Cerium ion-exchanged layered MCM-22: preparation,characterization and its application for esterification of fatty acids

A series of cerium ion-exchanged MCM-22 catalysts was prepared by post-synthetic ion-exchange route. The resultant cerium-exchanged MCM-22 zeolite was systematically characterized using FTIR, powder X-ray diffraction (XRD), N₂ adsorption and desorption analysis, scanning electron microscopy, thermogravimetric analysis and diffuse reflectance UV–Vis spectral studies. The XRD pattern and FTIR data confirmed the MCM-22 structure. The diffuse reflectance UV–Vis spectroscopy showed coordination nature of the cerium ions. The cerium exchange MCM-22 zeolite showed promising activity for the esterification of fatty acids, achieving a maximum conversion of 75% at 70 °C in 24 h. Importantly the catalytic activity increases upon recycle due to hydrophic nature of recycled catalyst.     

Ethanol steam reforming over Co-based catalysts: Role of oxygen mobility

The effect of oxygen mobility on the bio-ethanol steam reforming of ZrO₂- and CeO₂-supported cobalt catalysts was investigated. The supported catalysts were prepared by incipient wetness impregnation (IWI) and characterized through N₂ physisorption, X-ray photoelectron spectroscopy, temperature programmed oxidation, laser Raman spectroscopy, diffuse reflectance infrared Fourier transform spectroscopy, O₂ pulse chemisorption, isotopic labeling, and transmission electron microscopy techniques at various life stages of the catalyst. The results indicated that the catalyst deactivation was due mostly to deposition of various types of carbon on the surface although cobalt sintering could also be contributing to the deactivation. The addition of ceria was found to improve the catalytic stability as well as activity, primarily due to the higher oxygen mobility of ceria.     

Synthesis of nanosized ZSM-2 zeolite with potential acid catalytic properties

Nanosized ZSM-2 zeolite crystals (～100 nm) with suitable surface acid properties were prepared. ZSM-2 zeolite forms with improved acidity were obtained through thermal deammoniation and steam treatment. Detailed characterization of acidic ZSM-2 zeolite was carried out by powder X-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared spectroscopy (FTIR), diffuse reflectance infrared Fourier transform (DRIFT), nitrogen sorptometry, dynamic light scattering (DLS), thermogravimetry (TGA), potentiometric acidity measurements, and FTIR analysis of pyridine adsorption. Acid properties of ZSM-2 zeolite were significantly improved by conversion into its protonated (H-ZSM-2) and dealuminated (DEAL-ZSM-2) forms, in which bridged Si(OH)Al groups with Brönsted acidity (H-ZSM-2) and aluminium extraframework species with Lewis acid character (DEAL-ZSM-2) are generated. These acidic ZSM-2 zeolite forms also maintain adequate crystalline order and high surface area values, making this nanosized zeolite attractive for catalytic applications.In the context of catalyst supporting materials for the polymerization of olefins, the DEAL-ZSM-2 zeolite form showed Lewis acid properties similar to those of a traditional MAO-modified silica support. Thus, DEAL-ZSM-2 zeolite appears as a promising material to be evaluated as polymerization catalyst support when a reduction of the amount of high-cost MAO cocatalyst is desired.     

Preparation of silica‐supported late transition metal catalyst and ethylene polymerization

A Correction has been published for this article in Polymer International 51(6) 2002, 561 The late transition metal catalyst 2,6‐bis[1‐(2,6‐diisopropylphenylimino)ethyl]pyridine iron(II) chloride was supported on silica. Fourier transform infrared spectroscopy, scanning electronic micrograph and X‐ray photoelectron spectroscopy measurements were utilized to examine the process of supporting catalyst on silica and investigate the possible mechanism of support. Furthermore, ethylene polymerizations with the supported catalysts were carried out in various conditions such as different reaction temperatures and Al/Fe molar ratios. The results showed that MAO first reacted with the hydroxyl of silica forming Si? O? Al bonds and then the catalyst was bridged through MAO on the surface of silica. Compared with homogeneous catalysts, the supported catalysts show some decrease in catalyst activity. However, they can show good activity at a lower Al/Fe molar ratio with MAO as co‐catalyst and give rise to higher molecular weight and melting temperature of the polymer. Better morphology of polyethylene was obtained by a supported catalyst than by its corresponding homogeneous catalyst. The late transition metal catalyst 2,6‐bis[1‐(2,6‐diisopropylphenylimino)ethyl]pyridine iron(II) chloride was supported on silica. Fourier transform infrared spectroscopy, scanning electronic micrograph and X‐ray photoelectron spectroscopy measurements were utilized to examine the process of supporting catalyst on silica and investigate the possible mechanism of support. Furthermore, ethylene polymerizations with the supported catalysts were carried out in various conditions such as different reaction temperatures and Al/Fe molar ratios. The results showed that MAO first reacted with the hydroxyl of silica forming Si? O? Al bonds and then the catalyst was bridged through MAO on the surface of silica. Compared with homogeneous catalysts, the supported catalysts show some decrease in catalyst activity. However, they can show good activity at a lower Al/Fe molar ratio with MAO as co‐catalyst and give rise to higher molecular weight and melting temperature of the polymer. Better morphology of polyethylene was obtained by a supported catalyst than by its corresponding homogeneous catalyst. © 2002 Society of Chemical Industry     

Hierarchical ZSM-5 catalytic performance evaluated in the selective oxidation of styrene to benzaldehyde using TBHP

Hierarchical ZSM-5 catalysts with different Si/Al ratios (20, 60 and 100) were hydrothermally synthesized. The prepared samples were studied by several techniques, including X-ray diffraction (XRD), X-ray fluorescence (XRF) analysis, Fourier transform infrared (FTIR) spectroscopy, N₂ adsorption–desorption, high resolution transmission electron microscopy (HR-TEM), high resolution scanning electron microscopy (HR-SEM), and differential scanning calorimetry (DSC) technique. The average crystallite size and crystallinity decreases with increasing Si/Al ratio, which is confirmed by XRD. FTIR analysis further confirms the formation of ZSM-5 by the presence of characteristic bending, stretching and framework vibration. The HR-TEM images showed that all the samples having disc-like nanostructures are assembled by many primary nanocrystals. The as-synthesized ZSM-5 zeolites are thermally stable, which is confirmed by DSC. The catalytic activity of ZSM-5 zeolites was evaluated in the selective oxidation of styrene using tertiary-butyl hydroperoxide (TBHP) as the oxidant. Among the catalysts, ZSM-5(60) catalyst showed significantly higher yield of benzaldehyde at optimum conditions. The catalyst was recovered and recycled three times without a significant loss in activity and selectivity.     

Bonding characteristics and corrosion resistance of silane–cerium-treated aluminum adherend

A silane–cerium treatment was applied on an aluminum adherend to simultaneously improve the bonding performance and corrosion resistance of the adhesively bonded aluminum joint in cryogenic applications, such as with liquefied natural gas containment tanks. The lap shear strengths and corrosion performances of the adhesively bonded joints composed of treated aluminum adherends were measured with respect to the silane–cerium treatment and the surface pretreatment on the aluminum adherend. The bonding characteristics of the aluminum adherend were investigated by measuring the water contact angle and conducting the potentiodynamic polarization test after the aluminum adherends with different surface treatments of silane–cerium were immersed in a 0.5?M NaCl solution. In addition, the surfaces were analyzed with scanning electron microscopy, X-ray photoelectron spectroscopy, and Fourier transform infrared spectroscopy to characterize the chemical compositions of the silane–cerium-treated aluminum adherend. The experimental results show that an appropriate silane–cerium treatment on the aluminum adherend produces an effective corrosion-resistant layer and that it has a highly reliable bonding characteristic for the adhesive joint at a cryogenic temperature of ?150?°C.     

Structure,texture and surface acidity studies of a series of mixed zinc–aluminum (60–90 molar % Al) phosphate catalysts

A series of mixed zinc–aluminum phosphate (ZnAlP) catalysts containing 40–90 aluminum molar % were synthesized by a coprecipitation method and characterized by nitrogen adsorption–desorption, X‐ray diffraction, FTIR spectroscopy, thermogravimetric analysis (TGA), differential thermal analysis (DTA), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and temperature programmed desorption (TPD) of ammonia. The presence of aluminum greatly affected the surface properties of Zn₃(PO₄)₂ by delaying the crystallization process of Zn₃(PO₄)₂. All amorphous samples were shown to be mesoporous and they contained two types of aluminum surface hydroxyl groups and one type of phosphorus hydroxyl group, as shown by DRIFT spectra. The specific surface area and the acidity of ZnAlP increased on increasing the aluminum content. On the other hand, a great difference in the texture and the concentration of surface acid sites was found by changing the precipitating agent and calcination temperature. Thus these factors also play an important role in the final properties of these catalysts. © 2001 Society of Chemical Industry     

Waste-free Soft Reactive Grinding Synthesis of High-Surface-Area Copper–Manganese Spinel Oxide Catalysts Highly Effective for Methanol Steam Reforming

Cu–Mn spinel oxides with a high specific surface area were prepared by a simple and waste-free soft reactive grinding (SRG) technique involving the use of clean precursor salts as the starting materials. The samples were characterized by means of N₂ adsorption, X-ray diffraction (XRD), diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and temperature-programmed reduction (H₂-TPR). The results show that the catalysts obtained from the SRG route exhibited much higher catalytic activity in methanol steam reforming as compared to their wet-chemically synthesized counterparts prepared by conventional coprecipitation. The superior performance of the SRG-derived Cu–Mn materials was attributed to the favorable formation of Cu_1.5Mn_1.5O₄ spinel phase leading to the creation of much smaller copper nanoparticles with enhanced stability in the working catalyst.     

Characterization of palladium supported on sulfated zirconia catalysts by DRIFTS, XAS and n-butane isomerization reaction in the presence of hydrogen

Palladium supported on sulfated zirconia (PdSZ) has been characterized by the n-butane isomerization reaction in the presence of hydrogen, X-ray absorption spectroscopy (XAS) and diffuse reflectance Fourier transform infrared spectroscopy (DRIFTS) of adsorbed carbon monoxide. Catalyst calcination at 873 K followed by hydrogen reduction at 513 K results in the formation of 30–40 Å Pd metal clusters, but the surface can only weakly adsorb CO, though stronger than Pd-free, sulfated zirconia catalysts. In the presence of hydrogen, PdSZ has a lower n-butane isomerization activity than SZ, and the Pd function cannot stabilize the reaction at low H₂/n-butane ratios.     

A sonochemical route to fabricate the novel porous F, Ce-codoped TiO2 photocatalyst with efficient photocatalytic performance

A novel F, Ce-codoped TiO₂ photocatalyst with mesoporous structure was successfully fabricated by ultrasound irradiation. The obtained catalysts were characterized by X-ray diffraction, Fourier transform infrared spectrum, X-ray photoelectron spectroscopy, UV?Cvis diffuse reflectance spectra, scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, photoluminescence spectroscopy, and N₂ adsorption. The photocatalytic activity of the samples was evaluated by degradation of acid orange II under UV light irradiation. Results showed that F and Ce can be successfully doped into TiO₂ under ultrasonic irradiation conditions. All the single F or Ce-doped TiO₂ and F, Ce-codoped TiO₂ have shown good mesoporous structures, and this can be contributed to the ultrasound-induced aggregation effect. The F, Ce-codoped TiO₂ photocatalyst exhibits much higher photocatalytic activity than that of pure, single F or Ce-doped TiO₂, which could be attributed to that F, Ce-codoping increases its surface hydroxyl groups and effectively reduces the photo-generated electron/hole pair recombination rate.     

Synthesis of mesoporous aluminosilicates with low Si/Al ratios using a single-source molecular precursor under acidic conditions

A single molecular precursor, bis(sec-butoxy)-aluminoxy-triethoxysilane, was used as aluminum source for the synthesis of mesoporous aluminosilicates with Si/Al ratios ranging from 1 to 10 under acidic conditions. Aluminum can be stoichiometrically incorporated into the mesoporous materials at pH = 1.5. The mesoporous aluminosilicates synthesized with the single molecular precursor display larger unit cell parameter and pore diameter than that of the materials prepared with aluminum sulfate, aluminum nitrate, aluminum hydroxide, and aluminum isopropoxide as the aluminum sources. IR spectra of adsorbed pyridine and NH₃-TPD showed that both Br?nsted acidic sites and Lewis acid sites with medium strength are present in the materials. However, no direct relationship between the acidic properties and the content of aluminum was observed when the Si/Al ratios of the mesoporous aluminosilicates are lower than 10.     

Tuning the crystallite size of monoclinic ZrO_2 to reveal critical roles of surface defects on m–ZrO_2 catalyst for direct synthesis of isobutene from syngas

The effects of crystallite size on the physicochemical properties and surface defects of pure monoclinic ZrO_2 catalysts for isobutene synthesis were studied. We prepared a series of monoclinic ZrO_2 catalysts with different crystallite size by changing calcination temperature and evaluated their catalytic performance for isobutene synthesis from syngas. ZrO_2 with small crystalline size showed higher CO conversion and isobutene selectivity, while samples with large crystalline size preferred to form dimethyl ether(DME) instead of hydrocarbons, much less to isobutene. Oxygen defects(ODefects) analyzed by X-ray photoelectron spectroscopy(XPS) provided evidence that more ODefectsoccupied on the surface of ZrO_2 catalysts with smaller crystalline size. Electron paramagnetic resonance(EPR) and ultraviolet–visible diffuse reflectance(UV–vis DRS) confirmed the presence of high concentration of surface defects and Zr~(3+) on mZrO_2-5.9 sample, respectively. In situ diffuse reflectance infrared Fourier transform spectroscopy(in situ DRIFTS) analysis indicated that the adsorption strength of formed formate species on catalyst reduced as the crystalline size decreased. These results suggested that surface defects were responsible for CO activation and further influenced the adsorption strength of surface species, and thus the products distribution changed. This study provides an in-depth insight for active sites regulation of ZrO_2 catalyst in CO hydrogenation reaction.     

New high temperature amorphous protective coatings for Mg2Si thermoelectric material

Magnesium silicide is one of the most promising, inexpensive, environment friendly and low density (1.99?g?cm^?3) thermoelectric material. These attributes distinguish it from other well-known thermoelectric materials and therefore it is currently intensively studied. Since thermoelectric materials are used in elevated temperatures, they are prone to oxygen corrosion which results in deterioration of their properties and therefore require anticorrosion protection. The aim of the work was to develop anticorrosive coating for magnesium silicide using silane-based, amorphous coatings. High purity Mg₂Si samples were prepared by self-propagating high-temperature synthesis (SHS) and hot-pressing method supported by induction heater. The structural and phase compositions of the obtained samples were examined by means of X-ray diffraction (XRD) method and chemical composition analysis by scanning electron microscopy SEM, combined with EDS method. Fourier-transform infrared spectroscopy FT-IR, Raman spectroscopy, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), temperature-programmed reduction (TPR) and temperature-programmed oxidation (TPOx) methods were used in order to determine chemical stability of prepared samples. In final step, magnesium silicide samples were covered with selected amorphous coatings by dip-coating method and then annealed in Ar gas atmospheres in various temperatures between 400–550?°C. The obtained coatings were characterized using SEM-EDS and reflectance spectroscopy method.     

Preparation and characterization of layered silicate magadiite intercalated by Cu<Superscript>2+</Superscript> and Zn<Superscript>2+</Superscript> for antibacterial behavior

The purpose of this work is the synthesis of two series of layered silicate materials with different ratios (10, 30, 50, 80 and 100) of Cu(NO₃)₂, or Zn(NO₃)₂ by ion-exchange method. Several analysis techniques have been used such as X-ray diffraction, energy dispersive X-ray spectroscopy, thermogravimetric analysis, scanning electron microscope and Fourier transform infrared spectroscopy. The results revealed that ion-exchange method of copper and zinc with different ratios did not affect the structure of Na-magadiite. The gap between the theoretical and experimental ion-exchange are in agreement. Antibacterial activity test against Escherichia coli, Rhizobium sp. and Staphylococcus demonstrate that when ratio was (30, 50, 80 and 100) the antibacterial activity of the layered silicate materials showed high antibacterial activity.     

Bifunctional mesoporous Cu–Al–MCM-41 materials for the simultaneous catalytic abatement of NOx and VOCs

This study explored the possibility of using waste organic solvent as the source of volatile organic compound (VOC) and it served as a reducing agent of selective catalytic reduction (SCR) deNO_x process, in which the VOC itself can be catalytically oxidized on the mesoporous Cu and/or Al substituted MCM-41 catalysts. The synthesized Cu–Al–MCM-41 catalysts were extensively characterized by powder low-angle X-ray diffraction (XRD), N₂ adsorption–desorption measurements, transmission electron microscopy (TEM), UV–Visible diffuse reflectance spectroscopy (UV–Vis DRS), ²⁷Al magic angle spinning-nuclear magnetic resonance spectroscopy (MAS-NMR), electron paramagnetic resonance spectroscopy (EPR) and inductively coupled plasma–mass spectrometer (ICP–MS) analysis. The XRD, TEM and N₂ adsorption–desorption studies clearly demonstrated the presence of a well ordered long range hexagonal array with uniform mesostructures. The Cu–Al–MCM-41 materials showed a better long-term-stability than that of copper ion-exchanged H–ZSM-5 (Cu–ZSM-5) zeolite. The Cu–Al–MCM-41 material was found to be an efficient catalyst than that of Cu–MCM-41 without aluminum for the simultaneous catalytic abatement of NO_x and VOCs, which was attributed to the presence of well dispersed and isolated Cu²⁺ ions on the Cu–Al–MCM-41 catalyst as observed by UV–Vis DRS and EPR spectroscopic studies. And the presence of aluminum (Al³⁺ ions) within the framework of Cu–Al–MCM-41 stabilized the isolated Cu²⁺ ions thus it led to higher and stabilized activity in terms of NO_x reduction.     

Novel synthesis of ordered mesoporous materials Al-MCM-41 from bentonite

This paper reports the synthesis of ordered mesoporous materials Al-MCM-41 with a specific surface area of 1018 m²/g from bentonite. Pretreated bentonite was simultaneously used as silica and aluminum sources without addition of silica or aluminum reagents. Orthogonal experiments were adopted to optimize the processing parameters. The samples were characterized by X-ray diffraction (XRD), high-resolution transmission electron microscopy (HRTEM), N₂ adsorption–desorption measurements and Fourier transform infrared spectra (FTIR) techniques. The obtained materials were hexagonal Al-MCM-41. Calcination removed the surfactant while new bonds increased the crosslinking of the frameworks. Proper Si/Al molar ratio was critical for the formation of highly ordered mesoporous materials.     

微乳液法制备纳米球形YAG:Ce3+荧光粉及其发光性能

采用反相微乳液法,以水/曲拉通X-100/正己醇/(环己烷 正己烷)为微乳体系,铝(Al)、钇(Y)和(Ce)的硝酸盐和氯化物作为起始反应物,氨水作为沉淀剂,成功制备了纳米球形铈掺杂钇铝石榴石(cerium doped yttrium aluminum garnet,YAG:Ce3 )荧光粉.实验表明:单相YAG可以在800℃合成,比周相反应法合成温度(1 500℃)大幅度降低.用失重-差热分析仪、Fourier变换红外光谱仪、X射线衍射仪、透射电镜、荧光分光光度计等对粉体特性进行了表征.结果表明:粉体颗粒粒径约为50nm,粒度分布均匀,球形度好,分散性好,粉体的激发光谱为双峰结构,主激发波长为469nm,发射波长为532nm,适用于白光发光二极管.     

Dealumination kinetics of composite ZSM-5/mordenite zeolite during steam treatment: An in-situ DRIFTS study

To get a better understanding of structural deactivation of ZSM-5/MOR during the catalytic cracking of n-heptane in the steam atmosphere, a comprehensive mechanism of hydrothermal dealumination was proposed through in-situ diffuse reflectance Fourier transform infrared spectroscopy(DRIFTS) in this work. The mechanism can be divided into two steps: firstly, the hydrolysis of four Al\\O bonds, and secondly, the self-healing of Si\\OH bonds accompanied with partial condensation of the extra-framework Al species. Accordingly, the kinetics of dealumination process has also been fully discussed. In the IR spectra, the range of 3450–3850 cm~(-1) could be deconvolved to distinguish the hydroxyl groups on the different position and calculate the consumption of each hydroxyl group during the reaction. Based on results from the in-situ DRIFTS, the kinetics of dealumination was hence developed and also in well agreement with the kinetics of deactivation of ZSM/MOR catalysts during the reaction in the presence of little coke deposits.     

Synthesis of hierarchical MFI zeolite microspheres with stacking nanocrystals

MFI nanozeolite microspheres with intercrystal mesopores were synthesized by a steam-assisted crystallization–aggregation method, starting with close packed amorphous SiO₂ or Al-containing SiO₂ colloidal nanoparticles. The obtained samples with different Si/Al ratios were characterized by X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy (SEM)/ transmission electron microscopy (TEM) observations, nitrogen adsorption analyses and ²⁷Al magic angle spinning nuclear magnetic resonance (NMR). The SEM images clearly showed that the mean size of nanozeolite microspheres was ca. 0.5–3 μm, agglomerated from zeolite nanocrystals and varied with different Si/Al ratios. N₂ sorption analyses as well as TEM micrographs indicated the dual-porosity of samples, one is from intracrystal micropores, and the other is from intercrystal mesopores. ²⁷Al MAS-NMR suggested nearly all of the Al atoms were located at tetrahedral-coordinated sites in the framework. Furthermore, nanozeolite microspheres with various Si/Al ratios, even Si/Al equal to five, could be prepared by this facile route and less structure-directing agent was needed compared to conventional approach. This simple method could be easily extended to prepare other hierarchically structured zeolites.     

Characterization and catalytic behaviors of methylamine modified FAU zeolites

The methylamine (MA) modified FAU zeolites with 5.8 and 80 of silica alumina molar ratio were successfully prepared by the treatment of original FAU zeolites with MA. The obtained materials were investigated with diffuse reflectance infrared Fourier transform spectroscopy, X-ray diffraction, magic-angle spinning nuclear magnetic resonance, thermogravimetry, temperature-programmed desorption of CO₂ and NH₃ (CO₂-TPD and NH₃-TPD), nitrogen content analysis, and specific surface area analysis. The formations and thermal stabilities of different Si–N–C groups in the MA modified FAU zeolites were confirmed. The changing of aluminium species due to the interaction of MA and framework/extraframework aluminium (FAL/EFAL) in the modified samples was discovered. The acidity and basicity of the MA modified FAU zeolites were correlated to the hybrid aluminium species and variation of Si–N–C groups, respectively. The catalytic behaviors of the MA modified FAU zeolites were explored by Knoevenagel condensation reaction of benzaldehyde and malonic acid.