Synthetic and analytical considerations for the preparation of amorphous metal-organic frameworks

Metal-organic frameworks (MOFs) are hybrid porous materials presenting several tuneable properties, allowing them to be utilised for a wide range of applications. To date, focus has been on the preparation of novel crystalline MOFs for specific applications. Recently, interest in amorphous MOFs (aMOFs), defined by their lack of correlated long-range order, is growing. This is due to their potential favourable properties compared to their crystalline equivalents, including increased defect concentration, improved processability and gas separation ability. Direct synthesis of these disordered materials presents an alternative method of preparation to post-synthetic amorphisation of a crystalline framework, potentially allowing for the preparation of aMOFs with varying compositions and structures, and very different properties to crystalline MOFs. This perspective summarises current literature on directly synthesised aMOFs, and proposes methods that could be utilised to modify existing syntheses for crystalline MOFs to form their amorphous counterparts. It outlines parameters that could discourage the ordering of crystalline MOFs, before examining the potential properties that could emerge. Methodologies of structural characterisation are discussed, in addition to the necessary analyses required to define a topologically amorphous structure. Amorphous MOFs (aMOFs) are often prepared through introducing disorder to crystalline frameworks. This perspective aims to introduce directly synthesised aMOFs, expanding on synthetic methods, characterisation techniques and potential properties.