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碳排放的主要贡献者之一，因为与生产、精炼和将化石燃料转化为聚合物相关的高能量需求。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）的更有效的化学处理方法。FDCA是一种生物基化学物质，可以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，PET广泛用于生产薄膜、聚酯和尼龙。相应的基于FDCA的聚合物（聚呋喃酸酯，或PEF）对于食品和饮料包装（如塑料瓶）特别有吸引力，估计有2000亿美元的市场。然而，FDCA是通过氧化生物质前体5-羟甲基糠醛（HMF）来生产的，这有几个主要的生产限制。该项目解决了从HMF生产FDCA的几个挑战，从而使PEF及其相关产品的生产更加经济。该项目通过改进使用有机溶剂和非均相催化剂的反应，解决了FDCA合成的几个挑战。该项目特别关注与溶剂、反应物和产物与催化剂表面和活性位点的相互作用有关的基本方面。具体来说，研究集中在FDCA生产的两个主要限制：催化剂活性和产品浓度。在没有盐的情况下，确定具有高FDCA溶解度的溶剂将显著提高可用于反应的多相催化剂的范围。双金属和非贵金属催化剂将使用原子层沉积（ALD）来合成，以实现均匀的催化剂颗粒分散，同时控制颗粒的大小、结构和组成。ald合成的催化剂提供了一个平台，有助于识别催化剂的性质，从而实现hmf到fdca的高效转化，同时为所涉及的表面反应提供了基本的见解。此外，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，该项目还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，以激励年轻学生将STEM领域视为可能的职业道路。为此，将与蒙大拿州服务不足的农村地区的120多名四年级学生进行持续联系。该奖项反映了美国国家科学基金会的法定使命，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.