Conductive Metal-Organic Frameworks

导电金属有机框架

• 批准号: 1611525
• 负责人: Jeffrey Long
• 金额: $ 54万
• 依托单位: University of California-Berkeley
• 依托单位国家: 美国
• 项目类别: Standard Grant
• 财政年份: 2016
• 资助国家: 美国
• 起止时间: 2016-09-01 至 2019-08-31
• 项目状态: 已结题
• 来源: https://www.nsf.gov/awardsearch/showAward?AWD_ID=1611525&HistoricalAwards=false
• 关键词: Conductive; Metal; Organic; Frameworks

NON-TECHNICAL DESCRIPTION: Sponge-like crystals with precisely designed nanometer scale pores are critically important for the efficient separation and storage of gases. Technologically, nanoporous semiconductors also show promise as component materials in battery electrodes, chemical sensors, electrocatalysts, and electrochromic materials. Until recently, however, nanoporous crystals have been almost exclusively typecast as electronic insulators. This limitation originates from the trusswork of very strong chemical bonds needed to maintain a stable pore structure. As such, the synthesis of new, electrically conductive, porous crystals stands as an inherently counterintuitive challenge. Efforts toward producing such materials will push the limits of stability and charge delocalization across a crystalline latticework of transition metal nodes and organic linkers. TECHNICAL DESCRIPTION: Metal-organic frameworks are microporous network solids composed of inorganic nodes linked together by organic bridging ligands. While metal-organic frameworks have been extensively developed for their remarkable gas sorption and separation properties, like most porous inorganic materials, they are essentially ionic and electronic insulators. In spite of these properties, this class of materials offers a unique opportunity to explore long-range ion and electron transport in low-dimensional nanoporous systems. The apparent lack of conductive frameworks that have been investigated thus far is not an inherent structural limitation, but rather a result of a lack of focus on electronically interesting structural motifs. That is, the vast majority of frameworks are composed of redox-inactive, closed shell transition metals and organic ligands. In response, metal-organic frameworks engendered with bulk electronic conductivity through the synthesis of open shell and redox-ambiguous scaffolds will be developed. More broadly, the investigation of electronically conductive metal-organic frameworks will explore the limits of long-range electronic communication in low-density hybrid solids and elucidate the primary factors governing the resulting properties. Owing to their crystallinity and the ease of functionalization, metal-organic frameworks can also serve as excellent model systems to better understand and enhance ion transport in nanochannels and nanoporous solids. Thus, the synthesis and characterization of new ion conducting frameworks with a focus on ions that are notoriously difficult to conduct in the solid-state will be pursued.

非技术描述：具有精确设计的纳米尺度孔的海绵状晶体对于有效的分离和存储气体至关重要。从技术上讲，纳米多孔的半导体也表现出有望作为电池电极，化学传感器，电催化剂和电染色体材料的组件材料。然而，直到最近，纳米多孔晶体几乎完全被用作电子绝缘体。该限制起源于维持稳定孔结构所需的非常强的化学键的桁架。因此，新的，导电的多孔晶体的合成是固有的违反直觉挑战。生产此类材料的努力将在过渡金属节点和有机连接器的结晶晶格上推动稳定性的限制和电荷脱位。技术描述：金属有机框架是微孔网络固体，该固体由有机桥接配体连接在一起的无机节点组成。虽然金属有机框架已经广泛开发出其出色的气体吸附和分离特性，就像大多数多孔无机材料一样，它们本质上是离子和电子绝缘体。尽管具有这些特性，但此类材料为低维纳米多孔系统中的远距离离子和电子传输提供了独特的机会。到目前为止，已经研究的显然缺乏导电框架不是固有的结构限制，而是由于缺乏对电子有趣的结构基序的关注而导致的。也就是说，绝大多数框架都是由氧化还原易活的，封闭的壳过渡金属和有机配体组成的。作为响应，将开发出具有散装电子电导率的金属有机框架，并通过合成开放式壳和氧化还原的脚手架。更广泛地，对电子导电金属有机框架的研究将探索低密度杂交固体中远程电子通信的限制，并阐明了控制所得特性的主要因素。由于它们的结晶度和功能化的易用性，金属有机框架还可以作为优秀的模型系统，以更好地理解和增强纳米渠道和纳米固体中的离子传输。因此，将追求新的离子传导框架的综合和表征，重点是众所周知，这些离子在固态中很难进行。