Recent Publications Feed (ADMIN)

A new method for transferring chemical vapor deposition (CVD)-grown monolayer graphene to a variety of substrates is described. The method makes use of an organic/aqueous biphasic configuration, avoiding the use of any polymeric materials that can cause severe contamination problems. The graphene-coated copper foil sample (on which graphene was grown) sits at the interface between hexane and an aqueous etching solution of ammonium persulfate to remove the copper. With the aid of an Si/SiO₂ substrate, the graphene layer is then transferred to a second hexane/water interface to remove etching products. From this new location, CVD graphene is readily transferred to arbitrary substrates, including three-dimensional architectures as represented by atomic force microscopy (AFM) tips and transmission electron microscopy (TEM) grids. Graphene produces a conformal layer on AFM tips, to the very end, allowing easy production of tips for conductive AFM imaging. Graphene transferred to copper TEM grids provides large-area, highly electron-transparent substrates for TEM imaging. These substrates can also be used as working electrodes for electrochemistry and high-resolution wetting studies. By using scanning electrochemical cell microscopy, it is possible to make electrochemical and wetting measurements at either a freestanding graphene film or a copper-supported graphene area and readily determine any differences in behavior.

Scanning electrochemical microscopy (SECM) is a powerful tool that enables quantitative measurements of fast electron transfer (ET) kinetics when coupled with modeling predictions from finite-element simulations. However, the advent of nanoscale and nanogap electrode geometries that have an intrinsically high surface area-to-solution volume ratio realizes the need for more rigorous data analysis procedures, as surface effects such as adsorption may play an important role. The oxidation of ferrocenylmethyl trimethylammonium (FcTMA⁺) at highly oriented pyrolytic graphite (HOPG) is used as a model system to demonstrate the effects of reversible reactant adsorption on the SECM response. Furthermore, the adsorption of FcTMA²⁺ species onto glass, which is often used to encapsulate ultramicroelectrodes employed in SECM, is also found to be important and affects the voltammetric tip response in a nanogap geometry. If a researcher is unaware of such effects (which may not be readily apparent in slow to moderate scan voltammetry) and analyzes SECM data assuming simple ET kinetics at the substrate and an inert insulator support around the tip, the result is the incorrect assignment of tip–substrate heights, kinetics, and thermodynamic parameters. Thus, SECM kinetic measurements, particularly in a nanogap configuration where the ET kinetics are often very fast (only just distinguishable from reversible), require that such effects are fully characterized. This is possible by expanding the number of experimental variables, including the voltammetric scan rate and concentration of redox species, among others.

Oxidation of zero-valent phosphine complexes [M(P^tBu₃)₂] (M=Pd, Pt) has been investigated in 1,2-difluorobenzene solution using cyclic voltammetry and subsequently using the ferrocenium cation as a chemical redox agent. In the case of palladium, a mononuclear paramagnetic Pd^I derivative was readily isolated from solution and fully characterized (EPR, X-ray crystallography). While in situ electrochemical measurements are consistent with initial one-electron oxidation, the heavier congener undergoes C−H bond cyclometalation and ultimately affords the 14 valence-electron Pt^II complex [Pt(κ²_PC-P^tBu₂CMe₂CH₂)(P^tBu₃)]⁺ with concomitant formation of [Pt(P^tBu₃)₂H]⁺.