【摘要】：本研究以硫化鉛為載體固載四(對(duì)-羥基苯基)金屬卟啉(MTCPP),通過(guò)硫原子與金屬卟啉中心金屬配位,模擬細(xì)胞色素P-450酶的半胱氨酸巰基硫原子軸向配位調(diào)節(jié)催化活性作用,研究其催化分子氧氧化乙苯活性的調(diào)節(jié)作用;根據(jù)文獻(xiàn)和催化氧化實(shí)驗(yàn)結(jié)果探討了催化反應(yīng)機(jī)理。本研究主要包括以下工作內(nèi)容:1、歸納了固載金屬卟啉制備及其應(yīng)用和催化乙苯氧化的工藝研究進(jìn)展。2、研究合成載體硫化鉛、四(對(duì)-羧基苯基)金屬卟啉以及固載金屬卟啉催化材料。3、采用 UV-Vis、FT-IR、SEM、BET、TG-DTA、XPS 等表征方法對(duì)催化材料的結(jié)構(gòu)和化學(xué)特性進(jìn)行分析研究。4、實(shí)驗(yàn)采用單因素優(yōu)選法探索固載催化材料(M TCPP/PbS)催化氧氣氧化乙苯的最佳反應(yīng)條件,在最佳條件下研究固載催化材料的重復(fù)使用性能,并與未固載金屬卟啉同等條件下的催化性能進(jìn)行比較。5、對(duì)實(shí)驗(yàn)數(shù)據(jù)研究發(fā)現(xiàn):固載后四(對(duì)-羧基苯基)金屬卟啉催化活性比未固載卟啉均有顯著提高:FeTCPP(Cl)、MnTCPP(Cl)、CoTCPP固載后醇酮收率分別提高了 7.13%,7.74%和20.10%。催化材料重復(fù)使用四次,其平均催化活性仍高于未固載金屬卟啉:FeTCPP(Cl)/PbS,MnTCPP(Cl)/PbS、CoTCPP/PbS四次平均催化乙苯醇酮產(chǎn)率分別高出未固載金屬卟啉5.54%、4.25%和4.51%。。三種催化材料的催化活性大小次序?yàn)?CoTCPP/PbSMnTCPP/PbSFe TCPP/PbS。6、研究影響催化材料催化乙苯氧化活性的因素,并結(jié)合文獻(xiàn)和實(shí)驗(yàn)數(shù)據(jù)探討其催化氧化反應(yīng)機(jī)理。
[Abstract]:In this study, tetra- (p-hydroxyphenyl) metalloporphyrin (MTCPP),) was immobilized on the carrier of lead sulphide to coordinate with the central metal of metalloporphyrin via sulfur atom. The axial coordination of cysteine sulfhydryl sulfur atom was simulated by cytochrome P-450 enzyme to regulate the catalytic activity and to study the regulation of the catalytic activity of molecular oxygen oxidation of ethylbenzene. The mechanism of catalytic reaction was discussed according to the literature and the experimental results of catalytic oxidation. The main contents of this study are as follows: 1. The preparation and application of immobilized metalloporphyrins and the process of catalyzing the oxidation of ethylbenzene are summarized. Tetra- (p-carboxyphenyl) metalloporphyrins and immobilized metalloporphyrins. 3. The structure and chemical properties of the catalyst materials were studied by UV-Vis,FT-IR,SEM,BET,TG-DTA,XPS and other characterization methods. The optimum reaction conditions of oxygen oxidation of ethylbenzene by supported catalytic material (M TCPP/PbS) were investigated by single factor optimization method. The reusability of the supported catalyst material was studied under the optimum conditions. The catalytic activity of metalloporphyrin was compared with that of unsupported metalloporphyrin under the same conditions. 5. The experimental data showed that the catalytic activity of tetra (p-carboxyphenyl) metalloporphyrin was significantly higher than that of unsupported porphyrin compared with unsupported metalloporphyrin. The yield of alcohol and ketone increased by 7.13% and 20.10% respectively after MnTCPP (Cl), CoTCPP immobilization. When the catalyst was reused for four times, its average catalytic activity was still higher than that of unsupported metalloporphyrin: FeTCPP (Cl) / PbS,MnTCPP (Cl) / PbS,CoTCPP/PbS. The yield of ethylphenyl alcohol ketone was higher than that of unsupported metalloporphyrin 5.54, respectively. 4.25% and 4.51%. The order of catalytic activity of the three kinds of catalytic materials is as follows: CoTCPP/PbSMnTCPP/PbSFe TCPP/PbS.6, studies the factors affecting the catalytic activity of ethylbenzene, and discusses the mechanism of catalytic oxidation by combining the literature and experimental data.
【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

【參考文獻(xiàn)】

相關(guān)期刊論文 前10條

1 衛(wèi)炎勛;黃冠;劉W，

本文編號(hào)：2405777