硫化铅固载四（对—羧基苯基）金属卟啉催化乙苯氧化性能研究
发布时间：2019-01-09 15:01
【摘要】：本研究以硫化铅为载体固载四(对-羟基苯基)金属卟啉(MTCPP),通过硫原子与金属卟啉中心金属配位,模拟细胞色素P-450酶的半胱氨酸巯基硫原子轴向配位调节催化活性作用,研究其催化分子氧氧化乙苯活性的调节作用;根据文献和催化氧化实验结果探讨了催化反应机理。本研究主要包括以下工作内容:1、归纳了固载金属卟啉制备及其应用和催化乙苯氧化的工艺研究进展。2、研究合成载体硫化铅、四(对-羧基苯基)金属卟啉以及固载金属卟啉催化材料。3、采用 UV-Vis、FT-IR、SEM、BET、TG-DTA、XPS 等表征方法对催化材料的结构和化学特性进行分析研究。4、实验采用单因素优选法探索固载催化材料(M TCPP/PbS)催化氧气氧化乙苯的最佳反应条件,在最佳条件下研究固载催化材料的重复使用性能,并与未固载金属卟啉同等条件下的催化性能进行比较。5、对实验数据研究发现:固载后四(对-羧基苯基)金属卟啉催化活性比未固载卟啉均有显著提高:FeTCPP(Cl)、MnTCPP(Cl)、CoTCPP固载后醇酮收率分别提高了 7.13%,7.74%和20.10%。催化材料重复使用四次,其平均催化活性仍高于未固载金属卟啉:FeTCPP(Cl)/PbS,MnTCPP(Cl)/PbS、CoTCPP/PbS四次平均催化乙苯醇酮产率分别高出未固载金属卟啉5.54%、4.25%和4.51%。。三种催化材料的催化活性大小次序为:CoTCPP/PbSMnTCPP/PbSFe TCPP/PbS。6、研究影响催化材料催化乙苯氧化活性的因素,并结合文献和实验数据探讨其催化氧化反应机理。
[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.
【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 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.
【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】
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1 卫炎勋;黄冠;刘W，
本文编号：2405777
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