Silica Gel- and MCM-41-Supported MoS2 Catalysts for HDS Reactions

MCM-41- and silica gel-supported MoS₂ catalysts were prepared. MCM-41 was synthesized and impregnated with precursor, then activated to obtain the active phase. The sol–gel method was used for providing the SiO₂ support as well as for including the catalyst precursors in one single step of preparation. Such catalysts have applications particularly in hydrodesulfurization (HDS) and hydrodenitrogenation (HDN) processes. A comparison of the activities of the catalysts was made. The catalytic activity results showed the method of preparation used in this study was successful in producing very efficient catalysts for the HDS of dibenzothiophene (DBT).A higher selectivity for direct C–S bond cleavage was observed for the MoS₂ catalyst supported on SiO₂ by the sol–gel method. X-ray diffraction studies showed that the catalysts were poorly crystallized with a very weak intensity of the (002) line of 2H-MoS₂.     

Polymeric sol–gel coatings as protective layers of aluminium alloys

Sol–gel route is an emerging technology to synthesize coatings of a wide variety of properties taylored. In this work three low temperature cured coatings has been studied to evaluate their protective properties in order to be used as protective barrier coatings for aluminium alloys with potential architectural and automotive applications. These three coatings are novel modified silane nanocomposites coatings obtained mixing two sols separately prepared: a pre-hydrolysed 3-glycidyloxypropyl trimethoxysilane (GPTS) with acidic catalyst and another obtained from tetraethylorthosilicate/methyltriethoxysilane (TEOS/MTES). Particulated coatings were obtained by addition of 25 wt.% particles of Aerosil 300 and Aerosil R972, respectively. The protective properties of the coatings were evaluated by electrochemical impedance spectroscopy (EIS) which showed notably differences among them not only from the protective viewpoint but the hydrophobic nature of the coatings and the controlling corrosion mechanism in each case.     

二甲醚燃烧用掺杂钡、镍六铝酸盐催化剂的研究

二甲醚是易液化，便于运输，清洁化的新能源。当作为燃料使用时，采用催化燃烧的方法能使得燃烧的起燃温度降低和提高燃烧转化率，克服了普通燃烧的缺点，实现了清洁燃烧。对二甲醚催化燃烧用的催化剂BaNiAl11O19-δ进行了制备与研究。采用溶胶-凝胶法制备六铝酸盐催化剂BaNiAl11O19-δ,考察其对新能源二甲醚催化燃烧反应的活性，并用TG—DTA对催化剂的性质进行考察。结果表明，加入经800℃焙烧4h后又在1200℃焙烧了2h的催化剂，比未加催化剂的燃烧体系T10降低了50℃。用溶胶一凝胶法制备的六铝酸盐催化剂BaNiAl11O19-δ对二甲醚催化燃烧反应具有较高的催化活性。     

Biocidal hydantoinylsiloxane polymers. IV. N‐halamine siloxane‐functionalized silica gel

The monomer 5,5‐dimethyl‐3‐(3′‐triethoxysilylpropyl)hydantoin and its hydrolysis product polymer poly[3‐(5,5‐dimethylhydantoinylpropyl)hydroxysiloxane] were employed to functionalize the surfaces of silica gel particles in order to produce an adhered film that becomes biocidal upon chlorination with dilute sodium hypochlorite bleach. The biocidal efficacy of the functionalized silica gel was demonstrated in a cartridge filter experiment against the bacterial pathogens Staphylococcus aureus and Escherichia coli O157:H7. Complete 6 log inactivations of the two bacterial species were observed within 30 s of contact. Moreover, upon loss of biocidal activity due to depletion of bound chlorine, the coated silica gel particles could be recharged by further exposure to dilute bleach. Potential uses of the biocidal silica gel include disinfection and odor control in water treatment facilities and recirculating baths. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3448–3454, 2006     

Electrochemical performance of nanocrystalline Li3V2(PO4)3/carbon composite material synthesized by a novel sol–gel method

A novel sol–gel method based on V₂O₅·nH₂O hydro-gel was developed to synthesize nanocrystalline Li₃V₂(PO₄)₃/carbon composite material. In this route, V₂O₅·nH₂O hydro-gel, NH₄H₂PO₄, Li₂CO₃ and high-surface-area carbon were used as starting materials to prepare precursor, and the Li₃V₂(PO₄)₃/carbon was obtained by sintering precursor at 750 °C for 4 h in flowing argon. The sol–gel synthesis ensures homogeneity of the precursors and improved reactivity. The sample was characterized by XRD, SEM and TEM. X-ray diffraction results show Li₃V₂(PO₄)₃ sample is monoclinic structure with the space group of P2₁/n. The TEM image indicates that the Li₃V₂(PO₄)₃ particles modified by conductive carbon are about 70 nm in diameter. The Li₃V₂(PO₄)₃/carbon system showed that the discharge capacities in the first and 50th cycle are about 155.3 and 143.6 mAh/g, respectively, in the range of 3.0–4.8 V. The sol–gel method is fit for the preparation of Li₃V₂(PO₄)₃/carbon composite material which may offer some favorable properties for commercial application.     

Large deformation and ultimate properties of biopolymer gels: 2. Mixed gel systems

Biphasic, mixed gels of agarose and gelatin were prepared, and their mechanical behaviour in tensile tests was determined, up to failure, utilising four decades of (constant) strain rate. The behaviour of pure agarose and pure gelatin in such tests has been determined previously. Suitable ‘blending-laws’ relating the small deformation shear modulus of the composite to the moduli of the component phases have also been discussed elsewhere. This report extends the latter treatment to the more aggressive large deformation regime, deriving bounds for modulus and break stress which closely model observed behaviour.     

以硅胶为载体的茂金属催化剂研究进展

综述了近年来硅胶载体经甲基铝氧烷(MAO)化学处理后负载茂金属催化剂的一些研究进展，指出硅胶的化学活化是茂金属催化剂负载化的关键，单组分化学处理剂处理硅胶载体不能完全满足人们对负载型茂金属催化剂烯烃聚合的需求，采用含MAO的多组分化学处理剂化学活化硅胶后负载催化剂是该领域发展的趋势。     

Surface functionalized colloidal silica particles from an inverse microemulsion sol gel process

Colloidal silica particles are prepared via a sol gel technique carried out in an inverse microemulsion of water in a toluene solution of tetraethoxysilane (TEOS), stabilized by either an anionic surfactant AOT or isopropanol. Functionalized material was obtained using a functional coupling agent (RO)₃Si(CH₂)₃ X, X being a functional group such as methacryloyl, thiol, vinyl, amino group, or a chlorine atom. Functionalization can be carried out either directly via the direct copolycondensation of TEOS and the coupling agent, or in a two-step process involving a core-shell polycondensation of the coupling agent onto preformed silica particles. Kinetic studies of the copolycondensation are carried out using either²⁹Si NMR analysis or liquid chromatography. They show that the consumption of TEOS is more rapid than that of the coupling agent. The materials are characterized both chemically (elemental analysis, FTIR,¹³C and²⁹Si NMR CPMAS analysis), and by their particle size. The silica functionalized with a polymerizable methacryloyl group is encapsulated by a polymer layer in an inverse emulsion polymerization of acrylic acid. After inversion of the emulsion in water, the resulting material is covered with a layer of hydrophobic polymer in a conventional emulsion polymerization.     

Preparation and reaction mechanistic characterization of sol–gel indium/alumina catalysts developed for NO x reduction by propene in lean conditions

The impregnation and sol–gel preparation methods were investigated to develop high activity catalysts and understand the significance of the indium–aluminium interaction on aluminasupported indium catalysts in NO _x reduction with propene. Active In/alumina catalysts with a very high surface area (270 m²/g) and thermal stability were prepared in controlled conditions by sol–gel processing. When Al isopropoxide and In nitrate in ethyl glycol were used as precursors in aqua media, indium atoms were incorporated evenly distributed as a thermally stable form in the aluminium oxide lattice structure. In wet impregnation it was beneficial to use a certain excess of aqueous In solution (volumes of solution : pores = 2 : 1) to have the highest NO _x reduction activity. The catalyst containing dispersed Al on In oxide (58 wt% In, phaseequilibrium preparation method) showed activity at lower temperatures than any other In–Al oxide catalyst or pure In₂O₃. The adsorption of different reaction intermediates on alumina and stable In₂O₃ sites were detected by FTIR studies. In/alumina catalysts have active sites to oxidize NO to NO₂, partially oxidize HC, form the actual reductant which contains N–H or N–C bonding and react with NO to dinitrogen. The cooperation with indium and aluminium was evident even in the mechanical mixture of sol–gel prepared alumina (301 m²/g) and In₂O₃ powders (27 m²/g), where the probability for molecularscale intimate contact between indium and aluminium sites was very low (particle size 10–250 m). Shortlived gaseous intermediates and surface migration are the possible reasons for the high catalytic activities on the two physically separated active sites both necessary for the reaction sequence.     

UV photo‐stabilization of tetrabutyl titanate for aramid fibers via sol–gel surface modification

Tetrabutyl titanate was used as sol–gel precursor of a nanosized TiO₂ coating to improve the photo‐stability of aramid fibers. The nanosized TiO₂ coating was characterized by XRD and XPS. The influence of the TiO₂ coating on photo‐stability of aramid fibers was investigated by an accelerated photo‐ageing method. The photo‐stability of aramid fiber showed obvious improvement after coating. After 156 h of UV exposure, the coated fibers showed less deterioration in mechanical properties with the retained tensile strength and elongation at break greater than 36 and 50% of the original values, respectively, whereas the uncoated fibers degraded completely and became powdery. SEM analysis showed no significant surface morphological change on the coated fiber after the exposure, while some latitudinal crack fractures appeared on the uncoated aramid fiber. The effect of the nanosized TiO₂ coating was also well demonstrated by examining the difference of distributions of C1s in XPS deconvolution analysis on the surface of uncoated/coated fibers with increasing UV exposure time. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 3113–3119, 2007