Controlled gas adsorption properties of various pillared clays

Microporous pillared clays (PILC) were prepared by the intercalation of montmorillonite with particles of titania (Ti-PILC), zirconia (Zr-PILC), alumina (Al-PILC), iron oxide (Fe-PILC) and mixed lanthania/alumina (LaAl-PILC). Nitrogen adsorption isotherms (77 K) and XRD data provided information on the porosity, surface area, micropore volume and interlayer distance of these samples. The surface area varied between 198 and 266 m²/g for Ti- and Fe-PILC, respectively. The titania pillared clay had also the highest micropore volume (0.142 cc/g) and interlayer spacing (16–20 Å), compared to the Zr-PILC, which had the smallest spacing between the layers (max, 4 Å). Despite this fact, Zr-PILC always showed a high adsorption capacity for gases such as N₂, O₂, Ar or CO₂, due to its high adsorption field in the very small micropores.From gas adsorption experiments on these various PILCs, it became clear that their adsorption properties depend on the pillars in three ways: (i) the pillar height, (ii) the distribution of the pillars between the clay layers and (iii) the nature of the pillaring species.The incorporation of other elements in the pillars leads to specific adsorption sites in the pores. This was demonstrated by the preparation of mixed Fe/Cr and Fe/Zr pillared clays. Compared to the parent Fe-PILC, the incorporation of chromium and zirconium in the iron oxide pillars had a positive influence on the adsorption capacity. Also the modification of a PILC with cations increases both capacity and selectivity for gases. This was confirmed by the increased adsorption of N₂, O₂ and CO₂ at 273 K on a Sr²⁺ exchanged Al-PILC.     

Arsenic adsorption onto pillared clays and iron oxides

Arsenic adsorption was carried out on simple materials such as goethite and amorphous iron hydroxide, and more complex matrices such as clay pillared with titanium(IV), iron(III), and aluminum(III). These matrices were synthesized from a bentonite whose montmorillonitic fraction was pillared according to optimized parameters. These sorbents were characterized by various methods: XRD, FTIR, BET, DTA/TGA, surface acidity, and zetametry. Elimination of arsenite and arsenate as a function of pH was studied. Arsenate elimination was favored at acidic pH, whereas optimal arsenite elimination was obtained at 4相似文献   

Propene adsorption and reaction on zeolites and pillared clays

Comparative IR and UV-Vis spectroscopic studies of propene adsorption and reaction on H-mordenite, dealuminated H-mordenite, dealuminated mazzite, montmorillonite and Al₁₃-pillared montmorillonite have been carried out. On all systems propene is first transformed into polymeric species (C_nH_2n+1 ⁺). On HMOR (both as such and dealuminated), allylic carbocations are successively produced by loss of H₂, the monoenic species (C_nH_2n?1 ⁺) being formed at room temperature and the dienic (C_nH_2n?3 ⁺) and trienic (C_nH_2n?5 ⁺) species at higher temperatures. These species are not observed on the other systems, although they are presumably formed as unstable intermediates. In fact, on all the zeolites studied here two cyclic penta-atomic and hexa-atomic allylic carbocations have been observed for the first time. On all systems, the final products of reaction are polyaromatic species which, on the basis of their reaction with NH₃ still exhibit unsaturated carbocation behaviour. The activity of the various samples depends on their pore dimensions and on the nature of acidic sites involved: the larger the available pore space, the more branched is the polymer and the more difficult it is to observe allylic carbocations. Evidence is provided for a Brønsted-induced mechanism.     

Characterization of a delaminated clay and pillared clays by adsorption of probe molecules

Characterization of the textural and structural properties of a sodium form of a delaminated calcic montmorillonite, and of aluminium pillared materials prepared with and without amine pre-adsorption, was made using the adsorption of different probe molecules (nitrogen, toluene, methyl ethyl ketone and 1,1,1-trichloroethane). Due to the delaminated character of the prepared solids, the characterization by X-ray diffraction of the pillared materials was not possible. In this context, the adsorption of probe molecules revealed to be informative since, although the prepared materials were mainly mesoporous solids in consequence of their delaminated nature, when the amine pre-adsorption was used before the pillaring, microporosity was also formed.     

Acidity studies on pillared clays (PILCs) by pyridine adsorption and 1-butanol dehydration

A study was made on the acidic properties of clays, from different parent materials, pillared with aluminium or zirconium species. In conjunction with the well known method of pyridine desorption followed by infrared spectroscopy, the reaction test of 1-butanol dehydration was carried out. Also the heats of adsorption and the amounts of adsorbed pyridine, were determined by a thermogravimetry coupled with Differential Scanning Calorimetry (TG-DSC). The information on the acidic properties of the materials, obtained by the three methods, is discussed and it is concluded that the latter method (TG/DSC), although not currently used as one could expect, is sufficiently expedite and appropriate for this purpose.     

层柱状微孔材料吸附存储天然气的Monte Carlo模拟

采用巨正则系综MonteCarlo方法模拟了天然气中主要成分甲烷在层柱状微孔材料中T=300K下的吸附存储,在模拟中层柱状微孔采用Yi等人建立的柱子均匀分布在两炭孔墙之间的模型来表征。甲烷分子采用Lennard-Jones球型分子模型,炭孔墙采用Steele的10-4-3模型,对孔宽为1.36nm的层柱微孔,模拟了四个不同孔率的层柱材料吸附甲烷的情形。得到了孔中流体的局部密度分布以及吸附等温线,对比不同孔率下甲烷的吸附量,得到了此情形吸附甲烷的较佳孔率为0.94。     

Development of novel pillared clays for the encapsulation of inorganic complexes

Several pillared clays were prepared by using a polyalcohol (ethylene glycol or poly(vinyl alcohol)) or a poly(ethylene oxide) surfactant as an interlayer gallery template and an aluminum oligomer species as the pillaring agent. The use of polyalcohols or nonionic surfactants, such as Tergitol, gave materials which, in general, presented larger basal spacing than those found for the solids prepared by a similar procedure but without additives. The initial positive effect in the expansion of the clay interlayers was not totally retained after calcination of the materials; most probably, at the end, the basal spacing is still ruled by the intercalating aluminum species. The pillared clay with the largest basal spacing and specific surface area was used to encapsulate copper(II) complexes with pentadentate N3O2 Schiff base ligands derived from copper(II) acetylacetonate by in situ synthesis. The characterization made (X-ray diffraction, X-ray photoelectron spectroscopy, FTIR spectroscopy, chemical analysis, and low-temperature N2 adsorption) provided evidence that copper(II) complexes with pentadentate N3O2 Schiff base ligands were efficiently entrapped within the lower dimension pores of the pillared clay and that they interact strongly with the pillared clay matrix.     

Determination of the micropore volume distribution function of activated carbons by gas adsorption

A new method for the determination of the micropore volume distribution function of activated carbons is presented. It is based on the treatment of pure gas adsorption isotherms by a theoretical model derived from the Hill-de Boer theory. Adsorption data (isotherms and heat curves) for carbon dioxide, ethane and ethylene on activated carbon (F30/470 CHEMVIRON CARBON) have been provided by a thermobalance coupled to a calorimeter (TG-DSC 111 SETARAM) at different temperatures (233, 273, 303 and 323 K) for pressures up to 100 kPa. Adsorption isotherms of carbon dioxide and ethane at 303 and 323 K have been used for the determination of the micropore volume distribution function of the activated carbon of interest. The knowledge of its structure has then allowed the simulation of adsorption isotherms and heats for the same adsorbates at the same temperatures as those experimentally studied. Similar calculations have been conducted for ethylene. Whatever the adsorbate (carbon dioxide and ethane used for the determination of the micropore volume distribution function or ethylene), the mean deviation between experimental and calculated isotherms does not exceed 4% at quasicritical and supercritical temperatures (303 and 323 K). In the same temperature conditions, discrepancies between calculation and experiment reach about 10% for adsorption heats. For both isotherms and heats, large discrepancies appear at low temperature (233 and 273 K). This method allows the determination of the micropore volume distribution function of activated carbons. The validity of the results is insured using several isotherms of several adsorbates and taking into account the calorimetric effect of the phenomenon. That is the reason why this method can also be seen as a new possible model for pure gas adsorption data prediction. This paper also presents a brief summary of the state of the art in this field.     

Energetic aspects of micropore adsorption in carbon adsorbents

Russian Chemical Bulletin -     

Increased crystal porosity and enhanced gas adsorption by intracolumnar gliding for broadband gas detection

A new three-level structural approach based on anion-induced intracolumnar gliding of stacked coordinatively unsaturated units is described for design of metal-organic crystals which exhibit concentration- and gas-specific adsorption of a variety of small molecules and could be employed for multiple and rapid qualitative and quantitative broadband detection of gases or gaseous mixtures.     

Tailoring plasmonic substrates for surface enhanced spectroscopies

Our understanding of how the geometry of metallic nanostructures controls the properties of their surface plasmons, based on plasmon hybridization, is useful for developing high-performance substrates for surface enhanced spectroscopies. In this tutorial review, we outline the design of metallic nanostructures tailored specifically for providing electromagnetic enhancements for surface enhanced Raman scattering (SERS). The concepts developed for nanoshell-based substrates can be generalized to other nanoparticle geometries and scaled to other spectroscopies, such as surface enhanced infrared absorption spectroscopy (SEIRA).     

Tailoring CuO nanostructures for enhanced photocatalytic property

Composites of cobalt (hydr)oxide and graphite oxide (GO) were obtained and evaluated as adsorbents of hydrogen sulfide at ambient conditions. The surface properties of the initial and exhausted samples were studied by FTIR, TEM, SEM/EDX, XRD, adsorption of nitrogen, potentiometric titration, and thermal analysis. The results obtained show a significant improvement in their adsorption capacities compared to parent compounds. The importance of the OH groups of cobalt (hydr)oxide/GO composites and new interface chemistry for the adsorption of hydrogen sulfide on these materials is revealed. The oxygen activation by the carbonaceous component resulted in formation of sulfites. Water enhanced the removal process. This is the result of the basic environment promoting dissociation of H(2)S and acid-base reactions. Finally, the differences in the performance of the materials with different mass ratios of GO were linked to the availability of active sites on the surface of the adsorbents, dispersion of these sites, their chemical heterogeneity, and location in the pore system.     

Evaluation of pore size distribution in boundary region of micropore and mesopore using gas adsorption method

This paper discusses an accurate method of pore size distribution evaluation in boundary regions of micropores and mesopores using the gas adsorption process on the basis of the capillary condensation theory, which is liable to be underestimated with the existing BJH and DH methods. A typical nitrogen adsorption isotherm for highly ordered mesoporous silica, which has cylindrical pores with diameter smaller than 4 nm, is considered to be type IV and it is well known for the steep increase of the amount adsorbed through capillary condensation in the region of the relative pressure P/P0 smaller than 0.4. In calculating the distribution of the pore size from the change of the amount adsorbed due to capillary condensation, it is important to accurately predict both the multilayer thickness t of the adsorbed nitrogen molecules and the critical radius rc where capillary condensation occurs. It is necessary to consider the curvature of the adsorption layer-gas phase interface when predicting the multilayer thickness t of nitrogen adsorbed within the pore of highly ordered mesoporous silica. Revision of the Kelvin equation is also required when rc is to be predicted. While the predicted value of t based on the Broekhoff and de Boer theory is matched well with the value of t which is actually measured using highly ordered mesoporous silica, and the predicted value of rc based on the GTKB-Kelvin-cylindrical equation that has been revised considering the effect of the interfacial curvature on the interfacial tension of the adsorption layer-gas phase interface is matched with the value of rc which is actually measured using highly ordered mesoporous silica. A combination method of the Broekhoff and de Boer equation and the GTKB-Kelvin-cylindrical equation is proposed as a means of accurately evaluating, from the nitrogen adsorption isotherm, the pore size distribution in the highly ordered mesoporous silica in boundary region of micropore and mesopore. The proposed new method of pore size evaluation features high accuracy and offers the convenience of obtaining the pore size distribution without repeated calculations by employing the same algorithm as DH method. The pore size predicted by the Halsey equation and the Kelvin equation of the conventional DH method is about 20% smaller than the pore size predicted by the newly proposed evaluation method.     

Estimation of the dimensions of nano-capillaries from gas adsorption data

A new approach is presented to determine the dimensions of cylindrical nanopores from adsorption measurements.     

Density functional theory of adsorption in pillared slit-like pores

We propose a density functional theory to describe adsorption of Lennard-Jones fluid in pillared slit like pores. Specifically, the pillars are built of chains that are bonded by their ends to the opposite pore walls. The approach we propose combines theory of quenched-annealed systems and theory of nonuniform fluids involving chain molecules. We compare the results of theoretical predictions with grand canonical ensemble Monte Carlo simulations and compute theoretical capillary condensation phase diagrams for several model systems.     

Kinetic derivation of common isotherm equations for surface and micropore adsorption

The Langmuir equation is one of the most successful adsorption isotherm equations, being widely used to fit Type I adsorption isotherms. In this article we show that the kinetic approach originally used by Langmuir for 2D monolayer surface adsorption can also be used to derive a 1D analogue of the equation, applicable in ultramicropores with single-file diffusion. It is hoped that such a demonstration helps dispel the idea that the Langmuir isotherm equation cannot apply to some micropores as more than a mathematical correlation. We furthermore seek to extend the insight provided by the simple kinetic derivation of the Langmuir equation to other isotherm equations capable of modelling Type I isotherms. The same kinetic approach is thus also used to derive the Volmer, Fowler–Guggenheim and Hill–de Boer equations, both for surface (2D adsorbed phase) and micropore adsorption (1D and 3D adsorbed phases). It is hoped that this will help make more intuitively clear that these equations can be used as phenomenological models in some instances of adsorption in micropores.     

A model for cation adsorption to clays and membranes

A cation adsorption model is presented and its recent applications are discussed. The model combines electrostatic equations with specific binding, and considers neutral and positively charged complexes between the negative surface sites and organic cations in a closed system. Extensions in the model account for dye aggregation in solution, and for the formation of solution complexes of inorganic cations, such as [M⁺⁺ Cl^–]⁺. The amounts of 45Ca²⁺ adsorbed to vesicles extracted from the plasma membranes of melon root cells could be adequately simulated and predicted. The binding coefficients determined for Ca²⁺, Na⁺, and Mg²⁺ are in the range of values previously deduced for binding to phospholipid components. Model calculations were applied to the test of hypotheses on the effect of salt stress on the growth of roots. The adsorption of monovalent organic cations to montmorillonite is characterized by binding coefficients that are at least six orders of magnitude larger than those of Na⁺, Mg²⁺, Ca²⁺, and Cd²⁺, or those of CdCl⁺ or CaCl⁺. Monovalent organic cations were found to adsorb 140–200% of the cation exchange capacity of the clay and to cause charge reversal. Deductions from adsorption results of acriflavin are consistent with those drawn from the application of other experimental methods. Preliminary results on the adsorption of divalent organic cations are presented. Agro-environmental applications of organo-clays are discussed.