硫化镉固载四（4-羧基苯基）金属卟啉催化氧化环己烷研究
发布时间：2018-11-07 19:29
【摘要】：为了模拟细胞色素P-450酶中巯基的轴向配位作用功能,在本工作中,选用硫化镉(CdS)为载体,通过离子键和配位键作用固载四(4-羧基苯基)金属卟啉(M TCPP),制备硫化镉固载四(4-竣基苯基)金属卟啉非均相催化材料(M TCPP/CdS),探讨了其催化氧气氧化环己烷的催化性能,并提出可能的催化反应机理。本论文研究工作主要包括以下内容:概述固载金属卟啉和环己烷催化氧化的研究进展。合成载体硫化镉,四(4-羧基苯基)金属卟啉和硫化镉固载金属卟啉,并运用UV-Vis、FT-IR、TG、SEM、BET和XPS等技术对这些仿生催化材料进行结构表征分析。在没有还原剂和任何溶剂的条件下,采用单因素变量法探索M TCPP/CdS催化材料催化氧化环己烷的最优反应条件,在最优反应条件下,考察MTCPP/CdS固载催化材料的重复使用性,并与MTCPP未固载金属卟啉在同等条件下进行对比研究。催化结果表明:用仅含1.00 mgM TCPP当量的硫化镉固载四(4-羧基苯基)金属卟啉可循环催化氧化环己烷9次,比未固载金属卟啉M TCPP具有更好的催化性能和重复使用性。三种催化材料的催化活性大小顺序为:Co TCPP/CdSFe TCPP/CdSMn TCPP/CdS。根据对照实验和参考文献,推测硫化镉固载四(4-羧基苯基)金属卟啉催化氧化环己烷的反应机理可能是自由基反应机理。
[Abstract]:In order to simulate the axial coordination function of mercapto group in cytochrome P-450 enzyme, cadmium sulfide (CdS) was selected as the carrier in this work, and the tetra-( 4-carboxyphenyl) metalloporphyrin (M TCPP), was immobilized by ion bond and coordination bond. Cadmium sulphide supported tetra-metalloporphyrin heterogeneous catalytic material (M TCPP/CdS) was prepared. The catalytic performance of the catalyst for the oxidation of cyclohexane by oxygen was discussed, and the possible mechanism of catalytic reaction was proposed. The main work of this thesis is as follows: the progress of catalytic oxidation of supported metalloporphyrin and cyclohexane is reviewed. Cadmium sulfide, tetra- (4-carboxyphenyl) metalloporphyrins and cadmium sulfide supported metalloporphyrins were synthesized and characterized by UV-Vis,FT-IR,TG,SEM,BET and XPS techniques. The optimum reaction conditions for the catalytic oxidation of cyclohexane by M TCPP/CdS catalyst materials were investigated by single factor variable method without reducing agent and any solvent. The reusability of MTCPP/CdS supported catalytic materials was investigated under the optimum reaction conditions. The results were compared with that of MTCPP unimmobilized metalloporphyrin under the same conditions. The catalytic results show that the cyclohexane can be cyclically oxidized by cadmium sulphide (4-carboxyphenyl) metalloporphyrins containing only 1. 00 mgM TCPP equivalent, which has better catalytic performance and reusability than unsupported metalloporphyrin M TCPP. The order of catalytic activity of the three kinds of materials is as follows: Co TCPP/CdSFe TCPP/CdSMn TCPP/CdS. Based on the controlled experiments and references, it is speculated that the mechanism of oxidation of cyclohexane catalyzed by cadmium sulfide supported on tetra- (4-carboxyphenyl) metalloporphyrins may be free radical reaction mechanism.
【学位授予单位】：广西大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251
[Abstract]:In order to simulate the axial coordination function of mercapto group in cytochrome P-450 enzyme, cadmium sulfide (CdS) was selected as the carrier in this work, and the tetra-( 4-carboxyphenyl) metalloporphyrin (M TCPP), was immobilized by ion bond and coordination bond. Cadmium sulphide supported tetra-metalloporphyrin heterogeneous catalytic material (M TCPP/CdS) was prepared. The catalytic performance of the catalyst for the oxidation of cyclohexane by oxygen was discussed, and the possible mechanism of catalytic reaction was proposed. The main work of this thesis is as follows: the progress of catalytic oxidation of supported metalloporphyrin and cyclohexane is reviewed. Cadmium sulfide, tetra- (4-carboxyphenyl) metalloporphyrins and cadmium sulfide supported metalloporphyrins were synthesized and characterized by UV-Vis,FT-IR,TG,SEM,BET and XPS techniques. The optimum reaction conditions for the catalytic oxidation of cyclohexane by M TCPP/CdS catalyst materials were investigated by single factor variable method without reducing agent and any solvent. The reusability of MTCPP/CdS supported catalytic materials was investigated under the optimum reaction conditions. The results were compared with that of MTCPP unimmobilized metalloporphyrin under the same conditions. The catalytic results show that the cyclohexane can be cyclically oxidized by cadmium sulphide (4-carboxyphenyl) metalloporphyrins containing only 1. 00 mgM TCPP equivalent, which has better catalytic performance and reusability than unsupported metalloporphyrin M TCPP. The order of catalytic activity of the three kinds of materials is as follows: Co TCPP/CdSFe TCPP/CdSMn TCPP/CdS. Based on the controlled experiments and references, it is speculated that the mechanism of oxidation of cyclohexane catalyzed by cadmium sulfide supported on tetra- (4-carboxyphenyl) metalloporphyrins may be free radical reaction mechanism.
【学位授予单位】：广西大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：O621.251
【参考文献】
相关期刊论文 前10条
1 曲映红;;细胞色素P450的提取及检测研究进展[J];山东化工;2016年11期
2 李佳轩;董延茂;朱广爱;孙成龙;;界面聚合-原位制备聚吡咯/CdS纳米复合材料及其非线性光学性能[J];高分子材料科学与工程;2016年04期
3 冯泽;颉雨佳;郝芳;刘平乐;罗和安;;氧化锌负载四(4-硝基苯基)钴卟啉催化氧化环己烷性能[J];分子催化;2016年01期
4 卫炎勋;黄冠;刘W，
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