CAREER:Molecular level interrogations of metal-organic frameworks using electronic and structurally sensitive spectroscopy methods

职业：使用电子和结构敏感光谱方法对金属有机框架进行分子水平研究

• 批准号: 1455127
• 负责人: Jenny Lockard
• 金额: $ 62.5万
• 依托单位: Rutgers University Newark
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2015
• 资助国家: 美国
• 起止时间: 2015-05-01 至 2021-04-30
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1455127&HistoricalAwards=false
• 关键词: CAREER; Molecular; level; interrogations; metal

Non-Technical DescriptionThe research activities in this project involve the investigation of an emerging class of porous materials called metal-organic frameworks that have potential applications ranging from carbon sequestration to industrial chemical production to solar energy conversion. While significant progress has been made in developing novel frameworks for these uses, basic insight on exactly how these materials work is often sorely lacking. The research activities in this project meet this need by targeting a fundamental understanding of the processes behind the applications of these materials. The outcome of this work is crucial for facilitating the rational design of the next generation of these materials with improved performances and, therefore, has far reaching implications for a broad range of energy and environmental sustainability applications. Furthermore, as part of a broader mission to integrate research and education, the educational component of the project will provide not only hands-on research experiences for high school science teachers in the Newark region, but a mechanism for translating those experiences into meaningful high school science curricula that meet the specific needs of the students in this community. This outreach initiative stands to have a large impact on the students in these schools since it targets the educators that teach them. Technical DescriptionMetal organic frameworks are hybrid materials that are composed of metal ions or clusters connected by organic molecules to form crystalline microporous networks. These materials have great potential for adsorption-based functions since their intrinsic porosity and tunable architecture allows bandgap manipulation, gas/substrate selectivity and the incorporation of other synergistic characteristics. Synthetic strides in developing new frameworks with these properties have, however, far outpaced the progress in advancing the fundamental understanding of their adsorption-based processes, reaction mechanisms and photoactive properties. Consequently, there are often significant ambiguities in the structure/function relationships that give rise to their utility. This research aims to make those connections by producing molecular level understanding of metal organic framework behavior. The project focuses on framework systems with energy and environmental sustainability implications. This broad underlying theme allows the exploration of several exploitable properties ranging from gas adsorption to heterogeneous catalysis to light harvesting and photocatalysis. The objectives in studying these systems are to expose pertinent electronic and molecular level structural changes associated with the observed properties and to use these insights to help elucidate the mechanisms behind their functionalities. To accomplish these goals, a targeted set of vibrational, optical, and X-ray spectroscopy methods are employed for in situ, and in some cases time-resolved, studies of these systems to garner real time information on the important host-guest interactions and structural changes.

非技术描述本项目的研究活动涉及一类新兴的多孔材料的调查，称为金属有机框架，具有潜在的应用范围从碳封存到工业化学品生产到太阳能转换。虽然在开发用于这些用途的新框架方面取得了重大进展，但通常严重缺乏对这些材料如何工作的基本见解。该项目的研究活动通过对这些材料应用背后的过程的基本理解来满足这一需求。这项工作的结果对于促进下一代这些材料的合理设计具有改善的性能至关重要，因此，对广泛的能源和环境可持续性应用具有深远的影响。此外，作为更广泛的研究与教育相结合的使命的一部分，该项目的教育部分不仅将为纽瓦克地区的高中科学教师提供实践研究经验，而且还将提供一种机制，将这些经验转化为有意义的高中科学课程，满足该社区学生的具体需求。这一外联举措将对这些学校的学生产生巨大影响，因为它针对的是教他们的教育工作者。金属有机骨架材料是由金属离子或金属簇通过有机分子连接而形成结晶微孔网络的杂化材料。这些材料具有吸附功能的巨大潜力，因为它们的固有孔隙率和可调结构允许带隙操纵，气体/衬底选择性和其他协同特性的结合。然而，在开发具有这些特性的新框架方面的合成进展远远超过了对其基于吸附的过程、反应机制和光活性特性的基本理解。因此，在结构/功能关系中往往存在显著的模糊性，这导致了它们的效用。本研究旨在通过对金属有机框架行为的分子水平理解来建立这些联系。该项目侧重于具有能源和环境可持续性影响的框架系统。这一广泛的潜在主题允许探索从气体吸附到多相催化到光捕获和光催化的几种可利用的性质。研究这些系统的目的是揭示与所观察到的性质相关的相关电子和分子水平的结构变化，并使用这些见解来帮助阐明其功能背后的机制。为了实现这些目标，一组有针对性的振动，光学和X-射线光谱方法被用于原位，在某些情况下，时间分辨，这些系统的研究，以获得重要的主-客体相互作用和结构变化的真实的时间信息。