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.

非技术描述该项目的研究活动涉及对一种称为金属有机框架的新兴材料的研究，这些材料具有从碳固换到工业化学生产到太阳能转化的潜在应用。尽管在为这些用途开发新颖的框架方面取得了重大进展，但基本的洞察力往往严重缺乏这些材料的工作方式。该项目中的研究活动通过针对对这些材料应用背后的过程的基本了解来满足这一需求。这项工作的结果对于促进下一代这些材料的合理设计至关重要，因此，对这些材料的表现有所改善，因此对广泛的能源和环境可持续性应用具有很大的影响。此外，作为整合研究和教育的更广泛使命的一部分，该项目的教育组成部分不仅将为纽瓦克地区的高中科学教师提供动手研究经验，而且还将为将这些经验转化为有意义的高中科学课程，以满足该社区中学生特定需求的有意义的高中科学课程。这项宣传计划对这些学校的学生产生了很大的影响，因为它针对教会他们的教育者。技术描述金属有机框架是由有机分子连接的金属离子或簇组成的混合材料，形成了晶体微孔网络。这些材料具有基于吸附功能的巨大潜力，因为它们的固有孔隙率和可调式结构允许带隙操纵，气体/底物选择性以及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步伐已经超过了对基于吸附过程，反应机制和光活动特性的基本理解的基本理解的进展。因此，在结构/功能关系中通常存在重要的歧义，这引起了它们的效用。这项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连接。该项目着重于具有能源和环境可持续性影响的框架系统。这个广泛的基本主题允许探索从气体吸附到异质催化再到光收集和光催化的几种可剥削性能。研究这些系统的目标是揭示与观察到的特性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，采用了一组有针对性的振动，光学和X射线光谱方法，用于原位，在某些情况下，对这些系统进行了研究，以获取有关重要的主机相互作用和结构变化的实时信息。