Thin-film deposition of metal-organic frameworks (MOFs) is now possible, but little is known regarding the microscopic nature of hybrid hetero-interfaces. We first assess optimal substrate combinations for coherent epitaxy of MOFs based on a lattice matching procedure. We then perform a detailed quantum mechanical/molecular mechanical investigation of the growth of (011) MOF-5 on (110) rutile TiO2. The lowest energy interface configuration involves a bidentate connection between two TiO6 polyhedra with deprotonation of terephthalic acid to a bridging oxide site. The epitaxy of MOF-5 on the surface of TiO2 was modelled with a forcefield parameterised to quantum chemical binding energies and bond lengths. The microscopic interface structure and chemical bonding characteristics are expected to be relevant to other hybrid framework-oxide combinations.
Bibliographical noteFunding Information:
J. K. B. is funded by the EPSRC (grant no. EP/G03768X/1). J. D. G. thanks the Australian Research Council for funding under the Discovery Programme, as well as the Pawsey Supercomputing Centre and NCI for the provision of computing resources. A. W. acknowledges support from the Royal Society University Research Fellowship scheme. K. L. S. is funded under ERC Starting Grant 277757 and K. T. B. is funded under EPSRC grant no. EP/M009580/1. The work benefited from the high performance computing facility at the University of Bath. Access to the ARCHER supercomputer was facilitated through membership of the HPC Materials Chemistry Consortium (EP/L000202).
© The Royal Society of Chemistry.