Selective Oxidation of Toluene and Ethylbenzene over Vanadium-Based Catalysts

本论文以研究甲、乙苯的液相氧化和甲苯的气相选择氧化为目标反应，研究了钒基催化剂的合成、表征和催化性能，论文共分为两大部分。第一部分研究了在双氧水存在下若干钒基催化剂对甲、乙苯液相氧化的催化性能。结果表明，在乙氰为溶剂的反应体系中，所研究的钒基催化剂包括VPO、VOPO4、V2O5、VO(acac)2和NH4VO3等均表现出以苯甲醛为甲苯选择性氧化主产物和以苯乙酮为乙苯选择性氧化主产物的反应结果；从反应活性和主产物选择性来看，按以下顺序递减：VPO>V2O5>VOPO4~VO(acac)2>NH4VO3。对于具有(VO)2P2O7晶相的VPO催化剂，对甲苯选择性氧化主产物苯甲醛...This dissertation sets the selective oxidation of toluene and ethylbenzene as the objective of study, focusing on the synthesis, characterization and catalytic performance of vanadium-based catalysts, and is composed of two parts. In the first part, the selective oxidation of toluene and ethylbenzene using hydrogen peroxide over vanadium-based catalysts such as VPO, VOPO4, V2O5, VO(acac)2, NH4V...学位：理学硕士院系专业：化学化工学院化学系_物理化学(含化学物理)学号：20022507

Liquid Phase Selective Oxidation of Toluene and Ethylbenzene over V-based Catalysts in the Presence of Hydrogen Peroxide

研究了若干钒基催化剂在双氧水存在下对甲、乙苯的液相选择性氧化催化性能 .结果表明 :在乙腈为溶剂的反应体系中 ,所研究的钒基催化剂包括VPO ,VOPO4,V2 O5,VO(acac) 2 和NH4VO3 等均表现出以苯甲醛为甲苯选择性氧化主产物和以苯乙酮为乙苯选择氧化主产物的反应结果 ;从反应活性和主产物选择性来看 ,按以下顺序递减 :VPO >V2 O5>VOPO4>VO(acac) 2 >NH4VO3 .对于具有 (VO) 2 P2 O7晶相的VPO催化剂 ,在双氧水存在下对甲苯选择性氧化主产物苯甲醛的最高选择性为 5 8 8% ,乙苯选择性氧化主产物苯乙酮的最高选择性为 67 8% ;其催化性能与P/V比、焙烧条件、双氧水的使用量、反应溶剂等有关 .从已有的实验结果推测 ,钒基催化剂在双氧水存在下的甲、乙苯选择氧化反应与V5+ /V4+ 的“氧化 -还原”作用密切相关 .The selective oxidations of toluene and ethylbenzene using hydrogen peroxide over vanadium-based catalysts such as VPO, VOPO 4, V 2O 5, VO(acac) 2 and NH 4VO 3 have been studied. These catalysts were found to be active for the oxidation of toluene and ethylbenzene to benzaldehyde and acetophenone as main products in acetonitrile solvent, respectively. The activity and selectivity, however, in a sequence of decrease order, was found to be followed as: VPO>V 2O 5>VOPO 4>VO(acac) 2>NH 4VO 3. The highest selectivities to benzaldehyde from toluene and acetophenone from ethylbenzene were 58 8% and 66 1% over VPO catalyst with P/V=1 1 (molar ratio) in acetonitrile solvent, resepectively. The catalytic performance of VPO with (VO) 2P 2O 7 phase was affected by the molar ratio of P/V, hydrogen peroxide amount, solvent property and temperature. The active center for the oxidation was believed to be (VO) 2P 2O 7 sites (V 4+) in combination with dynamic V 5+ sites involving a reversible redox cycle.国家自然科学基金 (No.2 0 0 2 1 0 0 2 )资助项

肺鱼干扰素调节因子1基因(irf-1)的克隆及其在肉鳍类中的分子进化

肉鳍类是脊椎动物的重要类群,分为总鳍鱼类和四足类.其中总鳍鱼类现生的物种包括腔棘鱼和肺鱼.四足动物则包括两栖类、爬行类、鸟类和哺乳类.为了比较肉鳍类irf-1基因的结构特点和系统发育意义,本研究克隆了肺鱼irf-1基因cDNA全序列,并与肉鳍类中其他物种的irf-1基因进行了比对分析.IRF是与自然免疫相关的蛋白质,目前已发现了11个家族成员,其中irf-1和irf-2是最先被发现的2个成员,在天然免疫中起着重要的作用.但有关IRF-1的报道主要集中在哺乳动物,其他类群中鲜有报道.与已报道的irf-1基因一样,肺鱼的irf-1基因可读框的前345核苷酸非常保守,在其C端也含有1个反式激活区(transactivationdomain)和1个IRF结合域2(IAD2)的模体.虽然肺鱼与四足动物最近的共同祖先距今有417个百万年之久,但跨肉鳍类的序列分析显示,IRF-1氨基酸及其基因序列在肉鳍类中都具有较强的保守性和显著的系统发育意义.用IRF-1氨基酸序列所构建的肉鳍类系统发育与已有报道的结果也是一致的

肺鱼干扰素调节因子1基因（irf-1）的克隆及其在肉鳍类中的分子进化

肉鳍类是脊椎动物的重要类群,分为总鳍鱼类和四足类.其中总鳍鱼类现生的物种包括腔棘鱼和肺鱼.四足动物则包括两栖类、爬行类、鸟类和哺乳类.为了比较肉鳍类irf-1基因的结构特点和系统发育意义,本研究克隆了肺鱼irf-1基因cDNA全序列,并与肉鳍类中其他物种的irf-1基因进行了比对分析.IRF是与自然免疫相关的蛋白质,目前已发现了11个家族成员,其中irf-1和irf-2是最先被发现的2个成员,在天然免疫中起着重要的作用.但有关IRF-1的报道主要集中在哺乳动物,其他类群中鲜有报道.与已报道的irf-1基因一样,肺鱼的irf-1基因可读框的前345核苷酸非常保守,在其C端也含有1个反式激活区（transactivationdomain）和1个IRF结合域2（IAD2）的模体.虽然肺鱼与四足动物最近的共同祖先距今有417个百万年之久,但跨肉鳍类的序列分析显示,IRF-1氨基酸及其基因序列在肉鳍类中都具有较强的保守性和显著的系统发育意义.用IRF-1氨基酸序列所构建的肉鳍类系统发育与已有报道的结果也是一致的

Hydroformylation of 1-Hexene with Water-soluble Phosphine- rhodium Complexes in Room Temperature Ionic Liquids

研究了水溶性膦配体铑配合物在若干离子液体中的1 己烯氢甲酰化反应性能.通过改变离子液体的阴阳离子结构,可使水溶性TPPTS 铑配合物在离子液体中表现出较高的1 己烯氢甲酰化反应活性和选择性;在[BMI]BF4离子液体中加入适量的水,可提高TPPTS 铑配合物的催化活性;在[BMI]BF4离子液体中,水/有机两亲性膦配体与铑形成的配合物,反应后催化剂与产物自动分层,实现催化剂的循环使用.本文结果表明,水溶性膦配体铑配合物的催化活性与其在离子液体中的溶解度密切相关.This paper studied the catalytic performances of water-soluble phosphine-rhodium complexes in room temperature ionic liquids for 1-hexene hydroformylation. The higher reaction rate and normal aldehyde selectivity were obtained through choosing the proper anionic and cationic groups of the ionic liquids. Moreover, the catalytic activity of TPPTS-rhodium complex could be increased by increasing the solubility of TPPTS in the ionic liquids like [BMI]BF_4 and also by the addition of small amount of water into the [BMI]BF_4 ionic liquid. The recycling of the catalysts based amphiphilic phosphines was achieved in the [BMI]BF_4 ionic liquid without significant loss in the catalytic activity due to the easy phase separation. The experimental results inferred that the solubility of water-soluble rhodium complexes was key to obtain the reasonable catalytic activity.国家重点基础发展规划(G2000048008);; 国家自然科学基金(20021002)资助项目