Catalytic dehydration of 1,2-propanediol into propanal

Vapor-phase catalytic dehydration of 1,2-propanediol was investigated over several catalysts, such as acidic oxides and supported heteropoly acids. These acids catalyze the dehydration of 1,2-propanediol to produce propanal. In particular, silica-supported silicotungstic acid showed the highest catalytic activity in the formation of propanal. At low conversions, however, propanal reacted with another 1,2-propanediol to produce a cyclic acetal (2-ethyl-4-methyl-1,3-dioxolane). Such acetal formation reduced the selectivity to propanal. Under optimum reaction conditions, 100% conversion was attained with propanal selectivity higher than 93 mol% at 200 °C.     

Rhodium Containing Magnetic Nanoparticles: Effective Catalysts for Hydrogenation and the 1,4-Addition of Boronic Acids

New efficient rhodium catalysts supported on superparamagnetic iron oxide nanoparticles (NPs) have been prepared using a novel method involving sulfonated triphenylphosphine ligands. They successfully promote the hydrogenation of olefins as well as the addition of arylboronic acids to dimethyl itaconate (ItMe₂) in water for up to 10 recycles. The catalysts were stable towards leaching of the metal complexes and were readily recovered by applying an external magnetic field.     

Effect of active site distribution on liquid-phase olefin hydrogenation over polymer-supported palladium complex

Chloromethylated polystyrene beads with different distributions have been prepared and phosphinated. PdCl₂ was supported on the phosphinated supports to give polymer-supported Pd complex catalysts with different active site distributions. The effect of active site distribution on catalytic activity was investigated in the hydrogenation of olefins.     

Characteristics of phosphinated styrene-divinylbenzene copolymer containing RuCl2(PPh3)3 for 1-hexene isomerization

Summary Chloromethylated styrene-divinylbenzene(S-DVB) copolymer beads were prepared in macroporous type via direct copolymerization of chloromethylstyrene and divinylbenzene and then phosphinated. Dichlorotris(triphenylphosphine)ruthenium, RuCl₂(PPh₃)₃, was anchored on the phosphinated S-DVB copolymer, and then applied to the isomerization of 1-hexene. The physical properties of the catalysts varied with degree of crosslinking and type of pore-forming agents. Anchoring the ruthenium complex onto the phosphinated S-DVB resin favored trans-isomer and stabilized the catalyst in the isomerization of 1-hexene comparing with the homogeneous reaction. Solvent effects on catalytic activities of polymer-anchored catalysts were also discussed.     

Disperse Amphiphilic Submicron Particles as Non‐Covalent Supports for Cationic Homogeneous Catalysts

A simple method for the effective immobilization of homogeneous catalysts on polystyrene colloids via non‐covalent binding is demonstrated. Stable latices with sufficiently high loading of accessible borate anions are prepared via emulsion polymerization. Incorporation of cationic rhodium complexes, supported via their borate counter‐anion is efficient, and these supported homogeneous catalysts maintain constant catalytic activity for CC hydrogenation during several recycles, with very low metal leaching.     

A suitable synthesis of azlactones (4-benzylidene-2-phenyloxazolin-5-ones and 4-alkylidene-2-phenyloxazolin-5-ones) catalyzed by silica–alumina supported heteropolyacids

Eleven examples of azlactones (4-benzylidene-2-phenyloxazolin-5-ones and 4-alkylidene-2-phenyloxazolin-5-ones) were prepared via an Erlenmeyer-type synthesis from aromatic aldehydes, hippuric acid and acetic anhydride was added to the hot solution as a dehydrating agent. Molybdophosphoric or tungstophosphoric acids supported on silica–alumina, obtained by the sol–gel method, catalyze the reaction. The prepared catalysts were characterized by X-ray diffraction and diffuse reflectance spectroscopy. The specific surface area of the catalysts was determined by the nitrogen adsorption/desorption at 196 °C technique, and the catalyst acidity was measured by potentiometric titration with n-butylamine. The heteropolyacid amount removed from the catalysts during the leaching with toluene was lower than 1%. The products were obtained with high conversion and selectivity. The yields were in the 87–96% range for the majority of the selected samples, with the exception of the azlactones synthesized from 2-nitrobenzaldehyde and cyclohexanone, which gave yields in the 70–80% range. The same catalysts were used several times without appreciable loss of their catalytic activity. A rational mechanism for the azlactone formation catalyzed by the supported heteropolyacid is proposed.     

丁辛醇废铑催化剂焙烧铑回收工艺研究

每千克丁辛醇装置废铑催化剂中含有几百至几千毫克铑,铑价格昂贵,高效回收其中的铑十分必要,目前资料报道的铑回收方法或铑损失大,如萃取法、吸附分离法、焚烧法;或效率低,如液相消解法。针对这些问题,探索了一种焙烧和液相消解相结合的铑回收工艺,并重点对焙烧工艺进行了研究。结果表明,废铑催化剂首先经蒸馏浓缩得到铑渣,然后向铑渣中添加适当倍数的二氧化硅后,采取一定的程序升温焙烧,所得焙烧铑灰再液相消解得到可溶性铑盐,该过程效率高,铑收率大于99%。     

Ammonia removal from effluent streams of wet oxidation under high pressure

The formation of ammonia is inevitable during industrial-scale wet oxidation of wastewater if nitrogen-containing compounds are present. This undesired side-reaction requires additional measures for disposal. Common routes are either the use of noble metal-containing catalysts in the first oxidation step or end-of-pipe treatment. Problems rise for example from the insufficient stability of solid catalysts against hydrothermal impact. As most of the wet oxidation processes run at elevated pressure and temperature, running the heterogeneously catalysed oxidation of ammonia in the gas phase in a downstream reactor could protect the catalysts mainly from leaching and offers an economic alternative by avoiding loss of unused oxygen after depressurisation. This work reports on the oxidation of ammonia with air in steam atmosphere using Cu,Cr-containing supported and bulk catalysts at 235–305 °C and 30–60 bar. A copper chromite catalyst gave best performance (86% conversion at 305 °C, 45 bar, contact time 1 s). The spinel-type phase CuCr₂O₄ seems to be the active phase and shows superior stability. The results indicate that phase behaviour of water strongly influences activity and lifetime of catalysts. Characterisation of the solids (BET, XRD, XPS, ICP) proved that deactivation is mainly caused by leaching of Cr(VI) species from catalysts when the reaction runs near to dew point of water and by loss of BET surface area of supported catalysts due to hydrothermal impact.A member of the EU-funded Coordination Action of Nanostructured Catalytic Oxide Research and Development in Europe (CONCORDE).     

Noble metal catalysts supported on gadolinium doped ceria used for natural gas reforming in fuel cell applications

An attractive possibility to simplify a fuel cell system would be the use of a sulfur-tolerant reforming catalyst. In an effort to find such a catalyst, platinum, rhodium and ruthenium catalysts supported on ceria doped with 20% gadolinium and on pure ceria were synthesized and characterized. A temperature-programmed reduction study of the reduction behavior of the catalysts showed that the doping of ceria with gadolinium enhances the low temperature reduction, while the high temperature reduction is suppressed. The activity as well as the stability of the catalysts can be correlated with the reducibility of the materials. The most stable catalyst, rhodium supported on gadolinium doped ceria, shows promising sulfur-tolerance.     

Polymer and Silica Supported Tridentate Schiff Base Vanadium Catalysts for the Asymmetric Oxidation of Ethyl Mandelate – Activity,Stability and Recyclability

Homogeneous tridentate Schiff base vanadium catalysts derived from salicylaldehydes and tert‐leucinol or tert‐leucine are known to be excellent catalysts for the asymmetric oxidation of α‐hydroxy esters including ethyl mandelate. Herein, new analogous supported, semi‐soluble and insoluble catalysts are synthesized and their activities relative to the homogeneous catalyst are reported. The new catalysts are characterized by ¹H and ¹³C NMR spectroscopy, mass spectrometry (EI, ESI, FAB), X‐ray crystallography, elemental analysis, gel permeation chromatography (GPC), Fourier transform infrared (FT‐IR) spectroscopy, and nitrogen physisorption. The effects of support material, synthesis procedure, and reaction solvent are examined to probe the utility of these catalysts. Linear poly(styrene) supported catalysts are partially soluble under the reaction conditions, and it is shown that the soluble species contribute significantly to the catalytic reactivity. Insoluble catalysts based on the same vanadyl complexes supported on cross‐linked poly(styrene) resin or mesoporous silica allow for catalyst recovery and recycle, showing equivalent selectivities over multiple reaction cycles. The mesoporous silica supported catalyst exhibits greater selectivity than the analogous homogeneous and polymer supported catalysts. Rigorous recycle studies show a loss of activity in each recycle, which is attributed to the decomposition of some portion of the vanadyl complexes in each cycle.     

Pd/SiO2 as Heterogeneous Catalyst for the Heck Reaction: Evidence for a Sensitivity to the Surface Structure of Supported Particles

The contact of Pd(AcO)₂ in solution with thiouric tethered to a silica led to the formation of supported nanoparticles (ca. 2 nm in size) active in the Heck reaction, quite sensitive to the palladium leaching. A stable supported phase was obtained by subsequent calcination, but the catalytic activity resulted strongly dependent on the calcination temperature. Such a behaviour was related to differences in the surface structure of the supported particles, as those monitored by IR spectroscopy of CO adsorbed on catalysts reduced at various temperatures.     

Characterization of bimetallic rhodium-germanium catalysts prepared by surface redox reaction

The preparation of bimetallic rhodium-germanium/silica and rhodium-germanium/alumina catalysts was investigated by controlled surface reaction. Their catalytic performances were measured for two gas phase reactions (toluene hydrogenation at 323 K and cyclohexane dehydrogenation at 543 K) and for a liquid phase reaction (citral hydrogenation at 343 K).

Elemental analysis of bimetallic catalysts showed that germanium can be deposited by redox reaction between hydrogen activated on a parent monometallic rhodium catalyst and germanium tetrachloride dissolved in water (catalytic reduction method). EDX microanalysis of rhodium-germanium/silica catalysts indicated that rhodium and germanium were deposited in close contact on the silica support. However, on alumina-supported catalysts, germanium deposition occurred also separately on the support. For the different test reactions, the catalytic properties of rhodium were strongly altered by the addition of germanium. On alumina-supported catalysts, interesting catalytic effects were observed in citral hydrogenation when not only close contact exists between both metals but when, in addition, the second metal was deposited on the support in the close vicinity of rhodium.     

XPS and EXAFS study of supported PtSn catalysts obtained by surface organometallic chemistry on metals: Application to the isobutane dehydrogenation

In this work, well defined alumina and silica supported Pt and PtSn catalysts were prepared by surface organometallic reactions and were characterized by TEM, XPS and EXAFS. These catalysts were tested in the catalytic dehydrogenation of isobutane. XPS results show that tin is found under the form of Sn(0) and Sn(II,IV), being the percentage of Sn(0) lower for alumina supported than for silica supported catalysts. Tin modified platinum catalysts, always show a decrease of approximately 1 eV in the BE of Pt, what would be indicative of an electron charge transfer from tin to platinum. When the concentration of Sn(0) is high enough, in our case Sn(0)/Pt ∼ 0.3, EXAFS experiments demonstrated the existence of a PtSn alloy diluting metallic Pt atoms, for both PtSn/γ-Al₂O₃ and PtSn/SiO₂. This PtSn alloy seems to be not active in the dehydrogenation reaction; however, it is very important for selectivity and stability, inhibiting cracking and coke formation reactions. The ensemble of our catalytic, XPS and EXAFS results, show that bimetallic PtSn/γ-Al₂O₃ catalysts, prepared via SOMC/M techniques, can be submitted to several sequential reaction–regeneration cycles, recovering the same level of initial activity each time and that the nature of the catalytic surface remains practically without modifications.     

Hydrogenation of Carboxylic Acids and Synergistic Catalysts

Rhenium heptoxide, a known catalyst for hydrogenation of car-boxylic acids to alcohols, forms synergistic combinations with palladium, platinum, rhodium and ruthenium catalysts. This effect is also seen at lower presures (500 psi). Synergism is also mainfest when rhenium and palladium (or rhodium) are used as supported catalysts on silica and used in a flow mode. An interaction of un-known nature between the metals suggests itself. The process is not very efficient at lower pressures giving lower conversion in the flow mode. At higher temperatures needed for higher rates, significant participation of side reactions such as decarboxylation of the acid and hydrogenolysis of the alcohol occurs yielding hydrocarbons.     

Comparison of Au Catalysts Supported on Mesoporous Titania and Silica: Investigation of Au Particle Size Effects and Metal-Support Interactions

Au catalysts supported on mesoporous silica and titania supports were synthesized and tested for the oxidation of CO. Two approaches were used to prepare the silica-supported catalysts utilizing complexing triamine ligands which resulted in mesoporous silica with wormhole and hexagonal structures. The use of triamine ligands is the key for the formation of uniformly sized 2–3 nm Au nanoparticles in the silica pores. On mesoporous titania, high gold dispersions were obtained without the need of a functional ligand. Au supported on titania exhibited a much higher activity for CO oxidation, even though the Au particle sizes were essentially identical on the titania and the wormhole silica supports. The results suggest that the presence of 2–3 nm particle size alone is not sufficient to achieve high activity in CO oxidation. Instead, the support may influence the activity through other possible ways including stabilization of active sub-nanometer particles, formation of active oxygen-containing reactant intermediates (such as hydroxyls or O₂ ^?), or stabilization of optimal Au structures.     

负载金属卟啉用于催化氧化反应的进展

综述了近年来国内外金属卟啉在固载催化领域应用进展,包括:分子筛,蒙脱石,高岭石,硅胶,玻璃,炭黑,金等无机载体,以及聚苯乙烯,树脂,橡胶,高分子多糖,金属卟啉聚合物等有机载体.固载金属卟啉模拟酶催化剂在催化氧化反应中将有更大的应用前景.     

Dendritic SBA-15 supported Wilkinson's catalyst for hydroformylation of styrene

After PAMAM (polyamidoamine) dendrimers have been successfully grown in SBA-15 mesoporous materials, Wilkinson's catalyst (RhCl(PPh₃)₃) precursor has been tethered on these dendritic supports to produce heterogeneous catalysts for hydroformylation reaction of styrene. SBA-15 has been functionalized by two methods. In the passivation method, the silanols outside the SBA-15 pores have been passivated to preclude the rhodium precursor to be tethered outside the channels. The rhodium catalysts supported in the pore channels of this passivated SBA-15 show positive dendritic effects in enhancing the catalytic activity, regio-selectivity and stability of the catalyst by minimizing the leaching of the rhodium complex catalyst from the catalyst support to the liquid-phase media.     

Magnetically Recoverable Nanoparticles: Highly Efficient Catalysts for Asymmetric Transfer Hydrogenation of Aromatic Ketones in Aqueous Medium

Two magnetic chiral iridium and rhodium catalysts were prepared via directly postgrafting 1,2‐diphenylethylenediamine‐derived organic silica or 1,2‐cyclohexanediamine‐derived organic silica onto the silica‐coated iron oxide nanoparticles followed by complexation with iridium(III) or rhodium(III) complexes. During the asymmetric transfer hydrogenation of aromatic ketones in aqueous medium, the magnetic chiral catalysts exhibited high catalytic activities (up to 99% conversion) and enantioselectivities (up to 92% ee). Both catalysts could be recovered easily by magnetic separation and be reused ten times without significantly affecting their catalytic activities and enantioselectivities.     

On the role of the thermal treatment of sulfided Rh/CNT catalysts applied in the oxygen reduction reaction

Low loading sulfided rhodium catalysts supported on carbon nanotubes (CNTs) were prepared from RhCl₃ by deposition–precipitation using hydrogen peroxide, followed by an exposure to hydrogen sulfide and an additional thermal treatment in the range from 400 °C to 900 °C. Hydrogen sulfide was generated online from hydrogen and sulfur vapor over molybdenum disulfide as catalyst. By elemental analysis, the Rh loading of the prepared catalysts was found to be 1.4–1.8 wt%. Morphology and composition of the resulting catalysts were characterized by X-ray diffraction (XRD), scanning and transmission electron microscopy (SEM and TEM), and X-ray photoelectron spectroscopy (XPS). Nanoparticles were found to be highly dispersed on the CNTs with an average diameter as small as 1.0 nm determined by TEM. Sintering occurred during heat treatments at 650 °C and 900 °C in helium, as evidenced by XRD, TEM, and XPS. The treatment with hydrogen sulfide significantly enhanced the activity of the supported rhodium catalysts for the oxygen reduction reaction (ORR) in hydrochloric acid, as determined by rotating disc electrode measurements. The sulfided catalyst annealed at 650 °C with a particle size of about 2.5 ± 1.0 nm showed the best performance for the ORR, which is discussed based on the presence of a more stable rhodium sulfide layer on the metallic rhodium particles.     

Selective Catalytic Reduction of NO by Ammonia at Low Temperatures on Catalysts Based on Copper Oxide Supported on a Zirconium-Doped Mesoporous Silica

Copper-oxide-containing zirconium-doped mesoporous silica catalysts (1–12 wt% Cu) have been tested in the selective catalytic reduction of NO by ammonia in excess of oxygen. The catalyst with 6 wt% Cu exhibits a maximum NO conversion of 94% at low temperature (250 °C), with a stoichiometric conversion of ammonia and minimal N₂O formation. The catalytic behavior can be correlated with the high degree of dispersion and easy reduction of the supported CuO.