Catalytic conversion of biomass derived molecules over metal organic frameworks for the sustainable and renewable production of chemicals and fuels

由可再生生物质或生物质衍生平台化学品催化合成增值化学品是减少目前对化石燃料资源的依赖和减少化学工业碳足迹的重要途径。在这方面，多相催化反应将通过水相处理和无害环境的方法，在将平台分子加工成有价值的化学品、生物燃料和生物聚合物前体方面发挥重要作用。一个简单而有效的转化为有用的化学品和燃料的过程提供了产生经济、环境和社会影响的巨大潜力。需要开发新的催化剂，并充分了解它们在这些催化过程中的作用，以便开发出更经济、更具竞争力的加工路线，以取代目前以原油为基础的工业生产过程。该项目的目的是设计和开发具有所需功能化学基团的新的催化结构。在这个项目中，我们将遵循一种新的自下而上的催化剂开发方法；我们将检查所需的催化反应，并设计和开发具有所需官能团的新型化学结构。我们将特别关注生物质转化中的氧化反应。生物质的催化氧化可以产生多个产物，而挑战是将反应途径引导到所需的产物。生物质衍生化合物，如5-羟甲基呋喃甲醛(HMF)含有羟基，它们的氧化会导致羧酸的形成，是取代PET(聚对苯二甲酸乙二酯)塑料的重要前体。生物质化合物的水相转化为有价值的有机酸是可以实现的，但要扩大这一化学的范围和提高产品收率，需要一步一步的改变。目前的工艺在稀溶液中工作，需要高催化剂负载量，并使用高碱性条件。我们的新的自下而上的方法将识别过渡金属阳离子并将它们协调到定义良好的高结晶金属有机骨架中，以将生物质衍生的化合物氧化成它们的有机酸对应物。在水相中开发具有氧化还原能力的稳定的金属有机骨架是一个未被探索的化学。我们将以一种综合的方法将基础科学和工程研究结合起来，以发展对催化化学的详细的基础理解，这是实用的和容易应用的。实验研究将提供对新催化剂和工艺的基本了解，对化学的详细基础了解将支持改进技术的开发。实验方法将建立在我们在设计成分、形貌和结构可控的催化剂方面的经验和专业知识的基础上。详细的催化剂表征，包括非原位和原位，将提供关于催化剂结构和化学性质的基本信息。催化结果将以迭代的方式反馈给材料合成，以优化和微调材料的性能，从而实现高效的过程。该项目的最后阶段将是将该工艺从实验室扩大到工业应用的经济分析。该项目符合EPSRC的物理科学主题和催化研究领域。

Catalytic synthesis of value-added chemicals from renewable biomass or biomass-derived platform chemicals is an important way to reduce current dependence on fossil-fuel resources and reduce the carbon footprint of chemical industry. In this regard, heterogeneously catalysed reactions will play a major role in the processing of the platform molecules to valuable chemicals, biofuel and biopolymer precursors by means of aqueous-phase processing and environmentally sound methodologies. A simple and efficient process for conversion to useful chemicals and fuels offers significant potential to deliver economic, environmental and societal impact. New catalysts need to be developed and their role in these catalytic processes need be fully understood in order to develop more economical processing routes competitive enough to replace the current crude oil based industrial production processes. The aim of this project is to devise and develop new catalytic architectures with desired functional chemical groups. In this project we will follow a novel bottom up approach for catalyst development; we will examine the required catalytic reaction, and design and develop novel chemical architectures with desired functional groups. Our particular focus will be on the oxidation reactions in biomass conversion. Catalytic oxidation of biomass can lead to multiple products, and the challenge is to direct the reaction pathways to the desired products. Biomass derived compounds, such as 5-hydroxymethylfurfural (HMF) has hydroxyl groups and their oxidation lead to the formation of carboxylic acids; an important precursor to replace the PET (Polyethylene terephthalate) plastics. The aqueous phase conversion of biomass compounds into valuable organic acids can be achieved, but a step change is required to broaden the scope of this chemistry and improve product yield. The current processes work in dilute solutions, require high catalyst loadings and employ high alkaline conditions. Our novel bottom up approach will identify the transition metal cations and coordinate them in well-defined high crystalline metal organic frameworks to oxidise the biomass-derived compounds into their organic acid counterparts. Developing stable metal organic frameworks with oxidation and reduction (redox) capability in aqueous phase is an unexplored chemistry. We will combine fundamental science with engineering studies in an integrated approach, to develop a detailed fundamental understanding of the catalytic chemistry that is practical and easily applicable. Experimental studies will deliver fundamental understanding of new catalysts and processes and a detailed fundamental understanding of the chemistry will support development of improved technology. The experimental approach will build on our experience and expertise of design of catalysts with controlled composition, morphology and structure. Detailed catalyst characterisation, both ex situ and in situ, will provide essential information on catalyst structure and chemical properties. The catalytic results will feedback to the material synthesis in an iterative fashion to optimise and fine-tune the materials properties for an efficient process. Final stage in the project will be the economic analysis for a scale up of the process from laboratory to industrial application. This project is in line with the EPSRC theme of Physical sciences and the research area of Catalysis.