Remarkably stable metal-organic frameworks on an inert substrate: M-TCNQ on graphene (M = Ni, Fe, Mn)

Abstract

Potential applications of 2D metal-organic frameworks (MOF) require the frameworks to be monophase and well-defined at the atomic scale, to be decoupled from the supporting substrate, and to remain stable at the application conditions. Here,we present three systems meeting this elusive set of requirements: M-TCNQ (M = Ni, Fe, Mn) on epitaxial graphene/Ir(111). We study the systems experimentally by scanning tunneling microscopy, low energy electron microscopy and x-ray photoelectron spectroscopy. When synthesized on graphene, the 2D M-TCNQ MOFs are monophase with M1(TCNQ)1 stoichiometry, no alternative structure was observed with slight variation of the preparation protocol. We further demonstrate a remarkable chemical and thermal stability of TCNQ-based 2D MOFs: All the studied systems survive exposure to ambient conditions, with Ni-TCNQ doing so without any significant changes to its atomic-scale structure or chemical state. Thermally, the most stable system is Fe-TCNQ which remains stable above 500 °C, while all the tested MOFs survive heating to 250 °C. Overall, the modular M-TCNQ/graphene system combines the atomic-scale definition required for fundamental studies with the robustness and stability needed for applications, thus we consider it an ideal model for research in single atom catalysis, spintronics or high-density storage media.Potential applications of 2D metal-organic frameworks (MOF) require the frameworks to be monophase and well-defined at the atomic scale, to be decoupled from the supporting substrate, and to remain stable at the application conditions. Here,we present three systems meeting this elusive set of requirements: M-TCNQ (M = Ni, Fe, Mn) on epitaxial graphene/Ir(111). We study the systems experimentally by scanning tunneling microscopy, low energy electron microscopy and x-ray photoelectron spectroscopy. When synthesized on graphene, the 2D M-TCNQ MOFs are monophase with M1(TCNQ)1 stoichiometry, no alternative structure was observed with slight variation of the preparation protocol. We further demonstrate a remarkable chemical and thermal stability of TCNQ-based 2D MOFs: All the studied systems survive exposure to ambient conditions, with Ni-TCNQ doing so without any significant changes to its atomic-scale structure or chemical state. Thermally, the most stable system is Fe-TCNQ which remains stable above 500 °C, while all the tested MOFs survive heating to 250 °C. Overall, the modular M-TCNQ/graphene system combines the atomic-scale definition required for fundamental studies with the robustness and stability needed for applications, thus we consider it an ideal model for research in single atom catalysis, spintronics or high-density storage media.