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

金属-有机骨架（MOFs）是由有机配体和几何定向金属离子簇之间的配位键合形成的固有多孔扩展固体。自20世纪90年代后期该领域成立以来，由于其高孔隙率和化学可调性，这些材料已被广泛研究用于气体储存，分离和催化。然而，高电导率在MOF中是罕见的，即使这种特性将使电荷（能量）存储和电催化等多种可持续技术成为可能。事实上，直到最近，由于对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少于其物理MOF特性。这个博士项目的具体目的是证明三维或全局共轭通道设计的增强效益，以提供广泛的导电性途径内的有机杂化多孔配位聚合物（PCP），如MOFs的新能源存储。博士生将着手设计，制备并计算建模包含电化学活性有机连接体的导电MOF，所述电化学活性有机连接体布置在金属位点周围以形成三个-用于快速离子和电荷载流子移动的三维形状的通道。计算模型将允许学生可视化全局共轭途径，并确定哪些可能主导MOF导电特性。这些模型将通过与从实验室合成的MOF候选物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开发出非常清晰的原子级结构修饰和大规模的材料性质的MOF之间的关系，以期建立合理的设计原则，为一般类的3D共轭PCP。最有前途的产品将被集成到可充电锂离子电池和其他电化学设备中，提高了约克在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.