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.

非技术摘要与该项目，在材料研究部的固态和材料化学计划的支持下，Joshua S. Figueroa教授及其加州大学圣地亚哥的研究团队开发了新的金属/有机混合固态材料。目前，人们对具有高级功能和特性的固态材料的开发引起了重大兴趣，包括化学分离，化学储存，能量收集和化学催化。在此类材料中，金属有机框架（MOF）是一种杂种/有机固态材料，是一种杰出的材料。原因是因为MOF可以使用多种结构来制备，例如，材料的无机部分不同，并且相对容易调整有机成分以适合特定应用。尽管在过去的二十年中，MOF的合成和材料化学方面已显着提高，但遵循了常见的范式。这涉及氧化金属中心与阴离子有机接头组的相互作用。从基本的角度来看，这种特殊的宪法限制了材料的化学和物理特性，尤其是从介导的化学或吸附过程的角度来看，这些过程依赖于具有高电子计数的金属中心的存在。在这方面，该项目建立了一类中性接头组，用于将富含电子的金属中心的常规和可靠掺入网络材料中。这项奖项的科学工作是通过巨大的努力来扩大了在加利福尼亚大学，圣地亚哥分校的材料科学研究中的参与，并向当地的圣地亚哥地区高中学生介绍现代材料科学研究的现代方面。探索以低价值金属中心为二级建筑单元（SBU）的异氰化物配位网络的合成和特性。有机环氰化物已经建立了很好的确定，可以通过强大的sigma抑制和高效的pi-backbonding相互作用来形成稳健的金属配体连接。长期以来，这种电子二元性也已被认为可以稳定低价值金属中心。寻求将这些离散的分子特性传输到网络物质环境中，进行合成研究，以准备使用多型异氰化物接头的多孔的三维固态网络，这些网络具有低价值过渡金属节点。此外，为了同时在这些材料的金属节点上赋予协调性饱和，M-二苯基异氰化物配体拓扑是这些研究的主要特征。在其基本材料特性的背景下，研究了新制备的异氰化物协调网络。这些材料作为低价值金属中心融合的功能，重点放在这些材料的化学刺激特性上。作为该奖项的一部分进行的实验性工作是由针对加利福尼亚大学圣地亚哥分校的初级/社区大学转学学生提前纳入材料科学研究的教育计划的补充。这些努力的目的是增加更广泛的学生人群参与STEM研究和高级培训。最后，为了增强从事该项目的学生的培训经验，以课程增强形式向当地高中推广也是该项目的主要组成部分。该奖项反映了NSF的法定任务，并被认为是通过基金会的知识分子优点和更广泛的审查标准来评估值得通过评估来支持的。