Catalytic activity of Co/SiO2 and Co/TiO2 nanosized systems in the oxidation of carbon monoxide

The effects of the preparation procedure, active component concentration, and conditions of formation of nanosized cobalt-containing systems based on TiO₂ and SiO₂ mesoporous powders on their catalytic activity in the oxidation of carbon monoxide were studied. The active phase in the systems was cobalt spinel CoCo₂O₄ found in all samples. High catalytic activity was found in the samples characterized by relatively high contents of surface active centers (cobalt cations with octahedral surroundings).     

Isobutene hydroformylation in catalytic systems based on rhodium compounds and polyelectrolytes

The catalytic properties of water-soluble systems based on rhodium complexes and polyelectrolytes in isobutene hydroformylation were studied. All of the catalytic systems exhibited an unexpectedly high activity under the conditions where homogeneous hydroformylation virtually did not occur in the presence of conventional rhodium catalysts. A stable catalytic system based on acacRh(CO)₂-PEG complex was proposed, allowing isobutene hydroformylation to be performed with a high activity under mild conditions. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 705–707, April, 1999.     

Unveiling the Layer‐Dependent Catalytic Activity of PtSe2 Atomic Crystals for the Hydrogen Evolution Reaction

Two‐dimensional (2D) PtSe₂ shows the most prominent layer‐dependent electrical properties among various 2D materials and high catalytic activity for hydrogen evolution reaction (HER), and therefore, it is an ideal material for exploring the structure–activity correlations in 2D systems. Here, starting with the synthesis of single‐crystalline 2D PtSe₂ with a controlled number of layers and probing the HER catalytic activity of individual flakes in micro electrochemical cells, we investigated the layer‐dependent HER catalytic activity of 2D PtSe₂ from both theoretical and experimental perspectives. We clearly demonstrated how the number of layers affects the number of active sites, the electronic structures, and electrical properties of 2D PtSe₂ flakes and thus alters their catalytic performance for HER. Our results also highlight the importance of efficient electron transfer in achieving optimum activity for ultrathin electrocatalysts. Our studies greatly enrich our understanding of the structure–activity correlations for 2D catalysts and provide new insight for the design and synthesis of ultrathin catalysts with high activity.     

烷氧基氯化钛载体型催化体系用于丙烯聚合反应的研究——Ⅲ.不同烷氧基团对催化剂性能的影响

我们研究了烷氧基氯化钛Ti(OR)_nCl_(4-n)负载于MgCl_2-EB(EB为苯甲酸乙酯)做为丙烯定向聚合反应的催化剂。本文报告不同种类及不同数目的-OR基团对催化剂性能的影响。结果表明,它们能以高活性催化丙烯定向聚合并得到高等规度聚合物,其中以n-C_6H_(13)-OTiCl_3活性最好。由于空间位阻的缘故,-OR基团数目增多,对催化活性和等规度均不利。在钛活性组分中引入烷氧基团,聚合物分子量明显降低。     

均相催化体系对CO2与环氧化物耦合反应的研究进展

二氧化碳(CO₂)是造成温室效应的主要因素,同时也是集储量丰富、无毒和可再生等优点的C1资源。其与环氧化物的耦合反应具有高的原子经济性,产物环状碳酸酯作为高极性、低挥发性和良好生物降解性溶剂,可广泛应用于萃取剂、医药中间体和聚合物单体等研究方向。本文首先对CO₂与环氧化物耦合反应发生的机理进行了分析,然后鉴于均相催化体系易制备、高活性等优点,重点从设计思路、催化参数、催化效率等方面,系统综述了催化该耦合反应的不同均相催化体系。最后,总结了为实现均相催化体系可长久发展所必须逾越的阻碍和后续研究方向,希望能够为探索新型、高催化性能的催化体系提供一定的参考价值。     

Characterization of Polymer-Supported Rare-Earth Metal Complexes and Their Catalytic Behavior in Polymerization of Conjugated Dienes

The polymerization and catalytic behavior of catalyst systems composed of polymer-supported rare-earth metals were investigated. The catalyst systems show high catalytic activity and stereospecificity for butadiene polymerization. The catalytic efficiency for SMC (styrene-2-(methylsul-finyl)ethyl methacrylate copolymer).NdCl_3-Al(i-C₄H₉)₃ system is twice or three times that of the NdCl₃.4DMSO system. The activity of the ternary system SAAC (styrene-acrylic acid copolymer).Nd-Ph₃CCl-Al(i-C₄H₉)₃ was up to 170 kg polybutadiene/(g Nd-h). The cis-1,4 content of polybutadiene was more than 98%. This system was also used for isoprene polymerization. The cis-1,4 content of the polyisoprene obtained was about 96%     

Palladium catalysts deposited on silicon nitride in the deep oxidation of methane

The physicochemical and catalytic properties of palladium catalysts were studied in the deep oxidation of methane. The catalysts were deposited on silicon nitride from aqueous (Pd/Si₃N₄-a) and toluene (Pd/Si₃N₄-t) solutions of palladium acetate. The use of aqueous and organic solutions of palladium acetate, all other preparation conditions being equal, resulted in the formation of palladium systems with different catalytic properties. The sample from Pd/Si₃N₄-t was characterized by high activity and stability. The systems studied had different structures and adsorption properties of palladium nanoparticles, which influenced the form of reagent adsorption, catalytic properties, and mechanism of surface reactions. The suggestion was made that the solvent played a key role in the formation of the active surface of Pd-containing catalytic systems.     

Hydroformylation of olefins in the presence of rhodium carbonyl catalysts immobilized on polymeric pyrrolidinopyridines

The hydroformylation of olefins in the presence of catalytic systems based on RhCl₃ and polymeric pyrrolidinopyridines was studied. lt was shown that the catalytic system has high activity in the hydroformylation of isobutylene under conditions when the activity of conventional homogeneous catalysts is low. The polymeric catalysts are also thermostable. The effect of solvents on the catalytic properties of the system was studied.Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 7, pp. 1673–1675, July, 1996.     

Catalytic behavior tuning via structural modifications of silylated-diphosphine Ni(II) complexes for ethylene selective dimerization

The methylene spacers and an uncoordinated diphenylphosphine moiety in the scaffold of the CH₃Si(CH₂)_n(PPh₂)₃ and Si(CH₂PPh₂)₄-type silylated diphosphine Ni(II) complex systems have a marked impact on their catalytic performance in selective ethylene dimerization. Ni(II)-based precatalyst 1 , bearing two methylene spacers in its framework, exhibited the highest catalytic activity of 1.29 × 10⁸ g (mol_Ni)^-1 h^-1, while precatalyst 3 , with three methylene spacers, affords the highest product selectivity (88%) toward the C₄ fraction. Crystallographic investigations revealed that the precatalyst 3 adopts the mononuclear bidentate binding mode and the steric constraints of its uncoordinated diphenylphosphine moiety may successfully tailor the catalytic environment of the catalyst. The precatalyst 4 may form a dinuclear complex and exhibits high catalytic activity by changing the ligand/Ni molar ratio. The high C₄ selectivity of precatalyst 3 has been rationalized by density functional theory (DFT) calculations and found to be consistent with the experimental results. The study also revealed that designing new systems of Ni(II)-based complexes and their systematic modifications may further provide potential and industrially viable catalyst systems for selective ethylene oligomerization.     

Influence of nickel content on catalytic activity and stability of the systems, based on intermetallic Ni3Al in the conversion of natural gas using carbon dioxide

In CO₂ reforming of methane catalytic systems based on Ni₃Al with various nickel and aluminum content were investigated. Catalysts were obtained using the self-propagating high-temperature synthesis. The XRD technique was used to investigate the phase content of the studied systems. It was demonstrated that the catalytic activity of the samples grows upon an increase in the nickel content of the system. By means of scanning electron microscopy, elemental analysis, and differential thermal analysis, it was demonstrated that these catalytic systems undergo structural changes and carbonize negligibly with remaining catalytic activity in time.     

Catalytic Transfer Hydrogenation with a Methandiide‐Based Carbene Complex: An Experimental and Computational Study

The transfer hydrogenation (TH) reaction of ketones with catalytic systems based on a methandiide‐derived ruthenium carbene complex was investigated and optimised. The complex itself makes use of the noninnocent behaviour of the carbene ligand (M?CR₂→MH?C(H)R₂), but showed only moderate activity, thus requiring long reaction times to achieve sufficient conversion. DFT studies on the reaction mechanism revealed high reaction barriers for both the dehydrogenation of iPrOH and the hydrogen transfer. A considerable improvement of the catalytic activity could be achieved by employing triphenylphosphine as additive. Mechanistic studies on the role of PPh₃ in the catalytic cycle revealed the formation of a cyclometalated complex upon phosphine coordination. This ruthenacycle was revealed to be the active species under the reaction conditions. The use of the isolated complex resulted in high catalytic activities in the TH of aromatic as well as aliphatic ketones. The complex was also found to be active under base‐free conditions, suggesting that the cyclometalation is crucial for the enhanced activity.     

Structural studies of nanosized porous membrane catalytic systems highly active in dry reforming of biomass conversion products

The structures of porous ceramic membrane catalytic systems exhibiting high activity in dry reforming of biomass conversion products (methane, hydrocarbons C₂?CC₄, and alcohols) to a hydrogen-containing gas were studied. The membrane catalytic systems represent porous inorganic membranes (supports) prepared by self-propagating high-temperature synthesis and modified by nanosized metallocompex components, which are uniformly distributed in the internal pore volume. Structural studies were carried out using scanning electron microscopy with energy dispersive analysis, transmission electron microscopy, temperature-programmed reduction with hydrogen, and X-ray diffraction analysis.     

The modification of Ni<Subscript>3</Subscript>Al intermetallic compound with chromium and tungsten for carbon dioxide reforming of methane to synthesis gas

Catalytic systems based on the Ni₃Al intermetallic compound and modified with chromium and tungsten were studied in carbon dioxide reforming of methane. The catalysts were prepared by the self-propagating high-temperature synthesis method. The phase composition of the catalytic systems was determined by X-ray diffraction. The catalytic activity of the samples increased as the concentration of dopants decreased and was maximum at 2 wt % Cr and W. Scanning electron microscopy studies showed that the catalytic system underwent substantial structural changes responsible for catalytic activity loss with time.     

Recent advances in CO2/epoxide copolymerization—New strategies and cooperative mechanisms

The catalytic copolymerization of CO₂ with epoxides has been known for over 40 years. Even though many heterogeneous and homogeneous catalyst systems have been developed, catalyst activity and selectivity still remain too low for large scale industrial application.Recent investigations have identified new copolymerization pathways with strong evidence for cooperative (bifunctional) mechanisms. At high dilutions, traditional discrete mononuclear single-site catalyst systems generally show a loss in activity. This effect can be overcome with the help of recently developed dinuclear and binary linked systems that involve cooperative mechanisms and thus permit high catalyst efficiency.This review gives an overview on the most recent advances in CO₂/epoxide copolymerization, new mechanistic studies and strategies for future catalyst developments.     

Synthesis of hexaaluminate catalysts for methane combustion by reverse microemulsion medium

The aim of this study is to synthesize the catalysts of Fe- and Mn-substituted hexaaluminate by reverse microemulsion medium for methane catalytic combustion application. Pseudo-ternary phase diagrams in quaternary microemulsion systems of cetyltrimethylammonium bromide (CTAB), n-butanol, n-octane, and water [or Al(NO₃)₃ solution] were presented. The effects of the alcohol chain length, ratio of sur-factant to cosurfactant, and salt concentration on the formation and stability of microemulsion systems were studied. The phase behavior of microemulsion systems was confirmed through the varying of the conductivity with the water content. The performance and structure of the catalysts, La(Mn _x /Fe _x )Al_12−x ⁻ O_19-δ synthesized with the optimal parameter in the phase diagrams of microemulsions systems were characterized by BET, TG-DTA, and XRD. The micro fix-bed reactor was used to measure the catalytic activities of catalysts to methane combustion. The results showed that this synthesis method could yield non-agglomerated and highly dispersed precursors that would undergo crystallization at the lower temperature of 950°C. When temperature was raised up to 1050°C, the complete crystalline La-hexaaluminate was shaped. The hexaaluminate substituted with Fe had high-catalytic activity and stability at high temperature, while the Mn-substituted had higher catalytic activity at lower temperature. When the cooperation of Fe and Mn occurred, i.e., LaFeMnAl₁₀O_19−δ exhibited a high surface area and catalytic activity to CH₄ combustion, the CH₄ light-off temperature was only 475°C and the complete combustion temperature was 660°C. This was attributed to the synergistic effect between Fe and Mn. Supported by the National Natural Science Foundation of China (No. 20706004) and Beijing Natural Science Foundation (Nos. 2062017 and 8072018)     

Oxidation of CO on Mn-Containing Catalysts Prepared by Pyrolysis of Metal β-Diketonates on Synthetic Ceramic Foam

New catalytic systems for oxidation of CO to CO₂ were developed. These systems are based on composite Mn, Mn-Ni, and Mn-Cu coatings and are prepared by gas-phase thermolysis of metal β-diketonates on a ceramic foam support. The relative activity of the new catalytic systems was examined. The kinetic and activation parameters of the oxidation of CO on these catalysts were determined.     

Ruthenium-catalyzed methoxycarbonylation of styrene

Methoxycarbonylation of styrene in the presence of homogeneous Ru catalysts is reported for the first time. Available Ru₃(CO)₁₂ together with halide source such as [bmim]Br, NaBr or LiCl represents active and easy to handle methoxycarbonylation catalyst. The key advantage of the new catalytic systems over traditional Pd catalysts is their high activity at CO pressure as low as 5 bar.     

The influence of modifying admixtures on the catalytic properties of the Ni<Subscript>3</Subscript>Al intermetallic compound in the conversion of methane with carbon dioxide

Catalytic systems based on the Ni₃Al intermetallic compound and modified with niobium and chromium were studied in methane reforming with carbon dioxide. The catalysts were prepared under self-propagating high-temperature synthesis conditions. The phase composition of the catalytic systems was studied by X-ray diffraction. The catalytic activity of the samples increased as the concentration of modifying admixtures decreased and was maximum at 2% concentrations of Nb and Cr. The scanning electron microscopy data showed that the catalytic systems experienced substantial structural changes, which caused catalytic activity loss with time.     

Effect of gamma-irradiation on surface and catalytic properties of nanocrystalline CuO,NiO and Fe<Subscript>2</Subscript>O<Subscript>3</Subscript> supported on alumina

The effect of γ-irradiation on surface and catalytic properties of CuO/Al₂O₃, NiO/Al₂O₃ and Fe₂O₃/Al₂O₃ was investigated. The techniques employed were XRD, nitrogen adsorption at −196 °C and catalytic conversion of ethanol and isopropanol at 250–400 °C using micropulse technique. The results showed that the supported solids being calcined at 400 °C consisted of well crystallized CuO, NiO, Fe₂O₃ and AlOOH phases. The AlOOH crystallized into a poorly crystalline γ-Al₂O₃ upon heating at 600 °C. All phases present in different solids calcined at 400 and 600 °C showed that these solids are of nanocrystalline nature measuring an average crystallite size between 6 and 85 nm. The crystallite size of crystalline phases present was found to be much affected by the dose of γ-rays and the nature of the metal oxide. This treatment resulted in a progressive increase in the specific surface area reaching to a maximum limit at a dose of 0.8 MGy. The dose of 1.6 MGy exerted a measurable decrease in the S _BET. A radiation dose of 0.2 to 0.8 MGy brought about a progressive significant decrease in the catalytic activity of all the catalytic systems investigated. All the catalytic systems retained their high activity upon exposure to a dose of 1.6 MGy. The rise in precalcination temperature of the systems investigated from 400 to 600 °C brought about a measurable increase in their catalytic activity in the conversion of alcohols.     

Methane conversion with carbon dioxide on nickel aluminides

The catalytic activity of several samples based on nickel aluminides in methane conversion with carbon dioxide was studied. Nickel aluminides were prepared by the method of self-propagating high-temperature synthesis. The Ni₃Al system containing the nickel metal phase exhibited high activity at temperatures above 1073 K. The systems based on Ni₂Al₃ and NiAl only containing intermetallic compound phases were inactive.