Development of an experimentally validated semi-empirical fully-coupled performance model of a PEM electrolysis cell with a 3-D structured porous transport layer

A semi-empirical non-isothermal model incorporating coupled momentum, heat and mass transport phenomena for predicting the performance of a proton exchange membrane (PEM) water electrolysis cell operating without flow channels is presented. Model input parameters such as electro-kinetics properties and mean pore size of the porous transport layer (PTL) were determined by rotating disc electrode and capillary flow porometry, respectively. This is the first report of a semi-empirical fully coupled model which allows one to quantify and investigate the effect of the gas phase and bubble coverage on PEM cell performance up to very high current densities of about 5 A/cm². The mass transport effects are discussed in terms of the operating conditions, design parameters and the microstructure of the PTL. The results show that, the operating temperature and pressure, and the inlet water flowrate and thickness of the PTL are the critical parameters for mitigating mass transport limitation at high current densities. The model presented here can serve as a tool for further development and scale-up effort in the area of PEM water electrolysis, and provide insight during the design stage.     

Flow influenced electrochemical corrosion of nickel aluminium bronze – Part I. Cathodic polarisation

The cathodic polarisation behaviour of CA 104 nickel aluminium bronze (NAB) has been examined in fully characterised seawaters (filtered and artificial) using the rotating disc electrode (RDE) and the rotating cylinder electrode (RCE). Linear sweep voltammetry and a potential step, current transient technique were used to examine the charge transfer and mass transfer controlled cathodic response as a function of both laminar and turbulent fluid flow. For freshly polished surfaces, the rate of irreversible charge transfer controlled oxygen reduction is controlled by the exchange of a single electron and hydrogen evolution is only significant at potentials more negative than approximately –1.0 V vs. the saturated calomel electrode (SCE).     

Nucleation and growth of the electrodeposited iron layers in the presence of an external magnetic field

The effect of an uniform magnetic field with a flux density up to 1 T and different configurations relative to the electrode surface on the electrocrystallization of Fe on polycrystalline Au(1 1 1) from acidic sulphate electrolyte has been investigated. It was found, irrespective of the applied parameters, that the deposition proceeds through successive nucleation and growth steps. The first one related to 2D growth was followed by a second nucleation and 3D diffusion controlled growth. At potential of −1500 and −1550 mV_MSE nucleation proceeds via a progressive mode, while at −1650 mV_MSE it follows an instantaneous mode. A strong influence of the parallel-to-electrode magnetic field on the nucleation processes was found for the progressive mode, which leads to the increase of the growth rate and as a consequence to retardation of the nucleation rate of the 3D step. Additionally, in this configuration at a sufficiently high magnetic flux density a third nucleation step could be observed (3D), which was found to be also affected by a magnetic field. No effect of a perpendicular-to-electrode magnetic field on the nucleation has been observed. The effects of a magnetic field on the nucleation and growth processes are discussed with respect to the magnetohydrodynamic effect (MHD) and confirmed by rotating disc electrode (RDE) experiments.     

Single atom iron carbons supported Pd–Ni–P nanoalloy as a multifunctional electrocatalyst for alcohol oxidation

Exploring high-performance and multifunctional electrocatalysts for alcohols oxidation is the key to develop alkaline fuel cells. Herein, we prepared a novel palladium-nickel-phosphorus catalyst supported on single atom iron carbons (SAICs) with different diameter sizes (1000 nm, 200 nm, 100 nm, 50 nm, and 20 nm), which were synthesized by direct carbonization of Fe-doped Zeolitic Imidazolate Framework-8 (ZIF-8). Electrochemical tests reveal that the as-prepared PdNiP/50nmSAIC exhibited excellent electrooxidation activity and stability to the various alcohols (methanol, glycerol, and especially ethylene glycol) electrooxidation in the alkaline solution, which is much higher than that of commercial Pd/C and other advanced Pd-based catalysts. Meanwhile, the rotating disk electrode (RDE) and CO-stripping results proves that PdNiP/50nmSAIC possesses a faster kinetic process of ethylene glycol oxidation and enhanced anti-CO poisoning ability. Our efforts provide a new strategy for the development of MOFs-derived multielement electrocatalyst with excellent activity and stability, and a bright future for alcohol oxidation.     

Oxygen reduction reaction on carbon-supported CoSe2 nanoparticles in an acidic medium

We investigated the effect of CoSe₂/C nanoparticle loading rate on oxygen reduction reaction (ORR) activity and H₂O₂ production using the rotating disk electrode and the rotating ring-disk electrode techniques. We prepared carbon-supported CoSe₂ nanoparticles with different nominal loading rates and evaluated these samples by means of powder X-ray diffraction. All the catalysts had an OCP value of 0.81 V vs. RHE. H₂O₂ production during the ORR process decreased with an increase in catalytic layer thickness. This decrease was related to the CoSe₂ loading on the disk electrode. H₂O₂ production also decreased with increasing catalytic site density, a phenomenon related to the CoSe₂ loading rate on the carbon substrate. The cathodic current density significantly increased with increasing catalytic layer thickness, but decreased with increasing catalytic site density. In the case of 20 wt% CoSe₂/C nanoparticles at 22 μg cm⁻², we determined that the transfer process involves about 3.5 electrons.     

Promising nature-based nitrogen-doped porous carbon nanomaterial derived from borassus flabellifer male inflorescence as superior metal-free electrocatalyst for oxygen reduction reaction

In this present study, novel hierarchical nitrogen-doped porous carbon for use as a metal-free oxygen reduction reaction (ORR) electrocatalyst is derived from borassus flabellifer male inflorescences by calcining at 1000 °C in an inert atmosphere using metal hydroxides as activating agent and melamine as nitrogen doping agent. The BET surface areas of the lithium-ion (Li-ion), potassium-ion (K-ion) and calcium-ion (Ca-ion) activated carbon are observed to be 824.02, 810.88 and 602.88 m² g^-1 respectively. Another interesting fact is that the total surface energy calculated by wicking method (73.2 mJ/m²), is found to be higher for Li-ion activated carbons. Among the prepared nitrogen-doped porous carbon, Li-ion activated system, showed an outstanding performance in ORR reaction in alkaline medium, thanks to its high surface area and notable surface activity. An incontrovertible of note that ORR half-wave potential of Li-ion activated nitrogen-doped carbon (0.90 V) is relatively higher in comparison to the commercial 20 wt % Pt/C catalyst (0.86 V). Inspite of overwhelming performance, the ORR reaction followed the preferred 4- electron transfer mechanism involving in the direct reduction pathway in all activated carbons. The ORR performance is also noticeably better and comparable to the best results in the literature based on biomass derived carbon catalysts.     

Enhanced methanol oxidation on PtNi nanoparticles supported on silane-modified reduced graphene oxide

Developing low cost, highly efficient, and long-term stability electrocatalysts are critical for direct oxidation methanol fuel cell. Despite huge efforts, designing low-cost electrocatalysts with high activity and long-term durability remains a significant technical challenge. Here, we prepared a new kind of platinum-nickel catalyst supported on silane-modified graphene oxide (NH₂-rGO) by a two-step method at room temperature. Powder X-ray diffraction, UV–vis spectroscopy, Raman, FTIR spectroscopy and X-ray photoelectron spectroscopy results confirm that GO was successfully modified with 3-aminopropyltriethoxysilane (APTES), which helps to uniformly disperse PtNi nanoparticles. Cyclic voltammetry, chronoamperometry, CO-stripping and rotating disk electrode (RDE) results imply that PtNi/NH₂-rGO catalyst has significantly higher catalytic activity, enhance the CO toxicity resistance, higher stability and much faster kinetics of methanol oxidation than commercial Pt/C under alkaline conditions.     

Electrochemical Corrosion Behaviour of 90—10 Cu—Ni Alloy in Chloride-Based Electrolytes

The corrosion of 90–10 copper—nickel alloy in aqueous chloride electrolytes has received considerable attention in the literature due to its widespread use in seawater and saline environments. From an analysis of the electrochemical behaviour of the alloy, it is clear that both the polarization and mixed/corrosion potential characteristics show a close comparison to unalloyed copper. Important differences arise, however, due to the semi—conducting nature, composition and overall protectiveness of the corrosion products on the 90–10 copper—nickel alloy. In this work the metallurgy, electrochemistry and mechanism of passivation of the alloy are reviewed to provide a focused source of data regarding the electrochemical characteristics of the alloy in saline media.     

Electrochemically deposited Ni + WC composite coatings obtained under constant and pulsating current regimes

A series of Ni + WC composite coatings were obtained by electrodeposition on a rotating disc electrode (RDE) from a commercially available Watts bath containing additives for brightness and smoothing and insoluble WC particles, using either constant or pulsating current. It was shown that the amount of WC embedded in the coating could vary from a few percent to over 80% depending on the rotation rate and the current density of deposition. Higher amounts (over 50 mass%) of embedded WC particles could be obtained only at rotation rates higher than 2000 rpm. It was also shown that the concentration of insoluble WC particles in the Watts bath has no significant influence on the amount of WC embedded in the coating, enabling the use of dilute mixtures (2 mass% of WC in the solution). At higher amounts of embedded WC particles, rough deposits were obtained with the WC particles being mostly incorporated in agglomerates of different sizes (from about 50 RDER="0">m to about 100 RDER="0">m). It was also shown that under the same conditions of electrodeposition, higher amounts of embedded WC particles could be obtained from solutions containing smaller particles.     

Amplitude modulated instability in reactants plenum of a rotating detonation combustor

The pronounced interest in rotating detonation combustors (RDC) in recent years has witnessed the investigation of multiple facets of the combustor, like reactants, injection schemes and combustor geometry. The issue of instabilities in RDCs is a nascent field, and requires both the identification, and the subsequent explanation of different instability mechanisms. In particular, we are concerned with the low frequency instability exhibited by the detonation wave. This is attributed to two different types of low frequency instabilities—amplitude and frequency modulated—that are discovered in the air plenum of an RDC, and subsequently discussed. The occurrence of these instabilities is observed to depend on the fuel injection scheme used and the air flow rates through the combustor. The amplitude modulated instability in the air inlet is spatially varying, and rotates in a direction opposite to the direction of the detonation wave. At higher air flow rates, and thus higher pressure ratios across the air injection, this instability disappears. A preliminary hypothesis is proposed to explain this amplitude modulation.