Berlin 2024 – wissenschaftliches Programm
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O: Fachverband Oberflächenphysik
O 87: Focus Session: Molecular Nanostructures on Surfaces: On-Surface Synthesis and Single-Molecule Manipulation III
O 87.4: Vortrag
Donnerstag, 21. März 2024, 16:00–16:15, HE 101
Reactivity of Aromatic Amines on Metal Surfaces — Nan Cao1,2, Kaifeng Niu3, Wenchao Zhao2, Jonas Björk3, Lifeng Chi1, Johannes Barth2, and •Biao Yang1,2 — 1Soochow University, Suzhou 215123 (P. R. China) — 2Technical University of Munich, D-85748 Garching, (Germany) — 3Linköping University, 58183 Linköping (Sweden)
Aromatic amines are widely used as intermediates to dyes, pharmaceuticals, and agricultural chemicals, whereas the oxidation process is of great significance for their direct application and synthesis of other complex nitrogen-containing compounds. Dehydrogenation of the amino group in aromatic amines on copper surfaces is usually achieved with thermal treatment. However, amino has no reactivity reported on relatively inert surfaces of silver and gold. Herein, we combine STM and XPS studies to explore the reactivity of aromatic amines on silver and gold surfaces with the O2-gas mediation[1]. While oxidative dehydrogenation reaction is achieved on silver surfaces, forming the N-Ag complex with intrinsic Ag adatoms, aromatic amine layers remain intact on the gold surface with the O2-mediated treatment. Complementary insights from density functional theory calculations of reaction pathway, core level shift, and chemisorption energy reveal the thermodynamically substrate-dependent mechanics. The systematic study unveils the mechanism of catalytic oxidative dehydrogenation reaction of amines, enriching the on-surface synthesis toolbox for the production of low-dimensional organic materials. Reference [1] Nan Cao, Biao Yang et al. Nat. Commun. 14, 1255 (2023)
Keywords: on-surface chemistry; aromatic amines; STM; oxidative dehydrogenation