2D Surface MOFs

Metal-organic frameworks (MOFs) are formed though the coordination of metal ions with organic ligands and, due to their inherent structural porosity, they can effectively host a wide range of molecules. This leads to various practical applications that include drug delivery, gas storage, catalysis, sensing and gas separation.

2D MOFs have the potential to combine the advantages of traditional 3D MOFs with those of 2D materials, such as, for example, flexibility, light weight, light transparency and electrical conductivity. Their synthesis can occur through top-down or bottom-up strategies, with the former relying on stripping 2D layers from a 3D crystal, while the latter tend to directly make single layer MOFs by confining the synthesis to surfaces or interfaces. The direct synthesis of 2D MOFs on solid surfaces (or the grafting of solution-synthesised 2D MOFs onto solid surfaces), allows one to access high-resolution surface science analytical techniques to precisely characterise the structure, topology and defects of these material as well as their chemical, electronic and magnetic properties.

We have been mainly exploring 2D MOFs synthesised by depositing molecular building blocks and metal centres directly on surfaces and linking them via specific bonding motifs. .

1D MOF formed via substrate templating by trimesate molecules and copper atoms on Cu(110). Their [-Cu-TMA-Cu-]n structure is shown at the bottom, STM images on the top and DFT-simulated images in the middle [3.]

In this way we can fabricate extended 2D porous networks, discrete clusters and even 1D chains. We study their regular structure with exquisite spatial resolution by combining several structural characterisations techniques such as STM, LEED, NIXSW and SXRD, determine precise chemical and electronic properties via X-ray photoelectron spectroscopy, and often collaborate with theoretical colleagues who use density functional theory (DFT) calculations to interpret the experimental data.


Key publications:

  1. Re-evaluating how charge transfer modifies the conformation of adsorbed molecules
    P.J. Blowey, S. Velari, L.A. Rochford, D.A. Duncan, D.A. Warr, T.-L. Lee, A. De Vita, G. Costantini, and D.P. Woodruff
    Nanoscale 10, 14984 (2018).
  2. Metal—Organic Coordination Interactions in Fe—Terephthalic Acid Networks on Cu(100)
    S.L. Tait, Y. Wang, G. Costantini, N.Lin, A. Baraldi, F. Esch, L. Petaccia, S. Lizzit, and K. Kern
    J. Am. Chem. Soc. 130, 2108 (2008).
  3. Templated Growth of Metal-Organic Coordination Chains at Surfaces
    T. Classen, G. Fratesi, G. Costantini, S. Fabris, F.L. Stadler, C. Kim, S. de Gironcoli, S. Baroni, and K. Kern
    Angew. Chem. Int. Ed. 44, 6142 (2005).
  4. Engineering atomic and molecular nanostructures at surfaces
    J.V. Barth, G. Costantini, and K. Kern
    Nature 437, 671 (2005).
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