Aromatization of n-Butane Over Supported Mo2C Catalysts

Similarly to the case of methane, ethane and propane, Mo₂C deposited on ZSM-5 significantly enhanced the aromatization of n-butane observed on ZSM-5 (SiO₂/Al₂O₃ ratio of 80) alone. The catalytic performance of Mo₂C/ZSM-5 sensitively depended on its preparation and pretreatment. The selectivity of aromatics measured for pure ZSM-5 increased from 11-13% to 28-34% at the conversion level of 60-65%. The formation of aromatics was also observed over Mo₂C/SiO₂.     

Catalytic behavior of hybrid Co/SiO2-(medium-pore) zeolite catalysts during the one-stage conversion of syngas to gasoline

The catalytic properties of 10-MR (membered ring) zeolites (ZSM-5, MCM-22, IM-5, ITQ-2, all with a similar Si/Al ratio of ca. 15) in hybrid Co/SiO₂-zeolite catalysts for the direct conversion of syngas to mainly high-octane gasoline-range hydrocarbons has been studied under typical Fischer-Tropsch (FT) conditions: 250 °C, 2.0 MPa, and H₂/CO = 2. Special emphasis has been given to the deactivation behavior and the characterization of the amount and nature of the carbonaceous deposits formed by a combination of techniques (elemental analysis, TGA (thermogravimetric analyses), GC–MS, and DR (diffuse reflectance) UV–vis spectroscopy). The presence of the medium-pore zeolite increases the gasoline yield by about 20–50%, depending on the particular zeolite, and enhances the formation of branched products with respect to the base Co/SiO₂ catalyst, which is explained by the promotion of isomerization and cracking of long-chain (C₁₃₊) n-paraffins formed on the FT component. The initial zeolite activity is mostly determined by the surface acidity rather than by the total amount of Brønsted acid sites, pointing out to the existence of limitations for the diffusion of the long-chain n-paraffins through the 10-MR channels under FT conditions. Thus, ITQ-2 bearing the largest surface area presents the highest initial yield of branched gasoline-range products, followed by ZSM-5, IM-5, and MCM-22. All zeolites experience a loss of activity with TOS, particularly during the initial reaction stages. This deactivation is governed by the morphological and structural properties of the zeolite, which finally determine the amount and location of the coke species, and not by the acidity.     

Hydrocracking of petroleum gas oil over NiW/MCM-48-USY composite catalyst

MCM-48-USY composite materials were prepared by coating USY zeolite by a layer of MCM-48 mesoporous material at different meso/microporous ratios (SiO₂/USY ratios of 0.1, 0.2, 0.3, 0.4, 0.5) and used as support for nickel and tungsten. The NiW/MCM-48-USY catalysts were prepared using the incipient wetness method. The prepared catalysts were characterized by TPD-TGA acidity, TGA thermal stability, BET surface area, pore volume, pore size, XRD, SEM and TEM and then tested for hydrocracking of petroleum gas oil at reaction temperature of 450 °C, contact time of 90 min and catalyst to gas oil ratio of 0.04. In all prepared samples, the catalyst activity and properties were improved with increasing SiO₂/USY ratio and found that maximum values of a total conversion and liquid product (total distillate fuels) were obtained at SiO₂/USY ratio of 0.5. Finally, the obtained results from hydrocracking of gas oil over composite MCM-48-USY catalysts were compared with those obtained over physically mixed USY and MCM-48 catalysts.     

The preparation of Fe<Superscript>3+</Superscript> ion-exchanged mesopore containing ZSM-5 molecular sieves and its high catalytic activity in the hydroxylation of phenol

A series of Fe³⁺ containing catalysts were synthesized using ion-exchange technique over hierarchically porous ZSM-5 (M-ZSM-5) and micro-mesoporous composite ZSM-5/MCM-41 (ZSM-5/MCM-41), respectively. The prepared catalysts were characterized by X-ray diffraction, scanning electron microscope, transmission electron microscope, N₂ adsorption–desorption, UV–Vis spectroscopy, temperature programmed reduction and inductively coupled plasma-optical emission spectroscopy. The characterization results exhibit that the hierarchically porous ZSM-5 was synthesized with intracrystalline mesopores, while the micro-mesoporous composite ZSM-5/MCM-41 was prepared with the well-ordered mesopores. Furthermore, the results also prove that the existence of iron in the catalysts was mainly presented in the form of Fe³⁺ ions. Catalytic performances of the samples for phenol hydroxylation were compared by using H₂O₂ as oxidant. Under the optimized conditions, Fe³⁺ ion-exchanged M-ZSM-5 (Fe-M-ZSM-5) shows that a phenol conversion of 42.3% obtained with 92.5% selectivity to dihydroxybenzenes, whereas Fe³⁺ ion-exchanged ZSM-5/MCM-41 (Fe-ZSM-5/MCM-41) give 46.2% phenol conversion and 90.1% dihydroxybenzenes selectivity, which are all better than most reported results. The recyclability tests show that Fe-ZSM-5/MCM-41 with ordered mesoporous structure and bigger surface area has better anti-deactivation performance than Fe-M-ZSM-5. The excellent catalytic performances were due to the improved diffusion performance with newly created mesopores and the highly active Fe³⁺ species obtained by ion-exchange technique.     

Chemical Compounds Released from Specific Osteoinductive Bioactive Materials Stimulate Human Bone Marrow Mesenchymal Stem Cell Migration

In this work, a poly(L-lactide-co-glycolide) (PLGA)-based composite was enriched with one of the following sol-gel bioactive glasses (SBG) at 50 wt.%: A1—40 mol% SiO₂, 60 mol% CaO, CaO/SiO₂ ratio of 1.50; S1—80 mol% SiO₂, 20 mol% CaO, CaO/SiO₂ ratio of 0.25; A2—40 mol% SiO₂, 54 mol% CaO, 6 mol% P₂O₅, CaO/SiO₂ ratio of 1.35; S2—80 mol% SiO₂,16 mol% CaO, 4 mol% P₂O₅, CaO/SiO₂ ratio of 0.20. The composites and PLGA control sheets were then soaked for 24 h in culture media, and the obtained condition media (CM) were used to treat human bone marrow stromal cells (hBMSCs) for 72 h. All CMs from the composites increased ERK 1/2 activity vs. the control PLGA CM. However, expressions of cell migration-related c-Fos, osteopontin, matrix metalloproteinase-2, C-X-C chemokine receptor type 4, vascular endothelial growth factor, and bone morphogenetic protein 2 were significantly increased only in cells treated with the CM from the A1/PLGA composite. This CM also significantly increased the rate of human BMSC migration but did not affect cell metabolic activity. These results indicate important biological markers that are upregulated by products released from the bioactive composites of a specific chemical composition, which may eventually prompt osteoprogenitor cells to colonize the bioactive material and accelerate the process of tissue regeneration.     

L/ZSM-5复合分子筛的合成与表征

采用水热晶化法,旨在合成出具有双重孔结构和双重酸性中心的L/ZSM-5复合分子筛,合成条件为:n(SiO2/Al2O3)=35,pH=12.5。借助X射线衍射(XRD)、扫描电镜(SEM)和红外光谱(IR)对其进行表征,考察反应温度对其芳构化性能的影响。XRD和IR表明,样品中同时存在ZSM-5和L分子筛结构和特征吸收峰。SEM表明,L/ZSM-5复合分子筛显示出不规则的六方棱柱面状的大颗粒,其表面附晶生长类似圆球状的小颗粒,晶界不再明显,且大颗粒表面变粗糙;反应温度为520℃时,L/ZSM-5复合分子筛催化正戊烷生成BTX的收率最高,为29.9%。合成的L/ZSM-5复合分子筛,其骨架结构、表面形貌和催化性能明显不同于其机械混合物。     

Direct Solvothermal Formation of Nanocrystalline TiO2 on Porous SiO2 Adsorbent and Photocatalytic Removal of Nitrogen Oxides in Air over TiO2–SiO2 Composites

Solvothermal decomposition of titanium(IV) tert-butoxide (TTB) in toluene at 573 K in the presence of silica gel (SiO₂) with continuous stirring yielded a titanium(IV) oxide (TiO₂)–SiO₂ composite in which agglomerates of nanocrystalline TiO₂ were deposited on the surfaces of SiO₂ particles. Various TiO₂–SiO₂ composites having different TiO₂ contents can be synthesized by changing the ratio of TTB and SiO₂, and the composites had large surface areas corresponding to porous properties of SiO₂. These TiO₂–SiO₂ composites were used for photocatalytic removal of nitrogen oxides in air and their photocatalytic performances were compared with those of other TiO₂–SiO₂ samples prepared by different methods. Solvothermally synthesized 74 wt.%TiO₂–SiO₂ composite exhibited excellent photocatalytic performance (almost stoichiometric removal of NO _x (98%) and very low NO₂ release (0.3%)) attributable to high photocatalytic activity of TiO₂ and high adsorption property of SiO₂. Lesser performance of 74 wt.%TiO₂–SiO₂ composites prepared by other methods suggested that pore-mouth plugging of SiO₂ by TiO₂ and lower level of mixing of TiO₂ and SiO₂ decreased photocatalytic performance of the composites.     

Aromatization of ethanol on Mo2C/ZSM catalysts

The reaction of ethanol was investigated on Mo₂C, Mo₂C/SiO₂ and Mo₂C/ZSM-5 catalysts at temperature ranging 573–973 K under atmospheric pressure. Mo₂C and Mo₂C/SiO₂ catalyzed only the decomposition of ethanol to H₂, ethylene, acetaldehyde and different hydrocarbons. The main reaction pathway on pure ZSM-5 is the dehydration reaction yielding ethylene, small amounts of hydrocarbons and aromatics. Deposition of Mo₂C on zeolite greatly enhanced the yield of benzene and toluene by catalyzing the aromatization of ethylene formed in dehydration process of ethanol.     

Direct vapor phase oxidation of propylene by molecular oxygen over MCM-41 or MCM-22 based catalysts

Ti and Al containing MCM-41 (Al-c-MCM-41 and Al-Ti-c-MCM-41) have been synthesized and tested for direct oxidation of propylene with molecular oxygen. Al-Ti-c-MCM-41 is more effective than Al-c-MCM-41, while no product was formed for MCM-41 alone. It is also found that MCM-22 with Si/Al₂ ratio of 30 and Na/SiO₂ ratio of 0.18 is active for the reaction and a highest PO yield of 11.3% was obtained at 573 K.     

Modulating acid site spatial location of Zn/ZSM-5 catalyst to boost the stable aromatization of hexane

Engineering acid site spatial location of zeolite catalyst harbors tremendous potential to boost catalytic performance but still remains a grand challenge for aromatization reaction. Herein, we successfully manipulate acid site spatial location inside the ZSM-5 channels to promote the hexane aromatization via the simple SiO₂ coating treatment. Multi-techniques demonstrated that the medium strong L acid in the channel originated from the Si(Al) O Zn structure is mainly retained in the Zn/ZSM-5-Si catalyst by covering the acid sites outside the channel. Surprisingly, there is a good linear relationship between BTEX yield and this medium strong L acid content. Based on the reaction kinetics, in situ FT-IR and theoretical calculations, it is found that the L acid with confinement effect served as the main active site could prominently enhance the cyclization of propene intermediate and the dehydrogenation of cycloalkane due to the strong affinity between the C/H and ZnOx, and control the desorption of BTEX (mainly benzene, toluene, ethylbenzene, and p-xylene) by weakening the binding of hydrogen proton to π electrons. Compared with the ordinary Zn/ZSM-5 catalyst, the yield of BTEX is increased by nearly 10%, and the Zn/ZSM-5-Si catalyst exhibits excellent anti coking deactivation ability. This strategy together with mechanistic results may pave the rational design of efficient Zn/ZSM-5 catalysts for aromatization reaction.     

Epoxy composites reinforced by different size silica nanoparticles

Three series of epoxy/SiO₂ composites, containing 0.3–7 wt % nanosized SiO₂ with different specific surface area, were prepared by solution blending. The resulting composites exhibit the higher glass transition temperature (T_g) than that of pure epoxy. The T_g of composite showed a maximum increment of 35.3°C by the addition of 7 wt % A300. The trade name of A300 is Aerosil 300. It is one of the fumed silica nanoparticles products of Degussa. The decomposition temperatures (T_d) of composites were always higher than that of pure epoxy and showed a maximum increment of 20.8°C by the addition of 5 wt % A300. The light transmittance of composites was as a function of the SiO₂ content and size. The water permeability of composites decreased with increasing SiO₂ content and the 7 wt % A300 composite exhibits a maximum decrement percentage of 35.6%. The T_g, T_d, storage modulus, and water‐vapor barrier property are as a function of the SiO₂ content and size. These properties increased as the content of SiO₂ increased. The finer SiO₂ are more effective in increasing the T_g, T_d, and water‐vapor barrier property. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Exploring suitable ZSM-5/MCM-41 zeolites for catalytic cracking of n-dodecane: Effect of initial particle size and Si/Al ratio

In this study, various ZSM-5/MCM-41 micro/mesoporous zeolite composites have been prepared by alkalidesilication and surfactant-directed recrystallization of ZSM-5. The effects of particle size and Si/Al ratio of initial ZSM-5 zeolites on the structure and catalytic performance of ZSM-5/MCM-41 composites are studied. The results of XRD, TEM N₂-adsorption-desorption, NH₃-TPD and in situ FT-IR revealed that ordered hexagonal MCM-41 mesopores with 3-4 nm pore size were formed around ZSM-5 crystals, and the specific surface area and mesopore volume of composites increased with increasing the Si/Al ratio of initial ZSM-5. Catalytic cracking of n-dodecane (550 ℃, 4 MPa) showed that the ZSM-5/MCM-41 composites obtained from the high Si/Al ratio and nano-sized initial ZSM-5 zeolites exhibited superior catalytic performance, with the improvement higher than 87% in the catalytic activities and 21% in the deactivation rate compared with untreated zeolites. This could be ascribed to their suitable pore structure, which enhanced the diffusion of reactant molecules in pores of catalysts.     

Preparation of conductive polyaniline/nanosilica particle composites through ultrasonic irradiation

Polyaniline/nano‐SiO₂ particle composites were prepared through ultrasonic irradiation. Polymerization of aniline was conducted under ultrasonic irradiation in the presence of two types of nano‐SiO₂: porous nanosilica and spherical nanosilica. The stability of the colloid dispersion, UV–vis spectra, composition, interaction, conductivity, and other characteristics of the composites were examined. It was found that the aggregation of nano‐SiO₂ could be reduced under ultrasonic irradiation and that nanoparticles were redispersed in the aqueous solution. The formed polyaniline deposited on the surface of the nanoparticle, which led to a core–shell structure. Two particle morphologies, threadlike aggregates with a few spherical nanoparticles for porous nanosilica and spherical particles with a few sandwichlike particles for spherical nanosilica, were observed. X‐ray photoelectron spectroscopy showed that for two types of composites the ratio of Si atoms to N atoms (Si:N) on the surface was much higher than that in the bulk. The UV–vis spectra of the diluted colloid dispersion of polyaniline/nano‐SiO₂ composite particles were similar to those of the polyaniline system. Fourier transform infrared spectroscopy suggested strong interaction between polyaniline and nano‐SiO₂. The conductivity of the polyaniline/porous nanosilica (23.1 wt % polyaniline) and polyaniline/spherical nanosilica (20.6 wt % polyaniline) composites was 2.9 and 0.2 S/cm, respectively. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 87: 1811–1817, 2003     

Characterization and application of a Pt/ZSM-5/SSMF catalyst for hydrocracking of paraffin wax

The microstructured Pt/ZSM-5/SSMF catalysts, for hydrocracking of paraffin wax, have been developed by impregnation method to place Pt onto thin-sheet ZSM-5/SSMF composites obtained by direct growth of ZSM-5 on the sinter-locked stainless steel microfibers (SSMF). The best catalyst is the one with ZSM-5 having a SiO₂/Al₂O₃ weight ratio of 200, delivering ~ 95% conversion with 77.5% selectivity to liquid products or 64.4% selectivity to naphtha at 280 °C. This new approach is capable of increasing the naphtha selectivity with high activity maintenance in comparison with the literature catalysts.     

Physical properties and crystallization behavior of poly(lactide)/poly(methyl methacrylate)/silica composites

Poly(lactide)/poly(methyl methacrylate)/silica (PLA/PMMA/SiO₂) composites were fabricated using a twin‐screw extruder. Nanosilica particles were incorporated to improve the toughness of the brittle PLA, and a chain extender reagent (Joncryl ADR 4368S) was used to reduce the hydrolysis of the PLA during fabrication. Highly transparent PLA and PMMA were designated to blend to obtain the miscible and transparent blends. To estimate the performance of the PLA/PMMA/SiO₂ composites, a series of measurements was conducted, including tensile and Izod impact tests, light transmission and haze measurements, thermomechanical analysis, and isothermal crystallization behavior determination. A chain extender increases the ultimate tensile strength of the PLA/PMMA/SiO₂ composites by ～43%, and both a chain extender and nanosilica particles increase Young's modulus and Izod impact strength of the composites. Including 0.5 wt % nanosilica particles increase the elongation at break and Izod impact strength by ～287 and 163%, respectively, compared with those of the neat PLA. On account of the mechanical performances, the optimal blending ratio may be between PLA/PMMA/SiO₂ (90/10) and PLA/PMMA/SiO₂ (80/20). The total light transmittance of the PLA/PMMA/SiO₂ composites reaches as high as 91%, indicating a high miscible PLA/PMMA blend. The haze value of the PLA/PMMA/SiO₂ composites is less than 35%. Incorporating nanosilica particles can increase the crystallization sites and crystallinities of the PLA/PMMA/SiO₂ composites with a simultaneous decrease of the spherulite dimension. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42378.     

Oxidative dehydrogenation of n-butane over bimetallic mesoporous and microporous zeolites with CO2 as mild oxidant

Oxidative dehydrogenation of n-butane was tested using carbon dioxide as a mild oxidant over bimetallic Cr–V supported catalysts (MCM-41, ZSM-5, MCM-22 and mesoZSM-5). The textural properties of the catalysts were measured by means of XRD, N₂ adsorption, SEM-EDX, Raman, H₂-TPR, pyridine FT-IR, NH₃ and CO₂-TPD techniques. The metal content of Cr and V was maintained around 1.2 and 2.8 wt% for the catalytic test in packed bed reactor at different temperatures (525–600 °C) for 180 min. 1.2Cr2.8 V/MCM-41 and 1.2Cr2.8 V/ZSM-5 exhibited maximum conversion of 14 and 13.1 %, respectively at 10 min and 600 °C. Significantly, high butenes selectivity was observed over MCM-41 (86.27 %) than ZSM-5 support (58.1 %). The mesoporosity in ZSM-5 had a negative impact on conversion level (7.1 %) but improved the butenes selectivity slightly. 1.2Cr2.8 V/M-22 showed the highest cracking ability leading to overall reduced butenes selectivity (57.9 %). The study shows that over all catalysts, n-butane conversion is independent of CO₂ conversion. 1.2Cr2.8 V/M-22 showed highest CO₂ conversion in the range 2.35–2.2 % between 525 and 550 °C. The apparent activation energies of dehydrogenation and cracking reaction over the four catalysts were evaluated. The ratio of conversion to coke weight per cent over the four catalysts are observed in the following order: 1.2Cr2.8 V/M-41 > 1.2Cr2.8 V/Z-5 > 1.2Cr2.8 V/mesoZ-5 > 1.2Cr2.8 V/M-22.     

Facile synthesis of HZSM-5 with controlled crystal morphology and size as efficient catalysts for chlorinated hydrocarbons oxidation and xylene isomerization

ZSM-5 zeolites with controllable crystal morphologies (microsphere self-assembled from nanorod crystals, round-boat and cross shape) were synthesized in extremely diluted solutions (H₂O/SiO₂ = 350) by only adjusting the tetrapropylammonium hydroxide concentration under dynamic or static condition. The synthesized ZSM-5 were characterized by X-ray diffraction, infrared spectra, scanning electron microscopy, transmission electron microscopy, N₂ sorption and NH₃ temperature programmed desorption, and compared with the commercial ZSM-5 zeolite. Catalytic tests for the formation of p-xylene from o-xylene isomerization and the catalytic oxidation of chlorinated hydrocarbons showed that ZSM-5 microsphere composed of nanorod crystals exhibited both high conversion and improved p-xylene selectivity, and high catalytic activities for 1,2-dichloroethane and chlorobenzene oxidation and low selectivity to chlorinated by-products, which were attributed to the existence of nanosized ZSM-5 crystals and mesopores, high internal surface area and total acidity.     

Synthesis of Polystyrene/Hydrophobic SiO2 Composite Particles via Oil‐in‐Water Pickering Emulsion Polymerization

The aim of this work is to present a facile Pickering emulsion polymerization method for the synthesis of submicron polystyrene/SiO₂ core/shell composite particles. The commercial hydrophobic SiO₂ nanoparticles were used as stabilizing agent for creating a stable oil‐in‐water emulsion. Although the adsorption of hydrophobic SiO₂ nanoparticles in the emulsion system was unfavorable in terms of thermodynamics, by ultrasound treatment, self‐assembly of hydrophobic SiO₂ nanoparticles effectively stabilized oil‐in‐water Pickering emulsions during polymerization. Using 3 wt.% SiO₂ nanoparticles (based on styrene monomer) and 1:10 volume ratio of styrene monomer:water, the composite particles having average size of 790 nm and relatively narrow particles distribution were produced. With decreasing the volume ratio, smaller composite particles were created. Results from scanning electron microscope revealed that SiO₂ nanoparticles were located exclusively at the surface of the polystyrene latex particles. The SiO₂ content, determined by thermogravimetric analysis, was 12.6 wt.% in the composite particles. The route reported here may be used for the preparation of other composite nanostructures. POLYM. ENG. SCI., 59:E195–E199, 2019. © 2018 Society of Plastics Engineers     

Enhancing the Production of Light Olefins by Catalytic Cracking of FCC Naphtha over Mesoporous ZSM-5 Catalyst

The enhanced production of light olefins from the catalytic cracking of FCC naphtha was investigated over a mesoporous ZSM-5 (Meso-Z) catalyst. The effects of acidity and pore structure on conversion, yields and selectivity to light olefins were studied in microactivity test (MAT) unit at 600 °C and different catalyst-to-naphtha (C/N) ratios. The catalytic performance of Meso-Z catalyst was compared with three conventional ZSM-5 catalysts having different SiO₂/Al₂O₃ (Si/Al) ratios of 22 (Z-22), 27 (Z-27) and 150 (Z-150). The yields of propylene (16 wt%) and ethylene (10 wt%) were significantly higher for Meso-Z compared with the conventional ZSM-5 catalysts. Almost 90% of the olefins in the FCC naphtha feed were converted to lighter olefins, mostly propylene. The aromatics fraction in cracked naphtha almost doubled in all catalysts indicating some level of aromatization activity. The enhanced production of light olefins for Meso-Z is attributed to its small crystals that suppressed secondary and hydrogen transfer reactions and to its mesopores that offered easier transport and access to active sites.     

Structure and property of polyurethane/SiO2 composite elastomer prepared via in situ polymerization

A series of polyurethane (PU)/SiO₂ composites were prepared via in situ polymerization through a prepolymer process. The effect of SiO₂ content on mechanical and solvent‐resistant properties of PU/SiO₂ composites was investigated. It was found that with increasing SiO₂ content, the tensile strength and toughness, hardness, and modulus of PU composites increased. PU/SiO₂ composites exhibited only one loss peak corresponding to the glass transition temperature of the soft‐segment of PU, which shifted insignificantly with increasing SiO₂ content. The equilibrium swelling ratio and swelling rate constant in cyclohexanone and xylene were reduced by increasing SiO₂ content, indicating the enhancement of the solvent resistance of the PU elastomer. Morphology observation of PU/SiO₂ composites showed that the acicular SiO₂ dispersed uniformly in PU matrix, and there was no obvious aggregation even at 9 wt % loading of SiO₂. The reinforcing and toughening effects depended largely on the dispersion of SiO₂ in PU matrix and the interfacial layer formed between the two phases. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013