adsorption properties?

We have performed systematic Monte Carlo studies on the influence of shifting the walls in slit-like systems constructed from folded graphene sheets on their adsorption properties. Specifically, we have analysed the effect on the mechanism of argon adsorption (T = 87 K) and on adsorption and separation of three binary gas mixtures: CO2/N2, CO2/CH4 and CH4/N2 (T = 298 K). The effects of the changes in interlayer distance were also determined. We show that folding of the walls significantly improves the adsorption and separation properties in comparison to ideal slit-like systems. Moreover, we demonstrate that mutual shift of sheets (for small interlayer distances) causes the appearance of small pores between opposite bulges. This causes an increase in vapour adsorption at low pressures. Due to overlapping of interactions with opposite walls causing an increase in adsorption energy, the mutual shift of sheets is also connected with the rise in efficiency of mixtures separation. The effects connected with sheet orientation vanish as the interlayer distance increases