EFRI DCheM: Chemicals from Renewables Through Green Electrochemistry (ChaRGE)

该项目旨在开发一种新的分布式化学制造方法，将可持续性，性能和化学灵活性结合起来。它利用电化学，一种利用电场来增强化学转化并打开新反应途径的技术。该项目的研究人员将简化模块化反应器系统中的发酵和电化学，以利用区域碳（生物质）和风能/太阳能资源生产高价值化学品。为此，他们将开发从发酵中获得的中间体的电化学转化的基本见解，设计用于有机电还原和氧化的新催化剂，设计灵活操作的反应器系统，并合成新型高价值单体。此外，将探索所得单体的共聚和化学，以获得具有性能优势的尼龙。电化学实验、理论、反应器设计、聚合物工程和运营研究之间的持续反馈将产生分布式制造系统，其中能源管理、工厂规模和工厂位置在原料可用性和质量以及可再生能源供应的不确定性下被优化以获得最大预期经营利润。该项目的总体目标是使美国化学工业脱碳，发展电力和化学工业，推进美国在化学制造业的领导地位，改善农村经济，并为建立生物制造劳动力提供独特的推广和培训机会。该项目特别有助于在中西部培养扎根当地的STEM劳动力，提高STEM教育中代表性不足的学生的参与度。该项目解决了实施有机电合成用于化学品分布式制造的科学和技术障碍。该团队将设计催化剂和反应途径，用于生物生产的顺式，顺式粘康酸（MA）的多样化，这种二酸最近已被提升为平台化学品的地位，因为它具有战略性地推进生物经济的无与伦比的前景。该项目将侧重于三个具有工业重要性的转化，该项目将提供环境和经济效益：（i）以水为氢源的阴极氢化，（ii）使用绿色电子的阴极碳-碳耦合，以及（iii）使用氯离子作为介体的阳极环氧化。利用风能/太阳能产生的绿色电子和发酵液中已经存在的化合物，将为可持续制造、工艺强化和从废弃生物质中经济高效地生产单体创造新的机会。除了己二酸（一种用于制造尼龙6，6的商品单体）之外，拟议的研究还将提供具有不容易从石油中获得的功能的新型二酸。该项目的成果在多个层面上具有变革性，因为㈠它将阐明底物的分子结构、溶液中的离子、pH值、电催化剂的性质和结构以及电场对生物产品转化的作用;（ii）它还将突出生物量丰富的物种，即水和氯离子，可以分别有效地用作氢源和介体，以在环境条件下进行工业相关的氢化和环氧化反应;（iii）它将揭示电催化获得新单体和性能稳定的生物塑料的益处;以及（iv）它将揭示缓解化学制造业可再生能源间歇性的策略。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。

This project aims to develop a new approach to distributed chemical manufacturing that combines sustainability, performance, and chemical flexibility. It capitalizes on electrochemistry, a technology that uses electric fields to enhance chemical transformations and open new reaction pathways. The investigators in this project will streamline fermentation and electrochemistry in modular reactor systems to produce high-value chemicals from regional carbon (biomass) and wind/solar energy sources. To this end, they will develop fundamental insights into the electrochemical transformation of intermediates obtained from fermentation, design new catalysts for organic electro-reductions and -oxidations, engineer reactor systems for flexible operation, and synthesize novel high-value monomers. In addition, the copolymerization and chemistry of the obtained monomers will be explored with the intent to access Nylons with performance advantages. Constant feedback among electrochemical experiments, theory, reactor design, polymer engineering, and operations research will yield distributed manufacturing systems where energy management, plant scale and plant location are optimized for maximum expected operating profit under uncertainty in feedstock availability and quality, and in renewable energy supply. The overarching goal of this project is to decarbonize the U.S. chemical industry, evolve the power and chemical industries, advance the American leadership in chemical manufacturing, improve rural economies, and provide unique outreach and training opportunities for building a biomanufacturing workforce. The project is particularly relevant to develop a locally-rooted STEM workforce in the Midwest, with enhanced participation of underrepresented students in STEM education.The project addresses the scientific and technological barriers to the implementation of organic electrosynthesis for the distributed manufacturing of chemicals. The team will design catalysts and reaction pathways for the diversification of biologically-produced cis,cis-muconic acid (MA), a diacid that has recently been elevated to the status of platform chemical due to its unparalleled promise for strategically advancing the bioeconomy. The project will focus on three transformations of industrial importance for which the project will provide environmental and economic benefits: (i) cathodic hydrogenations using water as hydrogen source, (ii) cathodic carbon-carbon coupling using green electrons and, (iii) anodic epoxidations using chloride ions as a mediator. Using green electrons from wind/solar energy and compounds already present in the fermentation broth will create new opportunities for sustainable manufacturing, process intensification, and the cost-effective production of monomers from waste biomass. In addition to adipic acid, a commodity monomer used in the manufacture of Nylon 6,6, the proposed research will provide novel diacids with functionalities that are not readily accessible from petroleum. The outcomes of the project are transformative at multiple levels as (i) it will elucidate the role of the substrate’s molecular structure, ions in solution, pH, the nature and the structure of the electrocatalyst, and the electric field on the conversion of bioproducts; (ii) it will also highlight how species abundant in biomass, namely water and chloride ions, can be efficiently used as a source of hydrogen and as a mediator, respectively, to perform industrially-relevant hydrogenation and epoxidation reactions under ambient conditions; (iii) it will reveal the benefits of electrocatalysis to access new monomers and performance-advantaged bioplastics; and (iv) it will reveal strategies to mitigate the intermittent nature of renewable energy for chemical manufacturing.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.