CAREER: Theory-Guided Design of Porous Organic Frameworks for Energy Conversion and Storage

职业：用于能量转换和存储的多孔有机框架的理论指导设计

• 批准号: 1848067
• 负责人: Tim Kowalczyk
• 金额: $ 49.68万
• 依托单位: Western Washington University
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2019
• 资助国家: 美国
• 起止时间: 2019-07-01 至 2025-06-30
• 项目状态: 未结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1848067&HistoricalAwards=false
• 关键词: CAREER; Theory; Guided; Design; Porous

NONTECHNICAL SUMMARYThis CAREER award supports computational and theoretical research to develop and apply specialized computer simulations to understand how electrons and energy are transferred within a class of materials known as covalent organic frameworks. These materials can be porous at the scale of single molecules, making them strong candidates for the storage of gasses and for separation technologies; preliminary work suggests that they may also provide a valuable scaffold for applications in renewable energy harvesting and conversion. For example, these frameworks of molecules may be used to anchor and orient the light-absorbing parts of a material for efficient energy transfer or increased energy storage density. This project will accelerate the development of this promising class of materials for renewable energy applications by providing a targeted computer simulation strategy to predict the behavior of electrons in these materials after they absorb visible light.The PI mentors a team of undergraduate and Master's student researchers in the development and application of simulations. Their cross-disciplinary training will contribute to the preparation of a robust STEM workforce in the physical and computational sciences. The goals of this research also directly integrate with the PI's efforts as an educator to enhance energy literacy among undergraduate and high school students. Educational simulations that illustrate the energy conversion mechanisms at play in the materials studied here will be developed in collaboration with student researchers; employed in the PI's energy, materials, and chemistry classrooms; and shared with the public to broaden access to energy science resources. These research and educational objectives are directly linked to an undergraduate student-driven energy literacy outreach initiative, recently established by the PI at WWU, which will be further enhanced through development into a service learning program.TECHNICAL SUMMARYThis CAREER award supports computational and theoretical research on optical and electronic properties of covalent organic frameworks. The rational design of photoactive and electroactive covalent organic frameworks is hindered by a lack of predictive models at extended length and time scales to link the optical and electronic properties of these frameworks to their underlying structure. This project aims to address this knowledge gap through the development of a multireference computational approach that strategically links semiempirical ground- and excited-state electronic structure calculations to predict photophysical properties, energy transfer, and charge carrier mobility in electroactive and photoactive covalent organic frameworks. The approach builds on the PI's implementation of a time-independent approach to low-lying excited states in density-functional tight-binding to incorporate charge-transfer excitations as well as couplings between electronic states in these materials. This constrained density-functional tight-binding based configuration interaction (CDFTB-CI) approach will be deployed to study photoexcitation and electron/energy transfer in selected covalent organic frameworks as singlet fission materials and as photoswitchable energy storage materials. The models developed and applied here will also provide a partial blueprint for computational materials scientists to quantify links between structural and electronic properties in other topologically complex environments such as metal-organic frameworks.This project will directly enable the training and mentoring of a diverse group of 15-20 undergraduate and masters-level research students at a primarily undergraduate institution. To broaden the educational impact of this work and to communicate energy conversion and storage concepts to the public, the PI will create and assess the effectiveness of augmented materials simulations that support fluency in mathematical and physical models of energy conversion. This project will also establish a sustainable trajectory for the PI's Energy Ambassadors initiative, a program that couples undergraduate research across the science, engineering, economics, policy, and business of energy with cross-disciplinary communication skill-building and K-12 outreach.The Division of Materials Research and the Division of Chemistry contribute funds to this award.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.

非技术总结这个职业奖项支持计算和理论研究，以开发和应用专门的计算机模拟，以了解电子和能量是如何在一类称为共价有机框架的材料中转移的。这些材料可以是单分子规模的多孔材料，使它们成为储存气体和分离技术的有力候选者；初步工作表明，它们还可能为可再生能源收集和转换应用提供一个有价值的支架。例如，这些分子骨架可用于锚定和定向材料的光吸收部分，以实现有效的能量转移或增加能量存储密度。该项目将通过提供一种有针对性的计算机模拟策略来预测这些材料吸收可见光后电子的行为，从而加速这类有希望的可再生能源应用材料的开发。PI在模拟的开发和应用方面指导一组本科生和硕士研究生研究人员。他们的跨学科培训将有助于在物理和计算科学方面培养一支强大的STEM劳动力队伍。这项研究的目标也直接与PI作为教育者提高本科生和高中生的能源素养的努力相结合。将与学生研究人员合作开发说明在这里研究的材料中发挥作用的能量转换机制的教育模拟；将在PI的能源、材料和化学课堂中使用；并与公众分享，以扩大获得能源科学资源的途径。这些研究和教育目标与本科生推动的能源素养推广计划直接相关，该计划最近由西大的PI建立，将通过发展成为一个服务学习计划而得到进一步加强。技术总结这个职业奖支持关于共价有机框架的光学和电子性质的计算和理论研究。光活性和电活性共价有机骨架的合理设计由于缺乏扩展长度和时间尺度的预测模型来将这些骨架的光学和电学性质与其底层结构联系起来而受到阻碍。该项目旨在通过开发一种多参考计算方法来解决这一知识差距，该方法在战略上将半经验基态和激发态电子结构计算联系起来，以预测电活性和光活性共价有机框架中的光物理性质、能量转移和电荷载流子迁移率。该方法建立在PI对密度泛函紧束缚中低激发态的时间无关方法的基础上，以结合这些材料中的电荷转移激发以及电子态之间的耦合。这种基于约束密度泛函紧束缚组态相互作用(CDFTB-CI)的方法将被用来研究选定的共价有机骨架作为单重态裂变材料和作为光开关储能材料的光激发和电子/能量转移。这里开发和应用的模型也将为计算材料科学家提供一个部分蓝图，以量化其他复杂拓扑环境中结构和电子性质之间的联系，例如金属-有机框架。这个项目将直接使一个以本科生为主的机构对15-20名本科生和硕士研究生进行培训和指导。为了扩大这项工作的教育影响，并向公众传达能源转换和储存的概念，PI将创建和评估增强材料模拟的有效性，以支持流畅地使用能量转换的数学和物理模型。该项目还将为PI的能源大使倡议建立一个可持续的轨道，该计划将跨科学、工程、经济、政策和能源商业的本科生研究与跨学科的沟通技能建设和K-12外展相结合。材料研究部和化学部为该奖项提供资金。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。

项目成果

Exceptional electron conduction in two-dimensional covalent organic frameworks

• DOI: 10.1016/j.chempr.2021.08.015
• 发表时间: 2021-12-09
• 期刊: CHEM
• 影响因子: 23.5
• 作者: Jin, Enquan;Geng, Keyu;Jiang, Donglin
• 通讯作者: Jiang, Donglin