Berlin 2024 – scientific programme
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O: Fachverband Oberflächenphysik
O 15: Organic Molecules on Inorganic Substrates II: Electronic, Optical and other Properties
O 15.6: Talk
Monday, March 18, 2024, 16:15–16:30, MA 043
Dioxygen ligation and activation at a biomimetic 2D metal organic framework — •Stefania Baronio1, Michela De Col1, Davide Bidoggia1, Danilo Comini2, Mattia Scardamaglia3, and Erik Vesselli1,4 — 1Physics Department, University of Trieste, Trieste, Italy — 2II Physics Department, University of Cologne, Cologne, Germany — 3MAX IV Laboratory, University of Lund, Lund, Sweden — 4CNR-IOM, Istituto Officina dei Materiali, Trieste, Italy
The investigation of 2D metal organic frameworks at surfaces is a hot topic in surface science due to their potential applications also as single atom catalysts [1]. Our work focuses on the in situ spectroscopic characterization of a bimetallic MnTPyP-Co framework self-assembled on Gr/Ir(111) and structurally similar to previously investigated Fe- and Co-based systems active towards the oxygen evolution and reduction reactions [2,3]. By means of a combined approach exploiting Sum Frequency Generation Spectroscopy and Ambient Pressure XPS, we show how the tetra-coordination of Co ad-atoms by adjacent MnTPyPs affects the overall electronic and vibrational structure of the layer, including the oxidation state of the Mn centers. The bimetallic system is extremely reactive towards O2: while dioxygen weakly ligates at room temperature and under UHV conditions, at close-to-ambient pressure the molecule undergoes activation and dissociation at the Co sites, and CO oxidation becomes then possible.
[1] W. Auwärter et al., Nat. Chem. 7, 105-120(2015) [2] B. Wurster et al., J. Am. Chem. Soc. 138, 3623-3626(2016) [3] F. Armillotta et al., ACS Catal. 12, 7950-7959(2022)
Keywords: metal organic framework; ambient pressure; vibrational spectroscopy; xps; dioxygen