高活性Pt/WOx界面的构筑及其对甘油加氢脱氧制备1,3-丙二醇的作用机制

甘油作为生物质高值化过程中的主要副产物之一，通过加氢脱氧选择性脱去甘油中间位羟基，可将其转化为高附加值的1,3-丙二醇。针对甘油加氢脱氧向1,3-丙二醇转化过程热力学不利这一问题，通过创新设计催化剂结构形成适合的动力学环境是高选择性制备1,3-丙二醇的关键所在。在前期工作基础上，本项目拟选用特殊骨架结构分子筛为载体，通过载体缺陷位点对掺杂金属W以及活性金属Pt进行空间限域，调控载体-金属以及金属-金属间的相互作用，构筑高活性的Pt/WOx界面；借助系统表征手段剖析Pt/WOx界面结构，结合其在甘油加氢脱氧制备1,3-丙二醇过程的反应特性，揭示Pt/WOx界面作用下的C-O键断裂规律；通过DFT计算及原位动态分析，探究Pt/WOx界面的作用机制及甘油加氢脱氧的反应机理，获得甘油直接加氢脱氧制备1,3-丙二醇的高效途径，从而为甘油高值化利用和1,3-丙二醇绿色生产提供理论依据和技术参考。

Glycerol, as the main by-product of the biomass valorization, can be converted to value-added 1,3-propanediol through hydrodeoxygenation (HDO) process to selectively remove the secondary hydroxyl. However, the selective production of 1,3-propanediol is considerably more challenging because of the thermodynamically unfavorable process for 1,3-propanediol production, so kinetic control using a highly efficient catalyst is essential to attain both high glycerol reactivity and high 1,3-propanediol selectivity. Based on our previous work, this project will aim to construct highly active Pt/WOx interface through the interactions between metal-support and metal-metal using molecular sieve with special skeleton structure as the support to confine the doped metal W and active metal Pt through their defect sites. The Pt/WOx interface structure will be thoroughly analyzed through systematic characterizations and the reaction performance of Pt/WOx interface structures in the process of glycerol HDO to produce 1,3-propanediol will be investigated. Based on the structure and performance analysis, the function of the Pt/WOx interface for C-O bond cleavage behavior will be revealed. Through DFT calculations and the in situ characterization analysis, the reaction mechanism of glycerol HDO process under Pt/WOx interface were explored, so as to obtain an efficient pathway to produce 1,3-propanediol through glycerol HDO process.