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

在这个职业项目中，James Bour博士和他在韦恩州立大学的研究团队正在研究聚合物结构缺陷如何影响聚合物微孔，该项目由化学系(CHE)的化学结构、动力学和机理B(CSDM-B)计划和材料研究部(DMR)的固态材料化学(SSMC)计划联合资助。微孔率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性能的一个重要性质，但几乎没有控制它的设计原则。这个项目的目标是通过探索缺陷强烈影响微孔率的假设来解决这一知识鸿沟。鲍尔博士和他的团队的目标是通过开发化学反应来建立缺陷和孔隙率之间的关系，这种化学反应可以量化和模拟潜在的缺陷结构。这些研究有可能使人们更好地了解高微孔聚合物的关键结构特征。洞察力的获得将有助于以假设为导向的微孔聚合物合成方法的设计。在进行这些研究的同时，博博士还将为密歇根州的初中和高中教师主持每年一次的聚合物化学州立继续教育时钟小时项目。这项活动旨在与该州的早期科学教育任务直接对接，帮助为国家未来的聚合物科学劳动力做好准备。由于其高的微孔率、结构多样性和强大的化学稳定性，多孔有机聚合物在水净化、能量收集、气体储存/净化、催化和传感方面具有潜在的现代挑战。聚合物孔隙率，以及最终在这些目标应用中的性能，受到合成方法的强烈影响。然而，对于为什么某些反应持续且显著地优于其他合成策略，人们知之甚少。该项目旨在通过研究依赖于反应的缺陷结构如何影响体孔率来解决这一基本知识差距。微孔网络聚合物中缺陷的光谱询问在历史上具有挑战性。这项研究将转而专注于通过化学方法确定缺陷-孔隙率关系。专为多孔聚合物的刚性结构设计的网络拆解方法将用于表征模型聚合物的本征缺陷。缺陷发生率和结构之间的系统关系将通过传统单体与模拟缺陷或原缺陷单体的共聚来确定。综上所述，这些研究有望建立缺陷与孔隙率指标之间的定量关系，如表观表面积、孔体积和孔尺寸分布。所获得的见解将有助于指导改进和更受控制的合成方案的开发，特别是针对高表面积微孔聚合物的合成方案。该奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

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.