Preparation and Development of Metal-Isocyanide Framework Materials

金属异氰化物骨架材料的制备与开发

基本信息

批准号：
2106713
负责人：
Joshua Figueroa
金额：
$ 54.05万
依托单位：
University of California-San Diego
依托单位国家：
美国
项目类别：
Continuing Grant
财政年份：
2021
资助国家：
美国
起止时间：
2021-06-01 至 2024-05-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=2106713&HistoricalAwards=false
关键词：
Preparation Development Metal Isocyanide Framework

项目摘要

Non-technical AbstractWith this project, supported by the Solid State and Materials Chemistry Program in the Division of Materials Research, Professor Joshua S. Figueroa and his research team at the University of California, San Diego develop a new class of metal/organic hybrid solid-state materials. There is significant current interest in the development of solid-state materials with advanced function and properties for a range of technological and industrial applications, including chemical separations, chemical storage, energy harvesting and chemical catalysis. Among such materials, Metal-Organic Frameworks (MOFs), which are a type of hybrid inorganic/organic solid-state material, are a standout. The reason for this is because MOFs can be prepared with diverse structures, for example with different inorganic portions of the material, and it is relatively easy to tune the organic component for specific applications. While the synthetic and materials chemistry aspects of MOFs have significantly advanced over the past two decades, a common paradigm is followed for their preparation. This involves the interaction of oxidized metal centers with anionic organic linker groups. From a fundamental perspective, this particular constitution limits the chemical and physical properties of the materials, especially from the perspective of mediating chemical or adsorptive processes that rely on the presence of metal centers with high electron counts. In this respect, this project establishes a class of neutral linker groups for the routine and reliable incorporation of electron-rich metal centers into network materials. The scientific work of this award is augmented by a significant effort to broaden participation of junior- and community-college transfer student participation in materials science research at the University of California, San Diego, as well as to introduce local San Diego Area high school students to modern aspects of materials science research.Technical AbstractWith support from the Solid State and Materials Chemistry Program in the Division of Materials Research, Professor Joshua S. Figueroa of the University of California, San Diego explores the synthesis and properties of isocyanide coordination networks featuring low-valent metal centers as secondary building units (SBUs). Organoisocyanides are well established to form robust metal-ligand linkages via strong sigma-donation and highly efficient pi-backbonding interactions. This electronic duality has also been long recognized to stabilize low-valent metal centers. Seeking to transport these discrete molecular properties into a network-materials context, synthetic investigations are undertaken to prepare porous, three-dimensional solid-state networks featuring low-valent transition metal nodes using multi-topic isocyanide linkers. Furthermore, in an effort to simultaneously impart coordinative saturation on the metal nodes of these materials, the m-terphenyl isocyanide ligand topology are a predominant feature of these studies. Newly prepared isocyanide coordination networks are investigated in the context of their fundamental materials properties. An emphasis is placed on chemiabsorptive properties of these materials as function of the low-valent metal center incorporation. The experimental work undertaken as part of this award is complemented by an educational program targeting the early inclusion of junior/community college transfer students at the University of California, San Diego in materials science research. The goal of these efforts is to increase participation of a broader student demographic in STEM research and advanced training. Lastly, to augment training experiences for students working on this project, outreach to local area high schools in the form of curriculum augmentation is also a major component of the project.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.

非技术摘要加州大学圣地亚哥分校的 Joshua S. Figueroa 教授及其研究团队在材料研究部固态和材料化学项目的支持下，通过该项目开发了一种新型金属/有机杂化固体-国家材料。目前人们对开发具有先进功能和特性的固态材料产生了浓厚的兴趣，用于一系列技术和工业应用，包括化学分离、化学储存、能量收集和化学催化。在这些材料中，金属有机框架（MOF）是一种无机/有机杂化固态材料，是其中的佼佼者。原因是 MOF 可以制备成多种结构，例如材料的不同无机部分，并且相对容易调整有机成分以适应特定应用。尽管 MOF 的合成和材料化学方面在过去二十年中取得了显着进步，但其制备仍遵循共同的范式。这涉及氧化金属中心与阴离子有机连接基团的相互作用。从基本角度来看，这种特殊的构造限制了材料的化学和物理性质，特别是从依赖于高电子数金属中心的存在的介导化学或吸附过程的角度来看。在这方面，该项目建立了一类中性连接基团，用于将富电子金属中心常规且可靠地掺入网络材料中。该奖项的科学工作因扩大初中和社区学院转学生参与加州大学圣地亚哥分校材料科学研究以及介绍当地圣地亚哥地区高中生而做出的重大努力得到加强技术摘要在材料研究部固态与材料化学项目的支持下，加州大学圣地亚哥分校的 Joshua S. Figueroa 教授探索了低异氰化物配位网络的合成和性能。 -价金属中心作为二级建筑单元（SBU）。有机异氰化物可以通过强大的 σ 供体和高效的 pi 背键相互作用形成牢固的金属-配体键。这种电子二象性也早已被认为可以稳定低价金属中心。为了将这些离散的分子特性转移到网络材料环境中，进行了综合研究，以使用多主题异氰化物连接体制备具有低价过渡金属节点的多孔三维固态网络。此外，为了同时在这些材料的金属节点上赋予配位饱和，间三联苯异氰化物配体拓扑是这些研究的主要特征。新制备的异氰化物配位网络在其基本材料性能的背景下进行了研究。重点放在这些材料的化学吸收特性作为低价金属中心掺入的函数。作为该奖项的一部分进行的实验工作得到了一项教育计划的补充，该教育计划旨在尽早将加州大学圣地亚哥分校的大专/社区学院转学生纳入材料科学研究。这些努力的目标是增加更广泛的学生群体对 STEM 研究和高级培训的参与。最后，为了增加参与该项目的学生的培训经验，以课程扩充的形式向当地高中进行推广也是该项目的一个主要组成部分。该奖项反映了 NSF 的法定使命，并通过评估被认为值得支持基金会的智力价值和更广泛的影响审查标准。