CAREER: Molecular Approaches for Understanding Defect-Porosity Relationships in Microporous Organic Polymers

在这个由化学系（CHE）的化学结构、动力学机制-B（CSDM-B）项目和材料研究系（DMR）的固态材料化学（SSMC）项目共同资助的CAREER项目中，韦恩州立大学的James Bour博士和他的研究团队正在研究聚合物结构的缺陷如何影响聚合物微孔性。微孔性是影响聚合物在水净化、气体储存、气体净化、能量收集、传感和催化等应用中的性能的重要属性，但很少有控制微孔性的设计原则。本项目的目标是通过探索缺陷强烈影响微孔性的假设来解决这一知识空白。Bour博士和他的团队旨在通过开发化学反应来建立缺陷和孔隙率之间的关系，从而量化和模拟潜在的缺陷结构。这些研究有可能导致在高微孔聚合物的关键结构特征的理解。获得的见解将有助于微孔聚合物合成方法的假设导向设计。在这些研究的同时，Bour博士将为密歇根州的初中和高中教师举办一个年度高分子化学国家继续教育时钟小时计划。这项活动旨在直接与该州的早期科学教育使命对接，帮助培养国家未来的聚合物科学人才。由于其高微孔性、结构多样性和强大的化学稳定性，多孔有机聚合物具有解决水净化、能量收集、气体储存/净化、催化和传感等现代挑战的潜力。聚合物的孔隙率，以及最终它们在这些目标应用中的性能，受到合成方法的强烈影响。然而，很少有人知道为什么一些反应一贯和显着优于其他合成策略。该项目旨在通过研究反应相关的缺陷结构如何影响体积孔隙率来解决这一基本知识缺口。微孔网络聚合物中缺陷的光谱分析历来具有挑战性。本研究将侧重于通过化学方法确定缺陷-孔隙度关系。专门为多孔聚合物的刚性结构设计的网络拆卸方法将用于表征模型聚合物中的天然缺陷。缺陷发生率和结构之间的系统性关系将通过常规单体与缺陷模拟或前缺陷单体的共聚来确定。 总之，这些研究有望建立缺陷和孔隙度指标（如表观表面积、孔体积和孔径分布）之间的定量关系。获得的见解将有助于指导改进和更可控的合成方案的开发，特别是对于高表面积微孔聚合物。该奖项反映了NSF的法定使命，并被认为值得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来支持。

In this CAREER project, funded jointly by the Chemical Structure, Dynamics & Mechanisms-B (CSDM-B) program in the Division of Chemistry (CHE) and the Solid State & Materials Chemistry (SSMC) program in the Division of Materials Research (DMR), Dr. James Bour and his research team at Wayne State University are studying how imperfections in polymer structures affect polymer microporosity. Microporosity is an important property affecting the performance of polymers in applications such as water purification, gas storage, gas purification, energy harvesting, sensing, and catalysis, yet there are few design principles for controlling it. The goal of this project is to address this knowledge gap by exploring the hypothesis that defects strongly influence microporosity. Dr. Bour and his team aim to establish relationships between defects and porosity through the development of chemical reactions that allow quantification and simulation of potential defect structures. These studies have the potential to result in improved understanding of key structural features in high microporosity polymers. Insights gain will aid in the hypothesis-directed design of synthetic approaches to microporous polymers. In parallel with these studies, Dr. Bour will host a yearly state continuing education clock hour program in polymer chemistry for middle and high school teachers in Michigan. This activity is designed to interface directly with early science education mission in the state, helping to prepare the nation’s future workforce in polymer science. Owing to their high microporosity, structural diversity, and robust chemical stability, porous organic polymers have potential to address modern challenges in water purification, energy harvesting, gas storage/purification, catalysis, and sensing. Polymer porosity, and ultimately their performance in these targeted applications, is strongly affected by synthetic approach. However, little is known about why some reactions consistently and significantly outperform other synthetic strategies. This project aims to address this fundamental knowledge gap by studying how reaction-dependent defect structures impact bulk porosity. Spectroscopic interrogation of defects in microporous network polymers is historically challenging. This research will instead focus on determination of defect-porosity relationships through chemical methods. Network disassembly approaches specifically designed for the rigid structures of porous polymers will be used to characterize native defectivity in model polymers. Systematic relationships between defect incidence and structure will be determined through copolymerization of conventional monomers with defect-simulating or pro-defective monomers. Taken together, these studies are expected to establish quantitative relationships between defects and porosity metrics such as apparent surface area, pore volume, and pore size distribution. Insights gained will help guide the development of improved and more controlled synthetic protocols, particularly for high surface area microporous polymers.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.