Carboxyl-alkyl Functionalization for Sustainable Mixed Conduction Polymers: molecular design and mechanistic insights

可持续混合导电聚合物的羧基烷基官能化：分子设计和机理见解

• 批准号: 2408881
• 负责人: Elsa Reichmanis
• 金额: $ 55万
• 依托单位: Lehigh University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2024
• 资助国家: 美国
• 起止时间: 2024-06-01 至 2027-05-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=2408881&HistoricalAwards=false
• 关键词: Carboxyl; alkyl; Functionalization; Sustainable; Mixed

NON-TECHNICAL SUMMARY:Polymers (plastics) that can conduct both electronic and ionic charge promise to serve as central building blocks for applications ranging from environmental and electrophysiological sensors to energy storage. Key advantages of such mixed conduction polymers include their flexible form factor, their ability to be processed at low temperatures using additive printing approaches such as inkjet or screen printing, and their multifunctional technological capabilities. Through judicious choice of molecular structures, it is also possible to access water-soluble polymers that will enable development of environmentally benign options for a range of sensing, advanced computing, and energy applications. This project aims toward the discovery of new, sustainable mixed conduction polymer chemistries and processes and identify critical structure-function relationships. It will do so through a combination of chemical design and synthesis, molecular and structural characterization, property determination and optimization, as well as through an integrated theoretical and experimental approach. As a result, new generations of mixed conduction polymers having unprecedented performance may be identified. Students engaged in the proposed project will benefit from the multidisciplinary nature of the program, developing technical expertise in balance with the ability to communicate and collaborate with scientists and engineers in other fields. The co-PIs are committed to mentorship of diverse groups of graduate and undergraduate researchers and participation in K-12 student outreach programs to accelerate interest in STEM in underrepresented groups. TECHNICAL SUMMARY:Conjugated polymer semiconductors that undergo electrochemically induced doping through permeation of ions from an electrolyte promise to serve as central building blocks for applications ranging from environmental and electrophysiological sensors to light-emitting electrochemical cells, neuromorphic modules, and energy storage. Known as organic mixed ionic-electronic conductors (OMIECs), this class of polymers has characteristics believed to originate from ionically charged or polar side chains that readily solvate or interact with ionic species. To date, the choice of OMIEC chemistries is severely limited whereby transformational advancements in ab initio design require much improved fundamental insight into advantageous synthetically accessible molecular structures and thin-film morphologies that could allow for unprecedented levels of ionic-electronic coupling, compatibility with electrochemical doping, and ion percolation effects. To address limitations in materials design and transport phenomena in OMIECs, this project encompasses the following three Aims: (i) synthesize and characterize target OMIEC structures with unexplored side-chain and backbone paradigms; (ii) establish links between OMIEC backbone and side-chain chemistries and electrolyte gating, film swelling, and ion/electron transport properties through operando studies and molecular modeling; and (iii) explore mixed side-chain chemistries (via copolymerization and/or blending) as a route towards additional control over OMIEC properties. It is hypothesized that expanding the design space available to OMIEC materials via new side-chain chemistries, including additional design capabilities incorporated via copolymerization and blending, could enable unprecedented control over OMIEC properties and device performance. .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.

非技术摘要：可以同时进行电子和离子电荷的聚合物（塑料），有望作为从环境和电生理传感器到能量存储的应用中的中心构建块。这种混合传导聚合物的关键优势包括它们的柔性外形，使用添加剂打印方法（例如喷墨或丝网印刷）在低温下处理的能力以及它们的多功能技术能力。通过明智的分子结构选择，还可以访问水溶性聚合物，从而为各种感应，高级计算和能源应用开发环保选择。该项目旨在发现新的，可持续的混合传导聚合物化学和过程，并确定关键的结构功能关系。它将通过化学设计和合成，分子和结构表征，性质的确定和优化以及综合的理论和实验方法的结合来实现。 结果，可以确定具有前所未有的性能的新一代混合传导聚合物。从事该项目的学生将受益于该计划的跨学科性质，开发技术专长，以与其他领域的科学家和工程师进行沟通和合作的能力保持平衡。该副研究致力于对各种研究生和本科研究人员组成的指导，并参与K-12学生外展计划，以加快代表性不足的群体对STEM的兴趣。技术摘要：通过渗透到电解质承诺的渗透到电解质的渗透中，可以用作环境和电生理传感器到照明电化学电池，神经形态模块以及能源储存的相结合的聚合物半导体。这类聚合物被称为有机混合离子电导器（OMIEC），其特征据信源自离子带电或极性侧链，易于溶解或与离子物种相互作用。迄今为止，OMIEC化学的选择受到严格的限制，因此，从头开始设计中的变革性进步需要大大改进对有利合成的合成分子结构和薄膜形态的基本洞察力，这可以使离子电子辅助性，与电化学的兼容，与电化学的构成效果相同，并促进薄膜的形态。为了解决OMIEC中材料设计和运输现象的局限性，该项目涵盖了以下三个目的：（i）综合和表征未探索的侧链和骨干范式的目标OMIEC结构； （ii）通过Operando研究和分子建模之间建立OMIEC主链与侧链化学，膜肿胀以及离子/电子传输性能之间的联系； （iii）探索混合侧链化学（通过共聚和/或混合）作为对OMIEC特性进行额外控制的途径。假设，通过新的侧链化学分配扩展了OMIEC材料的设计空间，包括通过共聚和混合纳入的其他设计功能，可以实现对OMEIEC属性和设备性能的前所未有的控制。该奖项反映了NSF的法定任务，并通过使用基金会的智力优点和更广泛的影响审查标准来评估值得支持。