RARE-1: Understanding catalyst activity to improve the production of 2,5-furandicarboxylic acid

聚合物材料的制造是化学工业中碳排放的主要贡献者之一，因为与化石燃料到聚合物的生产、精炼和转化相关的高能量需求。 生物基聚合物是使用化石资源的一种更环保的替代品。 该项目研究了生产2，5-呋喃二甲酸（FDCA）的更有效的化学加工-FDCA是一种生物基化学品，可升级为类似于化石衍生的聚对苯二甲酸乙二醇酯（PET）的聚合物，广泛用于生产薄膜，聚酯和尼龙。 相应的FDCA基聚合物（聚呋喃二甲酸乙二醇酯，或PEF）对于食品和饮料包装（如塑料瓶）特别有吸引力，估计市场规模为2000亿美元。 然而，FDCA是通过生物质前体5-羟甲基糠醛（HMF）的氧化产生的，其具有几个主要的生产限制。 该项目解决了与从HMF生产FDCA相关的几个挑战，从而使PEF及其相关产品的生产更加经济。该项目通过使用有机溶剂和非均相催化剂改进反应来解决FDCA合成的几个挑战。 特别是，该项目侧重于与溶剂，反应物和产物与催化剂的表面和活性位点的相互作用有关的基本方面。具体而言，研究集中在FDCA生产的两个主要限制：催化剂活性和产物浓度。鉴定在不存在盐的情况下具有高FDCA溶解度的溶剂将显著改善可用于反应的非均相催化剂的范围。 双金属和非贵金属催化剂将使用原子层沉积（ALD）合成，以实现均匀的催化剂颗粒分散，同时还控制粒度，结构和组成。ALD合成的催化剂提供了一个平台，有助于识别催化剂性质，使高效的HMF到FDCA的转化，同时提供有关所涉及的表面反应的基本见解。 此外，将在高HMF浓度下进行无碱反应，以阐明反应物/产物/溶剂与催化剂的相互作用。 除了技术方面，该项目将研究与各级教育相结合，特别是通过针对代表性不足的少数民族的努力，以激励年轻学生考虑STEM领域作为可能的职业道路。为此，将与120多名服务不足的四年级学生保持联系，该奖项反映了NSF的法定使命，并通过使用基金会的知识价值和更广泛的影响审查标准进行评估，被认为值得支持。

The manufacturing of polymeric materials is one of the leading contributors to carbon emissions in the chemical industry due to the high energy requirements associated with the production, refining, and conversion of fossil fuels to polymers. A greener alternative to using fossil resources is bio-based polymers. The project investigates more efficient chemical processing for the production of 2,5- furandicarboxylic acid (FDCA) – a bio-based chemical that can be upgraded to polymers analogous to fossil-derived polyethylene terephthalate (PET), which is widely used in the production of films, polyesters, and nylons. The corresponding FDCA based polymer (polyethylene furanoate, or PEF) is particularly attractive for food and beverage packaging, such as plastic bottles, and is estimated to be a $200 billion market. However, FDCA is produced via oxidation of a biomass precursor, 5- hydroxymethylfurfural (HMF), which has several major production limitations. This project addresses several challenges associated with the manufacture of FDCA from HMF, thus enabling more economical production of PEF and its related products.The project addresses several challenges of FDCA synthesis by improving the reaction using organic solvents and heterogeneous catalysts. In particular, the project focuses on fundamental aspects related to the interactions of solvents, reactants, and products with the surface and active sites of the catalysts. Specifically, the research focuses on two main limitations of FDCA production: catalyst activity and product concentration. Identifying solvents that have high FDCA solubility in the absence of salts will significantly improve the range of heterogenous catalysts that can be used in the reaction. Bimetallic and non-noble metal catalysts will be synthesized using atomic layer deposition (ALD) in order to achieve uniform catalyst particle dispersion, while also controlling particle size, structure, and composition. The ALD-synthesized catalysts provide a platform conducive to identifying catalyst properties that enable efficient HMF-to-FDCA conversion, while providing fundamental insight regarding the surface reactions involved. Additionally, base-free reactions at high HMF concentrations will be run to elucidate reactant/product/solvent interactions with the catalysts. Beyond the technical aspects, the project integrates research with education at all levels, especially via efforts targeted towards underrepresented minorities with the goal of motivating young students to consider the STEM fields as a possible career path. To that end, sustained contact will be made with over 120 4th graders in under-served, rural areas of Montana.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.