Search

The electrodeposition of Pt nanoparticles (NPs) on two-dimensional single walled carbon nanotube (SWNT) network electrodes is investigated as a means of tailoring electrode surfaces with a well-defined amount of electrocatalytic material. Both Pt NP deposition and electrocatalytic studies are undertaken using the microcapillary electrochemical method (MCEM), enabling multiple microscale measurements to be performed quickly and easily on the same SWNT sample. Using this approach, Pt catalysts with high specific surface areas relative to the geometric electrode area (defined by the meniscus contact of the MCEM probe with the Si/SiO 2 substrate bearing the SWNT network) can be controlled precisely over three orders of magnitude. This enables the influence of the specific surface area of an electrocatalyst on activity to be investigated, as demonstrated by studies of the oxygen reduction reaction (ORR) and methanol oxidation reaction (MOR). [ABSTRACT FROM AUTHOR]

The meniscus-based microcapillary electrochemical method (MCEM) allows electrochemical measurements to be made quickly and easily at a wide range of materials, simply by connecting up the sample of interest as a working electrode and bringing a capillary containing an electrolyte solution and quasi-reference/counter electrode into meniscus contact. In this work, microcapillary-based electrochemical methodology is advanced by introducing a very high aspect ratio carbon fibre ultramicroelectrode (CF-UME) allowing generation/collection and shielding (redox competition) measurements to be made. The experimental concept is demonstrated with the outer sphere (ferrocenylmethyl) trimethylammonium ion (FcTMA +/2+ ) redox mediator on a single walled carbon nanotube (SWNT) network. It is then used to investigate electrochemical reactions on a complex electrode, i.e. a SWNT forest, which is not easily investigated using traditional techniques that would require the electrode material to be physically encapsulated. The technique is most powerful when used to probe the different mechanistic pathways of the oxygen reduction reaction (ORR). This aspect is illustrated through studies on platinum, glassy carbon and SWNT forest electrodes. By platinising the CF-UME, the electrode can be used as a local sensor for the intermediate H 2 O 2 and the O 2 reactant, and it is possible to track the evolving consumption of these species near the working electrode during voltammetric measurements. [ABSTRACT FROM AUTHOR]