Francisco Ruiz-Zepeda

Electrochemical Dissolution of Iridium and Iridium Oxide Particles in Acidic Media: Transmission Electron Microscopy, Electrochemical Flow Cell Coupled to Inductively Coupled Plasma Mass Spectrometry, and X-ray Absorption Spectroscopy Study

Iridium-based particles, regarded as the most promising proton exchange membrane electrolyzer electrocatalysts, were investigated by transmission electron microscopy and by coupling of an electrochemical flow cell (EFC) with online inductively coupled plasma mass spectrometry. Additionally, studies using a thin-film rotating disc electrode, identical location transmission and scanning electron microscopy, as well as X-ray absorption spectroscopy have been performed. Extremely sensitive online time-and potential-resolved electrochemical dissolution profiles revealed that Ir particles dissolve well below oxygen evolution reaction (OER) potentials, presumably induced by Ir surface oxidation and reduction processes, also referred to as transient dissolution. Overall, thermally prepared rutile-type IrO2 particles are substantially more stable and less active in comparison to as-prepared metallic and electrochemically pretreated (E-Ir) analogues. Interestingly, under OER-relevant conditions, E-Ir particles exhibit superior stability and activity owing to the altered corrosion mechanism, where the formation of unstable Ir(>IV) species is hindered. Due to the enhanced and lasting OER performance, electrochemically pre-oxidized E-Ir particles may be considered as the electrocatalyst of choice for an improved low-temperature electrochemical hydrogen production device, namely a proton exchange membrane electrolyzer.

Insights into electrochemical dealloying of Cu out of Au-doped Pt-alloy nanoparticles at the sub-nano-scale

Pt alloy nanoparticles present the most probable candidate to be used as the cathode cathodic oxygen reduction reaction electrocatalyst for achieving commercialization targets of the low-temperature fuel cells. It is therefore very important to understand its activation and degradation processes. Besides the ones known from the pure Pt electrocatalysts, the dealloying phenomena possess a great threat since the leached less-noble metal can interact with the polymer membrane or even poison the electrocatalyst. In this study, we present a solution, supported by in-depth advance electrochemical characterization, on how to suppress the removal of Cu from the Pt alloy nanoparticles.

Successful Synthesis of Gold Nanoparticles through Ultrasonic Spray Pyrolysis from a Gold(III) Nitrate Precursor and Their Interaction with a High Electron Beam

Abstract Herein, we report for the first time the successful preparation of a gold(III) nitrate [Au(NO3)3] water‐based precursor for use in a bottom‐up ultrasonic spray pyrolysis (USP) process. Due to its limited solubility in water, the precursor was prepared under reflux conditions with nitric acid (HNO3) as the solvent and ammonium hydroxide (NH4OH) as a neutralizer. This precursor enabled the USP synthesis of gold nanoparticles (AuNPs) and the in situ formation of low concentrations of NO2 − and NO3 − ions, which were caught directly in deionized water in a collection system. These ions were proven to act as stabilizers for the AuNPs. Investigations showed that the AuNPs were monodispersed and spherically shaped with a size distribution over three groups: the first contained 5.3 % AuNPs with diameters (2 r) <15 nm, the second contained 82.5 % AuNPs with 2 r between 15 and 200 nm, and the third contained 12.2 % AuNPs with 2 r>200 nm. UV/Vis spectroscopy revealed the maximum absorbance band of the AuNPs at λ=528 nm. Additionally, scanning transmission electron microscopy (STEM) observations of the smallest AuNPs (2 r<5 nm) revealed atomically resolved coalescence phenomena induced by interaction with the electron beam. Four stages of the particle‐growth process were distinguished: 1) movement and rotation of the AuNPs; 2) necking mechanism; 3) orientated attachment at matching facets; 4) reshaping of the AuNPs by surface diffusion. This provided important insight into the formation/synthesis process of the AuNPs.

Gold Doping in PtCu3/HSAC Nanoparticles and its Morphological, Structural and Compositional Changes During ORR Electrochemical Cycling

Pt‐based nanoparticles supported on high‐surface‐area carbon (HSAC) show very good properties as catalysts in polymer electrolyte membrane fuel cells (PEMFC). In many cases, however, the initial high activity of such catalysts rapidly drops as caused by various detrimental phenomena occurring in a typical electrochemical environment. In this work, a detailed study of a highly active system composed of PtCu3/HSAC nanoparticles with partially ordered structure and Pt skin with the addition of Au is performed. By using aberration‐corrected scanning transmission electron microscopy, the effects of adding small amounts of gold compared to the nonmodified sample are followed through the different stages of an electrochemical cycling degradation protocol. Various morphological changes such as faceting, reshaping, and thickening of the Pt skin are investigated for both sets of samples on the atomic level. Interesting features such as well‐defined shapes and surface defects are observed after degradation. However, the most important differences in terms of durability seem related to particle porosity. Finally, the experimental morphological observations are successfully reproduced by dealloying simulation with kinetic Monte Carlo modeling.