CAS: Radialene Radicals: Aqueous Soluble Organics for Energy Storage

CAS：Radialene 自由基：用于储能的水溶性有机物

• 批准号: 1955619
• 负责人: Christopher Bejger
• 金额: $ 45.64万
• 依托单位: University of North Carolina at Charlotte
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2020
• 资助国家: 美国
• 起止时间: 2020-04-15 至 2025-03-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1955619&HistoricalAwards=false
• 关键词: CAS; Radialene; Radicals; Aqueous; Soluble

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.

在这个由化学部化学结构、动力学和机理b项目资助的项目中，北卡罗来纳大学夏洛特分校化学系的Christopher Bejger教授与戴维森学院的Mitchell Anstey教授和Johnson C. Smith大学的Todd Coolbaugh教授合作，研究氧化还原液流电池（RFBs）的电化学储能。rfb作为一种电化学储能装置已经出现，能够补偿风能和太阳能等可再生能源的间歇性。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，由有机分子组成并在中性pH下工作的rfb是可取的。研究小组正在开发基于有机分子（取代放射二烯分子）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交叉点，因此非常适合本科科学家的教育。这个由三家机构组成的团队将计划并制作一个关于可再生能源存储的互动展览，以扩大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职员工和区域行业合作伙伴密切合作。该项目将在各种推广活动和拥有不同学生群体的当地学校的示范活动中接触到广泛的学生和成年人。放射二烯是支持多电子转移的交叉共轭有机分子，通常可以在各种氧化态下分离。几种取代的[3]放射性二烯离子表现出可逆的电化学反应，并在中性pH水溶液中进行稳定的恒流循环。在这个项目中，分子设计原理将用于逻辑定制用于水氧化还原液流电池（rfb）的有机放射二烯衍生物。RFB应用需要稳定的、可溶的、高压的活性物质作为电解质，而六取代[3]辐射二烯支架可以以可控的、逐步的方式组装，以允许系统的剪裁来满足这些规格。分层合成方法将用于调整[3]放射性二烯支架使用各种活性亚甲基构建块和两性离子放射性二烯中间体。引入亲水基团将用于提高水溶解度。提出了一种基于Hammett取代基常数（σ）的预测方法，可以精确地调节[3]放射性二烯阴离子的氧化势。具有稳定性、高溶解度和良好氧化还原电位的最有前途的缀合物将被电化学表征并用于制备全电池RFB原型。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。

项目成果

Simple Air‐Stable [3]Radialene Anion Radicals as Environmentally Switchable Catholytes in Water

简单空气 - 稳定 [3]Radialene 阴离子自由基作为水中环境可切换的阴极电解液

• DOI: 10.1002/chem.202302829
• 发表时间: 2023
• 期刊: Chemistry – A European Journal
• 作者: Hasan, Fuead;Gillen, Jonathan H.;Jayaweera, Amaya T.;McDearmon, Jr., William D.;Winter, Arthur H.;Bejger, Christopher M.
• 通讯作者: Bejger, Christopher M.