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    High-Quality Graphene Using Boudouard Reaction
    (Weinheim : Wiley-VCH, 2022) Grebenko, Artem K.; Krasnikov, Dmitry V.; Bubis, Anton V.; Stolyarov, Vasily S.; Vyalikh, Denis V.; Makarova, Anna A.; Fedorov, Alexander; Aitkulova, Aisuluu; Alekseeva, Alena A.; Gilshtein, Evgeniia; Bedran, Zakhar; Shmakov, Alexander N.; Alyabyeva, Liudmila; Mozhchil, Rais N.; Ionov, Andrey M.; Gorshunov, Boris P.; Laasonen, Kari; Podzorov, Vitaly; Nasibulin, Albert G.
    Following the game-changing high-pressure CO (HiPco) process that established the first facile route toward large-scale production of single-walled carbon nanotubes, CO synthesis of cm-sized graphene crystals of ultra-high purity grown during tens of minutes is proposed. The Boudouard reaction serves for the first time to produce individual monolayer structures on the surface of a metal catalyst, thereby providing a chemical vapor deposition technique free from molecular and atomic hydrogen as well as vacuum conditions. This approach facilitates inhibition of the graphene nucleation from the CO/CO2 mixture and maintains a high growth rate of graphene seeds reaching large-scale monocrystals. Unique features of the Boudouard reaction coupled with CO-driven catalyst engineering ensure not only suppression of the second layer growth but also provide a simple and reliable technique for surface cleaning. Aside from being a novel carbon source, carbon monoxide ensures peculiar modification of catalyst and in general opens avenues for breakthrough graphene-catalyst composite production.
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    Carbon Monoxide Coupling Reactions: A New Concept for the Formation of Hexahydroxybenzene
    (Weinheim : Wiley-VCH, 2020) Rosenthal, Uwe
    For linear and cyclic coupling reactions of CO, among other products, the formation of the hexapotassium salt of hexahydroxybenzene is of particular interesting. The interaction of metallic potassium and CO offers, via the assumed K[OC≡CO]K as the result of several carbon monoxide coupling reactions, the formation of C6(OK)6 among other products. To date, only speculations exist about the reaction pathway for these products, which were first described by Liebig in 1834. A novel concept is suggested here, which consists of the single steps (i) reductive coupling of CO, (ii) formation of dihetero-metallacyclopentynes (cis-2,5-diheterobutatriene as formal ethylenedione O=C=C=O complexes), (iii) formation of its dinuclear 1-metalla-2,5-dioxo-cyclopentyne complexes by external coordination of the triple bond, (iv) insertion of CO into the M−C bond of the formed metallacyclopropene, and (v) the reductive elimination of C6(OK)6. The novel aspect of this concept is the formation of dihetero-metallacyclopentynes (in analogy to the well characterized all-C-metallacyclopentynes), which have not been considered in the mechanism of reductive CO coupling reactions. It is expected that the presence of transition-metal impurities would promote the reaction. © 2020 The Authors. Published by Wiley-VCH GmbH