Fluorination of Metal-Organic Frameworks

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Background/ objective: Metal-organic frameworks (MOFs) are an exciting, and the largest, family of crystalline nanoporous material that is receiving global research attention for numerous uses including commercial and pilot plant applications for the storage of toxic gases, carbon capture, dehumidification - water harvesting and the control of fruit ripening. Due to the vast number of MOFs, a recent trend is to modify available MOFs in a designed manner to adapt their properties and enhance their application performance. One suitable modification route is to incorporate fluoride anions into the inorganic component of the MOF framework. Inclusion of fluoride anions in this framework component can produce MOFs with exceptional selectivity, recyclability and moisture stability for CO2 separations, or change the onset and degree of framework breathing transitions.Approach: This project aims to replace specific amounts of inorganic anions for fluoride anions in the subset of MOFs that contain inorganic anions as part of the zero-, one- or two-dimensional inorganic component of the MOF using a variety of materials' synthesis and post-synthesis approaches. The MOFs resulting from successful development of such methods will be fully characterized to determine the amount and nature of the fluoride incorporation that will involve powder and single crystal X-ray diffraction, solid state NMR spectroscopy, scanning electron microscopy, XPS and gas adsorption measurements. The resulting MOFs will also be tested for a range of properties including thermoresponsive, gas adsorption/ separation and electrical behaviours. The studentship will be based in Manchester but may involve trips to synchrotron sources for data collection.Novel engineering and/or physical sciences content: This research project will result in new routes to produce designed frameworks for MOFs and to understand the distribution of specific atoms/ groups within their framework. The functional MOFs produced will have modified and controllable properties particularly regarding their thermoresponsive and gas adsorption/ separation properties.Research areas: chemistry; energy; physical sciences; directed assembly; advanced materials