Catalytic characterization of pillared clays through toluene methylation reaction

Pillared clays (PILCs) with Al and Zr oxide pillars were studied in terms of their structure and texture. The catalytic properties of the samples were evaluated through toluene methylation reaction. As comparison material, a commercial zeolite HZSM-5 was used. The toluene conversion at short time-on-stream over PILCs, although smaller than the value obtained with HZSM-5, attains values of 37 (molar %). In all cases the reaction products are a mixture of xylene, ethyltoluene and trimethylbenzene isomers. All samples present higher selectivity to xylene isomers, which are the primary products. For Zr pillared clay, the percentage of these isomers is the highest.     

Adsorption and characteristics of base-treated pillared clays

The effect of base treatment on the cation exchange capacity (CEC) of pillared clays and their adsorption isotherms for Cu²⁺, Cr³⁺ and Pb²⁺ have been investigated. Results indicate that although the CEC of pillared clays are only about 15% of that of the parent clays, a large fraction of the native clays CEC may be recovered by treatment with base. The fraction of the CEC recovered depends upon the base strength, its concentration, and the temperature. Contrary to previous suggestions the mechanism of recovery is related to the destruction of pillars which is accompanied by the loss of surface area. It is possible under conditions specified to prepare these base treated pillared clays as a new class of useful, regenerable adsorbent for heavy metal adsorption from aqueous solution.     

Catalytic activity and acidity of Al pillared clays and zeolites in different hydrocarbon reactions

In comparison with zeolites, a variety of Al pillared clays did not prove as promising cracking catalysts, possibly because their Br?nsted sites are hidden. In the less demanding double bond shift isomerization, both catalyst types were comparable probably due to the presence of Lewis sites on both catalysts.     

Optimized procedure for clay pillaring with aluminum species used in depollution

This study presents the improved method of smectite type clays pillaring, using aluminum salts. To achieve this goal, natural clay with a percentage of more than 95% montmorillonite was used. In order to analyze the pillaring process, a thermal procedure was used (thermal programmed desorption). The results of the pillaring process show that a controlled distance between the foliar band structures as long as 18·10^–10 m can be obtained. The clays modified by pillaring can be used as molecular sieves in microfiltration processes or as agents in residual water chemical depolluting processes. They also have zeolite properties which make them reusable.     

Characterization of cationic pillared layer clays

Na-montmorillonite and its Al-, Ti-, Fe-, Cr-, Zr- and Sn-pillared derivatives (pillared layer clays) were prepared and characterized by instrumental methods and a chemical reaction. Structural characterization involved X-ray fluorescence (XRF) analysis, X-ray diffractometry (XRD),²⁹Si and²⁷Al MAS NMR spectroscopies, thermogravimetric (TG) and BET measurements. By the distinctly characteristic shapes of the d₀₀₁ vs. temperature curves two groups could be distinguished, (i) Al-PILC, Ti-PILC, Cr-PILC, Zr-PILC and (ii) Fe-PILC, Sn-PILC, Na-montmorillonite. On montmorillonite isomerization of cyclopropane only occurred while oligomerization followed isomerization over Al-PILC. This latter reaction was attributed to Lewis and (the considerably smaller number of) Br?nsted acid sites whose number, strength and accessibility increased due to pillaring.     

Acidity and aniline alkylation activity of mixed Fe-Al pillared montmorillonites

Al-pillared, Fe-pillared and mixed Fe-Al pillared systems have been prepared and characterized using EDX and XRD analyses, surface area pore volume and acidity measurements. Mixed systems are found to be superior to single oxide pillared systems in terms of acidity and aniline methylation activity. This revised version was published online in June 2006 with corrections to the Cover Date.     

Photodegradation of dye pollutants on TiO_2 pillared bentonites under UV light irradiation

TiO2 pillared bentonite samples dried under different conditions are used to degrade 2,4-dichlorophenol and orange II under UV light irradiation. The supercritical dried sample exhibits a high activity for the photodegradation of 2,4-dichlorophenol and orange II due to its structural features. TOC and COD are measured during the degradation of 2,4-dichlorophenol under UV light irradiation using P25 and TiO2 pillared bentonite samples dried under different conditions. The clay-based catalysts can be readily separated by filtration or sedimentation.     

Preparation and characterization of manganese- and samarium-manganese-alumina pillared montmorillonites

A Na-montmorillonite was intercalated with manganese- and samarium-manganese-aluminium solutions. The pillared montmorillonites were characterized by X-ray diffraction and nitrogen adsorption. The presence of manganese and samarium-manganese citrates in the intercalation process modify the distance between the clay sheets and the microporous structure of the pillared montmorillonites.     

Incorporation of Pure Fullerene into Organoclays: Towards C60‐Pillared Clay Structures

In this work, we demonstrate the successful incorporation of pure fullerene from solution into two‐dimensional layered aluminosilicate minerals. Pure fullerenes are insoluble in water and neutral in terms of charge, hence they cannot be introduced into the clay galleries by ion exchange or intercalation from water solution. To overcome this bottleneck, we organically modified the clay with quaternary amines by using well‐established reactions in clay science in order to expand the interlayer space and render the galleries organophilic. During the reaction with the fullerene solution, the organic solvent could enter into the clay galleries, thus transferring along the fullerene molecules. Furthermore, we demonstrate that the surfactant molecules, can be selectively removed by either simple ion‐exchange reaction (e.g., interaction with Al(NO₃)₃ solution to replace the surfactant molecules with Al³⁺ ions) or thermal treatment (heating at 350 °C) to obtain novel fullerene‐pillared clay structures exhibiting enhanced surface area. The synthesized hybrid materials were characterized in detail by a combination of experimental techniques including powder X‐ray diffraction, transmission electron microscopy, X‐ray photoemission, and UV/Vis spectroscopy as well as thermal analysis and nitrogen adsorption–desorption measurements. The reported fullerene‐pillared clay structures constitute a new hybrid system with very promising potential for the use in areas such as gas storage and/or gas separation due to their high surface area.     

X-ray diffraction study of zirconia pillared clays

X-ray powder diffraction (XRPD) and X-ray radial electronic distribution density (RED) of initial and zirconia-pillared interlayered clays (Zr-PILC) were studied. After pillaring, the basal (001) spacing was found to increase from 11 Å in the initial clay kept under air to 17.7 Å in Zr-PILC. The structure of zirconium nanopillars was characterized. The interatomic distances with corresponding coordination numbers obtained from the RED curves were close to those in zirconium tetramers.This revised version was published online in December 2005 with corrections to the Cover Date.     

Evolved gas analysis (EGA) of brick clays

Using a system based on non-dispersive infrared (NDIR) detectors, evolved gas analysis (EGA) was able to identify and quantify the principal volatiles produced by heating powdered samples of UK brick clays. From these results, atmospheric emissions likely to result from brick production can be predicted. In addition, EGA results for extruded brick clay test pieces are significantly different from those of powdered samples. Within an extruded brick clay body, evolved gases are contained within a pore system and evolved gas-solid phase reactions also occur. This EGA study provides further evidence on the nature of firing reactions within brick clay bodies. The qualitative and quantitative influence of heating rate — a key process condition in brick manufacture — on gas release is also outlined.Dedicated to Dr. Robert Mackenzie on the occasion of his 75th birthday     

Photodegradation of dye pollutants on TiO<Subscript>2</Subscript> pillared bentonites under UV light irradiation

TiO₂ pillared bentonite samples dried under different conditions are used to degrade 2,4-dichlorophenol and orange II under UV light irradiation. The supercritical dried sample exhibits a high activity for the photodegradation of 2,4-dichlorophenol and orange II due to its structural features. TOC and COD are measured during the degradation of 2,4-dichlorophenol under UV light irradiation using P25 and TiO₂ pillared bentonite samples dried under different conditions. The clay-based catalysts can be readily separated by filtration or sedimentation.     

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.     

新型层柱化合物合成、表征及催化活性

将含过氧铌一、三取代钨硅、钨磷过氧杂多阴离子利用离子交换法嵌入Zn2Al类水滑石中制得层柱化合物,利用XRD,IR,UV等方法对产物的结构进行了表征。结果表明在层柱化合物中过氧杂多阴离子仍然保持Keggin结构,并且过氧键没被破坏。层柱化合物在酯化反应中显示优良的催化性能。     

过氧杂多阴离子型层柱化合物的合成、表征及催化活性

通过离子交换法,将含Zr过渡金属离子1,3取代钨硅、钨磷过氧杂多酸盐嵌入Zn2Al类水滑石中,获得了层柱化合物,并用XRD,IR,UV等手段对产物的结构进行了表征.结果表明过氧杂多阴离子进入水滑石层间后,水滑石的层间距从0.92增大到1.47 nm,且过氧链没被破坏.层柱化合物在酯化反应中显示优良的催化性能.     

Acidity of montmorillonite pillared by alumina, zirconia and chromia

Acidic properties of Al-, Zr- and Cr- pillared montmorillonites prepared from Jelšovy Potok bentonite (Central Slovakia) have been investigated using temperature-programmed desorption of ammonia. The number of acid sites varied with different interlayer cations from 0.06 to 0.23 mmol g⁻¹. The character of acid sites was similar in the case of Al- and Zr- forms. It is obvious that the chromium analogue contains fewer acid sites, nevertheless, they seem to be stronger compared to Al- and Zr- pillared montmorillonites.     

Application of programmed thermodesorption of the liquid under quasi-isothermal conditions to investigate physicochemical properties of liquid layers and solid surfaces

This paper presents the results of measurements of the programmed thermodesorption of polar and nonpolar liquids from the surface of different types of solids. The course of thermodesoption was found to depend on the properties of the solid and the wetting liquid. Thermodesorption occurred not exponentially but in steps, which reflects the noncontinuous changes in the properties of the surface layer with the distance from the solid surface. This effect intensified with the increase in polarity of the wetting liquid and the heterogeneity of the solid surface. The earlier investigations showed that application of the method of differential thermal analysis allowed determination of the distribution of the adsorption potential of the liquid on the solid surface.The author is indebted to Prof. M. Jaroniec for very fruitful discussions and to Prof. J. Choma for the activated carbon samples.     

Assessment of Hydrophobic-Hydrophilic Properties of Microporous Materials from Water Adsorption Isotherms

The characterization of the hydrophobic-hydrophilic properties of different types of microporous materials, namely activated carbons, pillared clays and zeolites, was made by the determination of water adsorption isotherms. The data were analysed by the Dubinin and Astakhov (D-A) equation. The use of the E parameter of the D-A equation as a measure of the hydrophobic-hydrophilic character is proposed. When the information obtained from the E parameter is compared with the information that can be obtained from other parameters used in the literature to characterize the hydrophobicity of materials, it is found that the former is more sensitive and is more directly related with the shape of the adsorption isotherms which, ultimately, is the more direct manifestation of the hydrophobic-hydrophilic properties of a given material.     

Solar photooxidation of azo dye over mixed (Al-Fe) pillared bentonite using hydrogen peroxide

Summary The mixed Al-Fe pillared bentonite (Al/Fe-B) was tested as a heterogeneous catalyst for the photo-Fenton discoloration of azo dye X-3B under solar light irradiation. The structural characteristics of the catalyst were examined by XRD, BET, and TEM. The results indicate that the heterogeneous photo-Fenton process employing the Al/Fe-B as catalyst exhibits higher photo-catalytic activity compared to its corresponding homogeneous photo-Fenton process. The amount of Fe ions in solution leaching from the Al/Fe-B is less than 0.26% of the total iron content in the catalyst.     

Spectrophotometric determination of nitrite in polluted waters using 3-nitroaniline

Nitrite reacts with 3-nitroaniline in the presence of hydrochloric acid to form a diazonium cation, which is subsequently coupled with N-(1-naphtyl)ethylenediammonium chloride to form a stable purple azo dye. The method is suitable for the determination of 0.01–0.80 μg ml^?1 nitrite. The reactions are very fast and require no control of temperature. The observed molar absorptivity and Sandell's sensitivity of the azo dye are 4.9 × 10⁴ l mol^?1 cm^?1 and 9.4 × 10^?4 μg cm^?2, respectively. The method is free from most interferences. The method has been applied successfully to polluted river water.