Synergism of Clay and Heteropoly Acids as Nano-Catalysts for the Development of Green Processes with Potential Industrial Applications

A large number of inorganic oxides, mixed oxides, including alumina, silica, titania, zirconia, zeolites, carbon, clays and ion exchange resins have been employed as both supports and solid acid catalysts. Clay structure collapses at high temperatures and has to be stablilized. The thermal stability and pore size issues were addressed by pillaring of clays. Natural clays are acid treated or ion-exchanged to be used as solid acids, and the acidity and pore structure are dependent on the treatment methodology. Another important class of catalysts is the heteropoly acids (HPA), which are employed as homogeneous or heterogeneous catalysts, having both acid and redox properties. The focus of the current paper is to address the work done in our laboratory on the synergism between clays and heteropoly acids for the development of green processes. A comparison is also provided for the activity of these catalysts with other solid acids. Several alkylation, acylation, isomerization, condensation, dehydration, esterification, nitration and oxidation reactions which are useful in a wide spectrum of industries such as bulk, intermediates, dyes, plasticizer, pharmaceuticals, perfumes, flavours and other fine chemicals were investigated to improve the selectivity of the desired products.     

Sorption of cobalt on organic and inorganic intercalated clays

A Mexican montmorillonite clay was intercalated on the one hand with aluminium or zirconium polyhydroxications, and on the other with two organic compounds. Radioactive cobalt was used to study the Co²⁺ sorption curves in the original and pillared clays. It was found that pillaring in general does not favour the diffusion of cobalt between the layers specially the organic pillared clays. In equilibrium, the cobalt retention reached the highest level, around 0.7 meq/g in the Zr pillared clay.     

铁铝复合柱撑粘土的制备、柱结构和稳定性(I)

用两种方法合成了一系列不同Fe/Al比的铁铝复合柱撑牯土(FeAl-PlLC). 用~(27)Al-NMR、UV、ESR等手段考察了柱溶液的结构和状态, 用XRD、DTA、UV-DRS 等技术对其结构、稳定性进行了研究. 结果表明, 铁铝柱撑粘土的底面间距为1.98～1.55 nm, Fe/Al比对其柱结构、比表面积、热稳定性均有较大影响. Fe/Al<0.5时, 层间柱主要呈现Keggin结构, Fe/Al≥0.5时, 可能为三聚结构. 随Fc/Al比的增加, d(001)值, 比表面面、热稳定性逐渐下降.     

表面活性剂改性的铝交联粘土的表征及其水蒸汽减活动力学研究

以聚乙烯醇（ＰＶＡ）为支撑前体合成出改性的铝交联蒙脱土与铝交联累托土。采用ＸＲＤ、Ｎ２低温吸附脱附法、ＩＲ等手段对它们进行了表征，并研究了它们在不同时间与温度条件下的水蒸汽减活动力学。研究结果表明，ＰＶＡ的改性有助于铝交联粘土层间距与比表面积的增大及热稳定性与水热稳定性的提高，粘土基质对其热稳定性与水热稳定性有显著影响，该类催化材料的水蒸汽减活动力学遵循一级衰减反应方程式，其减活速率常数与温度的函数关系可用一个指数函数的经验式表示。     

Mixed Al/Ce oxide pillaring of montmorillonite: XRD and UV-VIS diffuse reflectance study

Ce and Al pillared clays were prepared by (i) pillaring Ce³⁺-exchanged montmorillonite with Al₁₃ polycation (Ce-Al-PILC) and (ii) by pillaring Na-montmorillonite with an oligomer obtained from cohydrolysis of Ce³⁺ and Al³⁺ salts (Al-Ce-PILC). Cohydrolyzed oligomer gives larger intercalating species with Ce³⁺ incorporated in it. The UV-DRS spectrum of clay sample intercalated with this species shows four distinct absorption bands at 224, 263, 294 and 342 nm, which are attributed to the 4f-5d interconfigurational transitions of Ce³⁺ ions associated with alumina pillars.     

混合金属络合物羟基镍铝交联蒙托土的合成

用取代法和共聚法合成了一系列羟基镍铝交联蒙托土。(27)~Al-NMR,UV谱表明两种合成方法都可以得到具有Kessin结构的羟基镍铝柱。取代法合成的交联蒙托土具有均一的(001)面衍射(d_(001)约1.80nm),而共聚法的样品有两种羟基镍铝柱支撑着层间,分别在1.80nm和1.55nm附近产生复合(001)面衍射。用高温老化处理可改善交联蒙托土的热稳定性。经过处理的样品在700℃焙烧后仍可保持稳定,与不经处理的样品相比,热稳定性提高200℃以上。     

Preparation and thermal stability of Al2O3-clay and Fe2O3-clay nanocomposites, with potential application as remediation of radioactive effluents

In the last years metal/clays, aluminosilicates with properties and characteristics of microporous materials, have received more attention, due to the possibility of their use as matrix for nanoparticles encapsulation and stabilization processes. Some types of clays were comparatively evaluated for treating the simulated radioactive wastewater. The raw clay from Valea Chioarului Romania and its pillared forms with Al, Fe, pillars for decontamination of waste-waters with medium and low radioactivity were used. Characterization of the obtained materials was carried out using techniques such as X-ray diffraction, Fourier transform infrared spectroscopy, BET analyses and thermogravimetric analysis (DTG-TG), respectively. Also, the thermal stability of nanocomposites was highly superior to native clay due to the presence of the well-dispersed clay nanolayer, which has a barrier property in a composite system. Clay nanocomposite sample materials were obtained with good thermal stability after calcination. Clay nanocomposites samples were evaluated for remediation of radioactive effluents by treating the radioactive wastes streams. The ion-exchange characteristics and the abilities to uptake radioisotopes of indigene clay from Valea Chioarului area-Romania were examined. The results showed that the precursor used in sample preparation influenced the structural and textural properties of nanocomposites and also capability of prepared modified clay samples by pillaring to be potential candidates for use in connection with environmental protection, remediation of radioactive effluents, respectively.     

AlFe层柱粘土催化剂催化甲苯在水中的降解

The catalytic wet peroxide oxidation (CWPO) of toluene on two bentonite-based AlFe-pillared clays (PILCs) with different iron contents was investigated. The PILCs were obtained using bentonite clay from Bogovina, Serbia. The change in chemical and phase composition and textural properties of the starting clay and synthesized catalysts was monitored using X-ray diffraction, inductively coupled plasma optical emission spectrometry, UV-Vis diffuse reflectance spectrometry, and physisorption of nitrogen. The catalytic performance was examined using gas chromatography. The Na-exchange process lowered the (001) smectite basal plane spacing, but the clay retained its swelling properties, while the pillaring process increased it. The surface areas of both synthesized pillared clays increased to similar values although their Fe content was different. At 37 ℃, both catalysts show significant toluene degradation, with the one richer in Fe having higher efficiency. The leaching of the active cations during reaction was negligible, and the catalysts were stable. AlFe-pillared clay catalysts can be used in CWPO for the elimination of BTEX compounds from plant effluent streams.     

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.     

Synthesis and Characterization of New Material——La/Zr/MMT Employed in Acetone Oxidation

A new material of zirconium pillared montmorillonite added with lanthanum （denoted as La/Zr/MMT） was prepared for acetone oxidation. Surface properties of the catalysts were investigated by means of XRD, TEM, TG-DTA and BET methods. The XRD result indicated that the interlayer space of the montmorillonite was enlarged from 1.57 to 4.85 um after the treatment with zirconium pillaring and the addition of lanthanum. N2 adsorption-desorption result showed that by the process of zirconium pillaring, the specific surface area of the sample was increased to 128.0 m^2/g, which was two times almost as large as pure montmorillonite. Simultaneously, the thermal stability was also enhanced. The activity of the new material on the total oxidation of acetone was investigated, and the results indicated that the catalytic activity of the montmorillonite was greatly improved. Over the sample of La/Zr/MMT, the T98 of acetone was obtained at 350 ℃, while it needs 400 ℃ over the pure montmorillonite. After 0.1% Pd was supported on the sample of La/Zr/MMT, the T98 decreased from 350 to 280 ℃, indicating the montmorillonite is a promising material for the control of some types of the volatile organic compounds such as acetone.     

Properties and performance of metakaolin pozzolanic cement pastes

The heating rate effect on the thermal behavior of clays from Arumetsa and Kunda deposits (Estonia) and an illitic clay from Füzérradvány (Hungary) was studied. Experiments were carried out under dynamic heating condition up to 1050 °C at the heating rates of 1.25, 2.5, 5 and 10 °C min^?1 in a stream of gas mixture containing 79 % of Ar and 21 % of O₂ with Setaram Labsys 1600 analyzer. Two different ashes were used as additives: the electrostatic precipitator ash from the first field and the cyclone ash formed, respectively, at circulating fluidized bed combustion (temperatures 750–830 °C) and pulverized firing (temperatures 1200–1400 °C) of Estonian oil shale at Estonian Power Plant. For calculation of kinetic parameters, the TG data were processed by the differential isoconversional Friedman method. The results of thermal analysis and the variation of the value of activation energy E along the reaction progress α indicated the complex character of decomposition of clays and their blends with Estonian oil shale ashes, and the certain differences in thermal behavior of different clays depending on their origin.     

Thermogravimetric Analysis for Acidity Determination in Pillared Clays

Thermogravimetric analysis of pyridine adsorption was applied to study the acidity at different temperatures of clays pillared with Al pillars and mixed Al-Ga pillars, in relation to the starting montmorillonite. These results were compared with those obtained by means of a pulse-chromatographic technique. The pillaring process produces a large number of acid centers in the samples. Al-Ga-PILC has a higher acidity than Al-PILC. This revised version was published online in July 2006 with corrections to the Cover Date.     

Clay minerals as photochemical reaction fields

This article surveys the intercalation characteristics of a number of clay minerals which can be utilized as host materials for photofunctional organic–inorganic hybrid systems as well as photochemical anisotropic reaction fields. The introduction of this review describes the chemical compositions and the structural features of various kinds of artificial as well as naturally produced clays. The chemical structures of these clays are often considered to be complicated due to their unfamiliar names which are sometimes taken from the areas where they originate although, structurally, only slight differences actually exist. The second chapter summarizes the adsorption and aggregation properties of typical organic dyes in clays. The aggregation behavior is sensitive to the kind and amount of metallic ions present in the lattice of the clays, the amount of adsorbed water as well as the structure of the organic guests to be intercalated. All of these factors are discussed in relation to the adsorption and aggregation behavior. In the third chapter, the photochemical reactions of excited metal complexes adsorbed in clays are discussed. Electron transfers for [Ru(bpy)₃]²⁺ in clays are described, showing that the clay layers provide reaction fields which stabilize the resulting charge separated species. This article aims to provide important insights into the fundamental mechanisms and properties of anisotropic reaction fields for the applications in design of promising, new photochemical and photobiological systems and processes.     

Synthesis,characterization, and challenges faced during the preparation of zirconium pillared clays

In this study, Zr-pillared montmorillonite clays (Zr-PILCs) were synthesized using two different precursor materials: raw montmorillonite (CM) and sodium ion-saturated montmorillonite (Na-CM) at different Zr/clay ratios (2.5, 5 and 10 mmol/g). To study the effect of Zr concentration and clay pre-treatment with NaCl on pillaring, the modified clay samples were characterized in detail using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA), high-resolution transmission electron microscopy (HRTEM), scanning transmission electron microscopy and energy-dispersive X-ray spectroscopy (STEM-EDX). The XRD analysis showed the increase of basal spacing of Zr-PILCs prepared from both precursor materials: from 1.26 to 1.74 nm in the case of CM, and from 1.13 to 1.93 nm for Na-CM. Results from FT-IR revealed new bands ascribed to Zr-O bonds in the range of 400–500 cm^?1 in Zr-pillared samples obtained from Na-CM at Zr/clay ratios of 2.5 and 5 mmol/g. The distribution and nature of Zr species in between the silicate layers were studied using STEM-EDX and HAADF imaging. They were found to be separated by a distance of 1.5–3 nm and their thickness lies in the range of 1–2 nm. Pillared clays prepared from pre-treatment with NaCl were more thermally stable at higher temperatures.     

Effect of pH on Electrocoagulation of Bentonite Suspensions in Batch Using Iron Electrodes

The electrocoagulation of a synthetic wastewater has been studied in this work. The electrochemical process was carried out in a batch electrochemical cell equipped with iron electrodes without agitation. Bentonite suspensions were used as a model of wastes polluted with colloids, as clays behave as hydrophobic colloids in water. The results obtained were useful to clarify the mechanisms that are involved in the electrocoagulation of this kind of waste and also to study the influence of pH in the process. Two primary coagulation mechanisms can explain the experimental behavior of the system: at acid pH the neutralization of the superficial charges of the clays and at alkaline pH the enmeshment of the kaolin particles into a sweep floc. At neutral pH, the formed cations (Fe²⁺ and Fe³⁺) neutralize colloidal particles and conduct to the hydroxides (Fe(OH)_2(s) and Fe(OH)_3(s)) which adsorbate colloids and enhance sweep flocculation.     

Organic Pillared Clays

Commonly used organophilic clays are modified by alkylammonium cations which hold apart the aluminosilicate layers permanently. The cations fill the interlayer space and are contemplated as flexible pillars, resulting from the mobility of the alkyl chains. Therefore, the interlayer distance varies depending on the layer charge and on the alkyl chain length. Contrary to these cations, rigid pillaring cations guarantee a constant interlayer distance without occupying the interlayer by themselves and show special adsorption properties such as hydrophilic behavior contrary to the generally hydrophobic ones. Smectites were modified by flexible organic cations, e.g., dimethyldioctadecylammonium, and by rigid ones, e.g., tetraphenylphosphonium. Their adsorption properties are compared. Our investigations showed improved adsorption properties for rigid organic cations on smectites using 2-chlorophenol as pollutant. Best adsorption results are achieved using pillaring cations in combination with low charged smectites, especially at low pollutant concentrations. The properties of organic modified smectites are discussed by a pollution intercalation model. The intercalation process of an organic pollutant into an organic modified smectite is expressed by a two-step Born-Haber cycle process: (i) the formation of an adsorbing position by layer expansion and (ii) the occupation of the adsorbing position by the pollutant. The first step of the formation of the adsorbing position is an endothermal transition state which lowers the total intercalation energy and therefore worsens the adsorption behavior. Thus, an already expanded organophilic smectite will show improved adsorption behavior. The formed adsorbing position state on organic modified smectites is comparable to the pillared state of inorganic pillared clays. Copyright 2001 Academic Press.     

Thermal behaviour and slow molecular mobility in two isomers of biphenylmethanol

This research was aimed to investigate the role of clay on the combustion and kinetic behavior of crude oils in limestone matrix. For this purpose, simultaneous TG (thermogravimetry) and DTA (differential thermal analysis) experiments were performed at three different heating rates as 10–15 and 20°C min^–1, respectively. A uniform trend of decreasing activation energies was observed with the addition of clay. It was concluded that clays surface area affects the values of Arrhenius constant, while it is the catalytic properties of clay, which lower the activation energies of all the reactions, involved in the combustion process.     

Influence of compatibilizer degradation on formation and properties of PA6/organoclay nanocomposites

Nanocomposites based on polyamide 6 (PA6) and commercial layered silicates have been prepared by both in situ polymerization and melt compounding. The main aim of the present work has been centred on compatibilizer degradation, caused by the preparation conditions, in terms of nanocomposite end features. Two montmorillonite (MMT)-type, organically-modified clays (OMLS), namely Cloisite 30B^® and Nanofil 784^®, and a sodium MMT (Cloisite Na^®) have been studied. Thermal properties of the layered silicates have been evaluated by TGA, IR, WAXD and pyrolysis-gas-mass. In order to better assess the influence of high temperature processes on clay modifications, a thermal treatment which mimics the conditions used during the in situ polymerization (4 h at 250 °C) has been applied on layered silicates. The above treatment, besides the elimination of absorbed water from all the clays, turned out to prove noteworthy differences in compatibilizer modification for the two organoclays. Indeed, in the case of Closite 30B^® only a removal of organic molecules outside the silicate galleries and a likely reorganization of those present inside the galleries have been detected, while a relevant chemical modification of Nanofil 784^® compatibilizer has been conversely found.As far as nanocomposite characteristics are concerned, the latter have been found to depend on both the preparation method and clay type. In the case of in situ polymerization, also thermally-treated layered silicates, coded (T), have been used, in order to put more clearly in evidence the role of compatibilizer decomposition on nanocomposite formation and properties. Indeed, nanocomposite samples containing Closite 30B^®(T) have been found to be completely exfoliated, while the same thermal treatment seems to make worse the properties of those based on Nanofil 784^®(T). Furthermore, with respect to nanocomposites based on pristine clays, samples containing thermally-treated silicates turned out to be different in terms of both molecular mass and crystal structure of the polymer matrix. Namely, PA6 γ-form seems to be promoted for all nanocomposites prepared in such a way, probably because of water removal at high temperature, which makes -OH groups of the layered silicate more free to interact with polyamide chains, thus causing a restriction of their mobility.     

Electrochemical behavior of silver-impregnated Al-pillared smectite in alkaline solution

In order to enhance silver effectiveness for oxygen reduction reaction, pillared clay was used as a support for silver nanodispersion. Silver particles incorporation into pillared clay pores was attempted by impregnation/thermal degradation technique. X-ray diffraction as well as adsorption-desorption isotherms confirmed that pillaring procedure was successful. Scanning electron microscopy evidenced that a part of silver appeared outside the pillared clay cavities. Ag-pillared clay composite homogenized with 10 wt.% of nanodispersed carbon black (Vulcan), was applied on a flat glassy carbon surface and used as an electrode material. Oxygen reduction reaction was investigated in an O₂-saturated aqueous 0.1 M NaOH solution.     

Structural and textural properties of Al,Fe-pillared clay catalysts

Metal oxide pillared interlayered clays (PILCs) represent a new class of materials that have found a wide range of potential applications including catalytic oxidative degradation of organic pollutants in water. Al,Fe-pillared smectite clays with different Fe content were synthesized for possible catalytic application. Starting clay and the obtained PILCs were characterized. Phase composition, textural and morphological properties of the starting clay and synthesized PILCs were determined using X-ray diffraction, physisorption of nitrogen and scanning electron microscopy. Chemical composition of the PILCs was determined using EDX. It was found that the synthesized PILCs have similar phasal composition, textural and morphological properties differing only in Fe content in accordance with the amount of Fe introduced to clay during the pillaring process. The article is published in the original.