Carbonyl allylation of aldehydes catalyzed by a silica-supported poly-γ-diphenylarsinopropylsiloxane palladium(0) complex

A silica-supported poly-γ-diphenylarsinopropylsiloxane palladium(0) complex has been prepared from γ-chloropropyltriethoxysilane via immobilization on fumed silica, followed by reacting with potassium diphenylarsenide and palladium chloride, and then the reduction with hydrazine hydrate. The palladium(0) complex has been found to catalyze the allylation of aldehydes via the formation of π-allylpalladium complexes, using allylic chlorides as allylating agent and SnCl₂ as reducing agent. This polymeric palladium complex can be recovered and reused.     

STUDIES OF MULTICOMPONENT COMPLEX OXIDE CATALYSTS FOR OXIDATIVE COUPLING OF METHANE VI.SURFACE BASICITY AND SURFACE ACTIVE OXYGEN SPECIES OF LiTi_xLa_(1-x)O_2 λ MULTICOMPONENT OXIDE CATALYSTS

The surface basicity of Ti-La-Li multicoinponent oxides has been investigated by means of CO2-TPD. The experiment results show that C2 (C2H6 C2H4) selectivity is related to surface basic strength. The surface active oxygen species have also been characterized by means of XPS, O2-TPD and so on. It has been indicated that C2 selectivity and CH4 conversion are correlated with lattice oxygen and the adsorbed oxygen on the surface of the catalyst respectively In the O2-TPD experiments, it has also been found that there are three kinds of oxygen species on the surface of the series catalvsts, which are a (100℃ 750℃) Among them α-oxvgen causes deep oxidation whileβand γ oxygen species are related to oxidalive coupling of methane (OCM).     

K对Mn—Co—O的结构及氧化活性的影响

利用XRD,TPD,TFD-MS及催化氧化反应等实验技术,研究了K对Mn-Co-O的结构及氧化活性的影响。XRD结果表明,Mn-Co-O系已形成反尖晶石型的MnCo_2O_4结构;K-Mn-Co-O系中除MnCo_2O_4型结构外,还有新相KMnO_2存在。根据O_2的TPD-MS及吡啶的TPD结果,Mn-Co-O中添加适量的K能提高供氧活性和增加供氧数目,但酸中心数目减少,强度降低。K对Mn-Co—O催化剂氧化活性的影响随反应物分子结构的不同而异,对乙酸乙脂、苯甲酰氯等极性有机物的完全氧化反应,K能提高氧化活性,但对苯、正己烷等非极性有机物的完全氧化反应,K使其活性降低。     

INTRAPARTICLE DIFFUSION EFFECTS IN FISCHER-TROPSCH SYNTHESIS Ⅰ. MODELING OF DIFFUSION AND REACTION

IntroductionCatal}ticrcactionsaffcctcdb}'diffosionaIlimitationincatal}'stporcshavcbccnextensive1}dcaltx`ithinlit.rat.rcll~5I.Scvcraltcchniqucsonthcspccialcase0fFischcr-Tropschs}'nthcsis(FTS)t\crcapplicdtocxplorcthebchaviorofthiscatal}ticrcactionundercxpcrimcntalandopcrationaIconditionsI3~5l.It`"ouldbeofvaluctoindicatchcrcthatthcseinvcstigationsx"ercmainl}'bascdonthesimplcstkineticsofthcfirstordcrinH2proposedbyAndersonl6]attheearIystages.However-thesetboents,striCtlyspeaking,areinvalidfor…     

Rhodium-catalyzed addition of arylboron compounds to nitriles, ketones, and imines

The rhodium-catalyzed addition reactions of sodium tetraphenylborate and arylboronic acids to nitriles, ketones, and imines were examined. The reaction of nitriles could be carried out efficiently in the presence of a catalyst system of [RhCl(cod)]₂-dppp and H₂O to give the corresponding monoarylated products selectively. Although unactivated ketones and imines are known to be poor electrophiles for rhodium-catalyzed arylation, the phenylation of them with use of sodium tetraphenylborate proceeded smoothly in the presence of [RhCl(cod)]₂ and Rh(acac)(cod) as catalysts, respectively. The addition of NH₄Cl was found to be crucial to effectively conduct the reaction of ketones and imines.     

A useful procedure for diiodination of carbazoles and subsequent efficient transformation to novel 3,6-bis(triethoxysilyl)carbazoles giving mesoporous materials

Bis(pyridine)iodonium tetrafluoroborate (IPy₂BF₄) was successfully used as a diiodination reagent for carbazole and its derivatives to give 3,6-diiodocarbazoles in excellent yield. Subsequent rhodium-catalyzed disilylation of 3,6-diiodocarbazoles with triethoxysilane gave the corresponding 3,6-bis(triethoxysilyl)carbazoles, which are precursors for sol-gel polymerization, in good yield.     

PRODUCTION OF LIGHTOLEFINS FROM CO_2 HYDROGENATION OVER Fe/SILICALITE-2 CATALYST Ⅱ. PROMOTION EFFECT OF MnO PROMOTER

IntroductionItilasbeenshot'-nthattileadditionofMnOpromotertoFocatal}stcanresultinaremarkableimprovementinthesclectivit}'to11ghtalkenesforCOh}!drogenationll'l.Ho-c'cvcr.thecadetofMnOonCH4formationandCOconversionisvery'ambigUouslltolMoreover.MnOpromotergrca…     

Racemization of chiral amino alcohols III: Effect of Mg or Ca addition on the activity and stability of the Co/γ-Al2O3 catalyst

The racemization of R-(-)-2-amino-1-butanol in a reaction using Co/γ-Al₂O₃ catalysts and catalysts modified by Mg or Ca was investigated in this paper. Complete racemization was achieved with a yield of over 83% at using the Mg modified Co/γ-Al₂O₃ catalyst under optimized reaction conditions of 170°C and 2.5 MPa of H₂. The catalysts were thoroughly characterized by XRD, XPS, TPR, SEM and TEM. The addition of Mg and Ca may be advantageous for dispersing and stabilizing the active species of the Co/γ-Al₂O₃ catalyst, protecting from sintering, significantly improving its catalytic activity and stability.     

催化膜和催化膜反应器:整合的高效和环保催化过程

 The design of new heterogeneous photooxygenation systems able to employ visible light, oxygen, mild temperatures, and solvent with a low environmental impact has been investigated. In particular, the heterogenization of decatungstate (W10O4-32), a polyoxometalate with photocatalytic activity in oxidation reactions, has been carried out in polymeric membranes of polyvinylidenefluoride. The polymeric catalytic membranes prepared by phase inversion technique have been successfully applied in the aerobic mineralization of phenol in water, which was used as an example of organic pollutant. In order to evaluate the effect of the polymeric environment on the overall catalyst behavior, we have also heterogenized the decatungstate (opportunely functionalized) in perfluorinated membrane made of Hyflon. The photocatalytic composite membranes are characterized by different and tuneable properties depending on the nature of the polymeric micro-environment, in which the catalyst is confined. Moreover, the selective separation function of the membrane results in enhanced performance in comparison with homogeneous reactions.     

金催化乙炔氢氯化的密度泛函理论研究进展

乙炔氢氯化(AH)是生产氯乙烯的主要途径之一,传统上使用高毒性的汞催化剂,因此开发无汞催化剂迫在眉睫。金(Au)催化剂是最有潜力的替代催化剂之一,然而其活性Au物种、反应物的活化过程或反应过渡态结构等催化机理仍不够清晰。密度泛函理论（DFT）在研究由Au催化AH的反应机理中发挥了极其重要的作用。本文综述了DFT对金催化剂活性位点、反应物在催化剂上的吸附性质及反应机理的研究进展。重点讨论了DFT对阳离子金和金簇催化AH反应过程的模拟计算,包括Au电子状态、其它原子掺杂及金簇尺寸和形状对催化AH反应影响的模拟。结果表明DFT模拟计算在微观分子尺度上研究反应物的吸附、反应中间体及过渡态等方面发挥了关键作用,对理解Au催化AH反应机理做出了重要贡献。