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To obtain highly efficient yet easily produced water-splitting cathodes, Ni-MoO2 composite coatings were electrodeposited at a Ni foam substrate with an open-pore structure, pore size of 450 µm, in a Watts-type bath. The concentration of MoO2 particles (about 100 nm) was varied, while the intensive mixing of the solution was provided by air bubbling with 0.5 L min−1. Electrodeposition was performed at different constant current densities at room temperature. The morphology and composition of the coatings were investigated by SEM and EDS. The hydrogen evolution reaction (HER) was tested in KOH of different concentrations, at several temperatures, in a three-electrode H-cell by recording polarization curves and EIS measurements. The lowest achieved HER overpotential was −158 mV at −0.5 A cm−2. Up-scaled samples, 3 × 3.3 cm2, were tested in a single zero-gap cell showing decreasing cell voltage (from 2.18 V to 2.11 V) at 0.5 A cm−2 over 5 h in 30% KOH at 70 °C with electrolyte flow rate of 58 mL min−1. Compared to pure Ni foams used as both cathode and anode under the same conditions, the cell voltage is decreased by 200 mV, showing improved electrode performance. [ABSTRACT FROM AUTHOR]

In the past, platinum–copper catalysts have proven to be highly active for the oxygen reduction reaction (ORR), but transferring the high activities measured in thin-film rotating disk electrodes (TF-RDEs) to high-performing membrane electrode assemblies (MEAs) has proven difficult due to stability issues during operation. High initial performance can be achieved. However, fast performance decay on a timescale of 24 h is induced by repeated voltage load steps with H2/air supplied. This performance decay is accelerated if high relative humidity (>60% RH) is set for a prolonged time and low voltages are applied during polarization. The reasons and possible solutions for this issue have been investigated by means of electrochemical impedance spectroscopy and distribution of relaxation time analysis (EIS–DRT). The affected electrochemical sub-processes have been identified by comparing the PtCu electrocatalyst with commercial Pt/C benchmark materials in homemade catalyst-coated membranes (CCMs). The proton transport resistance (Rpt) increased by a factor of ~2 compared to the benchmark materials. These results provide important insight into the challenges encountered with the de-alloyed PtCu/KB electrocatalyst during cell break-in and operation. This provides a basis for improvements in the catalysts' design and break-in procedures for the highly attractive PtCu/KB catalyst system. [ABSTRACT FROM AUTHOR]

Titanium oxynitride carbon composite nanofibers (TiON/C-CNFs) were synthesised with electrospinning and subsequent heat treatment in ammonia gas. In situ four-probe electrical conductivity measurements of individual TiON/C-CNFs were performed. Additionally, the TiON/C-CNFs were thoroughly analysed with various techniques, such as X-ray and electron diffractions, electron microscopies and spectroscopies, thermogravimetric analysis and chemical analysis to determine the crystal structure, morphology, chemical composition, and N/O at. ratio. It was found that nanofibers were composed of 2–5 nm sized titanium oxynitride (TiON) nanoparticles embedded in an amorphous carbon matrix with a small degree of porosity. The average electrical conductivity of a single TiON/C-CNF was 1.2 kS/m and the bulk electrical conductivity of the TiON/C-CNF fabric was 0.053 kS/m. From the available data, the mesh density of the TiON/C-CNF fabric was estimated to have a characteristic length of 1.0 µm and electrical conductivity of a single TiON/C-CNF was estimated to be from 0.45 kS/m to 19 kS/m. The electrical conductivity of the measured TiON/C-CNFs is better than that of amorphous carbon nanofibers and has ohmic behaviour, which indicates that it can effectively serve as a new type of support material for electrocatalysts, batteries, sensors or supercapacitors. [ABSTRACT FROM AUTHOR]

The oxygen reduction reaction (ORR) properties of a proprietary PtCu3/C alloy electrocatalyst produced on a multi-gram scale are characterized by the conventional rotating disc electrode (RDE) method and by constructing a membrane electrode assembly (MEA) proton exchange membrane (PEM) single cell. The PtCu3 nanoparticles become porous, enriched in Pt on the surface, and exhibit a high RDE activity. The single cell electrochemical study reveals that, contrary to most advanced catalysts, the high ORR activity can be transferred from the RDE to the MEA. In the latter case, at 0.9VIRfree, a mass activity of 0.53 A/mgPt, at a Pt electrode loading of 0.2 mg/cm2, is achieved. However, at high current density, oxygen transport becomes limited. This is proven by the analysis of polarization curves and electrochemical impedance spectroscopy (EIS) data with a Kulikovsky (physical) model. These indicate that this limitation is caused by the non-optimal microporosity of our catalyst, which hinders the mass transport of oxygen during ORR. Based on our prospective results, one can realistically plan for further efforts to bridge the gap between the RDE and MEA measurements completely and achieve high power densities for Pt-alloy electrocatalysts. [ABSTRACT FROM AUTHOR]

Nanoparticles of platinum-group metals (PGM) on carbon supports are widely used as catalysts for a number of chemical and electrochemical conversions on laboratory and industrial scale. The newly emerging field of single-atom catalysis focuses on the ultimate level of metal dispersion, i.e. atomically dispersed metal species anchored on the substrate surface. However, the presence of single atoms in traditional nanoparticle-based catalysts remains largely overlooked. In this work, we use aberration-corrected scanning transmission electron microscope to investigate four commercially available nanoparticle-based PGM/C catalysts (PGM = Ru, Rh, Pd, Pt). Annular dark-field (ADF) images at high magnifications reveal that in addition to nanoparticles, single atoms are also present on the surface of carbon substrates. Scanning electron microscopy, X-ray diffraction and size distribution analysis show that the materials vary in nanoparticle size and type of carbon support. These observations raise questions about the possible ubiquitous presence of single atoms in conventional nanoparticle PGM/C catalysts and the role they may play in their synthesis, activity, and stability. We critically discuss the observations with regard to the quickly developing field of single atom catalysis. [ABSTRACT FROM AUTHOR]

A profound understanding of the Au dissolution process is a prerequisite for optimal utilization of Au-based materials. This goes for either increasing the corrosion stability of materials in the sectors where the long-term functionality of Au is needed or decreasing the corrosion stability where the recovery of the Au component is crucial. By employing an extremely sensitive online analytical system, consisting of an electrochemical flow cell coupled to an inductively coupled plasma mass spectrometry, in situ potential-resolved dissolution of Au in the ppb range is enabled. A comparative study of two Au based materials, (i) a polycrystalline Au disk and (ii) carbon-supported Au nanoparticles, is presented. As a probe, chloride ions were used to elucidate the distinct differences in the corrosion behavior of the two analogues. [ABSTRACT FROM AUTHOR]