Tunable Synthesis of Predominant Semi-Ionic and Covalent Fluorine Bonding States on a Graphene Surface.

In this study, fluorinated graphene (FG) was synthesized via a hydrothermal reaction. Graphene oxides (GOs) with different oxygen bonding states and oxygen contents (GO(F), GO(P), and GO(HU)) were used as starting materials. GO(F) and GO(P) are commercial-type GOs from Grapheneall. GO(HU) was prepared using a modified Hummers method. The synthesized FGs from GO(F), GO(P), and GO(HU) are denoted as FG(F), FG(P), and FG(HU), respectively. The F atoms were bound to the graphene surface with predominantly semi-ionic or covalent bonding depending on the GO oxygen state. FG(F) and FG(HU) exhibited less extensive fluorination than FG(P) despite the same or higher oxygen contents compared with that in FG(P). This difference was attributed to the difference in the C=O content of GOs because the C=O bonds in GO primarily produce covalent C-F bonds. Thus, FG(F) and FG(HU) mainly exhibited semi-ionic C-F bonds. The doped F atoms were used to tune the electronic properties and surface chemistry of graphene. The fluorination reaction also improved the extent of reduction of GO.

Crystal growth of thiol-stabilized gold nanoparticles by heat-induced coalescence.

A monolayer of dodecanethiol-stabilized gold nanoparticles changed into two-dimensional and three-dimensional self-organized structures by annealing at 323 K. Subsequent crystal growth of gold nanoparticles occurred. Thiol molecules, although chemisorbed, form relatively unstable bonds with the gold surface; a few thiols desorbed from the surface and oxidized to disulfides at 323 K, because the interaction energy between thiol macromolecules is larger than that between a thiol and a nanoparticle. The gold nanoparticles approached each other and grew into large single or twinned crystals because of the van der Waals attraction and the heat generated by the exothermic formation of disulfides.