Atomic-layer deposition (ALD) within mesoroporous MOFs provides a means of synthesizing uniform ensembles of metal-oxide clusters featuring any of a broad range of predetermined compositions, including mixed-metal oxide compositions. By varying the number of ALD cycles, cluster size can be modulated. Keys to the utilization of ALD, a vapor-phase synthesis technique, with metal-organic frameworks are: a) large MOF channels and apertures (widths of a few tens of angstroms), b) availability of good ALD reaction sites (for example, hydroxide ligands on MOF nodes), c) good MOF thermal stability, and d) good MOF chemical stability (e.g. the ability to withstand repetitive exposure to steam at temperatures up to 180  celsius). We find that the clusters resulting from can impart to MOFs exceptional stability (including stability at extreme acid and alkaline pHs), redox activity, and/or catalaytic activity, while preserving MOF porosity.

Building functional inorganic clusters within mesoporous metal-organic frameworks

247th National Meeting (2014)

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