Single-atom catalysts (SACs) based on graphene derivatives are an emerging and growing class of materials functioning as two-dimensional (2D) metal-coordination scaffolds with intriguing properties. Recently, owing to the rich chemistry of fluorographene, new avenues have opened toward graphene derivatives with selective, spacer-free, and dense functionalization, acting as in-plane or out-of-plane metal coordination ligands. The particular structural features give rise to intriguing phenomena occurring between the coordinated metals and the graphene backbone. These include redox processes, charge transfer, emergence, and stabilization of rare or otherwise unstable metal valence states, as well as metal-support and metal-metal synergism. The vast potential of such systems has been demonstrated as enzyme mimics for cooperative mixed-valence SACs, ethanol fuel cells, and CO2 fixation; however, it is anticipated that their impact will further expand toward diverse fields, e.g., advanced organic transformations, electrochemical energy storage, and energy harvesting.

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We report successful grafting of alkynyl groups onto graphene via the Sonogashira reaction between fluorographene and terminal alkynes. Theoretical calculations revealed that fluorographene can efficiently bind and oxidize the palladium catalyst on electrophilic sites activated by fluorine atoms. This paves the way towards conductive and mechanically robust 3D covalent networks.

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• časopisecké články MeSH

Controllable synthesis of graphene derivatives with defined composition and properties represents the holy grail of graphene chemistry, especially in view of the low reactivity of graphene. Recent progress in fluorographene (FG) chemistry has opened up new routes for synthesizing a plethora of graphene derivatives with widely applicable properties, but they are often difficult to control. We explored nucleophilic substitution on FG combining density functional theory calculations with experiments to achieve accurate control over the functionalization process. In-depth analysis revealed the complexity of the reaction and identified basic rules for controlling the 2D chemistry. Their application, that is, choice of solvent and reaction time, enabled facile control over the reaction of FG with N-octylamine to form graphene derivatives with tailored content of the alkylamine functional group (2.5-7.5% N atomic content) and F atoms (31.5-3.5% F atomic content). This work substantially extends prospects for the controlled covalent functionalization of graphene.

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Fluorographene, formally a two-dimensional stoichiometric graphene derivative, attracted remarkable attention of the scientific community due to its extraordinary physical and chemical properties. We overview the strategies for the preparation of fluorinated graphene derivatives, based on top-down and bottom-up approaches. The physical and chemical properties of fluorographene, which is considered as one of the thinnest insulators with a wide electronic band gap, are presented. Special attention is paid to the rapidly developing chemistry of fluorographene, which was advanced in the last few years. The unusually high reactivity of fluorographene, which can be chemically considered perfluorinated hydrocarbon, enables facile and scalable access to a wide portfolio of graphene derivatives, such as graphene acid, cyanographene and allyl-graphene. Finally, we summarize the so far reported applications of fluorographene and fluorinated graphenes, spanning from sensing and bioimaging to separation, electronics and energy technologies.

• Klíčová slova
• Chemistry, Covalent functionalization, Fluorographene, Graphene derivatives,
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• časopisecké články MeSH
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