Comparative study of the textural and structural properties of the aerogel and xerogel sulphated zirconia

Aerogel and xerogel sulphated zirconia with defined atomic ratio S/Zr = 0.5 and molar hydrolysis ratio h = nH₂O/nZrO₂ = 3 show different textural and structural properties after calcination at high temperatures. The aerogel obtained just after solvent evacuation develops only the tetragonal phase, whereas the xerogel dried in an oven is amorphous. Heating to a temperature above 833 K, leads to transition of the tetragonal phase to the monoclinic one for the two solids, due to sulphur loss but the tetragonal phase remains stable for the aerogel . Raman, Infrared and XPS spectroscopies show that the loss of the sulphur at high temperatures seems to be easier for the xerogel than for the aerogel.     

A comparative study of structural, thermal and electrical properties of undoped and doped with dodecylbenzenesulphonic acid polypyrrole

Polypyrrole was synthesized and doped with dodecylbenzenesulphonic acid; the latter was confirmed by means of FTIR spectroscopy. The percentage of crystallinity of synthesized polymers was estimated from X-rays diffraction studies. The formation of flaky structure in doped polypyrrole was observed by means of SEM. DC conductivity was found to be influenced by dopant dodecylbenzenesulphonic acid. Temperature dependant DC shows three dimensional variable ranges hopping (3D VRH). Activation energy, density of states and hopping length were calculated and found to be influenced by adding dopant to polypyrrole. The doped polypyrrole was found to be more thermally stable as compared to that of pristine polypyrrole.     

Textural,structural and catalytic behavior of low specific area silica-supported copper catalysts: effect of preparation method

Supported copper catalysts on low surface area silica were prepared by several methods and characterized by AAS, XRD, N₂ adsorption, SEM, H₂-TPR, N₂O titration, TGA-DTA, UV–Vis techniques. Their hydrogenating properties were examined in the gas-phase hydrogenation of benzaldehyde. The analysis of characterization results revealed that the choice of preparation method affected the texture, composition, and structure of the calcined and reduced Cu/SiO₂ catalysts. The dispersion and size distribution of copper species was present in different forms in the catalysts that exhibited low specific surface areas. In gas-phase hydrogenation of benzaldehyde to benzyl alcohol, the catalysts tested at the reaction temperatures of 160 and 200 °C were stable and conducted to a good catalytic activity and benzyl alcohol selectivity ranging between 5 and 39 µmol min^?1 g^?1 and 0–95%, respectively. The activity of the catalysts in gas-phase hydrogenation also depended on the particle size and the nature of copper species formed on low surface area silica.     

Li doped and undoped ZnO nanocrystalline thin films: a comparative study of structural and optical properties

Thin films of ZnO were grown by the sol–gel method using spin-coating technique on (0001) sapphire substrates. The effect of doping after annealing on the structural and optical properties has been investigated by means of X-ray diffraction (XRD), cathodoluminescence (CL) spectrum, scanning electron microscopy (SEM) and atomic force microscopy (AFM). The films that were dried at 623 K and then post annealed at 873 K showed (0002) as the predominant orientation. Two emission bands have been observed from CL spectrum. Lithium doped film shows shift in the near band edge UltraViolet emission peak and suppressed defect level emission peak in the visible range. SEM analysis of the films exhibits many spherical shaped nanoparticles. Roughness of the films determined using atomic force microscopy.      

Silica supported sulfated zirconia prepared by a sol-gel process: Effect of solvent evacuation procedure on the structural, textural and catalytic properties

Sol-gel process was used to prepare silica supported sulfated zirconia catalysts. The main parameter studied in this work was the gel drying method through four different ways of solvent evacuation. Textural, structural as well as the acidic properties of the four samples were studied using N₂ physisorption, X-ray diffraction, mass spectrometry, sulfur chemical analysis and adsorption-desorption of pyridine. The isomerization of n-hexane was used as a catalytic test. The surface areas and the pore distributions are highly affected by the drying mode. One of the four drying methods leads to a solid having improved textural properties and presenting both the crystalline ZrO₂ tetragonal phase and a particular type of sulfate mode bond. It seems that these three conditions are necessary for achieving high catalytic activity.     

Relation between the catalytic and acidic properties of zeolite catalysts

Influence of the strength and concentration of non protic centers on the catalytic activity of metal-zeolite catalysts in isomerization of n-butane has been studied. A relationship between the specific activity and the center strength is suggested.

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Acid-base, electron donating and catalytic properties of sulfated zirconia

The electron donating properties of sulfated zirconia were studied from the adsorption of electron acceptors of various electron affinity. The surface acidity and basicity of the oxides have also been determined by titration method using a set of Hammett indicators. The data have been correlated with the catalytic activity of the oxide towards esterification of acetic acid usingn-butanol, reduction of cyclohexanol in 2-propanol and oxidation of cyclohexanol with benzophenone.     

A comparative study of the surface structure, acidity, and catalytic performance of tungstated zirconia prepared from crystalline zirconia or amorphous zirconium oxyhydroxide

Tungstated zirconias prepared from W deposition on zirconium oxyhydroxide are reportedly active for alkane isomerization, whereas solids synthesized by impregnation of zirconia are inactive. The origin of the differences between the two preparations is not fully understood. The present paper examines the influence of W surface density and the nature of the support on the surface structure, development of the acidity, and catalytic performance of WO(x)()/ ZrO(2) catalysts. Two series of catalysts containing W surface densities up to 5.2 at. W/nm(2) were prepared by pore volume impregnation of two different supports: zirconium oxyhydroxide and predominantly tetragonal zirconia (65% tetragonal, 35% monoclinic). The texture and structure of the catalysts were investigated by BET measurements, X-ray diffraction, Raman and infrared spectroscopy. The catalytic activity was tested for 2-propanol dehydration and n-hexane isomerization. For catalysts obtained by impregnation of Zr oxyhydroxide, Raman results showed that W was present as a surface phase. Infrared spectra indicated an increase in the degree of polymerization of W species with increasing W surface density. The development of the acidity was monitored by lutidine adsorption and desorption at 523 K, followed by infrared spectroscopy. The results indicated the presence of a threshold of W surface density at 1.3 at. W/ nm(2) for the detection of these acid sites, followed by a progressive increase in their abundance with increasing W surface density. The development of Br?nsted acidity correlated with the evolution of the infrared bands attributed to "extensively" polymerized W species. A direct relationship was observed between the abundance of Br?nsted acid sites and the catalytic activity for 2-propanol dehydration. For n-hexane isomerization, compared to 2-propanol dehydration, a higher threshold of W surface densities (3.4 at. W/ nm(2)) for the development of activity was observed. The difference was attributed to stronger Br?nsted acid sites required for n-hexane isomerization. The catalysts prepared by impregnation of zirconia exhibited comparable behavior. For a given W surface density, the crystalline composition of the support (tetragonal/monoclinic zirconia), the W surface structure, abundance of Br?nsted acid sites, and catalytic performance were similar. Thus, in an apparent variance with some of the results reported in the literature with respect to the influence of preparation methods, no significant effect of the initial form of the support (Zr oxyhydroxide versus predominantly tetragonal zirconia) was evidenced.     

Characterization and catalytic functionalities of copper oxide catalysts supported on zirconia

A series of zirconia supported copper oxide catalysts with varying copper loadings (1.2-19.1 wt %) were prepared by impregnation method. The catalysts were characterized by X-ray diffraction, UV-visible diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy (XPS), temperature-programmed reduction (TPR), and temperature-programmed desorption of CO2. Copper dispersion and metal area were determined by N2O decomposition method. X-ray diffraction patterns indicate the presence of crystalline CuO phase beyond 2.7 wt % of Cu on zirconia. UV-visible diffuse reflectance spectra suggest the presence of two types of copper species on the ZrO2 support. XPS peaks intensity ratio of Cu 2p3/2 and Zr 3d5/2 was compared with Cu dispersion calculated from N2O decomposition. TPR patterns reveal the presence of highly dispersed copper oxide at lower temperatures and bulk CuO at higher temperatures. The basicity of the catalysts was found to increase with Cu loading, and the activity of the catalysts was also found to increase with the increase in Cu loading up to 2.7 wt % Cu loading. The catalytic properties were evaluated for the dehydrogenation of cyclohexanol to cyclohexanone and were related to surface properties of the copper species supported on zirconia.     

Polyamide-bound metal complex catalysts: Synthesis,characterization and catalytic properties

A series of polyamides having different numbers of methylene groups in their repeating units have been synthesized by interfacial polycondensation of terephthaloyl chloride with piperazine and aliphatic diamines H₂N(CH₂)_nNH₂ (n = 2, 6, 10). These materials, which have high thermal stability, were used for immobilization of rhodium and platinum complexes. Chloroplatinic acid and the compounds PtCl₂(CH₃CN)₂ and [RhCl(CO)₂]₂ were used as precursors of the supported catalysts. Low molecular weight analogues of the polyamides were prepared for a study of the coordination mode between the metal ion and the polymer by IR spectroscopy. The results suggest that the carbonyl oxygen of the polyamide is the site of coordination to both rhodium and platinum. The bound catalysts exhibited high activity in hydrosilylation of hexene-1. The activities of the rhodium complexes were found to be dependent on the structure of the polyamide support, decreasing with increasing distance between the amide groups, and closely paralled the changes in the degree of crystallinity of the polymers. Repeated use of the polymers bearing rhodium complexes showed that the bond between the metal and polyamide is fairly stable.     

Synthesis, characterization, and catalytic activity of phosphomolybdic acid supported on hydrous zirconia

A series of ecofriendly solid acid catalyst was synthesized by phosphomolybdic acid impregnated on hydrous zirconia (ZPMA) by an incipient wetness impregnation technique. The support and the resulting catalysts were characterized by X-ray diffraction, FTIR, EPMA, BET surface area, acid sites, etc. These studies indicate that the phosphomolybdic acid keeps its Keggin-type structure unaltered up to 500 degrees C. Catalytic activities of the material were evaluated for the esterification of acetic acid reaction. The 12 wt% of phosphomolybdic acid supported on hydrous zirconia shows highest surface area, acid sites and gives about 86% conversion with 100% selectivity of n-butyl acetate.     

Improving catalytic converter performance by controlling the structural and redox properties of Zr-doped CeO2 nanorods supported Pd catalysts

Research on Chemical Intermediates - The work herein introduces a facile and novel synthesis procedure for producing Zr-doped CeO2 nanorod catalysts applicable for upgrading the car catalytic...     

An ab initio comparative structural study of alkenylphosphonic acid derivatives

A comparative study of the electronic structure and conformational properties of alkenylphosphonic acid derivatives with different substituents has been carried out by means of ab initio quantum mechanical methods. The ab initio calculations have been performed using different basis sets. A strongly polarized partial triple bond for the phosphoryl group has been found. A very weak π conjugation has been detected in the C=C/P=O system. Intramolecular hydrogen bonds have been found in 2-cis-carboxyvinylphosphonic acid.     

酸、盐处理对Pt/SAPO-11物化及其催化性能的影响

采用不同酸和盐浸渍处理SAPO-11分子筛,然后负载Pt制成改性的Pt/SAPO-11催化剂,用XRF、XRD、N_2吸附-脱附、SEM、NH_3-TPD和Py-IR对催化剂进行表征,分析其物理化学性能。结果表明,酸和盐处理没有破坏SAPO-11的骨架结构,还提高了催化剂的孔容、孔径、比表面积等性质,催化剂的酸性、酸量也明显发生了改变。在固定床反应器中,评价了改性的Pt/SAPO-11催化小桐子油一步加氢制异构烷烃性能;结合催化剂表征数据表明,颗粒粒径、比表面积、孔径、酸性和酸量影响催化剂的活性及产物分布。对比发现,经0.5 mol/L柠檬酸处理的Pt/SAPO-11催化剂孔径大小、酸性、B酸和L酸量分布合适,因此,一步加氢催化处理小桐子油性能优异;其中,生物航油组分(C_(8-16))的收率为32.47%,异构烷烃(C8-16)选择性为53.13%。     

Microporous aluminoborates with large channels: structural and catalytic properties

Channel zapping: PKU-1 and newly synthesized PKU-2 (Al(2)B(5)O(9)(OH)(3)?n?H(2)O; see picture) possess microporous structures with 18-ring and 24-ring channels, respectively. They show high reactivity and size selectivity in the cyanosilylation of aldehydes as heterogeneous Lewis acid catalysts. The different channel sizes determine the substrate selectivity. These examples demonstrate the potential of octahedron-based aluminoborate channels in catalysis.     

Charge reduction in a vermiculite by acid and hydrothermal methods: a comparative study

A comparative study on acid and hydrothermal methods as ways to reduce interlamellar charge has been carried out on a vermiculite. This study showed that the application of the hydrothermal treatment as a previous step to pillaring the vermiculites, reported here for the first time, is a new route to obtain the porous material with a particular interest as heterogeneous catalysts, starting from mineral clays with a high density of charge. Modified clays have been characterized by atomic absorption, emission spectrograph, X-ray diffraction, cation-exchange capacity, total acidity, infrared spectroscopy (DRIFT), and nitrogen adsorption. The results have shown that all solids have been structurally modified. However, acid and hydrothermal methods showed different behavior. For the vermiculite, the hydrothermal treatment did not produce major differences in terms of the crystalline structure, whereas the acid method caused severe structural damage. The catalytic properties have been tested over Pt-impregnated samples (1%) using the hydroisomerization of heptane. Important catalytic activity was established for all solids with high selectivity regarding the isomer products.     

Thermal and structural properties of sodium,potassium and carbonate doped strontium hydroxyfluorapatite

Ion-doping in hydroxyapatite bioceramics has attracted a lot of interest particularly for biomedical applications in repairing and replacing failure parts of musculoskeletal systems. Thus the multiple doping aims to mimic and resemble the chemical composition of the bone mineral component. Herein strontium hydroxyapatites bioceramics containing sodium Na⁺ and potassium K⁺ as cationic substituent and carbonate CO₃^2? and fluoride as anionic substituent were synthesized and characterized by several analysis techniques. Therefore the chemical assays indicated that obtained compounds were less stoichiometric comparably to bone tissues. The X-ray diffraction diagrams and the infrared spectra revealed that pure phases of hydroxyfluorapatite containg the cited ions were obtained. The triple insertion of sodium, potassium and carbonate into the apatite structure leaded to the B-type carbonate apatite. The FE-SEM micrographs of the powders were formed by agglomerates. Moreover, the particles' morphology strongly depends on the ions nature and amount. The D-GTA curves indicated that the heating of the powders from the room temperature to 1000 °C didn't affect the structural and thermal stability of the materials apart from a partial decomposition of the apatite inducing the formation of the β-tristrontium phosphate phase and enhancing the biomaterial character of the materials.