Electrowetting on conductors: Anatomy of the phenomenon

We have recently reported that reversible electrowetting can be observed on the basal plane of graphite, without the presence of a dielectric layer, in both liquid/air and liquid/liquid configurations. The influence of carbon structure on the wetting phenomenon is investigated in more detail here. Specifically, it is shown that the adsorption of adventitious impurities on the graphite surface markedly suppresses the electrowetting response. Similarly, the use of pyrolysed carbon films, although exhibiting a roughness below the threshold previously identified as the barrier to wetting on basal plane graphite, does not give a noticeable electrowetting response, which leads us to conclude that specific interactions at the water–graphite interface as well as graphite crystallinity are responsible for the reversible response seen in the latter case. Preliminary experiments on mechanically exfoliated and chemical vapour deposition grown graphene are also reported.</p

Oxidative IR Spectroelectrochemistry of Copper in Methanol Containing Carbon Monoxide

IR spectroelectrochemistry was used to examine the electro-oxidation behavior of carbon monoxide in methanol at a polycrystalline copper electrode. Under such neutral conditions copper electrodes are coated with ill-defined copper oxides and hydroxides and at the oxidative potentials can be expected to generate soluble copper species. The electrochemistry displayed complex behavior suggesting that methanol oxidation was one prominent reaction. However, the spectroscopy revealed that very little methanol oxidation had occurred and that carbon monoxide was not adsorbed to the copper electrode. Instead, the electro-oxidation generated an intense IR band at 2107 cm^–1 that was attributed to a soluble [Cu­(I)­CO]⁺ species

Electrografting of 4-Nitrobenzenediazonium Ion at Carbon Electrodes: Catalyzed and Uncatalyzed Reduction Processes

International audienceCyclic voltammograms for the reduction of aryldiazonium ions at glassy carbon electrodes are often, but not always, reported to show two peaks. The origin of this intriguing behavior remains controversial. Using 4-nitrobenzenediazonium ion (NBD), the most widely studied aryldiazonium salt, we make a detailed examination of the electroreduction processes in acetonitrile solution. We confirm that deposition of film can occur during both reduction processes. Film thickness measurements using atomic force microscopy reveal that multilayer films of very similar thickness are formed when reduction is carried out at either peak, even though the film formed at the more negative potential is significantly more blocking to solution redox probes. These and other aspects of the electrochemistry are consistent with the operation of a surface-catalyzed reduction step (proceeding at a clean surface only) followed by an uncatalyzed reduction at a more negative potential. The catalyzed reduction proceeds at both edge-plane and basal-plane graphite materials, suggesting that particular carbon surface sites are not required. The unusual aspect of aryldiazonium ion electrochemistry is that unlike other surface-catalyzed reactions, both processes are seen in a single voltammetric scan at an initially clean electrode because the conditions for observing the uncatalyzed reaction are produced by film deposition during the first catalyzed reduction step.[on SciFinder (R)

Mixed monolayer organic films via sequential electrografting from aryldiazonium ion and arylhydrazine solutions.

International audienceSequential electrografting at glassy carbon from aryldiazonium salt solutions, or an aryldiazonium salt followed by an arylhydrazine, leads to the formation of covalently attached monolayer films incorporating two modifiers. In the first step, a 4-((triisopropylsilyl)ethynyl)phenyl film is electrografted to the surface, followed by removal of the triisopropylsilyl group to give a submonolayer of phenylethynylene groups. Two general strategies can then be applied to "fill in" the sparse monolayer with a second modifier. In the first route, nitrophenyl groups are grafted to the phenylethynylene-modified surface by the oxidation of 4-nitrophenylhydrazine. Ferrocene can be coupled to the terminal alkyne groups on the surface via a click reaction with azidomethylferrocene; an electrochemical measurement of the amount of immobilized ferrocene demonstrates that the phenylethynylene layer retains close to full reactivity after the second grafting step. In the alternative strategy, ferrocene is coupled to the phenylethynylene layer prior to grafting nitrophenyl groups by the reduction of the 4-nitrobenzenediazonium ion or by the oxidation of 4-nitrophenylhydrazine. For all approaches, the optimization of the grafting conditions gives surface concentrations of ferrocene and nitrophenyl groups that are consistent with those of a mixed monolayer. The stepwise generation of mixed monolayers is also monitored by film thickness measurements by depth profiling using the atomic force microscope. Thickness values are consistent with the proposed film structure in each preparation step

Measuring the Capacitance at Few- and Many-Layered Graphene Electrodes in Aqueous Acidic Solutions

The differential capacitance of 1–2 layered and 6–7 layered graphene (LG) was measured in aqueous 0.01, 0.1, 1.0, and 3 M perchloric and sulfuric acid solutions. The total measured capacitance was evaluated for approx. ±500 mV either side of the potential of zero charge to observe the contribution from the quantum capacitance and shielding effects on the measured capacitance. The experimental results were compared to the recent theoretical evaluations of similar electrode–electrolyte interfaces for supercapacitor applications. At 6–7 LG electrodes, the measured differential capacitance was dependent on the solution and electrical double layer structures, and although the 1–2 layered electrode showed far fewer differences upon changing solution conditions, it was not strictly independent. The concept of shielding effects within the graphene electrode and a dielectric capacitance as proposed by theory would account for these observations