Cyclodehydrogenation of molecular nanographene precursors catalyzed by atomic hydrogen.

Zuzak, Rafal; Dabczynski, Pawel; Castro-Esteban, Jesús; Martínez, José Ignacio; Engelund, Mads; Pérez, Dolores; Peña, Diego; Godlewski, Szymon · Nat Commun · 2025

basic_science · Level V

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Abstract

Atomically precise synthesis of graphene nanostructures on semiconductors and insulators has been a formidable challenge. In particular, the metallic substrates needed to catalyze cyclodehydrogenative planarization reactions limit subsequent applications that exploit the electronic and/or magnetic structure of graphene derivatives. Here, we introduce a protocol in which an on-surface reaction is initiated and carried out regardless of the substrate type. We demonstrate that, counterintuitively, atomic hydrogen can play the role of a catalyst in the cyclodehydrogenative planarization reaction. The high efficiency of the method is demonstrated by the nanographene synthesis on metallic Au, semiconducting TiO<sub>2</sub>, Ge:H, as well as on inert and insulating Si/SiO<sub>2</sub> and thin NaCl layers. The hydrogen-catalyzed cyclodehydrogenation reaction reported here leads towards the integration of graphene derivatives in optoelectronic devices as well as developing the field of on-surface synthesis by means of catalytic transformations. It also inspires merging of atomically shaped graphene-based nanostructures with low-dimensional inorganic units into functional devices.