Highly active and reusable catalyst for fries rearrangement of phenyl acetate

Silica-12-tungstophosphoric acid core-shell nanoparticles were prepared by sol-gel method followed by steaming. The catalytic activity of fresh and steamed catalysts was studied in Fries rearrangement of phenyl acetate. The reaction parameters, such as catalyst loading and reaction temperature, were optimized. The structural properties of the prepared catalysts were analyzed by X-ray diffraction and transmission electron microscopy techniques. The nature and strength of acid sites in the catalysts were analyzed by pyridine adsorption followed by infrared spectroscopy and differential scanning calorimetry measurements. The XRD and TEM analyses confirm the formation of silica-12-tungstophosphoric acid core-shell nanoparticles during steaming process. Acidity measurement indicates that both fresh and steamed catalyst samples carry weak acid sites and Brøsted acid sites. In addition, the steaming of heteropoly acid contained silica enhances the strength of Brøsted acid sites. The catalytic activity of fresh as well as steamed catalysts in liquid-phase Fries rearrangement showed that the steam treated sample exhibits higher conversion and selectivity to the desired product compared to the fresh catalyst sample. The higher activity of steam treated catalysts has been explained in terms of surface acidity of the catalysts. Reusability of the steamed catalyst shows that there is no appreciable change either in the conversion rate or product selectivity.     

二氧化硅负载磷钼钒酸铯选择性催化硝化苯酚为邻硝基苯酚

采用溶胶-凝胶法制备了二氧化硅负载磷钼钒酸铯催化剂,利用XRD、红外、SEM以及物理吸附等技术手段对催化剂进行了表征分析,并以稀硝酸（30%）为硝化剂,考察了该催化剂对苯酚硝化反应的催化性能,系统研究了反应时间、催化剂用量、硝酸与苯酚用量以及催化剂重复利用等对催化反应的影响。 结果表明,制备的负载磷钼钒酸铯催化剂具有典型的Keggin结构,在温和的苯酚硝化反应条件下,表现出优良的催化活性和高的邻硝基苯酚选择性,在实验优化条件下,邻硝基苯酚收率达到88%,催化剂回收方便可多次重复使用。 负载磷钼钒酸铯催化苯酚硝化反应结合水蒸汽蒸馏提供了一种简单可行的制备邻硝基苯酚的方法。     

The preparation of silica entrapped homogeneous hydrogenation catalysts by conventional and ionic liquid mediated sol-gel routes

[RhCl(PPh₃)₃] has been entrapped inside silica matrices by two methods: a conventional sol-gel synthesis in ethanol/water and a new route performed in an ionic liquid. The activity of these heterogenised catalysts has been tested for the hydrogenation of styrene. The catalyst prepared in an ionic liquid was found to be more active and have low Rh leaching.     

Preparation and properties of amino-terminated anionic waterborne-polyurethane-silica hybrid materials through a sol-gel process in the absence of an external catalyst

A series of polymer-silica hybrid materials consisting of amino-terminated anionic waterborne-polyurethane (WPU) and inorganic silica particles have been prepared through a sol-gel process in the absence of an external catalyst. Typically, amino-terminated anionic WPU was first synthesized from polycaprolactone, dimethylol propionic acid, and 4,4′-methylenebis(cyclohexyl isocyanate) with specific molar ratios, followed by further reaction with triethylamine and triethylene tetramine to give as-prepared WPU. The WPU obtained was characterized by FTIR spectroscopy and gel permeation chromatography. Subsequently, a series of hybrid materials with different silica contents were prepared by performing sol-gel reactions with tetraethyl orthosilicate (TEOS) in an amino-terminated WPU matrix without the addition of an external catalyst. This was followed by examination by transmission electron microscopy and ²⁹Si solid-state NMR. The terminated primary amine groups attached to the as-prepared WPU chains functioned as an internal base catalyst for the sol-gel process of TEOS. The effect of composition on the thermal stability, mechanical strength, surface wettability, and optical clarity of the hybrid materials was evaluated by the thermogravimetric analysis, dynamic mechanical analysis, contact angle measurement, and UV-visible transmission spectroscopy, respectively.     

The Co‐Entrapment of a Homogeneous Catalyst and an Ionic Liquid by a Sol–gel Method: Recyclable Ionogel Hydrogenation Catalysts

Molecular hydrogenation catalysts have been co‐entrapped with the ionic liquid [Bmim]NTf₂ inside a silica matrix by a sol–gel method. These catalytic ionogels have been compared to simple catalyst‐doped glasses, the parent homogeneous catalysts, commercial heterogeneous catalysts, and Rh‐doped mesoporous silica. The most active ionogel has been characterised by transmission electron microscopy, X‐ray photoelectron spectroscopy, and solid state NMR before and after catalysis. The ionogel catalysts were found to be remarkably active, recyclable and resistant to chemical change.     

Catalytic upgrading of lignin derived bio-oil model compound using mesoporous solid catalysts

The catalytic upgrading of a lignin-derived bio-oil model compound, the hydrodeoxygenation of guaiacol, was performed using mesoporous solid catalysts. Platinum supported on silica and mesoporous silica (SBA-15 and KIT-6) were used as catalysts. The level of platinum incorporation and aluminum grafting did not alter the physical properties of the supports, such as surface area and pore size distribution. On the other hand, these treatments drastically affected the catalytic activities. A catalyst with platinum alone converted guaiacol to oxygenate compounds. In contrast, a series of catalysts with both platinum incorporation and aluminum grafting enhanced hydrodeoxygenation by converting guaiacol into hydrocarbons (cyclohexane and benzene). A comparison of the catalyst supports revealed the ordered mesoporous silica, SBA-15 and KIT-6, with high surface area, to have a higher hydrocarbon yield than conventional silica.     

Hybrid silica materials derived from Hoveyda-Grubbs ruthenium carbenes. Electronic effects of the nitro group on the activity and recyclability as diene and enyne metathesis catalysts

The preparation of several organic-inorganic hybrid materials by sol-gel process derived from Hoveyda-type monomers is described. One of them presents a nitro group at the para position with respect to the alkoxy moiety. These materials were treated with Grubbs catalysts to generate the corresponding Hoveyda-Grubbs carbene ruthenium complexes covalently bonded to the silica matrix, which were tested as recyclable catalysts for diene and enyne RCM. Electronic effects of the nitro group resulted in enhanced activity of the catalyst. Whereas the recyclability decreased in RCM of dienes, the presence of this electron-withdrawing group was highly advantageous for the RCM of enynes, the reusability being greatly improved.     

Nuclear magnetic resonance study of the vapor contribution to diffusion in silica glasses with micrometer pores partially filled with liquid cyclohexane or water

The contribution of the vapor phase to molecular diffusion in porous silica glass (Vitrapor#5; mean pore diameter 1 micrometer) partially filled with cyclohexane (nonpolar) or water (polar) was investigated with the aid of field-gradient NMR diffusometry. Due to the vapor phase, the effective diffusion coefficient of cyclohexane increased up to ten times relative to the value in bulk liquid upon reduction of the pore space filling factor. On the other hand, the effective diffusion coefficient of water first decreases and then increases when the liquid content is reduced. A two-phase exchange theory is presented accounting well for all experimental diffusion features. The diffusion behavior in the samples with micrometer pores under investigation here is in contrast to previous findings for the same solvents in a material with nanometer pores (Vycor; mean pore diameter 4 nm) where the fast-exchange limit had to be assumed [Ardelean et al., J. Chem. Phys. 119, 10358 (2003)]. It is concluded that the pore size plays a crucial role for the relevance of molecular exchange limits relative to the experimental diffusion/exchange time.     

Supported ionic liquid phase rhodium nanoparticle hydrogenation catalysts

Rh(0) nanoparticles (ca. 4 nm) dispersed in an ionic liquid (1-n-butyl-3-methylimidazolium tetrafluoroborate) were immobilized within a silica network, prepared by the sol-gel method. The effect of the sol-gel catalyst (acid or base) on the encapsulated ionic liquid and Rh(0) content, on the silica morphology and texture, and on the catalyst alkene hydrogenation activity was investigated. The Rh(0) content in the resulting xerogels (ca. 0.1 wt% Rh/SiO(2)) was shown to be independent of the sol-gel process. However, acidic conditions afforded higher contents of encapsulated ionic liquid and xerogels with larger pore diameters, which in turn might be responsible for the higher catalyst activity in hydrogenation of the alkenes.     

NMR cryoporometry with octamethylcyclotetrasiloxane as a probe liquid. Accessing large pores

Octamethylcyclotetrasiloxane is presented and investigated as probe liquid for NMR cryoporometry or DSC-based thermoporometry. This compound which may imbibe into both hydrophilic and hydrophobic pores is shown to exhibit a melting point depression that is larger than that for other cryoporometric probe materials such as cyclohexane. The transverse relaxation time differs by more than three orders of magnitude between the solid and liquid states, separated by a sharp phase transition. Hence, as demonstrated in controlled pore glasses, octamethylcyclotetrasiloxane can provide pore size distributions for materials with pore sizes up to the micrometer range.     

Molecular exchange dynamics in partially filled microscale and nanoscale pores of silica glasses studied by field-cycling nuclear magnetic resonance relaxometry

Nuclear magnetic spin-lattice relaxation experiments have been performed in partially filled porous glasses with wetting and nonwetting fluids. The frequency dependence of the spin-lattice relaxation rate in Vycor (4 nm pores) and VitraPOR #5 (1 microm pores) silica glasses was studied as a function of the filling degree with the aid of field-cycling NMR relaxometry. The species of primary interest were water ("polar") and cyclohexane ("nonpolar"). Spin-lattice relaxation was examined in the frequency range from 1 kHz to 400 MHz with the aid of a field-cycling NMR relaxometer and an ordinary 400 MHz NMR spectrometer. Three different mobility states of the fluid molecules are distinguished: The adsorbed state at the pore walls, the bulklike liquid phase, and the vapor phase. The adsorbate spin-lattice relaxation rate is dominated by the "reorientation mediated by translational displacements" (RMTD) mechanism taking place at the adsorbate/matrix interface at frequencies low enough to neglect rotational diffusion of the molecules. The experimental data are analyzed in terms of molecular exchange between the different mobility states. Judged from the dependence of the spin-lattice relaxation rates on the filling degree, limits for slow and fast exchange (relative to the RMTD time scale) can be distinguished and identified. It is concluded that water always shows the features of slow exchange irrespective of the investigated pore sizes and filling degrees. This is in contrast to cyclohexane which is subject to slow exchange in micrometer pores, whereas fast exchange occurs in nanoscopic pores. The latter case implies that the vapor phase contributes to molecular dynamics in this case at low filling degrees while it is negligible otherwise.     

苯基磺酸官能化中孔硅基材料的制备及催化性能研究

通过溶胶-凝胶法制得了苯基聚硅氧烷, 进一步磺化制备了苯基磺酸官能化的中孔硅基催化材料, 并通过BET, SEM和固体核磁技术对其进行了表征. BET结果表明, 该催化剂比表面积为722 m²/g, 平均孔径为9.06 nm, 孔容0.59 mL/g. ¹³C CPMAS NMR和²⁹Si CPMAS NMR表征显示磺酸基键合于苯环间位, 苯基以共价方式进入无机-有机杂化硅基材料的内部结构. 该固体酸的活性中心磺酸基在表面呈均匀分布, 在芳族羧酸和取代酚的直接酯化反应中表现出优异的催化性能.     

Sol-Gel Derived Binder for Inorganic Composites

A new low cost inorganic binder system for large volume products like fiber insulation, building materials, etc. has been developed based on sol-gel technology. The precursor for the binder system is an amorphous mineral raw material containing silica as the major component. The sol was prepared by dissolving the amorphous mineral material in formic acid and the mineral was dissolved in a few hours dependent on the molarity of the formic acid. The sol stability was dependent on the solids content and the pH. The gel formation was studied using light scattering and NMR. The results show a growing particle size of particles mainly consisting of silica while the other cations were dissolved in the pore liquid. During the drying of the wet gels, salts of these cations were crystallized in the pores and further decomposed during heating. The derived binder shows good wetting properties to mineral fiber surfaces and a good strength of paper-binder composites. The new binder system applicable to approximately 800°C has a great potential as a substitute for some traditional organic systems.     

Characterization of the Structure and Catalytic Activity of Pt/Sepiolite Catalysts

Four catalysts containing 1% w/w Pt deposited on various sepiolite supports were prepared. Two natural sepiolites and another two obtained by acid treatment of one of them were used. Both the sepiolites used as metal supports and the catalysts were characterized for structure and surface properties, using (1)H and (29)Si MAS NMR spectroscopy, and (29)Si CP/MAS NMR spectroscopy, in addition to hydrogen, pyridine, and CO(2) chemisorption measurements. The activity of the catalysts in the hydrogenation of benzene to cyclohexane and the dehydrogenation of cyclohexane to benzene was examined and the catalyst supported on the natural sepiolite called Pangel was found to be the most active of all. Copyright 2000 Academic Press.     

Catalytic cracking of polyethylene waste in horizontal tube reactor

In this study catalytic and thermal cracking of polyethylene waste were investigated in continued tube reactor system. HZSM-5 and equilibrium FCC type catalysts were tested. Both the resistance to deactivation and the regeneration process of the catalyst were studied. Reaction temperature of 545 °C and residence time of 20 min were used during the cracking treatment. The reaction products were analyzed and the textural properties of catalysts were also determined. It was found that after the first reaction run the FCC catalyst lost 75% of its cracking activity, in case of HZSM-5 the rate of deactivation was higher. The cracking activity of catalyst could be improved by regeneration process with only 2-3% compared to the coked catalyst. The isomerisation effect of the catalysts was also observed. The effect of coked FCC catalyst could be improved by the regeneration process with 50% in case of HZSM-5 it was only 25%.     

Removal of Zinc Ions by Sol-Gel Silica Doped with Cibacron Blue

Chemically doped sol-gel silica has been developed by entrapping organic dye cibacron blue as a complexing reagent in porous silica prepared by the sol-gel method for removal of metal ions from water samples. In the doped sol-gel silica, the large reagent molecules are entrapped inside the pores while small metal ions can diffuse into the pores where they are complexed by the reagent and retained inside the pores. This new solid sorbent was tested for removal of Zn(II) from aqueous solutions. The kinetics, isotherm, and pH effect of the removal were investigated. With a loading of 0.10 mmol cibacron blue/g, the sol-gel silica sorbent had a capacity of 0.09 mmol Zn/g. It was demonstrated that the sol-gel silica sorbent could be regenerated and reused repeatedly.     

介孔分子筛SBA-15-SO3H催化合成油酸甲酯

在成功合成出含磺酸基的介孔分子筛SBA-15-SO3H的基础上，用于油酸与甲醇的酯化反应，考察该催化剂的催化性能，结果表明：在高级脂肪酸的酯化反应中，SBA-15-SO3H催化剂的活性高于沸石分子筛，与等摩尔数的硫酸的活性接近。考察了反应条件对SBA-15-SO3H催化剂性能的影响，得到油酸与甲醇酯化反应的最佳条件：反应温度60 ℃，甲醇与油酸的原料比为2∶1（摩尔），催化剂与原料比为1.5∶35（重量）。最后对催化剂的稳定性进行了考察，反应结果认为该催化剂在重复使用过程中活性未发生明显变化，反应前后的XRD分析结果认为，SBA-15-SO3H具有较高的水热稳定性。     

Modulated large-pore mesoporous silica as an efficient base catalyst for the Henry reaction

In this study, mesoporous silica materials with tuned pores and surface areas were successfully synthesized by adjusting the amount of applied hexane and controlling the hydrothermal temperature. The synthesized silica materials were then functionalized by an amine group to produce solid base catalysts and be applicable as efficient heterogeneous base catalysts for the Henry reaction. The mesoporous silica catalysts possessing large-pores and surface area expose their active catalytic sites and thereby improve contacts with reactants fulfilling the reactions expeditiously in comparison with solid base catalysts possessing small-pores and surface area. The results indicated that the yield of the products is significantly dependent on the structure of the applied solid base catalysts. The modulated large-pore solid base catalysts presented high catalytic activity in Henry reactions and could be reused for five consecutive cycles.     

A new mesoporous micelle-templated silica route for enzyme encapsulation

A new mesoporous micelle-templated silica (MTS) route for enzyme encapsulation is presented. The pore structure is given by a new association oflecithin (double chain surfactant) and dodecylamine as cosurfactant. To enhance and to well protect the enzyme activity, lactose was loaded in the synthesis. The mixed-micelles give after the addition of tetraethyl orthosilicate a well-ordered mesoporous material with a spongelike rigid structure stable after calcination at 550 degrees C. The size of the pores lies between 30 and 40 A, matching well with the size of the lipases. The activity of this heterogeneous catalyst was tested in the hydrolysis of the ethylthiodecanoate. These new biocatalysts were very active, more than hydrophobic sol-gel materials and commercially available sol-gel encapsulated lipase. This new MTS synthesis route allows one to encapsulate in one-step various enzymes, even those that are very fragile.     

干气制乙苯结炭沸石催化剂烧炭再生研究

以苯和炼厂干气中的乙烯合成乙苯结炭催化剂为研究对象，对结炭催化剂上积炭的性质及不同温度下的烧炭情况进行了研究，考察了再生前后催化剂的酸性、活性、晶相、比表面及孔结构等性能的变化。结果表明，催化剂孔的内表面积炭占据了酸性中心，致使催化剂活性降低；在烧炭时温度大于300 ℃才开始烧炭，最佳烧炭温度应控制在500℃～550℃，600 ℃可将炭完全烧净。程序升温脱附（TPD）实验表明，550 ℃实验室烧炭后催化剂酸种类及其比例可完全恢复，酸量可恢复到95%。晶相、孔结构基本未变，催化剂的活性得到良好恢复。