cps微球固载的阳离子苯基金属卟啉杂多酸复合催化剂的制备及其催化氧化特性分析word格式论文.docxVIP

察研究了催化特性。研究结果表明，在分子氧氧化乙苯的氧化反应中，复合催化剂具有很高的催化活性，可使乙苯高选择性地转化为苯乙酮，反应 12 h，苯乙酮的产率达 30.1%； 复合催化剂的催化活性比单纯的固载化钴卟啉高 75%；CoPPW-CPS 的催化活性高于 CoPPMo-CPS。复合催化剂具有最适宜的投加量，过量催化剂的加入，会抑制钴卟啉的 催化活性。复合催化剂还具有良好的循环使用性能。最后，本文将制备三种固载化阳离子金属卟啉（CoTMAPP-CPS、FeTMAPP-CPS及 MnTMAPP-CPS）用于构建复合催化剂，制备了多种固载化阳离子金属卟啉/杂多阴离 子复合催化剂，并将它们用于分子氧氧化环己烷的氧化反应，并考察了主要因素对催化 活性的影响。实验结果表明，复合催化剂的催化活性明显高于固载化阳离子金属卟啉； 使用CoPPW-CPS的体系，反应8 h，环己醇的产率为44.8%，且具有良好的重复使用性能； 在复合催化剂中的结构中，固载化的杂多阴离子不具有催化活性，起催化作用的组分是 金属卟啉，而杂多阴离子起保护作用，能大大地提高金属卟啉的催化活性；三种不同金 属离子配位的固体复合催化剂相比较，CoPPW-CPS的催化活性最高，FePPW-CPS的催 化活性居中，MnPPW-CPS的催化活性最差。总之，将固载化的阳离子金属卟啉与杂多 阴离子相复合，是发展高性能非均相金属卟啉催化剂的新途径。关键词：交联聚苯乙烯，阳离子金属卟啉，杂多酸，复合催化剂，催化氧化Studies on Immobilized Cationic Phenyl Metalloporphyrin/Heteropolyanion Composite Catalysts on CPS Microspheres and Catalytic Oxidation PropertyAbstractSimulating the structure and function of porphyrin and metalloporphyrin, all kinds of special structure of metalloporphyrin compounds can be designed and produced, hydrocarbons catalytic oxidation achieved efficient and high selectivity, compelling in heterogeneous metalloporphyrin catalyst . In this paper, Synchronously Synthsizing and Immobilizing Cationic Phenyl Porphyrins on CPS Microspheres, and immobilized cationic cobalt porphyrin was obtained through a coordination reaction. On this basis, The combination of the cationic cobalt porphyrin with the heteropoly anions of phosphotungstic acid and phosphomolybdic acid with Keggin structure by electrostatic interaction led to the formation of the immobilized composite catalysts. and their catalytic characters were examined and investigated.The substitution reaction between CMCPS microspheres and p-hydroxybenzaldehyde (HBA) was carried out, and benzaldehyde as a group was introduced on the surfaces of CPS microspheres, obtaining BA-CPS. so that the tertiary amine-containing phenyl porphyrin (TAPP) synchronistic synthesis and immobilization on the crosslinked microspheres CPS was realized. Finally, TAPP was transferred meso-three(4-trimethyla