Defects and Doping in Metal-Organic Frameworks

非技术SUMMARY金属-有机骨架是一系列高度结晶和多孔的材料，由分子积木构建。大多数金属有机骨架被认为是无缺陷的支架，从它们高度有序、重复的化学结构中收集它们的性质。然而，越来越清楚的是，缺陷在决定这些材料的性能方面可能发挥着比迄今所认为的更重要的作用。该奖项支持利用计算材料和化学技术研究金属-有机框架中缺陷位置出现的机会。PI将使用最先进的计算方法来检查导致支架中电子传导性增加的缺陷，这可能使新的能量存储技术成为可能，以及创建位置以附加和执行催化转化的缺陷。该奖项还支持加强PI现有的外展计划，该计划以通过咖啡的镜头教授化学来提高科学素养为中心。特别是，国际咖啡协会将(I)创建一个与同行评议的咖啡相关科学文章的开源图书馆，并为这些文章的关键数据和学习成果撰写单页摘要，以及(Ii)在非洲咖啡生产国组织一次研讨会之旅，目的是提高国际咖啡协会的工作意识，招收学生，并向这些社区学习。TECHNICAL SUMMARY金属-有机框架是一种新兴的多孔固态材料，其性能被广泛认为由其体积组成和拓扑结构决定。前人的工作表明，对晶体结构的电子结构计算对预测各种支架的光物理性质和电子性质都有指导意义。然而，越来越清楚的是，缺陷可能在决定这些材料的性能方面发挥比迄今所认为的更重要的作用。该奖项支持旨在通过应用第一原理缺陷计算来评估一系列已知缺陷支架的热力学、电子和光物理性质的计算研究。研究活动包括：i)探索空位和间隙原子的影响，以及与这些缺陷相关的新出现的电子性质；ii)研究氢化间隙耦合电子转移反应，这将使一系列已知的导电金属-有机骨架中的n型和p型掺杂成为可能；以及iii)研究绝缘金属-有机骨架中的氢/阳离子缺陷，以此作为通过电导带布居稳定奇异氧化态的途径。该奖项还支持加强PI现有的外展计划，该计划以通过咖啡的镜头教授化学来提高科学素养为中心。特别是，国际咖啡协会将(I)创建一个同行评议的咖啡相关科学文章的开源图书馆，并为这些文章的关键数据和学习成果撰写单页摘要，以及(Ii)在非洲咖啡生产国组织一次研讨会之旅，目的是提高对国际咖啡协会工作的认识，招收学生，并向这些社区学习。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。

NONTECHNICAL SUMMARYMetal-organic frameworks are a family of highly crystalline and porous materials, constructed from molecular building blocks. Most metal-organic frameworks have been assumed to be defect-free scaffolds that glean their properties from their highly ordered, repeating chemical structures. However, it is becoming increasingly clear that defects may play a more important role in determining the properties of these materials than so far assumed. This award supports research utilizing computational materials and chemistry techniques to examine the opportunities that emerge from defect sites in metal-organic frameworks. The PI will employ state-of-the-art computational methods to examine defects that give rise to increased electronic conductivity in the scaffolds, which could enable novel energy storage technologies, as well as defects that create sites to append and perform catalytic transformations. This award also supports strengthening the PI's existing outreach program centered around improving scientific literacy by teaching chemistry through the lens of coffee. In particular, the PI will (i) create an open-source library of peer-reviewed coffee-related scientific articles and write single-page summaries of the articles' key data and learning outcomes, and (ii) organize a seminar tour in African coffee-producing countries with the purpose of increasing awareness of the PI's work, recruiting students, and learning from these communities.TECHNICAL SUMMARYMetal-organic frameworks are an emergent class of porous, solid-state materials whose properties are widely thought to be determined by their bulk composition and topologies. Previous work has shown that electronic structure calculations on the crystallographic structures are instructive in predicting both photophysical properties and electronic properties in a wide variety of scaffolds. However, it is becoming increasingly clear that defects may play a more major role in determining the properties of these materials than so far assumed. This award supports computational research aimed at assessing the thermodynamic, electronic, and photophysical properties of a range of known defective scaffolds through the application of first principles defect calculations. The research activities include i) an exploration of the impact of vacancies and interstitials, and the emergent electronic properties associated with these defects; ii) examine hydrogenic interstitial-coupled electron transfer reactions that will enable both n- and p-type doping in the series of known conductive metal-organic frameworks; and iii) examination of hydrogenic/cationic defects in insulating metal-organic frameworks as a route to stabilizing exotic oxidation states through population of the conduction band. This award also supports strengthening the PI's existing outreach program centered around improving scientific literacy by teaching chemistry through the lens of coffee. In particular, the PI will (i) create an open-source library of peer-reviewed coffee-related scientific articles and write single-page summaries of the articles' key data and learning outcomes, and (ii) organize a seminar tour in African coffee-producing countries with the purpose of increasing awareness of the PI's work, recruiting students, and learning from these communities.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.