FMSG: Eco: Electrocatalytic Production of Valuable Polymer Feedstocks from Biomass-derived Furanics and CO2

在生物质衍生的中间化合物中，呋喃化合物作为特别吸引人的目标脱颖而出，因为它们在化学转化为各种增值终端产品（包括重要的生物聚合物前体2,5-呋喃二羧酸（FDCA））方面表现出巨大的前景。虽然已经报道了几种由糠醛或2-呋喃酸合成FDCA的热化学方法，但化学计量氧化剂、昂贵的催化剂、有毒溶剂/试剂和/或潜在的恶劣条件使得这些合成方法不适合大规模生产FDCA。该项目由辛辛那提大学的孙玉杰（Yujie Sun）领导，与普度大学的Arun Mannodi Kanakkithodi合作，旨在开发一种创新的电化学工艺，即电催化溴介导的羧基化（EBrC），在环境条件下从2-呋喃酸和二氧化碳中生产FDCA。由于二氧化碳在这一过程中被直接用作最后羧化步骤的C1原料，因此拟议的EBrC FDCA生产策略基本上是碳负的，具有潜在的环境和社会效益。使用计算和机器学习对反应条件进行数据驱动筛选将有助于指导有效电催化系统的设计和开发。该种子基金的总体目标是开发一种电催化方法，利用生物质衍生和工业生产的糠醛和二氧化碳合成一种重要的生物聚合物前体，即2,5-呋喃二羧酸（FDCA），并为新兴的有机电催化领域的未来研究科学家建立人才库。生成的数据、模拟框架以及用于训练模型和预测属性的工具将以可查找、可访问、可互操作、可重复使用（FAIR）的格式公开发布，以造福材料社区，通过材料数据设施和nanoHUB，这是普渡大学的一个在线存储库，为教育工作者和学生提供免费和开放的访问这些信息。辛辛那提大学的PI（太阳）小组将积极参与外展项目，包括加州大学社区日开放日，加州大学化学夏令营和加州大学野外研究中心的科学日。普渡大学的联合负责人Mannodi Kanakkithodi小组将基于该项目的密度泛函理论计算和机器学习结果开发新的nanoHUB资源。这些资源将用于教育和推广，包括纳入普渡大学的研究生课程，以及代表nanoHUB组织的材料信息学实践研讨会的内容，该研讨会通常由来自世界各地的100至300名学生和研究人员参加。这个未来制造奖是由数学和物理科学理事会化学部资助的。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。

Among biomass-derived intermediate compounds, furanics stand out as particularly appealing targets in that they exhibit great promise for chemical transformation to a variety of value-added end products including the important biopolymer precursor 2,5-furandicarboxylic acid (FDCA). Although several thermochemical synthetic strategies of FDCA from furfural or 2-furoic acid have been reported, the requirements of stoichiometric oxidants, expensive catalysts, toxic solvents/reagents, and/or potentially harsh conditions render these synthetic strategies non-optimal for the large-scale manufacturing of FDCA. This project, led by Yujie Sun (University of Cincinnati) in collaboration with Arun Mannodi Kanakkithodi (Purdue University), aims to develop an innovative electrochemical process, namely electrocatalytic bromine-mediated carboxylation (EBrC), to produce FDCA from 2-furoic acid and carbon dioxide under ambient conditions. Since carbon dioxide is directly utilized in this process as a C1 feedstock for the final carboxylation step, the proposed EBrC strategy for FDCA production is essentially carbon-negative with potential environmental and societal benefits. Data-driven screening of reaction conditions using computation and machine learning will help guide the design and development of competent electrocatalytic systems.The overall objective of this seed grant is to develop an electrocatalytic approach for the synthesis of an important biopolymer precursor, namely 2,5-furandicarboxylic acid (FDCA), using biomass-derived and industrially produced furfural and carbon dioxide, and also build the talent pool of future research scientists in the emerging field of organic electrocatalysis. The generated data, simulation frameworks, and tools for training models and predicting properties will be publicly released in a Findable, Accessible, Interoperable, Reusable (FAIR) format for the benefit of the materials community, via the Materials Data Facility and nanoHUB, an online repository housed at Purdue University which provides free and open access to this information for educators and students. The PI’s (Sun) group at the University of Cincinnati (UC) will build on its active involvement in outreach programs including the UC Community Day Open House, the UC-Chem Summer Camp, and Science Day at the UC Center for Field Studies. The co-PI’s (Mannodi Kanakkithodi) group at Purdue University will develop new nanoHUB resources based on the density functional theory calculations and machine learning results from the project. These resources will be used for education and outreach, including incorporation into graduate courses at Purdue University and as content for hands-on workshops on materials informatics organized on behalf of nanoHUB, which is typically attended by 100 to 300 students and researchers from across the world.This Future Manufacturing award was supported by funding from the Division of Chemistry in the Directorate for Mathematical and Physical Sciences.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.