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，呋喃类化合物是特别吸引人的目标，因为它们显示出巨大的化学转化前景，可以转化为各种增值最终产品，包括重要的生物聚合物前体2，5-呋喃二酸(FDCA)。尽管已报道了以呋喃甲醛或2-呋喃甲酸为原料的几种热化学合成策略，但化学计量比氧化剂、昂贵的催化剂、有毒溶剂/试剂和/或潜在的苛刻条件的要求使得这些合成策略对于大规模生产FDCA来说并不是最优的。该项目由辛辛那提大学孙玉杰领导，普渡大学Arun Mannodi Kanakkithodi联合开展，旨在开发一种创新的电化学工艺，即电催化溴介导的羧化反应(EBRC)，在环境条件下由2-呋喃甲酸和二氧化碳合成FDCA。由于二氧化碳在这一过程中被直接用作最终羧化步骤的氯化原料，因此拟议的用于生产FDCA的EBRC战略基本上是碳负的，具有潜在的环境和社会效益。利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合格电催化系统的设计和开发。这项种子基金的总体目标是开发一种电催化方法，用于利用生物质衍生和工业生产的呋喃和二氧化碳合成重要的生物聚合物前体2，5-呋喃二酸(FDCA)，并建立未来研究科学家在新兴有机电催化领域的人才库。生成的数据、模拟框架和用于训练模型和预测性能的工具将以可找到的、可访问的、可互操作的、可重复使用的(FIRE)格式公开发布，以造福材料社区，通过材料数据设施和NanHUB，该在线存储库位于普渡大学，为教育工作者和学生提供免费和开放的信息访问。辛辛那提大学(UC)的少年派(Sun)小组将积极参与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田野研究中心科学日在内的外联计划。普渡大学的合作者(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纳米HUB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，并作为代表NanHUB组织的材料信息学动手研讨会的内容，该研讨会通常有来自世界各地的100至300名学生和研究人员参加。这个未来制造奖得到了数学和物理科学局化学部的资助。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势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.