Modulated Metal-Organic Frameworks for Hydrogen Storage

这项高影响力的提案将通过开发新型金属有机框架（MOF）材料的设计、合成和放大，为汽车工业应用提供高容量储氢材料。我们将通过制备具有专门设计的气体吸附孔的多孔MOFs来提供具有增强储氢能力的材料。这些新材料将减少重量和体积，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氢吸收动力学的方法，允许直接管理换料时间，并增加存储的可逆性和预期寿命。形成窄孔，从而诱导来自孔壁的重叠电势，ii.在M0 F孔内产生游离金属配位位点以允许氢直接更强地结合到金属和簇节点，以及iii.我们将开发具有一系列有机、无机和金属抗衡阳离子封装在骨架孔内的阴离子MOF的制备。这样的方法将通过阳离子门控提供具有受控滞后吸附性质的材料，从而导致储存系统的受控补给燃料/再装填。该提案的最后一个方面将是利用微波技术扩大选定MOFs的合成规模。扩大规模是交通运输部门使用MOFs的关键问题，我们的方法将针对特别高性能的材料。本研究亦将探讨使用近临界溶剂及机械化学方法制备功能性多孔材料的新途径。将评估使用微波合成和近临界溶剂的连续流方法，以降低规模扩大的成本。该提案的最终目标是将MOFs作为储氢材料的应用带到可以在现实世界系统中应用的阶段，从而克服一个主要的技术障碍，释放氢作为化石燃料的可行的清洁替代品的潜力，让氢经济成为现实。

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.