苯乙烯-甲基丙烯酸羟基乙酯共聚物微球固载金属卟啉催化剂的制备及其催化性能

 将酰氯化的羧基金属卟啉 (MP) 与表面含羟基的苯乙烯-甲基丙烯酸羟基乙酯共聚物微球 (P(St-co-HEMA)) 进行酯化反应, 制备了共聚物微球固载的金属卟啉催化剂 (P(St-co-HEMA)MP). 采用扫描电镜、紫外-可见光谱、红外光谱和热重等手段对微球进行了表征, 并考察了它在“金属卟啉?抗坏血酸?分子氧”体系中催化环己烷羟化反应性能. 结果表明, 共聚物微球固载的金属卟啉比非固载的金属卟啉具有更高的催化活性, 催化剂重复使用 4 次, 仍保持较高催化活性. 各共聚物微球固载的金属卟啉催化活性顺序为 P(St-co-HEMA)FeP > P(St-co-HEMA)MnP > P(St-co-HEMA)CoP.     

组合曲线回归法计算螺旋扁管管内对流传热系数

针对螺旋扁管壁面温度难于准确测试的特点,提出采用线性曲线回归与非线性曲线回归相结合的方法进行管内传热系数计算.进行了光管与螺旋扁管管内对流传热实验,并用该方法计算管内对流传热系数.光管传热系数计算值与经典公式的大偏差小于6%.螺旋扁管管内传热系数的计算值略大于通过测量壁温获得的传热系数值,分析了二者存在差异的原因.组合...     

Mechanism into selective oxidation of cinnamaldehyde using β-cyclodextrin polymer as phase-transfer catalyst

Selective oxidation of cinnamaldehyde to benzaldehyde in the presence of bicarbonate and hydrogen peroxide and catalyzed by β-cyclodextrin polymer (β-CDP) was investigated. β-CDP was utilized as the phase-transfer catalyst in this study. The immobilized β-cyclodextrin possessing a hydrophobic host cavity was found to be efficient as mass-transfer promoters for the oxidation of cinnamaldehyde. Benzaldehyde could be obtained in 63% yield under optimal reaction conditions. The results indicate the complex formed between cinnamaldehyde and β-CDP via the intermolecular weak interactions, e.g., hydrogen bond was the reason why the conversion and selectivity could be significantly promoted. Finally, the reusability of the catalyst was also evaluated. Its catalytic activity remained unchanged even after recycled for six times, which suggests it is an efficient catalyst for oxidation of cinnamaldehyde.     

Green synthesis of natural benzaldehyde from cinnamon oil catalyzed by hydroxypropyl-β-cyclodextrin

The efficient synthesis of natural benzaldehyde from natural cinnamon oil catalyzed by 2-hydroxypropyl-β-cyclodextrin (2-HPβ-CD) in water under rather mild conditions has been developed. Various analysis methods, e.g., DSC, UV-vis, ¹H NMR, ROESY, and fluorescence measurements had been utilized to demonstrate formation of the 1:1 (molar ratio) complexes between 2-HPβ-CD and cinnamaldehyde. The inclusion equilibrium constant K_a was 928 M⁻¹ at 298 K. The inclusion complex activated the substrate and promoted the reaction selectivity. The yield for benzaldehyde could reach 70% under the optimized conditions (323 K, 5 h, 2% NaOH (w/v), cinnamaldehyde: 2-HPβ-CD=1:1 (molar ratio)). Further investigation on kinetics and solubilization revealed that the binding ability between 2-HPβ-CD and cinnamaldehyde is primarily responsible for the catalytic effects.     

环糊精-卟啉超分子体系的构筑及应用进展

环糊精具有分子识别和选择包结客体分子的独特性质,而卟啉具有模拟酶催化、电子转移和光能转移等功能,本工作通过对环糊精-卟啉超分子体系构筑方式的介绍,详细综述了环糊精-卟啉超分子体系在模拟酶催化、生命科学、药物控释、电子转移过程等方面的应用,认为环糊精-卟啉超分子体系具有卟啉和环糊精双重性质的优点,而以键联环糊精-卟啉为主体分子构筑的超分子体系能更有效地模拟生物酶,表现出优异的区域和立体选择性,在仿生催化方面将具有更广泛的应用前景.     

Facile Synthesis of Metalloporphyrins-Ba2+ Composites as Recyclable and Efficient Catalysts for Olefins Epoxidation Reactions

A facile co-precipitation method was developed to prepare the novel metalloporphyrins-Ba^2+composites with ca.3μm diameter and olive-like morphology.Olefins epoxidation reactions were employed to investigate their catalytic performance.Compared with the free metalloporphyrins,the composites exhibited not only the improved stability and recyclability,but also the enhanced catalytic activity.Such catalytic behaviors could be related to the unique stnictiire of the composites,e.g.,the strong interaction between R-SO3^-and Ba^2+ions and the uniform distribution of metalloporphyrins on the catalyst surface,respectively.Furthermore,the composites showed good compatibility with a wide range of substrates.The well-designed composites are expected to be efficient catalysts,alternative to many sophisticated-synthesized metalloporplirins-based materials,in the industrially important reactions.     

水溶性金属卟啉应用于催化反应的研究进展

综述了水溶性金属卟啉作为催化剂应用于均相或非均相的催化反应的研究进展,重点介绍了水溶性金属卟啉在水或水与有机溶剂混合介质中催化底物氧化反应的催化性能,其中包括烷烃的羟基化,烯烃的环氧化,含氧、含硫及含氮化合物的氧化反应.另外水溶性金属卟啉还可用于催化Suzuki-Miyaura反应、氧化偶联反应、C=C氧化断裂反应等.水溶性金属卟啉催化剂具有水溶性、催化效率高、反应条件温和等优点,因此将在催化反应特别是氧化反应中得到更广泛的应用.     

酞菁锌高效催化以二氧化碳、含氢硅烷和有机胺为原料合成甲酰胺类衍生物

目前为了有效地利用好CO2,主要策略有以下几种:(1)"水平途径"——无价态及能量变化,譬如生成尿素、环状碳酸酯、聚碳酸酯及噁唑烷酮类衍生物等;(2)"垂直途径"——有价态及能量变化,譬如直接加氢转化成碳一产品(甲酸、甲醛、甲醇、甲烷)等;(3)"对角线途径"——有价态及能量变化,即结合石油化工原料将CO2还原生成醇、醚、羧酸、亚胺、酰胺、酯等系列高附加值的精细有机化工产品.其中以二氧化碳和含氢硅烷为原料,通过有机胺的N-甲酰化反应合成甲酰胺类衍生物符合绿色化学和可持续发展的要求.基于仿生催化CO2分子活化的基本理论,我们借鉴强极性的有机溶剂可有效活化硅氢键的性质,创新性地将廉价易得的酞菁锌(ZnPc)作为类酶催化剂,并以化学计量的N,N'-二甲基甲酰胺(DMF)为添加剂,构成组分新颖并高效绿色的类酶协同催化体系,实现了在温和反应条件下高效高选择性地合成甲酰胺类衍生物.研究发现:以苯硅烷作为还原剂,当加入0.5 mol%ZnPc和2 mmol DMF,在25℃和0.5 MPa下仅需反应6 h,可得到收率为99%的N-甲基甲酰苯胺.更值得注意的是,当以更易得的聚甲基氢硅烷(PMHS)为还原剂时,加入5 mol%ZnPc和1 mL DMF,在80℃和1 MPa下反应8 h,N-甲基甲酰苯胺的收率也高达99%.实验结果表明:添加剂DMF可以通过溶剂化和强极性作用高效活化含氢硅烷中的Si?H键,然后具有亲电性的金属活性中心能够稳定氢负离子生成高活性锌氢中间体.即ZnPc/DMF之间的协同催化作用能够促进氢化物从含氢硅烷转移到CO2分子,进而有利于CO2分子的高效活化.综上所述,利用类酶催化剂反应专一性的特点,通过有机胺的N-甲酰化反应,实现了以CO2和含氢硅烷为原料在温和条件下甲酰胺类衍生物的绿色高效合成.这对于设计和开发更加高效的催化体系具有一定的指导作用和借鉴意义.