Electrografting using aryldiazonium salts provides a fast and efficient technique to functionalize commercially available 3-5 layered graphene (vapour-deposited) on nickel. In this study, Raman spectroscopy is used to quantify the grafting efficiency of cyclic voltammetry which is one of the most versatile, yet simple, electrochemical techniques available. To a large extent the number of defects/substituents introduced to the basal plane of high-quality graphene by this procedure can be controlled through the sweeping conditions employed. After extended electrografting the defect density reaches a saturation level ( ∼ 10(13) cm(-2)) which is independent of the quality of the graphene expressed through its initial content of defects. However, it is reached within fewer voltammetric cycles for low-quality graphene. Based on these results it is suggested that the grafting occurs (a) directly at defect sites for, in particular, low-quality graphene, (b) directly at the basal plane for, in particular, high-quality graphene, and/or (c) at already grafted molecules to give a mushroom-like film growth for all films. Moreover, it is shown that a tertiary alkyl bromide can be introduced at a given surface density to serve as radical initiator for surface-initiated atom transfer radical polymerization (SI-ATRP). Brushes of poly(methyl methacrylate) are grown from these substrates, and the relationship between polymer thickness and sweeping conditions is studied.

An electrochemical approach is introduced for the versatile carboxylation of multi-layered graphene in 0.1 M Bu4NBF4/MeCN. First, the graphene substrate (i.e., graphene chemically vapor-deposited on Ni) is negatively charged at -1.9 V versus Ag/AgI in a degassed solution to allow for intercalation of Bu4N(+) and, thereby, separation of the individual graphene sheets. In the next step, the strongly activated and nucleophilic graphene is allowed to react with added carbon dioxide in an addition reaction, introducing carboxylate groups stabilized by Bu4N(+) already present. This procedure may be carried out repetitively to further enhance the carboxylation degree under controlled conditions. Encouragingly, the same degree of control is even attainable, if the intercalation and carboxylation is carried out simultaneously in a one-step procedure, consisting of simply electrolyzing in a CO2-saturated solution at the graphene electrode for a given time. The same functionalization degree is obtained for all multi-layered regions, independent of the number of graphene sheets, which is due to the fact that the entire graphene structure is opened in response to the intercalation of Bu4N(+). Hence, this electrochemical method offers a versatile procedure to make all graphene sheets in a multi-layered but expanded structure accessible for functionalization. On a more general level, this approach will provide a versatile way of forming new hybrid materials based on intimate bond coupling to graphene via carboxylate groups.

We report on the microstructure, morphology, and growth of 5,5´-bis(naphth-2yl)-2,2´-bithiophene (NaT2) thin films deposited on graphene, characterized by grazingincidence X-ray diffraction (GIXRD) and complemented by atomic force microscopy (AFM) measurements. NaT2 is deposited on two types of graphene surfaces: custom-made samples where CVD-grown graphene layers are transferred onto a Si/SiO 2 substrate by us and common commercially transferred CVD graphene on Si/SiO 2 . Pristine Si/SiO 2 substrates are used as a reference. The NaT2 crystal structure and orientation depend strongly on the underlying surface, with the molecules predominantly lying-down on the graphene surface (face-on orientation) and standing nearly out-of-plane (edge-on orientation) on the Si/SiO 2 reference surface. Post growth GIXRD and AFM measurements reveal that the crystalline structure and grain morphology differ depending on whether there is polymer residue left on the graphene surface. In situ GIXRD measurements show that the thickness dependence of the intensity of the (111) reflection from the crystalline edge-on phase does not intersect zero at the beginning of the deposition process, suggesting that an initial wetting layer, corresponding to 1-2 molecular layers, is formed at the surface-film interface. By contrast, the (111) reflection intensity from the crystalline face-on phase grows at a constant rate as a function of film thickness during the entire deposition.

Highly oriented pyrolytic graphite (HOPG) and graphene grown on Ni (Ni‐Gra) or Cu (Cu‐Gra) by chemical vapour deposition were modified with thick anthraquinone (AQ) films (7−60 nm) by redox grafting of the pertinent diazonium salt. Glassy carbon (GC) electrodes were used for comparison. The AQ‐modified GC electrodes showed excellent blocking properties towards the Fe(CN)63−/4− redox probe, although it was noted that in the case of Ni‐Gra and Cu‐Gra, the blocking ability depended strongly on the underlying substrate. Oxygen reduction studies revealed good electrocatalytic activity of AQ‐modified HOPG, Ni‐Gra, and Cu‐Gra, compared with the bare electrodes.

Electrochemically driven intercalation of tetraalkylammonium ions can facilitate the delamination of graphene films fabricated by chemical vapour deposition (CVD) from their supporting metal catalyst and, hereby, ease the transfer of the graphene to other substrates. The electroinduced intercalation is performed by applying a negative potential to the metal/graphene cathode, while immersed into an electrolyte solution of the tetraalkylammonium ions in acetonitrile. As part of the double layer the cations intercalate the interface between the metal and the graphene, which increases the interfacial distance as well as weakens the interaction with and the screening effect of the metal. The individual stages of the intercalation and delamination were studied for CVD grown graphene on Cu, Pt, and Ir. Experimentally, the intercalation is seen to give a significant increase in the intensity of the recorded Raman spectra and most of the compressive strain in graphene is released. The electroinduced intercalation does not increase the defect or doping levels of graphene. Also, it is shown that easy transfer of the intercalated graphene to Si/SiO2 can be accomplished.