The Application Study Of Microporous Polymer And Microporous Carbon Support Metal Catalysts In Catalysis And Electrocatalysis

Porous materials with high surface areas exerts excellent properties in heterogeneous catalyst materials research, which not only can stabilize metal ions in the process of preparing supporting metal catalysts, but also can prevent the reunion and growth of metal nanoparticles. But in traditional synthesis, it's very difficult to control the special pore structures in the synthesis of catalytic materials, and the relationship between pore structures and applicative activity is also rarely researched. Studying the control of synthesizing skeleton polymer materials and structure-function relationship between structure and activity are very challenging but also of great practical value.The main work of this paper is focused on preparing new type of microporous materials supporting metal catalysts. We design and fabricate catalysts with high activity through the methods of carbonization, N-doped, in situ synthesis and controlling morphology. The catalysts possess high acticity in cross-coupling reaction, hydrogenation reaction and electric catalytic oxidation reaction. We tried to explore the relationship between pore structure and particle size, the dispersion of metal nanoparticles on the base of being able to fabricate the microporous skeleton materials of which the synthesis can be controlled, and further to apply these advantages in catalysis research.We designed a porous substrate supporter with hollow microporous organic capsules structure, which is very stable. Through the method of introducing condensation polymer in the cavity to stabilize Pt nano-particles, we prepared highly dispersed PtNPs catalyst wrapped by organic micro capsule, the Pt nano-particles not only owed small size but also exhibited high dispersity, the catalyst can be recycled 15 times in the hydrogenation reaction of nitro-compound, which exhibited the recycling advantage of organic micro hollow capsulated catalysts. Over the course of studying microcapsule structure and activity, we found the introduction of micro-pore wall and condensation polymer played a decisive role in enhancing the catalytic activity.MOPs materials with high surface area, low skeletal density and multidimensional pore size distribution is very important in supporting metal catalysts and they has great advantage in maintaining the stability and dispersion of metal particles due to its complex pore channel. But in this condition, the interaction forces between metal and support is only caused by physical adsorption which has many limitations, for example, it can't maintain the catalyst' stability for a long time, because the interaction between metal and carrier is not as stable as chemical bond. We doped ligands like NHCs and TPP with strong interaction to metal in the situ synthesis of microporous skeleton materials which are then bonded with Pd or Co to prepared Pd-NHC-2-Pd2+ and HUST-1-Co catalysts, the catalysts have a good yield in Suzuki reaction and CO2 adsorption and transformation.Active carbon as a traditional carrier material although possess a broad applications in catalytic, but they also have some disadvantages compared to N-doped MOPs-derived carbon supports, the incorporation of N heteroatom into carbon network affects the reaction process, like acting as trapping sites for anchoring the metal nanoparticles (NPs) to improve the dispersibility on the support surface and prevent the aggregation during reaction; altering the electronic structure of carbon framework as well as metal NPs through metal/support interfacial interactions to influence their activity and stability for specific reactions. Therefore, this work opens up new insights for the rational design and development of novel highly-efficient carbon for supporting metal or metal oxide for ORR by simply modulating the framework as well as electronic structure of such polymers.