FePVAsMo杂多化合物膜催化低碳醇选择氧化反应的研究

用组合法合成HxFe01.7P1.1V1.1As0.44-1.1Mo2Oy杂多化合物，并将其以浸渍法负载于多孔钛片上制成催化剂膜，在自制膜式反应釜中选择性催化氧化低碳醇，探讨了As,Fe含量及不同膜焙烧温度对催化剂催化性能的影响；用TPR，IR，TG－DTA对杂多化合物进行表征。结果表明，Fe的引入，可大大提高催化剂的活性和反应的选择性；As的引入，使催化剂的氧化脱氢能力大幅提高；膜焙烧温度为400℃时，催化剂的活性，选择性与稳定性最佳。组成为HxFe0.84P1.1V1.1As0.75Mo12Oy的杂多化合物膜催化剂对低碳醇具有良好的催化氧化活性，稳定性及再生能力。在适宜的条件下催化乙醇氧化，乙醛收率可达95．2％，对丙醇，丁醇也有良好的催化活性。     

杂多化合物膜在乙酸乙酯合成中的催化性能

乙酸乙酯是一种重要的有机物,有着广泛应用。杂多酸作催化剂具有催化活性高、选择性好、用量少、产品质量高、对设备无腐蚀、对环境无污染等优点[1-6]。本文从膜催化[7-9]、多相催化的角度、采用多孔钛片载磷钨酸膜研究杂多化合物在乙酸乙酯合成中的催化性能,探讨反应温度、酸醇比对酯收率的影响。1　实验部分1.1　主要仪器与试剂ＧＣ102-Ｎ气相色谱仪(上海分析仪器厂);Ｎ2000色谱数据工作站(浙江大学智能信息工程研究所);ＸＭＴ数显调节仪,ＺＫ-1可控硅电压调整器(联泰仪表有限公司);ＡＢ204电子天平(ＭＥＬＥＲＴＯＬＥＤＯＣＯＭＰＡ…     

杂多化合物膜催化异丁烯选择氧化反应

 以多孔钛片为支撑体,将组成为HxCu1．2PAs0．6Mo12Oy的杂多化合物与具有氧溢流效应的氧化物Sb2O4制成催化膜,在特制的膜催化反应器中进行异丁烯选择氧化反应．结果表明,杂多化合物－Sb2O4催化膜具有较高的催化活性;在适宜的条件下,甲基丙烯酸收率可达26.3％,甲基丙烯醛收率可达22.4％,液体产物（即可用产物,包括甲基丙烯酸、甲基丙烯醛、乙酸和丙酮）收率可达67.4％．     

杂多化合物催化低级烷烃部分氧化的研究进展

本文回顾了近年来杂多化合物用于低级烷烃的部分氧化的一些典型反应，对此提出了可能的反应机理，并预测了此类反应可能的改进方案和应用前景。     

杂多化合物催化丙烷的选择性氧化

杂多化合物由杂多阴离子和阳离子组成,杂多阴离子具有一定的空间结构,多种不同结合强度的晶格氧能够在氧化-还原反应中起传递电子和氧的作用。杂多化合物具有很强的酸性,可用作双功能催化剂。本文以磷、钼、钒杂多酸中掺杂过渡金属离子Cs^2 、Cu^2 、Fe^3 为催化剂,对丙烷氧化反应进行了研究。     

磷钨杂多化合物催化H2O2氧化十八醇制十八酸

合成了磷钨杂多化合物,考察了其对十八醇经过氧化氢催化氧化制十八酸的反应活性,探讨了温度,催化剂用量、反应时间以及Ｈ２Ｏ２与底物的摩尔比等一系列条件对反应的影响,确定了最佳反应条件。通过ＩＲ,ＩＣＰ,ＵＶ和ＮＭＲ等技术对催化剂进行了表征,考察了反应前后催化剂的变化情况,讨论了活性中心。     

杂多化合物催化性能的研究——第四周期过渡金属取代的钼磷三元杂多…

过渡金属单取代的杂多化合物（ｎ－Ｃ４Ｈ９）４Ｎ ８－ｎ对以过氧化氢为氧化剂的环己烯氧化反应具有良好的催化性能。基于动力学、红外光谱及电化学方法的研究，对反应机理作了讨论。认为这类取代的杂多化合物与Ｈ２Ｏ２作用形成了活性中间体，活性中心为参与取代的过渡金属离子。     

CsCuHPVAsMoO杂多化合物对异丁烯选择性氧化反应的催化性能

 用组合法合成了CsCuHPVAsMoO系列杂多化合物催化剂，并采用FT－IR，H2－TPR，NH3－TPD和TG－DTA等方法对催化剂进行了表征．在自制固定床反应器中对异丁烯进行选择性氧化，考察了Cs，Cu和As含量、催化剂焙烧温度及反应条件对催化剂催化性能的影响．结果表明，Cs的引入有利于提高催化剂的选择性；Cu和As的引入在提高催化剂活性的同时，也提高了催化剂的选择性；当焙烧温度为340℃时，催化剂的活性和选择性最高．组成为Cs0．1Cu0．2HxPVAs0．2Mo10Oy的催化剂对异丁烯具有很强的选择性氧化能力，在最佳反应条件下，甲基丙烯酸、甲基丙烯醛和乙酸的收率分别可达52．84％，12．05％和18．21％．     

Selective Oxidation of Propane over CsFePVAsMo Heteropoly Compound Catalyst

Both the partially reduced and non-reduced multi-component heteropoly compound catalysts with Keggin structure were prepared and used for the selective oxidation of propane. The catalysts were characterized by IR, H2-TPR, NH3-TPD, SEM and XRD. The addition of Cs increased the selectivity of acrylic acid and acetic acid. The selective oxidation performance was greatly improved with the addition of As. Among all of the tested catalysts, the catalytic performance of the Cs1.8Fe0.16HxPVAs0.4Mo11O40 (non-reduced) was the best and the maximum yield of acrylic acid reached 16.42%.     

金属卟啉/MgAl水滑石催化醇选择性氧化制备羰基化合物

将MgAl水滑石引入到金属四苯基卟啉(MTPPs,M=Co,Fe,Mn,Ni)催化氧化体系中,实现了醇的选择性氧化。 结果表明,在分子氧/异丁醛体系中,CoTPP在苯甲醇氧化制苯甲醛反应中表现出优异的催化活性,MgAl水滑石添加剂可有效地提高醛的选择性。 在苯甲醇1 mmol、乙腈2 mL、CoTPP 5 mg、MgAl水滑石18 mg、异丁醛5 mmol、反应温度60 ℃、氧气气氛下反应2 h,苯甲醇的转化率和苯甲醛的选择性分别达到94%和92%。 另外,此催化体系在其它醇类化合物的氧化反应中也具有较好催化活性。     

Solid Phase Catalytic Oxidation of Alcohols by Polymer Supported Rare Earth Catalysts

Oxidation of alcohols to the corresponding aldehydes or ketones is one of the most fundamental reactions in organic chemistry [1,2]. Some of the products of the oxidation exhibit an important role in the organic synthesis as well as pharmaceutical synthesis. In most reactions, the lanthanide complexes show satisfied catalytic activities for some compounds. Furthermore, there has been increasing interest in the lanthanide complexes and several reports have appeared in the literature [3, 4]. But the exploitation of these complexes for the oxidation of some organic substrates has been limited. Here we reported a method for the preparation and the catalytic properties as well as the recycling of lanthanide complexes in oxidation of alcohols.The synthetic procedure for the polymer supported lanthanide complexes is shown as following(scheme 1):●-NH2+CICH2COOH(C2Hs)3N→●-NHCH2COOHM=Ce(Ⅲ), Tb(Ⅲ), Sm(Ⅲ)scheme 1The oxidation of benzyl alcohol was carried out in the presence of iodosylbenzene by the polymer supported Ce(Ⅲ), Tb(Ⅲ) and Sm(Ⅲ) catalysts at 80℃ for 4.0h, the yields of benz-aldehyde are as following (table 1):Table 1 Oxidation of benzyl alcohol with the supported catalysts**Reaction condition: benzyl alcohol 0.1 mmol, iodosylbenzene 0.15mmol,catalyst 0.2mg, 80℃ for 4.0h in 1,2-dichloroethane.It can be seen from the table that the Tb(Ⅲ) complex shows higher catalytic activity for the oxidation of benzyl alcohol. Further investigation is now being carded on to optimize the results.     

掺杂多孔碳材料催化醇选择性氧化研究进展

羰基化合物是重要的有机中间体,醇类化合物的选择性氧化是合成羰基化合物的一类重要反应.在这类反应中,掺杂多孔碳材料因其独特的性能可直接作为催化剂或者催化剂载体.我们综述了单一掺杂多孔碳材料、共掺杂多孔碳材料和负载型掺杂多孔碳材料的制备方法,可能存在的活性位点和催化机理.最后,讨论了掺杂多孔碳材料目前需要解决的问题,指出设计绿色高效的负载非贵金属的掺杂多孔碳材料是未来的一个重要发展方向.     

Catalytic Film and Selective Oxidation of Iso-butylene

Selective oxidation is an important unit process in petrochemistry and fine chemical industry. As a thermodynamically profitable reaction, selective oxidation of hydro- carbons usually takes place with a lot of side-reactions and a great deal of reaction heat at high temperature. To prevent the side-reactions and accelerate heat exchanges are two principal aims in catalytic oxidation1. Using the catalytic film not only can remove the target products from the reaction area in time, but also avo…     

Mg-Al类水滑石负载金催化醇选择氧化中Mg/Al比例的影响

为研究Mg/Al比例对Mg-Al类水滑石(LDH)负载Au催化醇选择氧化的影响,采用共沉淀—水热晶化法合成了不同Mg/Al比的y Mg-Al LDH,采用液相还原法负载纳米Au颗粒.对样品进行XRD、N_2物理吸附、ICP-AES、AAS、TEM、CO_2-TPD、CO_2-In-situ DRIFTS和XPS等表征.在无附加碱条件下,Au/yMg-Al LDH催化剂催化1-苯乙醇选择氧化的催化活性随Mg/Al比增大呈现递增趋势,Au/4Mg-Al LDH活性最佳.载体表面弱碱性强度随Mg/Al比增大变化不大,弱碱位略有增多,对醇羟基脱氢有促进作用.载体层板Mg_3OH基团随Mg/Al比增大而增多有利于Au在层板边缘沉积,二者可形成有效协同,促进醇氧化过程进行.     

Liquid Phase Selective Oxidation of Alcohols over VPO Catalysts Supported on Mesoporous Hexagonal Molecular Sieves (HMS)

The vanadium phosphorous oxide (VPO) catalysts, supported on mesoporous hexagonal molecular sieves (HMS) with different vanadium loadings, were prepared by precipitation method on organic phase. Techniques such as XRD, BET and SEM, were used for characterization of the catalyst. The bulk VPO catalyst contains vanadyl pyrophosphate phase ((VO)₂P₂O₇), and a small amount of VOPO₄. The high surface area, large pore volume and pore size of HMS in VPO/HMS samples, provide an excellent dispersion of same phase of VPO compound on the support surface. Oxidation of various alcohols was studied in the liquid phase over VPO/HMS catalyst, using tert‐butylhydroperoxide (TBHP) as an oxidant. The activity of VPO/HMS samples were considerably increased with respect to bulk VPO catalyst. At 90 °C, the obtained activities were 0.567 and 6.545 g_pro.g^?1_VPOh^?1 over the bulk VPO and 20 wt% VPO/HMS catalysts, respectively. The effects of substrates, reaction time, reaction temperature, solvents, catalyst recycling and leaching of VPO in liquid phase reaction were also investigated. The following order has been observed for the percentage of conversions of alcohols: Benzylic alcohol > Secondary alcohol ～ Primary alcohol. The kinetic of benzyl alcohol oxidation using excess TBHP over VPO/HMS catalyst was investigated at temperatures of 27, 60 and 90 °C, and followed a pseudo‐first order with respect to benzyl alcohol.