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

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 requi...

Full description

Saved in:
Bibliographic Details
Published in:Nanoscale 2022-07, Vol.14 (26), p.957-9515
Main Authors: Jakub, Zden k, Kurowská, Anna, Herich, Ondrej, erná, Lenka, Kormoš, Lukáš, Shahsavar, Azin, Procházka, Pavel, echal, Jan
Format: Article
Language:English
Subjects:
Atomic structure
Graphene
Iron
Manganese
Metal-organic frameworks
Microscopy
Modular systems
Nickel
Photoelectrons
Scanning tunneling microscopy
Spintronics
Stoichiometry
Substrates
Thermal stability
Citations: Items that this one cites
Items that cite this one
Online Access:Get full text
Tags: Add Tag
No Tags, Be the first to tag this record!
Description
Summary: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 M 1 (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. We present three isostructural substrate-decoupled 2D metal organic frameworks, which are stable in ambient environment and can be studied with atomic-scale precision.
ISSN:2040-3364
2040-3372
DOI:10.1039/d2nr02017c