Selective electrochemical functionalization of the graphene edge.

We present a versatile and simple method using electrochemistry for the exclusive functionalization of the edge of a graphene monolayer with metal nanoparticles or polymeric amino groups. The attachment of metal nanoparticles allows us to exploit surface-enhanced Raman scattering to characterize the chemistry of both the pristine and the functionalized graphene edge. For the pristine patterned graphene edge, we observe the typical edge-related modes, while for the functionalized graphene edge we identify the chemical structure of the functional layer by vibrational fingerprinting. The ability to obtain single selectively functionalized graphene edges routinely on an insulating substrate opens an avenue for exploring the effect of edge chemistry on graphene properties systematically.

pH sensitivity of interfacial electron transfer at a supported graphene monolayer.

Electrochemical devices based on a single graphene monolayer are often realized on a solid support such as silicon oxide, glassy carbon or a metal film. Here, we show that, with graphene on insulating substrates, the kinetics of the electron transfer at graphene with various redox active molecules is dictated by solution pH for electrode reactions that are not proton dependent. We attribute the origin of this unusual phenomenon mainly to electrostatic effects between dissolved/dissociated redox species and the interfacial charge due to trace amounts of ionizable groups at the supported graphene-liquid interface. Cationic redox species show higher electron transfer rates at basic pH, while anionic species undergo faster electron transfer at acidic pH. Although this behavior is observed on graphene on three different insulating substrates, the strength of this effect appears to differ depending on the surface charge density of the underlying substrate. This finding has important implications for the design of electrochemical sensors and electrocatalysts based on graphene monolayers.

Correction: pH sensitivity of interfacial electron transfer at a supported graphene monolayer.

Correction for 'pH sensitivity of interfacial electron transfer at a supported graphene monolayer' by Michel Wehrhold et al., Nanoscale, 2019, DOI: 10.1039/c9nr05049c.

Binding Kinetics of Methylene Blue on Monolayer Graphene Investigated by Multiparameter Surface Plasmon Resonance.

In this paper, we study the interaction of a small dye molecule, namely, methylene blue (MB) with graphene surfaces using surface plasmon resonance (SPR). We show that by utilizing all of the parameters of the SPR angular dip and exploiting the fact that MB absorbs light at the operating wavelength, it is possible to detect the binding of small molecules that would otherwise not give a significant signal. The binding of MB to unmodified graphene is found to be stronger than that for gold. By studying the interaction at modified surfaces, we demonstrate that electrostatic effects play a dominant role in the binding of MB on to graphene. Furthermore, following the binding kinetics at various concentrations allows us to estimate apparent equilibrium binding and rate constants for the interaction of MB with graphene.

Interplay of non-uniform charge distribution on the electrochemical modification of graphene.

Graphene is considered a model material for surfaces because it is stable despite being composed of a single layer of carbon atoms. Although the thermal and electronic properties of graphene are well reported, the behavior of graphene sheets with the addition of charges to the structure is not well understood. Combining infrared spectroscopy, electrochemical analysis, and computational simulations, we report the effect of an electrochemically induced covalent anchoring of 4-carboxyphenyl (4-CP) units on the optical and electronic properties of graphene. Charges in graphene become concentrated at specific sites of the sheet when electrochemically perturbed and the functionalization occurs inhomogeneously along the graphene sheet. We observed that, when graphene is covalently functionalized, the resistance to heterogeneous electron transfer is increased by a factor of 1.4. Furthermore, scattering-type scanning near-field optical microscopy and atomic force microscopy show that the covalent functionalization affects drastically the optical and physical properties of the graphene/SiO2 system, especially the plasmon-phonon coupling after the functionalization. In addition, from these we infer that a comparatively higher degree of functionalization occurs near the electrode edges. These results are supported by computational simulations, which show that the covalent anchoring of 4-CP units weakens electron transfer because the charges are retained on the sp3-hybridized carbon atoms generated upon functionalization, suggesting that graphene properties are deeply influenced by the way the molecules are immobilized on its structure.