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Patterned formation of enolate functional groups on the graphene basal plane

Abstract : Chemical functionalization of graphene is one method pursued to engineer new properties into a graphene sheet. Graphene oxide is the most commonly used chemical derivative of graphene. Here we present experimental evidence for the formation of enolate moieties when oxygen atoms are added to the graphene basal plane. The exotic functional groups are stabilized by simultaneous bond formation between the graphene sheet and the underlying Ir(111) substrate. Scanning tunneling microscopy images demonstrate the patterned nature of CO bond formation and x-ray photoelectron spectroscopy and high resolution electron energy loss spectroscopy are used to characterize the enolate moiety. The results present a new mechanism for the formation of patterned graphene oxide and provide evidence of a functional group rarely considered for graphene oxide materials. Graphene is a 2D semi-metal in which all carbon atoms are sp 2 hybridized. 1 Chemical functionalization of graphene is driven by the desire to engineer the physical and chemical properties of pristine graphene sheets, and to introduce new means of incorporating graphene interfaces with other materials. 2-4 The addition of simple atomic species, such as hydrogen, 5 oxygen 6,7 or fluorine, 8 has been shown to change the electronic band structure of graphene from that of a semi-metal to that of a semiconductor or insulator. Graphene oxide is a term used to describe graphene materials that have been subjected to oxidation reactions. Supported graphene oxide materials have been studied as sensor materials, for their potential magnetic properties and as clusters to form graphene oxide quantum dots. 9-12 The growth of metallic nanoparticles on supported graphene sheets is also facilitated by the presence of CO bonds at the graphene basal plane, 4 with attachment or cleavage of particle growth initiators dependent on the nature of the CO bond. 13 This may be a viable method for atomic layer deposition on graphene films, allowing for integration of graphene sheets in more complex electronic devices. 14 Consequently, the nature of the CO bond formed during synthesis of graphene oxide is of general interest and importance. It is widely assumed that an oxygen atom bonding to the basal plane of a graphene sheet is initially covalently bound through the formation of an epoxy group. 15-18 The stability of different oxygen moieties on metal-supported graphene sheets was, however, recently explored for graphene islands on Ru(0001). 19 Those authors, building on theoretical results from Jung et al., 20 provided the first experimental evidence for the existence of the enolate moiety when oxygen atoms bind to a graphene sheet supported by a metal substrate. Their calculations indicate that interaction with an underlying metallic substrate can guide the formation of enolate groups when an oxygen atom binds to one carbon atom, and the adjacent carbon atom is suitably positioned to bind down to an underlying metal atom. A 370 meV gain in energy was reported for the formation of an enolate group, versus an epoxy group, in certain areas of the moiré pattern formed between the graphene lattice and atoms from the Ru(0001) surface. 19 Graphene on Ru(0001), however, is already a strongly coupled system with good evidence for the preexistence of a carbon-metal bond even before oxygen atoms are introduced. 21 Hence, it is timely to consider the nature of the CO bond for other, less strongly coupled systems. Graphene on Ir(111) (Gr/Ir(111)) demonstrates weak van der Waals interaction between the graphene sheet and the Ir(111) surface atoms. 22 Moreover, single crystal graphene sheets with a low concentration of defects and highly oriented domains are routinely prepared on Ir(111) substrates following chemical vapour deposition. 23 The attachment of oxygen atoms to Gr/Ir(111) has been reported previously but the possibility of enolate formation was not considered. 15,16 Here, we revisit this system adding new high-resolution electron energy loss spectroscopy (HREELS) data to demonstrate that at a low flux of oxygen atoms, enolate formation dominates and occurs only at select sites on the Gr/Ir(111) surface, generating a long-range pattern of graphene oxide nano-dots. The slight lattice mis-match between the carbon atoms in the graphene sheet and the Ir(111) surface atoms leads to a long-range repeating moiré pattern. 23 The moiré unit cell contains: TOP regions where Ir surface atoms are positioned directly beneath the center of a hexagonal ring in the graphene sheet; and HCP and FCC regions, where every second C atom is positioned directly above an Ir atom. HCP and FCC regions differ in the arrangement of Ir atoms in the second and third Ir layer. The remaining carbon atoms, in between
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Andrew Martin Cassidy, Stine Pedersen, Hendrik Bluhm, Valentin Calisti, Thierry Angot, et al.. Patterned formation of enolate functional groups on the graphene basal plane. Physical Chemistry Chemical Physics, Royal Society of Chemistry, 2018, 20 (45), pp.28370-28374. ⟨hal-01954159⟩



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