Modulated Metal-Organic Frameworks for Hydrogen Storage

这项高影响力的提案将通过开发新的金属有机骨架(MOF)材料的设计、合成和放大，为汽车工业应用提供高容量的储氢材料。我们将通过制备具有特殊设计的气体吸附孔的多孔MOF来提供具有增强储氢能力的材料。这些新材料将减轻重量和体积，从而提高整体储能密度和效率。我们的MOF孔调节策略还开发了控制吸氢动力学的方法，允许直接管理加油时间，并提高了存储的可逆性和预期寿命。该提议将提供新的方法，通过I增加氢结合能来增强MOF结构设计和合成，从而形成窄孔，从而从孔壁诱导重叠势，II。在MOF孔内产生自由金属配位，以允许氢直接与金属和团簇节点更强地结合；将自由配基供体结合到孔内。我们将开发一系列有机、无机和金属反阳离子包裹在骨架孔中的阴离子MOF的制备。这种方法将通过阳离子门控提供具有受控滞后吸附性能的材料，从而导致存储系统的受控加油/再充电。该提案的最后一个方面将是利用微波技术扩大选定MOF的合成规模。扩大规模是在运输部门使用MOF的一个关键问题，我们的方法将特别针对高性能材料。还将研究使用近临界溶剂和机械力化学方法获得功能多孔材料的新途径。将评估使用微波合成和近临界溶剂的连续流动方法，以降低扩大规模的成本。该提案的最终目标将是使MOF作为储氢材料的应用达到可以在现实系统中应用的阶段，从而克服重大技术障碍，释放氢作为可行的、清洁的化石燃料替代品的潜力，使氢经济成为现实。

This high-impact proposal will deliver high capacity hydrogen storage materials for applications in the automobile industry by developing the design, synthesis and scale-up of new metal-organic framework (MOF) materials. We will deliver materials with enhanced hydrogen storage capability by preparing porous MOFs with specifically designed pores for gas adsorption. These new materials will have reduced weight and volume, and thus improve overall energy storage density and efficiency. Our strategy of MOF pore modulation also develops approaches to controlling the kinetics of hydrogen uptake allowing direct management of refuelling times, and increasing the reversibility and life expectancy of the store.The proposal will deliver new methodologies for enhancing MOF structural design and synthesis by increasing hydrogen binding energies by i. formation of narrow pores thus inducing overlapping potentials from pore walls, ii. generation of free metal coordination sites within MOF pores to allow stronger binding of hydrogen directly to metal and cluster nodes, and iii. incorporation of free ligand donor sites within pores.We will develop the preparation of anionic MOFs with a range of organic, inorganic and metal counter-cations encapsulated within framework pores. Such an approach will afford materials with controlled hysteretic adsorption properties via cation gating leading to controlled refuelling/recharging of the storage system. The final aspect of the proposal will be to develop the scale-up of synthesis for selected MOFs using microwave technologies. Scale-up is a key issue for the use of MOFs in the transport sector and our approaches will target particularly high performance materials. Novel routes to functional porous materials using near critical solvents and mechanochemical methods will also be investigated. Continuous flow methods using microwave synthesis and near critical solvents will be assessed with the aim of reducing costs of scale-up.The ultimate goal of the proposal will be to bring the application of MOFs as hydrogen storage materials to a stage where they can be applied in real-world systems, thus overcoming a major technological barrier and unlocking the potential of hydrogen as a viable, clean replacement for fossil fuels, and enabling the Hydrogen Economy to become a reality.