Electrically conductive metal-organic frameworks and porous coordination polymers for energy storage

金属有机骨架（MOFs）是由有机配体与几何定向金属离子簇之间的配位键形成的多孔扩展固体。自20世纪90年代末该领域成立以来，由于其高孔隙率和化学可调性，这些材料在气体储存、分离和催化方面的应用得到了广泛的研究。然而，高导电性在mof中是罕见的，尽管这种特性可以实现多种可持续的储能和电催化等技术。事实上，直到最近，由于全球可持续能源议程的重新承诺，MOF的电子特性受到的关注相对较少。该博士项目旨在展示三维或全局共轭通道设计的增强优势，以在有机杂化多孔配位聚合物（pcp）（如mof）中提供广泛的导电途径，用于新型能量存储。该博士生将着手设计、制备和计算导电mof的模型，该mof包括围绕金属位点排列的电化学活性有机连接体，以形成快速离子和电荷载流子运动的三维形状通道。计算模型将允许学生可视化全局共轭路径，并确定哪些路径可能主导MOF导电特性。这些模型将通过与实验室合成的候选MOF获得的基本实验和能量装置数据进行比较来证实和改进。先进的材料显微镜、热分析和电化学技术将使学生能够在原子级结构修饰和MOF的体尺度材料性能之间建立非常清晰的关系，从而为一般类型的3D共轭pcp建立合理的设计原则。最有前途的产品将集成到可充电锂离子电池和其他电化学设备中，提高了约克郡可持续能源领域技术创新的可能性。

Metal-organic frameworks (MOFs) are intrinsically porous extended solids formed by coordination bonding between organic ligands and geometry-directing metal ion clusters. Since the inception of the field in the late 1990s, these materials have been investigated extensively for applications in gas storage, separations, and catalysis because of their high porosity and chemical tunability. However, high electrical conductivity is rare in MOFs, even though this property would enable diverse sustainable technologies in charge (energy) storage and electrocatalysis, among others. Indeed, the electronic properties of MOFs have received comparatively less attention than their physical MOF properties until recently, driven by renewed commitments to global sustainable energy agenda. This PhD project specifically aims to demonstrate the enhanced benefit of three-dimensional or globally conjugated channel designs to afford extensive electrical conductivity pathways within organic hybrid porous coordination polymers (PCPs) like MOFs for novel energy storage.The PhD student will set out to design, prepare and computationally model electrically-conductive MOFs comprising electrochemically active organic linkers arranged around a metal site to form three-dimensionally shaped channels for fast ion and charge carrier movement. Computational models will allow the student to visualise global conjugation pathways and identify which ones may dominate MOF conductive properties. These models will be corroborated and refined by comparison to fundamental experimental and energy device data obtained from MOF candidates being synthesised in the laboratory. Advanced materials microscopy, thermal analysis and electrochemical techniques will allow the student to develop very clear relationships between atomic-level structural modifications and bulk-scale material properties of the MOF with a view to establishing rational design principles for the general class of 3D conjugated PCPs. The most promising products will be integrated into rechargeable lithium-ion batteries and other electrochemical devices, raising the possibility for technological innovation in the sustainable energy area from York.