P-B/N/S插层类石墨烯多孔碳的制备及其催化甲基丙烯醛氧化为甲基丙烯酸的研究

甲基丙烯醛氧化为甲基丙烯酸是一种重要的化工反应，是生产大宗化学品甲基丙烯酸甲酯的关键步骤。该反应所用传统催化剂为以磷钼钒酸为基础的杂多酸催化剂，但该催化剂存在寿命短，易受热分解失活，难以再生的问题。本项目拟以生物质原料通过微波-热处理法制备的P-B/N/S插层类石墨烯碳催化剂代替杂多酸催化剂用于该反应。通过改变制备条件，对不同催化剂表征，原位实验及DFT计算模拟等手段，重点研究多孔碳催化该反应的机理、杂原子提高催化性能的机理、杂原子在热处理过程中插层石墨化多孔碳机制。针对碳催化剂活性较低的问题，通过在碳环中掺杂杂原子，改善碳催化剂表面电子结构，增强表面酸性；通过杂原子插层石墨化多孔碳，增大石墨化碳的比表面积，改善其孔结构，加快反应物和产物的内扩散过程及吸附反应物在催化剂表面迁移到氧化位的步骤，本项目的实施将为不饱和醛选择性氧化为不饱和酸高效绿色催化剂的提供新的思路和理论依据。

Oxidation of methacrolein to methacrylic acid is an important chemical reaction, which is the key reaction step for the production of methyl methacrylate, one of the important bulk chemicals. The traditional catalyst for this reaction is heteropoly acid based on molydbovanadylphosphoric compounds. However, this catalyst suffers from the problems of short catalytic life, thermal decomposition and hard to be regenerated. In this project, P-B/N/S intercalated graphene like porous carbon catalysts will be prepared from biomass raw materials by microwave-heat treatment method to replace heteropoly catalysts for this reaction. The catalytic mechanism of this reaction, the improvement of heteroatoms for catalytic performance and the formation mechanism of heteroatoms intercalated graphene like porous carbon during heat treatment will be researched by changing preparation situation, characterization, in-situ experiments and DFT simulation. To solve the problem of low catalytic activity of carbon catalysts, heteroatoms will be added in the carbon ring to improve the electronic structure of carbon catalysts and enhance the surface acidity. The surface area and pore structure of carbon catalysts will be improved by the intercalation of heteroatoms into the graphite layers of carbon catalysts. The diffusion of reactants and products and migration of adsorbed MAL to oxidation sites will be accelerated. The application of this project will provide a new way and theory evidences to prepare green and efficient catalysts for the oxidation of unsaturated aldehydes to unsaturated carboxylic acid.