CAS: Radialene Radicals: Aqueous Soluble Organics for Energy Storage

在这个项目中，由化学部的化学结构，动力学机制-B计划资助，夏洛特的北卡罗来纳州大学化学系的Christopher Bejger教授与戴维森学院的Mitchell Anstey教授和约翰逊C.的托德Coolbaugh教授合作。史密斯大学研究氧化还原液流电池（RFBs）的电化学能量存储。 RFB已经成为能够补偿可再生能源（如风能和太阳能）的间歇性性质的有能力的电化学能量存储装置。传统的RFB依赖于昂贵的金属基材料和腐蚀性电解质。从成本和安全的角度来看，包含有机分子并在中性pH下操作的RFB是期望的。 该研究小组正在开发基于有机分子（取代的radialene分子）的新型RFB，该分子在水中具有可逆的氧化还原行为。 该项目位于有机合成，材料化学和分析电化学的接口，因此非常适合本科科学家的教育。 这三个机构的团队将计划和制作一个关于RFB的互动展览，以提高公众对电网规模可再生能源存储的认识并吸引地区公众参与。参与研究的学生有机会与每个机构的教师和区域行业合作伙伴密切合作。该项目将在各种外联活动和学生群体多样化的当地学校的演示中接触到广大的学生和成年人。辐射烯是支持多电子转移的交叉共轭有机分子，并且通常可以以各种氧化态分离。几种取代的[3]radialene dianions表现出可逆的电化学，并在中性pH水溶液中进行稳定的恒电流循环。在这个项目中，分子设计的原则将被用来逻辑定制有机radialene为基础的衍生物用于水氧化还原液流电池（RFBs）。RFB应用需要稳定的、可溶的和高电压的活性物质作为电解质，并且六取代的[3]放射性烯支架可以以可控的、逐步的方式组装，以允许系统地定制以满足这些规格。 将使用分级合成方法来使用各种活性亚甲基结构单元和两性离子型径向烯中间体来调节[3]径向烯支架。亲水部分的引入将用于增强水溶性。基于Hammett取代基常数（σ）的预测方法将被导出以精确地调节[3]radialene二价阴离子的氧化电位。表现出稳定性、高溶解度和良好氧化还原电位的最有前途的结合物将进行电化学表征，并用于制备全电池RFB原型。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。

In this project, funded by the Chemical Structure, Dynamics & Mechanisms-B Program of the Chemistry Division, Professor Christopher Bejger of the Department of Chemistry at the University of North Carolina at Charlotte is working with Professor Mitchell Anstey of Davidson College and Professor Todd Coolbaugh of Johnson C. Smith University to examine redox flow batteries (RFBs) for electrochemical energy storage. RFBs have emerged as capable electrochemical energy storage devices capable of compensating for the intermittent nature of renewable energy sources like wind and sun. Traditional RFBs rely on expensive metal-based materials and corrosive electrolytes. RFBs that comprise of organic molecules and operate at neutral pH are desirable from a cost and safety perspective. The research team is developing new RFB based on organic molecules (substituted radialene molecules) with reversible redox behavior in water. The project lies at the interface of organic synthesis, materials chemistry, and analytical electrochemistry, and is therefore well suited to the education of undergraduate scientists. The three-institution team will plan and fabricate an interactive exhibit on RFBs to expand awareness and engage the regional public regarding grid-scale renewable energy storage. Students involved in the research have the opportunity to work closely with faculty members at each institution and a regional industry partner. This project will reach a broad audience of students and adults alike during demonstrations at various outreach events and local schools with diverse student populations. Radialenes are cross-conjugated organic molecules that support multielectron transfer and can often be isolated in various oxidation states. Several substituted [3]radialene dianions exhibit reversible electrochemistry and undergo steady galvanostatic cycling in neutral pH aqueous solutions. In this project, principles of molecular design will be used to logically tailor organic radialene-based derivatives for use in aqueous redox flow batteries (RFBs). RFB applications require stable, soluble, and high voltage active species as electrolytes, and the hexasubstituted [3]radialene scaffold can be assembled in a controllable, stepwise fashion to allow systematic tailoring to meet these specifications. A hierarchical synthetic approach will be used to tune the [3]radialene scaffold using various active methylene building blocks and zwitterionic radialene intermediates. Introduction of hydrophilic moieties will be used to enhance aqueous solubility. A predictive method based on Hammett substituent constants (σ) will be derived to adjust oxidation potentials of the [3]radialene dianions with precision. The most promising conjugates that exhibit stability, high solubility, and favorable redox potential will be electrochemically characterized and used to prepare full cell RFB prototypes.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.