The special features of equilibrium adsorption of argon on homogeneous and inhomogeneous surfaces

Comparative patterns of equilibrium adsorption of argon on the surface of graphitized thermal carbon black (GCB) and the inhomogeneous surfaces of nongraphitized carbon black and silica at 77 and 87.3 K were considered. It was shown that argon acquires the properties of a special phase with a layered structure and exhibits two-dimensional phase transitions with the formation of crystal-like layers near the homogeneous surface of GCB even at a temperature exceeding the triple point. However, already at a distance of three-four molecular diameters from the surface, adsorbed argon behaves as a bulk phase in a weak external field. The defect surface of nongraphitized carbon black and the amorphous surface structure of silica destroy the longrange order of adsorbed argon and lower its solidification temperature. Therefore, argon adsorbed at a temperature of 77 K, i.e., below the triple point, exhibits the properties of a supercooled liquid. The applicability of density functional theory to describe argon isotherms and heat of adsorption on inhomogeneous surfaces was demonstrated.     

On the physical adsorption of gases on carbon materials from molecular simulation

In this paper we present a series of work covering a range of aspects relating molecular simulation to experiment. The importance of surface mediation type effects to the adsorption of simple and complex gases is demonstrated. Coupled with the adsorption of simple gases is their projection area when used for surface area determination. The pressure dependence of a projection area is demonstrated for argon at 77 and 87.3 K. A simple model is used to account for the degree of graphitisation of a surface is demonstrated and used to account for the isosteric heat behaviour of non-graphitised carbon blacks. Turning from surfaces to porous solids, an alternative treatment of experiment data (either sub or super critical) is presented that avoids the ambiguity of excess amounts adsorbed. Using this method one is able to obtain pore size distributions and amounts adsorbed without relying on such things as helium expansion volumes. Since this type of method is usually applied to composite solids we also demonstrate the correct method for calculating the heat of adsorption using independent sets of simulations. The final topic covered in this paper is an example of the information that can be gained from the heat capacity of an adsorbed phase.     

Adsorption of simple fluid on silica surface and nanopore: effect of surface chemistry and pore shape

This paper reports a molecular simulation study on the adsorption of simple fluids (argon at 77 K) on hydroxylated silica surfaces and nanopores. The effect of surface chemistry is addressed by considering substrates with either partially or fully hydroxylated surfaces. We also investigate the effect of pore shape on adsorption and capillary condensation by comparing the results for cylindrical and hexagonal nanopores having equivalent sections (i.e., equal section areas). Due to the increase in the polarity of the surface with the density of OH groups, the adsorbed amounts for fully hydroxylated surfaces are found to be larger than those for partially hydroxylated surfaces. Both the adsorption isotherms for the cylindrical and hexagonal pores conform to the typical behavior observed in the experiments for adsorption/condensation in cylindrical nanopores MCM-41. Capillary condensation occurs through an irreversible discontinuous transition between the partially filled and the completely filled configurations, while evaporation occurs through the displacement at equilibrium of a hemispherical meniscus along the pore axis. Our data are also used to discuss the effect of surface chemistry and pore shape on the BET method. The BET surface for fully hydroxylated surfaces is much larger (by 10-20%) than the true geometrical surface. In contrast, the BET surface significantly underestimates the true surface when partially hydroxylated surfaces are considered. These results suggest that the surface chemistry and the choice of the system adsorbate/adsorbent is crucial in determining the surface area of solids using the BET method.     

Calorimetry by immersion into liquid nitrogen and liquid argon: a better way to determine the internal surface area of micropores

The aim of this work is to assess the internal surface area of a set of samples (either carbons or oxides, either porous or nonporous, either microporous or mesoporous) by microcalorimetry via immersion into liquid nitrogen or argon. We have made use of an isothermal, heat-flux microcalorimeter, initially designed and built in our laboratory for the sake of gas adsorption experiments at 77 or 87 K. It seems that immersion calorimetry into liquid nitrogen and argon makes it possible to go one step further in the determination of the internal surface area of micropores.     

Assessment of the surface areas of silica and clay in acid-leached clay materials using concepts of adsorption on heterogeneous surfaces

Two clays of the areas of Kaélé and Kousseri (extreme North Cameroon) containing mainly smectites and minor amounts of kaolinite were activated with sulfuric acid (1 to 8 N). Crystal-chemical properties were studied using X-ray diffraction, Fourier transform infrared spectroscopy, and chemical analysis, while textural properties were analyzed by step-by-step nitrogen adsorption at 77 K and low-pressure quasi-equilibrium argon adsorption at 77 K. As is generally observed, smectite is more sensitive to acid leaching than kaolinite. As a result of smectite decomposition, amorphous Al-containing silica forms, leading to an increase in the specific surface area of the leached materials. The content of the clay minerals and amorphous silica can be estimated on the basis of changes in the chemical composition of the samples upon acid leaching. As far as adsorption energy distributions derived from low-pressure argon derivative adsorption isotherms are concerned, the main modifications occur when 1 N sulfuric acid is used, due to the replacement of calcium and sodium compensating cations by protons. When higher acid concentrations are used, variations in adsorption energy distribution can be assigned to the presence of amorphous silica. It was possible to model experimental adsorption energy distributions as weighted sums of argon adsorption energy distributions obtained on (i) 1 N samples representing protonated clays and (ii) a silica gel used as a reference aluminous silica. Using such an approach, increasing acid concentration results in an increase in the surface area of silica, whereas the surface area of the remaining clay minerals remains roughly constant.     

Investigation of hydrogen physisorption active sites on the surface of porous carbonaceous materials

Hydrogen physisorption in different carbonaceous materials was investigated in liquid nitrogen (77 K). The total hydrogen adsorption was found to have a linear relationship with the surface area of pores <30 A. The surface area and porosity of the carbon materials were determined by dinitrogen adsorption at 77 K and density function theory (DFT). The active sites for hydrogen adsorption were investigated and found to be related to the edge orientation of defective graphene micro-sheet domains.     

Explanation of the unusual peak of calorimetric heat in the adsorption of nitrogen, argon and methane on graphitized thermal carbon black

Heats of adsorption and adsorption isotherms of argon, nitrogen and methane on a perfect graphitic surface and a defective graphitic surface are studied with a Grand Canonical Monte Carlo Simulation (GCMC). For the perfect surface, the isosteric heat versus loading shows a typical pattern of adsorption of simple fluids on graphite. Depending on adsorbate, degree of graphitization and temperature, a spike in the heat curve versus loading is observed when the first layer is mostly covered with adsorbate molecules. The heat spike is observed for argon and nitrogen at 77 K while for argon at 87.3 K it is no longer present. These simulation results are consistent with the experimental data of J. Rouquerol, S. Partyka and F. Rouquerol, J. Chem. Soc., Faraday Trans. 1, 1977, 73, 306. In the case of methane we observe heat spikes at low temperatures, 84.5, 92.5 and 104 K. The heat spike shifts to higher loading with temperature and it then disappears at high temperatures. These observations are in qualitative agreement with the experimental data of A. Inaba, Y. Koga and J. A. Morrison, J. Chem. Soc., Faraday Trans. 2, 1986, 82, 1635. In all cases where heat spikes are observed, the GCMC simulation results indicate that the heat spike is associated with the squeezing of molecules into the already dense first layer, and the rearrangement of molecules to form a highly structured fluid of this layer. While this squeezing into the first layer is happening, molecules continue to adsorb onto the relatively sparse second layer.     

Studies of heterogeneity properties of selected high-temperature superconductor surfaces

Nitrogen adsorption measured at 77 K was used to characterize the surface heterogeneity of high-temperature superconductor surfaces. Properties relating to adsorption and porosity of the solids (adsorption capacity, specific surface area, radii and volume of the pores, pore-size distribution function) were determined from nitrogen adsorption–desorption isotherms and atomic force microscopy (AFM) for a series of oxide superconductors. It is shown that the adsorption isotherms of all samples are S-shaped and belong to type II according to the IUPAC classification. On the basis of the nitrogen adsorption isotherms and AFM data, fractal dimensions were determined and correlations found with adsorption and porosity parameters.     

Calculation of the BET Compatible Surface Area from Any Type I Isotherms Measured below the Critical Temperature

It may occur in practice that the nitrogen isotherm should be measured at 77 K only in order to determine the Brunauer-Emmett-Teller (BET) specific surface area [as(N2, 77)]. This fact has given cause for an elaborate method to calculate the value of as(N2, 77) from Type I isotherms measured on any adsorbents at any temperature. Since Type I isotherms are measured most often in practice the proposed method makes it possible to calculate the value of as(N2, 77) from isotherms of adsorptives which are the actual topics of the investigations. Thus, in these cases the determination of nitrogen isotherms at 77 K can be omitted. The proposed method is based on the Tóth (T) equation and on its modified and extended forms. In these equations are present the parameters chim, chio, and t with the following physical meanings: chim and chio are integral constants originating from the Gibbs equation integrated between definite limits of pressure and coverage and t is a parameter characterizing the heterogeneity of the adsorbents. The parameters chim and chio assure the thermodynamic consistence of these relationships. It is proven that the parameters (chim)1/t and (chio)1/t depend only on the structure of adsorbents (micro-, mezoporous, or smooth surfaces). These parameters, calculated from Type I isotherms measured under the critical temperature of the adsorptives, are the bases of the calculation of the BET compatible surface areas. Copyright 1999 Academic Press.     

Microcalorimetric study of argon,oxygen, nitrogen and carbon monoxide adsorption on crystalline zirconia

The adsorption of argon, oxygen, nitrogen and carbon monoxide at 77 K on crystalline zirconia and microporous zirconia gels has been studied by adsorption volumetry and isothermal microcalorimetry.The microporous structure of the zirconia gel may explain the higher enthalpy of adsorption obtained for argon. Both crystalline samples are mesoporous and in each case, the polar sites on the surface give specific interactions with dipolar (CO) or quadrupolar (N₂, O₂) molecules, which can be deduced from the adsorption isotherms and the corresponding differential enthalpy curves.M. J. T. acknowledges for a 2 month invited professorship at Université de Provence.     

Assessing surface chemistry and pore structure of active carbons by a combination of physisorption (H2O, Ar, N2, CO2), XPS and TPD-MS

In order to address open questions concerning the surface chemistry and pore structure characterization of nanoporous carbons, we performed extensive experiments by combining various experimental techniques on a series of commercially available activated carbons which exhibit diverse surface chemistry characteristics. Pore size analysis was performed on Ar (87 K), N₂ (77 K) and CO₂ (273 K) adsorption isotherms using state-of-the art methods based on density functional theory, including the recently developed quenched solid density functional theory (QSDFT). A detailed study of the surface chemistry was obtained by applying temperature programmed desorption coupled with mass spectrometry (TPD-MS) as well as XPS (X-Ray-Photoelectron Scattering). This information together with the pore structure information leads to a reliable interpretation of systematic water adsorption measurements obtained on these materials. Our results clearly suggest that water adsorption is indeed a sensitive tool for detecting differences in surface chemistry between chemically and physically activated active carbon materials with comparable ultramicropore structure. The occurrence of sorption hysteresis associated with the filling of micro- and narrow mesopores (in a range where nitrogen and argon isotherms are reversible) provides additional structural information, complementary to the insights from argon/nitrogen/carbon dioxide adsorption.     

Template transformations in preparation of MCM-41 silica

Template transformation in MCM-41 material during thermal treatment under different conditions was investigated on the basis of thermogravimetry (TG-DTA), X-ray diffraction (XRD) and positron annihilation lifetime spectroscopy (PALS). Micelle templated silica was prepared using C18 trimethylammonium bromide. The pore structure of MCM-41 samples obtained after removal of the surfactant in air, argon flow and vacuum was analyzed on the basis of the adsorption isotherms of nitrogen at 77 K and XRD experiments. The TG-DTA experiments confirm the mechanism of the template removal known from literature. However, the sequence of the processes during thermal treatment of as-synthesized sample and temperature of transformations depended strongly on the presence of oxygen and the heating rate. The main template degradation took place below 573 K and was independent of the kind of atmosphere above the sample. Residual carbonaceous species are removed from pores and the external surface of MCM-41 silica upon heating to 823 K by combustion or evaporation. The latter process as well as translocation of liquid-like products of template degradation from the pore interior to external surface was confirmed by PALS experiment in vacuum.     

Role of exchangeable cations on geometrical and energetic surface heterogeneity of kaolinites

Textural and energetic proprieties of kaolinite were studied by low-pressure argon adsorption at 77 K. The heterogeneity of four kaolinites (two low-defect and two high-defect samples) modified on their surface by cation exchange with Li+, Na+, or K+ was studied by DIS analysis of the derivative argon adsorption isotherms. The comparison between the derivative adsorption isotherms shows that the nature of the surface cation influences the adsorption phenomena on edge and basal faces. In the case of basal faces, two adsorption domains are observed: for the first one, argon adsorption is slightly sensitive to the nature of the surface cation; for the second one, argon adsorption energy depends on the nature of surface cation suggesting their presence on theoretically uncharged basal faces. This study also shows that the shape of elementary particles, as derived from basal and edge surface areas, changes with the nature of cation. This anomalous result is due to the decrease of edge surface area with increasing the size of the cation. This surface cation dependence can be accounted for the area occupied by the edge surface cations in the first argon monolayer.     

Matrix effect in the cryotrapping of gas samples in the ppbv range

A gas mixture containing ppbv concentrations of volatile chlorinated and aromatic hydrocarbons was prepared in helium, nitrogen, or argon in a plastic (Nalophan) bag, in which it was found the mixture could be safely stored for several days. Samples of the mixture were subsequently analyzed by gas chromatography after direct cryotrapping in an empty metal U-tube. The cooling medium used was liquid nitrogen, liquid argon, or a dry ice-acetone slurry (197 K). The efficiency of cryotrapping in liquid nitrogen was over 90% when the aromatic hydrocarbon mixture was prepared in the helium matrix, but between 50 and 70% when it was prepared in nitrogen or argon, the recovery from the argon matrix being somewhat higher. The poor recovery in nitrogen at 77 K and argon at 87 K was explained by the reduced rate of diffusion to the wall owing to mist or aerosol formation. At 197 K condensation was negligible if the partial pressures were lower than the saturated vapor pressures.     

Comparative features of ar adsorption on smooth and amorphous surfaces examined by density functional theory

We analyze argon adsorption isotherms and isosteric heat of adsorption on graphitized and nongraphitized carbon black and silica surfaces by means of nonlocal density functional theory (NLDFT). It is shown that in the case of graphitized carbon black the behavior of the adsorbed phase is nearly identical to that in the bulk phase at a distance larger than about 3-4 molecular diameters from the surface. At a smaller distance argon forms solid-like molecular layers at a temperature at least 3.5 K above the triple point, with the interlayer distance being markedly smaller than the argon collision diameter. In the case of defected or amorphous surfaces adsorbed argon is liquid-like below its triple point. Our extension of the Tarazona NLDFT to amorphous solids (NLDFT-AS) and the Kierlik and Rosinberg version of NLDFT excellently fit argon adsorption isotherms and properly predict the isosteric heat of adsorption. We showed that the surface roughness affects the calculated heat of adsorption, which allowed us to adjust the width of the diffuse zone of the nongraphitized carbon black and the silica surface.     

BET specific surface area and pore structure of MOFs determined by hydrogen adsorption at 20 K

Low-pressure high-resolution hydrogen adsorption for the metal-organic framework MIL-101 are measured at 19.5 K and pressures below 57 kPa. The BET specific surface area and micropore volume are determined and compared to results from nitrogen adsorption at 77 K. Steps in the hydrogen adsorption isotherm are correlated to the pore structure of MIL-101.     

Influence of anodic treatment on heavy metal ion removal by activated carbon fibers

In this work, the effect of electrochemical oxidation treatment on activated carbon fibers (ACFs) was studied in the context of Cr(VI), Cu(II), and Ni(II) adsorption behavior. Ten weight percent phosphoric acid (A-ACFs) and ammonia (B-ACFs) were used for acidic and basic electrolytes, respectively. Surface properties of ACFs were determined by X-ray photoelectron spectroscopy (XPS). The specific surface area and the pore structure were evaluated from nitrogen adsorption data at 77 K. As a result, the electrochemical oxidation treatment led to an increase in the amount of oxygen-containing functional groups. Also, the adsorption capacity of the electrochemically oxidized ACFs was improved in the order B-ACFs > A-ACFs > untreated-ACFs, in spite of a decrease in specific surface area which resulted from pore blocking by functional groups and pore destruction by acidic electrolyte. It was clearly found that the heavy metal ions were largely influenced by the functional groups on the ACF surfaces.     

Comparative simulation study of nitrogen and ammonia adsorption on graphitized and nongraphitized carbon blacks

Grand canonical Monte Carlo simulation is used to study the adsorption of nitrogen at 77 K and ammonia at 240 K to represent weakly polar and polar molecules, respectively, on infinite and finite graphite surfaces. These graphite surfaces were modeled with different percentages of carbons removed (defects) from the top graphite layer. Increasing the number of defects increases the adsorption and the isosteric heat of nitrogen at low pressure. At moderate pressures the amount adsorbed is less due to the disruption in the packing of the nitrogen in the first layer. In contrast, the adsorption of ammonia at all pressures is reduced as the percentage of defects is increased. This is due to the disruption in ammonia bonding caused by the defects. The condensation-like step change in the ammonia isotherm on the perfect graphite surface is not observed for any of these surfaces with defects even for the case of only 10% defects. At high percentage of defects the adsorption isotherm is close to Henry law behavior for much of the pressure range. The adsorption on finite surfaces shows that the amount adsorbed for both molecules decreases compared with that of the infinite surfaces, resulting from interaction potentials with the surface and other fluid molecules at the edge. The decrease is much greater for the ammonia adsorption because the bonding between ammonia molecules is disrupted, meaning that the adsorption cannot follow the mechanism of condensation seen for the infinite surface.     

Structure and Adsorption Properties of Nanocrystalline Silicon

The structure of the particles of nanocrystalline silicon synthesized in argon plasma with added oxygen is studied. An amorphous shell composed of silicon oxide is formed on the surface of silicon nanoparticles. The particles form clusters with a fractal structure. The adsorption of nitrogen on a powder of nanocrystalline silicon at 77 K is studied, and adsorption isotherms obtained for nanocrystalline silicon and nonporous silica adsorbents with identical specific surface areas are compared. The values of surface fractal dimension of powdered nanocrystalline silicon are calculated using the Frenkel-Halsey-Hill equation for multilayer adsorption under the dominant contribution of van der Waals or capillary forces. It is shown that surface fractal dimension is a structure-sensitive parameter characterizing both the morphology of clusters and the structure (roughness) of the surface of particles and their aggregates.__________Translated from Kolloidnyi Zhurnal, Vol. 67, No. 4, 2005, pp. 541–547.Original Russian Text Copyright © 2005 by Tutorskii, Belogorokhov, Ishchenko, Storozhenko.