Experimental and theoretical investigations of adsorption hysteresis and criticality in MCM-41: Studies with O-2, Ar, and CO2

MCM-41 materials of six different pore diameters were prepared and characterized using X-ray diffraction, transmission electron microscopy, helium pycnometry, small-angle neutron scattering, and gas adsorption (argon at 77.4 and 87.4 K, nitrogen and oxygen at 77.4 K, and carbon dioxide at 194.6 K). A recent molecular continuum model of the authors, previously used for adsorption of nitrogen at 77.4 K, was applied here for adsorption of argon, oxygen, and carbon dioxide. While model predictions of single-pore adsorption isotherms for argon and oxygen are in satisfactory agreement with experimental data, significant deviation was found for carbon dioxide, most likely due to its high quadrupole moment. Predictions of critical pore diameter, below which reversible condensation occurs: were possible by the model and found to be consistent with experimental estimates, for the adsorption of the various gases. On the other hand, existing models such as the Barrett-Joyner-Halenda (BJH), Saito-Foley, and Dubinin-Astakhov models were found to be inadequate, either predicting an incorrect pore diameter or not correlating the isotherms adequately. The wall structure of MCM-41 appears to be close to that of amorphous silica, as inferred from our skeletal density measurements.

Molecular engineered porous clays using surfactants

Quaternary ammonium surfactants were used to control the pore structure of bentonite intercalated with a mixed hydro-sol of silicon and titanium. Porous clay heterostructures of alumina and laponite were prepared in the presence of polyethylene oxide (PEO) surfactants. Participation of the surfactants in the synthesis results in significant changes in the structure of porous clay products. Surfactants are involved in different mechanisms, In the case of bentonite, the mean size of the framework pores was directly proportional to the chain length of the quaternary ammonium surfactants. This indicates a molecular templating mechanism, similar to that observed in the synthesis of MCM41. However, in the case of laponite, the size and volume of the mesopores were related to the amount of PEO surfactants used. By using an appropriate surfactant, we can obtain highly porous clays with various pore structures. Introducing surfactants during intercalation is an efficient strategy for the molecular engineering of porous clay adsorbents and catalysts. (C) 2002 Elsevier Science B.V. All rights reserved.

Porous solids from layered clays by combined pillaring and templating approaches

The pore structure formation in bentonite, pillared with a mixed sol of silicon and titanium hydroxides and treated subsequently with quaternary ammonium surfactants, is investigated. The surfactant micelles act as a template, similar to their role in MCM41 synthesis. Because both the surfactant micelles and the sol particles are positively charged, it is greatly favorable for them to form meso-phase assembles in the galleries between the clay layers that bear negative charges. Besides, the sol particles do not bond the clay layers strongly as other kinds of pillar precursors do, so that the treatment with surfactants can result in radical structure changes in sol-pillared clays. This allows us to tailor the pore structure of these porous clays by choice of surfactant. The surfactant treatment also results in profound increases in porosity and improvement in thermal stability. Therefore, the product porous clays have great potential to be Used to deal with large molecules or at high operating temperatures. We also found that titanium in these samples is highly dispersed in the silica matrix rather than existing in the form of small particles of pure titania. Such highly dispersed Ti active centers may offer excellent activities for catalytic oxidation reactions such as alkanes into alcohols and ketones.

Comprehensive structural characterization of MCM-41: From mesopores to particles

In the present work the meso- and macro-structural characteristics of the mesoporous adsorbent MCM-41 have been estimated with the help of various techniques. The structure is found to comprise four different length scales: that of the mesopores, the crystallites, the grains and of the particles. It was found that the surface area estimated by the use of small angle scattering techniques is higher, while that estimated by mercury porosimetry is much lower, than that obtained from gas adsorption methods. Based on the macropore characterization by mercury porosimetry, and the considerable macropore area determined, it is seen that the actual mesopore area of MCM-41 may be significantly lower than the BET area. TEM studies indicated that MCM-41 does not have an ideal mesopore structure; however, it may still be treated as a model mesoporous material for gas adsorption studies because of the large radius of curvature of the channels.

The Applicability Of Ordered Mesoporous Sba-15 And Its Hydrophobic Glutaraldehyde-bridge Derivative To Improve Ibuprofen-loading In Releasing System.

The mesoporous SBA-15 silica with uniform hexagonal pore, narrow pore size distribution and tuneable pore diameter was organofunctionalized with glutaraldehyde-bridged silylating agent. The precursor and its derivative silicas were ibuprofen-loaded for controlled delivery in simulated biological fluids. The synthesized silicas were characterized by elemental analysis, infrared spectroscopy, (13)C and (29)Si solid state NMR spectroscopy, nitrogen adsorption, X-ray diffractometry, thermogravimetry and scanning electron microscopy. Surface functionalization with amine containing bridged hydrophobic structure resulted in significantly decreased surface area from 802.4 to 63.0 m(2) g(-1) and pore diameter 8.0-6.0 nm, which ultimately increased the drug-loading capacity from 18.0% up to 28.3% and a very slow release rate of ibuprofen over the period of 72.5h. The in vitro drug release demonstrated that SBA-15 presented the fastest release from 25% to 27% and SBA-15GA gave near 10% of drug release in all fluids during 72.5 h. The Korsmeyer-Peppas model better fits the release data with the Fickian diffusion mechanism and zero order kinetics for synthesized mesoporous silicas. Both pore sizes and hydrophobicity influenced the rate of the release process, indicating that the chemically modified silica can be suggested to design formulation of slow and constant release over a defined period, to avoid repeated administration.

Comparison of adsorbent films obtained by plasma polymerization of oxygenated organic compounds

Thin films obtained by plasma polymerization of ethyl ether, methyl or ethyl acetate, acetaldehyde, acetone and 2-propanol were compared. Infrared spectroscopy (FFIR), resistance to chemicals, contact angle measurements, X-ray photoelectron spectroscopy (XPS), optical and scanning electron microscopy (SEM), and quartz crystal microbalance (QCM) were carried out. For all films FTIR showed high intensity for polar bonds yet the films are not resistant to polar solvents. Contact angle measurements revealed hydrophilic and organophilic surfaces and XPS pointed out a high proportion of oxygenated bonds. All films showed good step coverage and peeling was significant only with acetone and 2-propanol. All films are adsorbent for organic compounds in a large scale of polarity but acetaldehyde and 2-propanol act like a selective membrane. Also, deposition of these films on hydrophobic substrates leads to island formation. A possible model to explain the results must consider the hydrogen bridge formation on 2-propanol and acetaldehyde films. Ethyl ether, ethyl and methyl acetate showed good characteristics for development of sensor and sample pretreatment using miniaturized devices. (C) 2007 Elsevier B.V. All rights reserved.

Thickness and stability of adsorbed film in cylindrical mesopores

The adsorbed film in small cylindrical mesopores is studied by using MCM-41 samples of uniform cylindrical channels as model systems. It is found that at a given relative pressure, the smaller the pore radius, the thicker the adsorbed film is, as postulated by Broekhoff and De Beer. Thermodynamics analysis established that the stability of the adsorbed film is determined by interface curvature and the potential of interaction between adsorbate and adsorbent. A semiempirical equation is proposed to describe the state of stable adsorbed films in cylindrical mesopores. It is also shown to be useful in calculations of pore size distributions of mesoporous solids.

Characterization of pore size distributions of mesoporous materials from adsorption isotherms

In this article, a new hybrid model for estimating the pore size distribution of micro- and mesoporous materials is developed, and tested with the adsorption data of nitrogen, oxygen, and argon on ordered mesoporous materials reported in the literature. For the micropore region, the model uses the Dubinin-Rudushkevich (DR) isotherm with the Chen-Yang modification. A recent isotherm model of the authors for nonporous materials, which uses a continuum-mechanical model for the multilayer region and the Unilan model for the submonolayer region, has been extended for adsorption in mesopores. The experimental data is inverted using regularization to obtain the pore size distribution. The present model was found to be successful in predicting the pore size distribution of pure as well as binary physical mixtures of MCM-41 synthesized with different templates, with results in agreement with those from the XRD method and nonlocal density functional theory. It was found that various other recent methods, as well as the classical Broekhoff and de Beer method, underpredict the pore diameter of MCM-41. The present model has been successfully applied to MCM-48, SBA's, CMK, KIT, HMS, FSM, MTS, mesoporous fly ash, and a large number of other regular mesoporous materials.

Recent advances in processing and characterization of periodic mesoporous MCM-41 silicate molecular sieves

The discovery of periodic mesoporous MCM-41 and related molecular sieves has attracted significant attention from a fundamental as well as applied perspective. They possess well-defined cylindrical/hexagonal mesopores with a simple geometry, tailored pore size, and reproducible surface properties. Hence, there is an ever-growing scientific interest in the challenges posed by their processing and characterization and by the refinement of various sorption models. Further, MCM-41-based materials are currently under intense investigation with respect to their utility as adsorbents, catalysts, supports, ion-exchangers, and molecular hosts. In this article, we provide a critical review of the developments in these areas with particular emphasis on adsorption characteristics, progress in controlling the pore sizes, and a comparison of pore size distributions using traditional and newer models. The model proposed by the authors for adsorption isotherms and criticalities in capillary condensation and hysteresis is found to explain unusual adsorption behavior in these materials while providing a convenient characterization tool.

Characterization of micro-mesoporous carbonaceous materials. Calculations of adsorption isotherm of hydrocarbons

In this paper we apply a method recently developed by Do and co-workers(1) for the prediction of adsorption isotherms of pure vapors on carbonaceous materials. The information required for the prediction is the pore size distribution and the BET constant, C, of a corresponding nonporous surface (graphite). The dispersive adsorption force is assumed to be the dominant force in adsorption mechanism. This applies to nonpolar and weakly polar hydrocarbons. We test this predictive model against the adsorption data of benzene, toluene, n-pentane, n-hexane, and ethanol on a commercial activated carbon. It is found that the predictions are excellent for all adsorbates tested with the exception of ethanol where the predicted values are about 10% less than the experimental data, and this is probably attributed to the electrostatic interaction between ethanol molecules and the functional groups on the carbon surfaces.

Effects of adsorbate-adsorbate interaction in the description of adsorption isotherm of hydrocarbons in micro-mesoporous carbonaceous materials

In this paper, we present a model accounting for the adsorbate-adsorbate interaction in the adsorbed phase in the description of adsorption of pure vapors on carbonaceous materials. The details of the adsorbate-adsorbate interaction of a particular species are obtained from the analysis of its adsorption data on non-porous carbon black. The predictability of the model is tested against the adsorption isotherm data for benzene, toluene, n-pentane, n-hexane, carbon tetrachloride, methanol and ethanol on microporous activated carbon. It was found that the model prediction for non-polar adsorbates are satisfactory while it under-predicts for polar adsorbates, which is attributed to their additional interaction with functional groups. (C) 2002 Elsevier Science B.V. All rights reserved.

Prediction of multilayer adsorption and capillary condensation phenomena in cylindrical mesopores

MCM-41 periodic mesoporous silicates with a high degree of structural ordering are synthesized and used as model adsorbents to study the isotherm prediction of nitrogen adsorption. The nitrogen adsorption isotherm at 77 K for a macroporous silica is measured and used in high-resolution alpha(s)-plot comparative analysis to determine the external surface area, total surface area and primary mesopore volume of the MCM-41 materials. Adsorption equilibrium data of nitrogen on the different pore size MCM-41 samples (pore diameters from 2.40 to 4.92 nm) are also obtained. Based on the Broekhoff and de Boer' thermodynamic analysis, the nitrogen adsorption isotherms for the different pore size MCM-41 samples are interpreted using a novel strategy, in which the parameters of an empirical expression, used to represent the potential of interaction between the adsorbate and adsorbent, are obtained by fitting only the multilayer region prior to capillary condensation for C-16 MCM-41. Subsequently the entire isotherm, including the phase transition, is predicted for all the different pore size MCM-41 samples without any fitting. The results show that the prediction of multilayer adsorption and total adsorbed amount are in good agreement with the experimental isotherms. The predictions of the relative pressure corresponding to capillary equilibrium (coexistence) transition agree remarkably with experimental data on the adsorption branch even for hysteretic isotherms, confirming that this is the branch appropriate for pore size distribution analysis. The impact of pore radius on the adsorption film thickness and capillary coexistence pressure is also investigated, and found to agree with the experimental data. (C) 2003 Elsevier Inc. All rights reserved.

An EDTA-β-cyclodextrin adsorbent for the adsorption of rare earth elements and its application in preconcentration of ultratrace rare earth elements from seawater

The objectives of this work were synthesizing an EDTA-β-CD adsorbent and investigating its adsorption potential and applications in preconcentration of REEs from aqueous phase. The adsorption capacity of EDTA-β-CD was investigated. The adsorption studies were performed by batch techniques both in one- and multi-component systems. The effects of pH, contact time and initial concentration were evaluated. The analytical detection methods and characterization methods were presented. EDTA-β-CD adsorbent was synthesized successfully with high EDTA coverage. The maximum REEs uptake was 0.310 mmol g-1 for La(III), 0.337 mmol g-1 for Ce(III) and 0.353 mmol g-1 for Eu(III), respectively. The kinetics of REEs onto EDTA-β-CD fitted well to pseudo-second-order model and the adsorption rate was affected by intra-particle diffusion. The experimental data of one component studies fitted to Langmuir isotherm model indicating the homogeneous surface of the adsorbent. The extended Sips model was applicable for the isotherm studies in three-component system. The electrostatic interaction, chelation and complexation were all involved in the adsorption mechanism. The preconcentration of RE ions and regeneration of EDTA-β-CD were successful. Overall, EDTA-β-CD is an effective adsorbent in adsorption and preconcentration of REEs.