Defects and Doping in Metal-Organic Frameworks

金属有机框架中的缺陷和掺杂

• 批准号: 1956403
• 负责人: Christopher Hendon
• 金额: $ 33万
• 依托单位: University of Oregon Eugene
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2020
• 资助国家: 美国
• 起止时间: 2020-08-01 至 2025-07-31
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1956403&HistoricalAwards=false
• 关键词: Defects; Doping; Metal; Organic; Frameworks

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.

非技术概述金属有机框架是一类高度结晶和多孔的材料，由分子结构单元构成。大多数金属有机框架被认为是无缺陷的支架，它们从其高度有序、重复的化学结构中收集其性质。然而，越来越清楚的是，在决定这些材料的性能方面，缺陷可能起着比迄今为止所假设的更重要的作用。该奖项支持利用计算材料和化学技术的研究，以研究金属有机框架中缺陷位点出现的机会。 PI将采用最先进的计算方法来检查导致支架中电子电导率增加的缺陷，这可以实现新的能量存储技术，以及创建附加和执行催化转化的位点的缺陷。该奖项还支持加强PI现有的外展计划，通过咖啡的透镜教授化学，以提高科学素养为中心。特别是，PI将（i）创建一个同行评审的咖啡相关科学文章的开源图书馆，并编写文章关键数据和学习成果的单页摘要，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PI工作的认识，招募学生，技术概述金属有机骨架是一类新兴的多孔固态材料，其性质被广泛认为是由其本体组成和拓扑结构决定的。以前的工作已经表明，电子结构计算的晶体结构是有益的预测在各种各样的支架的物理性质和电子性质。然而，越来越清楚的是，在决定这些材料的性能方面，缺陷可能起着比迄今为止所假设的更重要的作用。该奖项支持旨在通过应用第一原理缺陷计算评估一系列已知缺陷支架的热力学，电子和物理性质的计算研究。研究内容包括：i）探索空位和缺陷的影响，以及与这些缺陷相关的电子性质; ii）研究在一系列已知的导电金属有机框架中实现n型和p型掺杂的类氢空位耦合电子转移反应;和iii）检测绝缘金属-有机骨架中的类氢/阳离子缺陷，作为通过导带的布居来稳定外来氧化态的途径。该奖项还支持加强PI现有的外展计划，通过咖啡的透镜教授化学，以提高科学素养为中心。特别是，PI将（i）创建一个同行评审的咖啡相关科学文章的开源图书馆，并编写文章关键数据和学习成果的单页摘要，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PI工作的认识，招募学生，该奖项反映了NSF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

Electronic Challenges of Retrofitting 2D Electrically Conductive MOFs to Form 3D Conductive Lattices

• DOI: 10.1021/acsaelm.0c01135
• 发表时间: 2021-04-29
• 期刊: ACS APPLIED ELECTRONIC MATERIALS
• 影响因子: 4.7
• 作者: Le, Khoa N.;Mancuso, Jenna L.;Hendon, Christopher H.
• 通讯作者: Hendon, Christopher H.

Conductivity in Open-Framework Chalcogenides Tuned via Band Engineering and Redox Chemistry

• DOI: 10.1021/acs.chemmater.1c04285
• 发表时间: 2022-02-22
• 期刊: CHEMISTRY OF MATERIALS
• 影响因子: 8.6
• 作者: McKenzie, Jacob;Le, Khoa N.;Brozek, Carl K.
• 通讯作者: Brozek, Carl K.

Giant Redox Entropy in the Intercalation vs Surface Chemistry of Nanocrystal Frameworks with Confined Pores

有限孔纳米晶体框架插层与表面化学中的巨大氧化还原熵

• DOI: 10.1021/jacs.2c12846
• 发表时间: 2023
• 期刊: Journal of the American Chemical Society
• 影响因子: 15
• 作者: Huang, Jiawei;Marshall, Checkers R.;Ojha, Kasinath;Shen, Meikun;Golledge, Stephen;Kadota, Kentaro;McKenzie, Jacob;Fabrizio, Kevin;Mitchell, James B.;Khaliq, Faiqa
• 通讯作者: Khaliq, Faiqa

Understanding Photocatalytic Activity Dependence on Node Topology in Ti-Based Metal–Organic Frameworks

• DOI: 10.1021/acsmaterialslett.2c01115
• 发表时间: 2023-04
• 期刊: ACS Materials Letters
• 影响因子: 11.4
• 作者: Nikita Kolobov;A. Zaki;Katarzyna Świrk;P. Maity;L. Garzón‐Tovar;G. Angeli;A. Dikhtiarenko;G. Delahay;P. Trikalitis;A. Emwas;A. Cadiau;O. Mohammed;Christopher H. Hendon;K. Adil;J. Gascón

Assembling Phenothiazine into a Porous Coordination Cage to Improve Its Photocatalytic Efficiency for Organic Transformations

将吩噻嗪组装到多孔配位笼中以提高其有机转化的光催化效率

• DOI: 10.1002/anie.202214055
• 发表时间: 2022
• 期刊: Angewandte Chemie International Edition
• 作者: Lin, Hengyu;Xiao, Zhifeng;Le, Khoa N.;Yan, Tian‐hao;Cai, Peiyu;Yang, Yihao;Day, Gregory S.;Drake, Hannah F.;Xie, Haomiao;Bose, Riya
• 通讯作者: Bose, Riya