【摘要】：為了模擬細(xì)胞色素P-450酶中巰基的軸向配位作用功能,在本工作中,選用硫化鎘(CdS)為載體,通過離子鍵和配位鍵作用固載四(4-羧基苯基)金屬卟啉(M TCPP),制備硫化鎘固載四(4-竣基苯基)金屬卟啉非均相催化材料(M TCPP/CdS),探討了其催化氧氣氧化環(huán)己烷的催化性能,并提出可能的催化反應(yīng)機(jī)理。本論文研究工作主要包括以下內(nèi)容:概述固載金屬卟啉和環(huán)己烷催化氧化的研究進(jìn)展。合成載體硫化鎘,四(4-羧基苯基)金屬卟啉和硫化鎘固載金屬卟啉,并運(yùn)用UV-Vis、FT-IR、TG、SEM、BET和XPS等技術(shù)對(duì)這些仿生催化材料進(jìn)行結(jié)構(gòu)表征分析。在沒有還原劑和任何溶劑的條件下,采用單因素變量法探索M TCPP/CdS催化材料催化氧化環(huán)己烷的最優(yōu)反應(yīng)條件,在最優(yōu)反應(yīng)條件下,考察MTCPP/CdS固載催化材料的重復(fù)使用性,并與MTCPP未固載金屬卟啉在同等條件下進(jìn)行對(duì)比研究。催化結(jié)果表明:用僅含1.00 mgM TCPP當(dāng)量的硫化鎘固載四(4-羧基苯基)金屬卟啉可循環(huán)催化氧化環(huán)己烷9次,比未固載金屬卟啉M TCPP具有更好的催化性能和重復(fù)使用性。三種催化材料的催化活性大小順序?yàn)?Co TCPP/CdSFe TCPP/CdSMn TCPP/CdS。根據(jù)對(duì)照實(shí)驗(yàn)和參考文獻(xiàn),推測硫化鎘固載四(4-羧基苯基)金屬卟啉催化氧化環(huán)己烷的反應(yīng)機(jī)理可能是自由基反應(yīng)機(jī)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.
【學(xué)位授予單位】：廣西大學(xué)
【學(xué)位級(jí)別】：碩士
【學(xué)位授予年份】：2017
【分類號(hào)】：O621.251

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本文編號(hào)：2317353