Thermodynamics of hydrogen adsorption in slit-like carbon nanopores at 77 K. Classical versus path-integral Monte Carlo simulations

Hydrogen in slit-like carbon nanopores at 77 K represents a quantum fluid in strong confinement. We have used path-integral grand canonical Monte Carlo and classical grand canonical Monte Carlo simulations for the investigation of the "quantumness" of hydrogen at 77 K adsorbed in slit-like carbon nanopores up to 1 MPa. We find that classical simulations overpredict the hydrogen uptake in carbon nanopores due to neglect of the quantum delocalization. Such disagreement of both simulation methods depends on the slit-like carbon pore size. However, the differences between the final uptakes of hydrogen computed from both classical and quantum simulations are not large due to a similar effective size of quantum/classical hydrogen molecules in carbon nanospaces. For both types of molecular simulations, the volumetric density of stored energy in optimal carbon nanopores exceeds 6.4 MJ dm(-3) (i.e., 45 kg m(-3); Department of Energy target for 2010). In contrast to the hydrogen adsorption isotherms, we found a large reduction of isosteric enthalpy of adsorption computed from the quantum Feynman's path-integral simulations in comparison to the classical values at 77 K and pressures up to 1 MPa. Depression of the quantum isosteric enthalpy of adsorption depends on the slit-like carbon pore size. For the narrow pores (pore width H in [0.59-0.7] nm), the reduction of the quantum isosteric enthalpy of adsorption at zero coverage is around 50% in comparison to the classical one. We observed new phenomena called, by us, the quantum confinement-inducing polymer shrinking. In carbon nanospaces, the quantum cyclic polymers shrink, in comparison to its bulk-phase counterpart, due to a strong confinement effect. At considered storage conditions, this complex phenomenon depends on the size of the slit-like carbon nanopore and the density of hydrogen volumetric energy. For the smallest nanopores and a low density of hydrogen volumetric energy, the reduction of the polymer effective size is the highest, whereas an increase of the pore size and the density of hydrogen volumetric energy causes the polymer swelling up to a value slightly below the one computed from the bulk phase. Quantum confinement-inducing polymer shrinking is of great importance for realizing the potential of quantum molecular sieves.     

Some remarks on the calculation of the pore size distribution function of activated carbons

Different authors investigated the effects of geometric and energetic heterogeneities on adsorption and on carbon characterization methods. In most theoretical studies carbon structure is modeled as parallel infinite graphite walls that form ideal slit-shaped pores of the fixed widths. In the literature there is the lack of systematic studies showing the influence of pore structural and Lennard-Jones (LJ) potential parameters on the pore-size distribution functions. Moreover, the parameters characterizing the properties of the adsorbed phase and the heterogeneity of the adsorbent surface should be taken into account. The Nguyen and Do method with proposed by us ASA algorithm, were utilized for the assessment of the porosity from the series of almost few thousands numerically generated local adsorption isotherms. The values of the mentioned-above parameters are varied over the wide range (ca. +/-20%) of the reference ones. Different types of the theoretical and experimental adsorption isotherms (nitrogen at 77 K) were taken into account as the global ones. They were related to the mechanism of the primary, secondary or mixed micropore filling. The variations in some above-mentioned parameters have significant effects only for PSDs (and for average pore widths) corresponding to the primary micropore filling mechanism. On the other hand, for the process of the secondary micropore filling, the influence of these parameters (without the BET coefficient for adsorption on a "flat" surface, c(s,B)) is rather insignificant. Nevertheless the differences between local and global adsorption isotherms (in the whole range of relative pressures) the absence of micropores having pore half width equal to ca. 1 nm on PSDs was observed for studied adsorbate-adsorbent systems with exceptions of the strictly microporous adsorbents and/or the low values of c(s,B). Comparison of the experimental data with the generated theoretical isosteric enthalpy of adsorption indicates that the phenomenal uptake observed from experiment can be explained in terms of the reasonable solid-fluid interaction parameters. Therefore, we varied the heterogeneity of the adsorbent surface via the strength and the range of the solid-fluid potential and the parameter c(s,B) in order to reproduce the experimental data of enthalpy of adsorption. Note that similar procedure was applied by Wang and Johnson to reproduce some hydrogen adsorption data measured for carbon nanofibres. The analysis of the obtained results shows that the selection of the values of the parameters of the intermolecular interactions and the quantities characterizing the properties of the adsorbed phase and the heterogeneity of the adsorbent walls for molecular simulations should be made with care and the influence of possible errors should be considered.     

Changes of the porous structure of activated carbons applied in a filter bed pilot operation

The paper investigates the changes in porosity (i.e., in the accessible adsorption capacity of carbonaceous adsorbents for pollutants during filter bed maturation) of three activated carbons applied in a filter bed pilot operation. The results of this investigation may help to reduce operating costs, increase granular activated carbon bed life, maximize the useful life of biofilters, and understand the mechanism of water purification by carbon adsorbents. The analysis of the pore structure was limited to the first year of service of the beds, since this was when the largest decrease in the available pore capacity occurred. Low-temperature nitrogen adsorption isotherms were used to evaluate the structural parameters and pore size distributions (PSDs) of carbon samples (virgin (reference) and mature adsorbents for different periods of water treatment) on the basis of the Nguyen and Do (ND) method and density functional theory (DFT). These results were compared with small-angle X-ray scattering (SAXS) investigations (PSDs calculated by Glatter's indirect transformation method (ITP)). The results show that in general, the ND and ITP methods lead to almost the same qualitative distribution curve behavior. Moreover, the enthalpy of immersion in water, mercury porosimetry, densities (true and apparent), and the analysis of ash are reported and compared to explain the decrease in adsorptive capacity of the carbons investigated. On the other hand, the efficacy of TOC (total organic carbon, i.e., a quantity describing the complex matrix of organic material present in natural waters) removal and the bacteria count were analyzed to explain the role of adsorption in the elimination of contaminants from water. Finally, a mechanism of organic matter removal was suggested on the basis of the above-mentioned experimental data and compared with mechanisms reported by other authors.     

Monolayer aspects of high-resolution αs-plots

The problem of the estimation of high resolution comparative plots (α_s method) is revised. Adsorption isotherms of Ar (T = 87 K) are simulated (GCMC) on the bundles of closed and opened multiwalled carbon nanotubes. Those materials are chosen in order to observe the influence of porosity on Ar adsorption, and consequently, on the comparative plots. The introduction of the structural heterogeneity (defects in the external and internal walls of osculating and separated nanotubes) is also studied. The monolayer and multilayer parts of adsorption are extracted from the total amount adsorbed for all studied adsorbents and the reference one (the bundle of the ideal 3-layered carbon tubes with very wide diameters). The significant influence of the distance between carbon nanotubes and defects (in the external and internal walls) is observed on the monolayer α_s-plots. In the case of comparative plots calculated for the multilayer adsorption the differences are also visible; however, the expected linear dependence of the amount adsorbed on a porous solid plotted against the amount adsorbed on a reference nonporous solid (the layer-by-layer adsorption occurs on both solid surfaces) in a wide range of relative pressures is not observed. The obtained results demonstrate the complexity of α_s method when both microporosity and surface heterogeneity are present. A comparison of isotherms shows that for the studied adsorbents Ar is sensitive to the appearance of the geometrical and structural defects, even at low coverage.     

A Simple Method of the Determination of the Structural Heterogeneity of Microporous Solids

A new procedure for determining the structural heterogeneity of microporous solids is presented. Applying the concept of a general adsorption isotherm equation, a method for solving this equation for adsorption in micropores is developed, and the applicability of a new simple algorithm for determining the parameters of microporous structure of two commercial carbons is shown. Copyright 2001 Academic Press.