Conductive Metal-Organic Frameworks

导电金属有机框架

• 批准号: 1309066
• 负责人: Jeffrey Long
• 金额: $ 52.34万
• 依托单位: University of California-Berkeley
• 依托单位国家: 美国
• 项目类别: Continuing Grant
• 财政年份: 2013
• 资助国家: 美国
• 起止时间: 2013-09-15 至 2016-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1309066&HistoricalAwards=false
• 关键词: Conductive; Metal; Organic; Frameworks

TECHNICAL SUMMARY:With the support of the Solid State and Materials Chemistry program in the Division of Materials Research, new synthetic strategies will be developed in pursuit of metal-organic frameworks that exhibit facile ionic and/or electronic charge mobility. The synthetic tunability of metal-organic frameworks is expected to stimulate inquiry into new physical phenomena such as nanometer scale pore confinement effects and framework-centered charge distribution on ion mobility as well as, electron correlation in one-dimensional materials, and the electronic and magnetic properties of low dimensional systems. Such investigations are of immediate interest for their potential battery applications as electrode or solid electrolyte component materials, electrocatalysis, thermoelectric devices and ultra-capacitors. Porous materials with high ion mobility can be prepared by engendering frameworks with delocalized or otherwise inaccessible charges in order to yield uncoordinated and pore-confined single-ion conductors. This will include the preparation of materials containing ionic metal clusters, ionic organic linkers, inclusion of bulky counterions, and characterizing ion mobility trends with respect to ion identity, pore dimensions, pore topography, framework topology, and crystallite morphology. Leveraging the modular nature of metal-organic frameworks in order to include reversible redox couples in both the inorganic and organic components of the material will target new electronically conductive frameworks. Other synthetic strategies not yet developed in this class of materials will also be explored. This will include optimization of electron correlation along one-dimensional chains of metal centers, the inclusion of stable organic radical, and tuning the band structure via ligand functionalization and inclusion of adventitious guest species. Doing so will allow investigation of charge mobility in porous structures from the perspective of fundamental coordination chemistry, a technique commonly reserved only for molecular species. NON-TECHNICAL SUMMARY:Metal-organic frameworks are a new class of solid materials with porous network structures the surfaces of which can be chemically modified to suit a wide range of potential applications, notably gas storage, chemical separations, and catalysis. By adapting these materials to be electrically conductive through the movement of ions and electrons, new phenomena will be explored that are of fundamental interest in chemistry, energy storage, and condensed matter physics. This work will expand the understanding of how to control the formation of new materials and manipulate the electronic and ionic charge transport properties therein. With the support of the Solid State and Materials Chemistry program in the Division of Materials Research, new porous materials will be created of potential interest as component materials in advanced batteries, electrocatalysis, thermoelectric devices, and ultra-capacitors. In doing so, this work will broadly impact these key technologies, resulting in a legacy of new synthetic techniques and a fundamental understanding of conductive materials, while additionally contributing to the education and training of undergraduate, graduate, and postdoctoral students in the synthesis and characterization of new materials. As a related endeavor, the principle investigator will continue to lead an effort in the Department of Chemistry at UC Berkeley to found a materials chemistry major.

在材料研究部门的固态和材料化学计划的支持下，将开发新的合成策略，以追求表现出易离子和/或电子电荷迁移性的金属有机框架。金属有机骨架的合成可调谐性有望激发对新物理现象的探索，如纳米尺度的孔限制效应和骨架中心电荷分布对离子迁移率的影响，以及一维材料中的电子相关性，以及低维系统的电子和磁性。这些研究对于它们作为电极或固体电解质组分材料、电催化、热电器件和超级电容器的潜在电池应用具有直接的意义。具有高离子迁移率的多孔材料可以通过产生具有离域或以其他方式不可接近的电荷的框架来制备，以产生非配位和孔限制的单离子导体。这将包括制备含有离子金属簇、离子有机连接体、包含大体积抗衡离子的材料，以及表征关于离子身份、孔尺寸、孔形貌、骨架拓扑和微晶形态的离子迁移率趋势。利用金属-有机框架的模块化性质，以便在材料的无机和有机组分中包括可逆的氧化还原对，这将针对新的电子导电框架。还将探索在这类材料中尚未开发的其他合成策略。这将包括优化电子相关沿着一维链的金属中心，包括稳定的有机自由基，并通过配体官能化和包括外来的客体物种调整能带结构。这样做将允许从基本配位化学的角度研究多孔结构中的电荷迁移率，这是一种通常仅用于分子物种的技术。非技术概述：金属有机框架是一类具有多孔网络结构的新型固体材料，其表面可以进行化学改性以适应广泛的潜在应用，特别是气体储存，化学分离和催化。通过使这些材料通过离子和电子的运动而具有导电性，将探索在化学、能量存储和凝聚态物理学中具有根本意义的新现象。这项工作将扩大对如何控制新材料的形成和操纵其中的电子和离子电荷传输特性的理解。在材料研究部门的固态和材料化学计划的支持下，新的多孔材料将作为先进电池，电催化，热电器件和超级电容器的组件材料产生潜在的兴趣。在这样做的过程中，这项工作将广泛影响这些关键技术，从而产生新的合成技术的遗产和对导电材料的基本理解，同时还有助于本科生，研究生和博士后学生在新材料的合成和表征方面的教育和培训。作为一个相关的奋进，主要研究者将继续领导在加州大学伯克利分校化学系的努力，以建立一个材料化学专业。