GCMC-surface area of carbonaceous materials with N-2 and Ar adsorption as an alternative to the classical BET method

In this paper we apply a new method for the determination of surface area of carbonaceous materials, using the local surface excess isotherms obtained from the Grand Canonical Monte Carlo simulation and a concept of area distribution in terms of energy well-depth of solid–fluid interaction. The range of this well-depth considered in our GCMC simulation is from 10 to 100 K, which is wide enough to cover all carbon surfaces that we dealt with (for comparison, the well-depth for perfect graphite surface is about 58 K). Having the set of local surface excess isotherms and the differential area distribution, the overall adsorption isotherm can be obtained in an integral form. Thus, given the experimental data of nitrogen or argon adsorption on a carbon material, the differential area distribution can be obtained from the inversion process, using the regularization method. The total surface area is then obtained as the area of this distribution. We test this approach with a number of data in the literature, and compare our GCMC-surface area with that obtained from the classical BET method. In general, we find that the difference between these two surface areas is about 10%, indicating the need to reliably determine the surface area with a very consistent method. We, therefore, suggest the approach of this paper as an alternative to the BET method because of the long-recognized unrealistic assumptions used in the BET theory. Beside the surface area obtained by this method, it also provides information about the differential area distribution versus the well-depth. This information could be used as a microscopic finger-print of the carbon surface. It is expected that samples prepared from different precursors and different activation conditions will have distinct finger-prints. We illustrate this with Cabot BP120, 280 and 460 samples, and the differential area distributions obtained from the adsorption of argon at 77 K and nitrogen also at 77 K have exactly the same patterns, suggesting the characteristics of this carbon.

Adsorption of argon on homogeneous graphitized thermal carbon black and heterogeneous carbon surface

In this paper we investigate the effects of surface mediation on the adsorption behavior of argon at different temperatures on homogeneous graphitized thermal carbon black and on heterogeneous nongraphitized carbon black surface. The grand canonical Monte Carlo (GCMC) simulation is used to study the adsorption, and its performance is tested against a number of experimental data on graphitized thermal carbon black (which is known to be highly homogeneous) that are available in the literature. The surface-mediation effect is shown to be essential in the correct description of the adsorption isotherm because without accounting for that effect the GCMC simulation results are always greater than the experimental data in the region where the monolayer is being completed. This is due to the overestimation of the fluid–fluid interaction between particles in the first layer close to the solid surface. It is the surface mediation that reduces this fluid–fluid interaction in the adsorbed layers, and therefore the GCMC simulation results accounting for this surface mediation that are presented in this paper result in a better description of the data. This surface mediation having been determined, the surface excess of argon on heterogeneous carbon surfaces having solid–fluid interaction energies different from the graphite can be readily obtained. Since the real heterogeneous carbon surface is not the same as the homogeneous graphite surface, it can be described by an area distribution in terms of the well depth of the solid–fluid energy. Assuming a patchwise topology of the surface with patches of uniform well depth of solid–fluid interaction, the adsorption on a real carbon surface can be determined as an integral of the local surface excess of each patch with respect to the differential area. When this is matched against the experimental data of a carbon surface, we can derive the area distribution versus energy and hence the geometrical surface area. This new approach will be illustrated with the adsorption of argon on a nongraphitized carbon at 87.3 and 77 K, and it is found that the GCMC surface area is different from the BET surface area by about 7%. Furthermore, the description of the isotherm in the region of BET validity of 0.06 to 0.2 is much better with our method than with the BET equation.

Equilibrium adsorption in cylindrical mesopores: A modified Broekhoff and de boer theory versus density functional theory

This paper presents a thermodynamic analysis of capillary condensation phenomena in cylindrical pores. Here, we modified the Broekhoff and de Boer (BdB) model for cylindrical pores accounting for the effect of the pore radius on the potential exerted by the pore walls. The new approach incorporates the recently published standard nitrogen and argon adsorption isotherm on nonporous silica LiChrospher Si-1000. The developed model is tested against the nonlocal density functional theory (NLDFT), and the criterion for this comparison is the condensation/evaporation pressure versus the pore diameter. The quantitative agreement between the NLDFT and the refined version of the BdB theory is ascertained for pores larger than 2 nm. The modified BdB theory was applied to the experimental adsorption branch of adsorption isotherms of a number of MCM-41 samples to determine their pore size distributions (PSDs). It was found that the PSDs determined with the new BdB approach coincide with those determined with the NLDFT (also using the experimental adsorption branch). As opposed to the NLDFT, the modified BdB theory is very simple in its utilization and therefore can be used as a convenient tool to obtain PSDs of all mesoporous solids from the analysis of the adsorption branch of adsorption isotherms of any subcritical fluids.

Modeling of adsorption in finite cylindrical pores by means of density functional theory

Adsorption of argon at its boiling point infinite cylindrical pores is considered by means of the non-local density functional theory (NLDFT) with a reference to MCM-41 silica. The NLDFT was adjusted to amorphous solids, which allowed us to quantitatively describe argon adsorption isotherm on nonporous reference silica in the entire bulk pressure range. In contrast to the conventional NLDFT technique, application of the model to cylindrical pores does not show any layering before the phase transition in conformity with experimental data. The finite pore is modeled as a cylindrical cavity bounded from its mouth by an infinite flat surface perpendicular to the pore axis. The adsorption of argon in pores of 4 and 5 nm diameters is analyzed in canonical and grand canonical ensembles using a two-dimensional version of NLDFT, which accounts for the radial and longitudinal fluid density distributions. The simulation results did not show any unusual features associated with accounting for the outer surface and support the conclusions obtained from the classical analysis of capillary condensation and evaporation. That is, the spontaneous condensation occurs at the vapor-like spinodal point, which is the upper limit of mechanical stability of the liquid-like film wetting the pore wall, while the evaporation occurs via a mechanism of receding of the semispherical meniscus from the pore mouth and the complete evaporation of the core occurs at the equilibrium transition pressure. Visualization of the pore filling and empting in the form of contour lines is presented.

Effect of pore constriction on adsorption behaviour in nanoporous carbon slit pore: a computer simulation

A Grand Canonical Monte Carlo simulation (GCMC) method is used to study the effects of pore constriction on the adsorption of argon at 87.3 K in carbon slit pores of infinite and finite lengths. It is shown that the pore constriction affects the pattern of adsorption isotherm. First, the isotherm of the composite pore is greater than that of the uniform pore having the same width as the larger cavity of the composite pore. Secondly, the hysteresis loop of the composite pore is smaller than and falls between those of uniform pores. Two types of hysteresis loops have been observed, irrespective of the absence or presence of constriction and their presence depend on pore width. One hysteresis loop is associated with the compression of adsorbed particles and this phenomenon occurs after pore has been filled with particles. The second hysteresis loop is the classical condensation-evaporation loop. The hysteresis loop of a composite pore depends on the sizes of the larger cavity and the constriction. Generally, it is found that the pore blocking effect is not manifested in composite slit pores, and this result does not support the traditional irkbottle pore hypothesis.

Modeling of adsorption on nongraphitized carbon surface: GCMC simulation studies and comparison with experimental data

We model nongraphitized carbon black surfaces and investigate adsorption of argon on these surfaces by using the grand canonical Monte Carlo simulation. In this model, the nongraphitized surface is modeled as a stack of graphene layers with some carbon atoms of the top graphene layer being randomly removed. The percentage of the surface carbon atoms being removed and the effective size of the defect ( created by the removal) are the key parameters to characterize the nongraphitized surface. The patterns of adsorption isotherm and isosteric heat are particularly studied, as a function of these surface parameters as well as pressure and temperature. It is shown that the adsorption isotherm shows a steplike behavior on a perfect graphite surface and becomes smoother on nongraphitized surfaces. Regarding the isosteric heat versus loading, we observe for the case of graphitized thermal carbon black the increase of heat in the submonolayer coverage and then a sharp decline in the heat when the second layer is starting to form, beyond which it increases slightly. On the other hand, the isosteric heat versus loading for a highly nongraphitized surface shows a general decline with respect to loading, which is due to the energetic heterogeneity of the surface. It is only when the fluid-fluid interaction is greater than the surface energetic factor that we see a minimum-maximum in the isosteric heat versus loading. These simulation results of isosteric heat agree well with the experimental results of graphitization of Spheron 6 (Polley, M. H.; Schaeffer, W. D.; Smith, W. R. J. Phys. Chem. 1953, 57, 469; Beebe, R. A.; Young, D. M. J. Phys. Chem. 1954, 58, 93). Adsorption isotherms and isosteric heat in pores whose walls have defects are also studied from the simulation, and the pattern of isotherm and isosteric heat could be used to identify the fingerprint of the surface.

Comparison of nitrogen adsorption at 77 K on non-porous silica and pore wall of MCM-41 materials by means of density functional theory

Nitrogen adsorption on a surface of a non-porous reference material is widely used in the characterization. Traditionally, the enhancement of solid-fluid potential in a porous solid is accounted for by incorporating the surface curvature into the solid-fluid Potential of the flat reference surface. However, this calculation procedure has not been justified experimentally. In this paper, we derive the solid-fluid potential of mesoporous MCM-41 solid by using solely the adsorption isotherm of that solid. This solid-fluid potential is then compared with that of the non-porous reference surface. In derivation of the solid-fluid potential for both reference surface and mesoporous MCM-41 silica (diameter ranging front 3 to 6.5 nm) we employ the nonlocal density functional theory developed for amorphous solids. It is found that, to out, surprise, the solid-fluid potential of a porous solid is practically the same as that for the reference surface, indicating that there is no enhancement due to Surface curvature. This requires further investigations to explain this unusual departure from our conventional wisdom of curvature-induced enhancement. Accepting the curvature-independent solid-fluid potential derived from the non-porous reference surface, we analyze the hysteresis features of a series of MCM-41 samples. (c) 2005 Elsevier Inc. All rights reserved.

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.

Adsorption of benzene on graphitized thermal carbon black: Reduction of the quadrupole moment in the adsorbed phase

The performance of intermolecular potential models on the adsorption of benzene on graphitized thermal carbon black at various temperatures is investigated. Two models contain only dispersive sites, whereas the other two models account explicitly for the dispersive and electrostatic sites. Using numerous data in the literature on benzene adsorption on graphitized thermal carbon black at various temperatures, we have found that the effect of surface mediation on interaction between adsorbed benzene molecules must be accounted for to describe correctly the adsorption isotherm as well as the isosteric heat. Among the two models with partial charges tested, the WSKS model of Wick et at. I that has only six dispersive sites and three discrete partial charges is better than the very expensive all-atom model of Jorgensen and Severance.(2) Adsorbed benzene molecules on graphitized thermal carbon black have a complex orientation with respect to distance from the surface and also with respect to loading. At low loadings, they adopt the parallel configuration relative to the graphene surface, whereas at higher loadings (still less than monolayer coverage) some molecules adopt a slant orientation to maximize the fluid-fluid interaction. For loadings in the multilayer region, the orientation of molecules in the first layer is influenced by the presence of molecules in the second layer. The data that are used in this article come from the work of Isirikyan and Kiselev,(3) Pierotti and Smallwood,(4) Pierce and Ewing,(5) Belyakova, Kiselev, and Kovaleva,(6) and Carrott et al.(7)

Effects of graphene layer size on the adsorption of fluids on graphitized thermal carbon black. A computer simulation study

The adsorption of Lennard-Jones fluids (argon and nitrogen) onto a graphitized thermal carbon black surface was studied with a Grand Canonical Monte Carlo Simulation (GCMC). The surface was assumed to be finite in length and composed of three graphene layers. When the GCMC simulation was used to describe adsorption on a graphite surface, an over-prediction of the isotherm was consistently observed in the pressure regions where the first and second layers are formed. To remove this over-prediction, surface mediation was accounted for to reduce the fluid-fluid interaction. Do and co-workers have introduced the so-called surface-mediation damping factor to correct the over-prediction for the case of a graphite surface of infinite extent, and this approach has yielded a good description of the adsorption isotherm. In this paper, the effects of the finite size of the graphene layer on the adsorption isotherm and how these would affect the extent of the surface mediation were studied. It was found that this finite-surface model provides a better description of the experimental data for graphitized thermal carbon black of high surface area (i.e. small crystallite size) while the infinite- surface model describes data for carbon black of very low surface area (i.e. large crystallite size).

Adsorption study for removal of basic red dye using bentonite

Colored wastewater poses a challenge to the conventional wastewater treatment techniques. Solid-liquid phase adsorption has been found to be effective for the removal of dyes from effluent. In this paper, the ability of bentonite as an adsorbent for the removal of a commercial dye, Basic Red 2 (BR2), from an aqueous solution has been investigated under various experimental conditions. The adsorption kinetics was shown to be pseudo-second-order. It was found that bentonite had high adsorption capacity for BR2 due to cation exchange. The adsorption equilibrium data can be fitted well by the Langmuir adsorption isotherm model. The effect of the experimental parameters, such as temperature, salt, and pH was investigated through a number of batch adsorption experiments. It was found that the removal of dye increased with the increase in solution pH. However, the change of temperature (15-45 degrees C) and the addition of sodium chloride were found to have little effect on the adsorption process. The results show that electrostatic interactions are not dominant in the interaction between BR2 and bentonite. It was found that the adsorption was a rapid process with 80-90% of the dye removed within the first 2-3 min. Bentonite as an adsorbent is promising for color removal from wastewater.

Structural characterisation and environmental application of organoclays for the removal of phenolic compounds

Modified montmorillonite was prepared at different surfactant (HDTMA) loadings through ion exchange. The conformational arrangement of the loaded surfactants within the interlayer space of MMT was obtained by computational modelling. The conformational change of surfactant molecules enhance the visual understanding of the results obtained from characterization methods such as XRD and surface analysis of the organoclays. Batch experiments were carried out for the adsorption of p-chlorophenol (PCP) and different conditions (pH and temperature) were used in order to determine the optimum sorption. For comparison purpose, the experiments were repeated under the same conditions for p-nitrophenol (PNP). Langmuir and Freundlich equations were applied to the adsorption isotherm of PCP and PNP. The Freundlich isotherm model was found to be the best fit for both of the phenolic compounds. This involved multilayer adsorptions in the adsorption process. In particular, the binding affinity value of PNP was higher than that of PCP and this is attributable to their hydrophobicities. The adsorption of the phenolic compounds by organoclays intercalated with highly loaded surfactants was markedly improved possibly due to the fact that the intercalated surfactant molecules within the interlayer space contribute to the partition phases, which result in greater adsorption of the organic pollutants.

Synthesis and characterisation of titanium sol-gels in varied gravity environments

Sol-gel synthesis in varied gravity is only a relatively new topic in the literature and further investigation is required to explore its full potential as a method to synthesise novel materials. Although trialled for systems such as silica, the specific application of varied gravity synthesis to other sol-gel systems such as titanium has not previously been undertaken. Current literature methods for the synthesis of sol-gel material in reduced gravity could not be applied to titanium sol-gel processing, thus a new strategy had to be developed in this study. To successfully conduct experiments in varied gravity a refined titanium sol-gel chemical precursor had to be developed which allowed the single solution precursor to remain un-reactive at temperatures up to 50oC and only begin to react when exposed to a pressure decrease from a vacuum. Due to the new nature of this precursor, a thorough characterisation of the reaction precursors was subsequently undertaken with the use of techniques such as Nuclear Magnetic Resonance, Infra-red and UV-Vis spectroscopy in order to achieve sufficient understanding of precursor chemistry and kinetic stability. This understanding was then used to propose gelation reaction mechanisms under varied gravity conditions. Two unique reactor systems were designed and built with the specific purpose to allow the effects of varied gravity (high, normal, reduced) during synthesis of titanium sol-gels to be studied. The first system was a centrifuge capable of providing high gravity environments of up to 70 g’s for extended periods, whilst applying a 100 mbar vacuum and a temperature of 40-50oC to the reaction chambers. The second system to be used in the QUT Microgravity Drop Tower Facility was also required to provide the same thermal and vacuum conditions used in the centrifuge, but had to operate autonomously during free fall. Through the use of post synthesis characterisation techniques such as Raman Spectroscopy, X-Ray diffraction (XRD) and N2 adsorption, it was found that increased gravity levels during synthesis, had the greatest effect on the final products. Samples produced in reduced and normal gravity appeared to form amorphous gels containing very small particles with moderate surface areas. Whereas crystalline anatase (TiO2), was found to form in samples synthesised above 5 g with significant increases in crystallinity, particle size and surface area observed when samples were produced at gravity levels up to 70 g. It is proposed that for samples produced in higher gravity, an increased concentration gradient of water is forms at the bottom of the reacting film due to forced convection. The particles formed in higher gravity diffuse downward towards this excess of water, which favours the condensation reaction of remaining sol gel precursors with the particles promoting increased particle growth. Due to the removal of downward convection in reduced gravity, particle growth due to condensation reaction processes are physically hindered hydrolysis reactions favoured instead. Another significant finding from this work was that anatase could be produced at relatively low temperatures of 40-50oC instead of the conventional method of calcination above 450oC solely through sol-gel synthesis at higher gravity levels. It is hoped that the outcomes of this research will lead to an increased understanding of the effects of gravity on chemical synthesis of titanium sol-gel, potentially leading to the development of improved products suitable for diverse applications such as semiconductor or catalyst materials as well as significantly reducing production and energy costs through manufacturing these materials at significantly lower temperatures.

Plasmon-tuned silver colloids for SERRS analysis of methemoglobin with preserved nativity

Optically tuned silver nanoparticles (AgNP's) functionalized with ω-mercaptoalkanoic acids are synthesized and used as a signal amplifier for the surface-enhanced resonance Raman scattering (SERRS) study of heme cofactor in methemoglobin (metHb). Even though both mercaptopropionic acid (MPA)- and mercaptononanoic acid (MNA)-functionalized AgNP's exemplify vastly enhanced SERRS signal of metHb, MNA-AgNP's amplify the SERRS signal amid preservation of the nativity of the heme pocket, unlike MPA-AgNP's. The electrostatic interaction between MNA-AgNP's and metHb leads to instant signal enhancement with a Raman enhancement factor (EF(SERS)) of 4.2 × 10(3). Additionally, a Langmuir adsorption isotherm has been employed for the adsorption of metHb on the MNA-AgNP surface, which provides the real surface coverage and equilibrium constant (K) of metHb as 139 nM and 3.6 × 10(8) M(-1), respectively. The lowest detection limit of 10 nM for metHb has been demonstrated using MNA-AgNP's besides retaining the nativity of the heme pocket.

Protein loaded mesoporous silica spheres as a controlled delivery platform

Background The adsorption of bovine serum albumin (BSA) onto mesoporous silica spheres (MPS) synthesized from silica colloids was studied employing real time in situ measurements. The stabilities of the BSA at different pH values, their isoelectric points and zeta potentials were determined in order to probe the interactions between the protein and the mesoporous silica. Results The pore size of MPS was designed for protein, and this, coupled with an in depth understanding of the physico-chemical characteristics of the protein and MPS has yielded a better binding capacity and delivery profile. The adsorption isotherm at pH 4.2 fitted the Langmuir model and displayed the highest adsorption capacity (71.43 mg mL-1 MPS). Furthermore, the delivery rates of BSA from the MPS under physiological conditions were shown to be dependent on the ionic strength of the buffer and protein loading concentration. Conclusion Economics and scale-up considerations of mesoporous material synthesized via destabilization of colloids by electrolyte indicate the scaleability and commercial viability of this technology as a delivery platform for biopharmaceutical applications.