Metal-Organic Layers (MOLs) represent an emerging class of tunable and functionalizable two-dimensional materials. We developed scalable solvothermal synthesis of self-supporting MOLs composed of [Hf6O4(OH)4(HCO2)6] secondary building units (SBUs) and benzene-1, 3, 5-tribenzoate (BTB) bridging ligands. The MOLs structures were directly imaged by TEM and AFM, and doped with 4’-(4-benzoate)-(2,2’,2’’-terpyridine)-5,5’’-dicarboxylate (TPY) before being coordinated with iron centers to afford highly active and reusable single-site solid catalysts for hydrosilylation of terminal olefins. Previous kinetic studies on MOF catalysis have shown that in many cases the MOF catalyzed reactions are under diffusional control. The extension of MOF channel sizes to over 2 nm can greatly enhance the diffusion rate of typical small organic molecules, but is still not suitable for large medicinal substrate. MOL-based heterogeneous catalysts are free from the diffusional constraint placed on all known porous solid catalysts including metal-organic frameworks. This easily scalable synthesis of MOLs uncovers an entirely new strategy for designing single-site solid catalysts and opens the door to a new class of two-dimensional coordination materials with molecular functionalities.

Bottom-up assembly of self-supporting metal-organic layers

254th National Meeting (2017)

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