中空二氧化硅微球固载M-N-C催化剂的制备及其选择性催化氧化乙苯反应的机理研究

It is very important to develop M-N-C catalysts (denoted as M-N-C, M = Co, Mn, Fe) with high catalytic performance for the environmentally friendly chemical processes of ethylbenzene oxidation. In this study, M-N-C catalysts grafted on hollow silica spheres with high catalytic performance for ethylbenzene oxidation are prepared through the preparation method of ship-in-bottle. The effect of the hydro-thermal conditions and the modification of the pores in the shell on the structures of the M-N-C catalysts is investigated. Moreover, the influence of the concentration of M-N-C precursors and heating conditions on the catalytic performance of the M-N-C catalysts has also been studied. And the structure-activity relationship between the structures of the hollow spheres and the catalytic performance of the catalysts and the synergistic effect among the factors exerting effect on their catalytic performance are also explored. The key factors to determine the catalytic performance of the catalysts are presented. Consequently, via the modification of the templates and preparation conditions to adjust the structure and properties of the catalysts, a novel M-N-C catalyst immobilized on hollow silica spheres with a high catalytic performance for selective oxidation of ethylbenzene are synthesized. All these may lay a foundation for the practical application of environmentally friendly chemical processes for selective catalytic oxidation of ethylbenzene.

研发具有高催化性能的金属氮碳催化剂（简称M-N-C,M=Co,Mn,Fe）对实现环境友好的绿色催化氧化乙苯反应过程具有重要的意义。本项目通过”瓶中造船”法制备对催化氧化乙苯反应具有高活性和选择性的中空二氧化硅微球固载M-N-C催化剂。研究催化剂制备过程中水热反应条件和壳层孔道修饰等对中空二氧化硅微球固载M-N-C催化剂结构的影响；研究金属氮碳前驱体浓度及焙烧条件等对催化剂催化性能的影响；研究中空二氧化硅微球固载M-N-C催化剂的构效关系，以及各影响因素之间的协同作用机理。考察在选择性催化氧化乙苯反应中影响催化剂催化反应性能的主要因素，并通过对模板剂及制备条件的调节，对催化剂的结构和性质进行调控，从而提高催化剂的催化性能，研发出对选择性催化氧化乙苯反应具有高催化性能的新型中空二氧化硅微球固载M-N-C催化剂，为绿色环保的选择性催化氧化乙苯反应工艺的应用提供了参考。

为了达到我国的双碳战略目标，研发具有高催化性能的金属氮碳催化剂对实现环境友好的绿色催化氧化乙苯反应过程具有重要的意义。本项目通过多种制备方法，如”瓶中造船”法，制备对催化氧化乙苯反应具有高活性和选择性的中空二氧化硅微球固载金属氮碳催化剂。在本工作中，研究了催化剂制备过程中水热反应条件和通过碳修饰壳层孔道等对中空二氧化硅微球固载金属氮碳催化剂结构的影响；研究了金属氮碳前驱体浓度及焙烧条件等对催化剂催化性能的影响；研究了中空二氧化硅微球固载金属氮碳催化剂的构效关系，以及各影响因素之间的协同作用机理。考察在选择性催化氧化乙苯反应中影响催化剂催化反应性能的主要因素，比如限域效应和协同效应，并通过对模板剂及制备条件的调节，对催化剂的结构和性质进行调控，从而提高催化剂的催化性能，研发出了多种对选择性催化氧化乙苯反应具有高催化性能中空二氧化硅微球固载金属氮碳催化剂，为绿色环保的选择性催化氧化乙苯反应工艺的工业应用提供了一定的参考价值。