Highly active nano-sized iridium catalysts: synthesis and operando spectroscopy in a proton exchange membrane electrolyzer.

A stable and cost effective oxygen evolution reaction (OER) catalyst is crucial for the large-scale market penetration of proton exchange membrane (PEM) water electrolyzers. We show that the synthesis of iridium nanoparticles in either low purity ethanol or water, or in the absence of a surfactant, is detrimental to the electrocatalytic properties of the materials. Adding NaBH4 in excess improves the purity of the catalyst enhancing the OER activity up to 100 A gIr-1 at 1.51 V vs. RHE, the highest value reported so far for high purity Ir nanoparticles. The measured OER activity correlates with the capacitive current rather than with the charge corresponding to the IrIII/IrIV oxidation peak. Operando near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) on membrane electrode assemblies (MEAs) with the synthesized catalysts reveals a metallic core surrounded by a thin layer of IrIII/IV oxides/hydroxides. Oxidation of IrIII leaves behind a porous ultrathin layer of IrIV oxides/hydroxides, which dominate the surface during the OER, while IrV was not detected.

Oscillations in an array of bistable microelectrodes coupled through a globally conserved quantity.

The dynamical behavior of an array of microelectrodes is investigated under controlled current conditions during CO electrooxidation, a bistable electrochemical reaction with an S-shaped negative differential resistance (S-NDR) current-potential curve. Under these conditions, the total current constitutes a globally conserved quantity, thus coupling all microelectrodes globally. Upon increasing the total current, the microelectrodes activate one by one, with a single microelectrode being on its intermediate S-NDR current branch and the other ones being either on their passive or their active branches. When a few coupled microelectrodes are activated, the electrochemical system exhibits spontaneous potential oscillations. Mathematical analysis shows that oscillations arise already in a two group approximation of the dynamics, the two groups consisting of 1 electrode and n - 1 electrodes with n ≥ 3, respectively, with each group being described by a single evolution equation. In this minimal representation, oscillations occur when the single electrode is on the intermediate branch and the larger group is on the active branch.

Electrocatalysis of hydrogen peroxide reactions on perovskite oxides: experiment versus kinetic modeling.

Hydrogen peroxide has been identified as a stable intermediate of the electrochemical oxygen reduction reaction on various electrodes including metal, metal oxide and carbon materials. In this article we study the hydrogen peroxide oxidation and reduction reactions in alkaline medium using a rotating disc electrode (RDE) method on oxides of the perovskite family (LaCoO3, LaMnO3 and La0.8Sr0.2MnO3) which are considered as promising electrocatalytic materials for the cathode of liquid and solid alkaline fuel cells. The experimental findings, such as the higher activity of Mn-compared to that of Co-perovskites, the shape of RDE curves, and the influence of the H2O2 concentration, are rationalized with the help of a microkinetic model.