负载型类贵金属磷化物在氢甲酰化反应中的应用及反应机理研究

This project reports on a novel class of compounds that have substantial promise as next-generation catalysts. The materials are the transition metal phosphides, a group of stable, sulfur-resistant, metallic compounds that have exceptional hydroprocessing properties. Transition metal phosphides have recently been shown to have excellent activity for hydrodesulfurization and hydrodenitrogenation. Basically, these phosphides have physical properties similar to those of ordinary metallic compounds such as carbides, nitrides, borides, and silicides. Thus, they are good conductors of heat and electricity, are hard and strong, and have high thermal and chemical stability. This project is aimed to develop a convenient, economical and simple method for the synthesis of supported transition metal phosphides and extend their application in syngas conversion, especially in hydroformylation, probed by the hydroformylation of low olefins. The mechanism of the formation of supported transition metal phosphides and their catalytic activity will be investigated by in situ FTIR, MAS NMR, XRD, XPS, HRTEM, CO-desorption et al., and theoretical calculation methods.. This study will show a new way of syngas conversion on supported transition metal phosphides, which are substitutes of rare and noble metallic catalysts, showing social significance and academic value in reducing the pressure on the oil shortage. It also provides scientific and theoretical basis for the formation and catalytic mechanism of supported transition metal phosphides .

本项目利用过渡金属磷化物的类贵金属性质和独特性能，通过对磷化方法的探索、助剂的调变及载体的作用，开发出制备条件温和、操作简单和价格低廉的负载型类贵金属磷化物催化剂。以低碳烯烃的氢甲酰化反应为探针反应，运用原位谱学表征手段和理论计算方法，对负载型类贵金属磷化物催化剂的结构以及反应活性中心的形成及性质进行深入探究，理解过渡金属磷化物、载体的相互作用及纳米孔道限阈效应对于氢甲酰化反应性能的影响，为深入研究过渡金属磷化物的形成机理以及催化机理提供科学证据和理论基础。本项目不仅反应路线具有创新性，在过渡金属磷化物催化剂的制备和应用方面也具有创新性。本项目能够推进过渡金属磷化物代替贵金属参与合成气催化转化过程的研究，对解决合成气转化过程的经济性及产业化瓶颈具有重要意义，并可以开拓与现有石油化工生产路线相竞争的合成气转化的新路径，对缓解石油紧缺带来的能源结构问题具有重要社会意义和学术研究价值。

本项目经过2年的探索性试验，成功的开发了负载型类贵金属磷化物催化剂，包括常规载体和含膦多孔有机聚合物担载的钴催化剂。Co/POL-PPh3催化剂在1-己烯氢甲酰化反应中表现出了优异的催化性能，一方面是由于载体的大表面积和多级孔结构等特点，另一方面是有机聚合物具有载体和配体两方面的作用。在Co基催化剂上的氢甲酰化反应中，金属前驱体和反应溶剂的选择对催化剂的活性和选择性有明显的影响。本项目制备的常规载体担载的类贵金属磷化物催化剂和多孔有机聚合物担载的Co催化剂(Co/POL-PPh3) 的制备方法及其应用具有创新性。多孔有机聚合物担载的Co催化剂将为过渡金属代替贵金属参与合成气催化转化过程开辟一条新的路径，对解决合成气转化过程的经济性及产业化瓶颈具有重要意义。对负载型类贵金属磷化物催化剂的深入探究具有重要社会意义和学术研究价值。