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The study introduces flexible and scalable manufacturing approach for electrodes utilizing boron-doped silicon as conductive support for iridium nanoparticles, addressing the challenges of cost and scarcity associated with noble catalysts for oxygen evolution reaction (OER). Colloidal Ir nanoparticles are synthesized via pulsed-laser ablation (≈4–7 nm) and decorated on B-doped Si (≈100 nm) through electrostatic adsorption. Titanium substrates are ultrasonically sprayed with Si:B – Ir and Ir nanoparticles with very low iridium loading of 12 wt.%. Crystalline Ir phases (Ir(111), Ir(200)) are observed and known to enhance the OER mechanism. Additionally, atom probe tomography confirms that the Si support particles contained 0.03-0.5 at.% of boron throughout the entire particle, while electrical permittivity and through-plane measurements reveal a positive impact of B-doped Si on the electrical conductivity of the nanocatalysts and of the ultralow-loaded catalyst coated Ti substrates (0.12 mgIr cm−2), respectively. Rotating disk electrode results show pronounced oxidation peaks for decorated Ir nanoparticles. The Si:B-Ir 4 nm catalyst exhibits the highest turnover frequency (2.62 s−1) and a competitive electrochemical surface area (25 m2 gIr−1) compared to Si:B-Ir 7 nm (0.96 s−1; 37.5 m2 gIr−1) and Ir black (0.24 s−1; 5 m2 gIr−1). The overall analysis of the parameters highlights a performant catalytic efficiency, through balancing activity and reaction kinetics effectively.
This study presents the correlation between electrolyte pH, surface morphology, chemical speciation and electro-catalytic oxygen evolution activity of additive-free electrodeposited NiFe catalysts for application in anion exchange membrane water electrolysis. Spherical morphologies were identified at pH 0, shifting towards honey-combed structures at pH 4 with increasing surface area, especially at pH 3. Further, the electrolyte pH was found to influence the NiFe composition and electro-catalytic activity. Enhanced OER activity was noted at pH 2 with overpotentials of 214 mV at 10 mA cm−2 and 267 mV at 100 mA cm−2. The results reveal that the electrolyte pH is a parameter not only influencing the morphology but also tailoring the surface area, Fe oxide and Fe hydroxide composition and consequently the catalytic activity. Further, the outcomes highlight the electrolyte pH as a key process parameter that should be adjusted according to the application, and may substitute the addition of electrolyte-additives, proposing a simpler method for improving catalyst electrodeposition.
Electrodeposited Mo-rich NiMo catalysts offer enhanced catalytic activity for the alkaline hydrogen evolution reaction (HER) and provide an electrically conductive, binder-free substrate connection, making them promising catalysts for green hydrogen production. However, creating Mo-rich deposits is challenging, as the codeposition process typically favors Ni. Optimal deposition conditions for Mo-rich NiMo catalysts remain insufficiently explored. This article investigates Mo-rich NiMo electrodeposition from an ammonia-free citrate bath using NaSO4 as a chlorine-free support electrolyte. The effects of the deposition parameters, 1) sodium molybdate concentration in the electrolyte, 2) deposition current density, and 3) enhanced mass transport via working electrode rotation on the alkaline HER activity, were studied. The electrodeposits, containing 44–66 wt% Mo, exhibited increased surface area due to a rough, cracked morphology and variable oxygen content of the catalyst. The oxygen content was linked to HER activity, revealing an inhibiting effect. The lowest overpotential of 118 mV at −10 mA cm−2 for the alkaline HER was achieved using an electrolyte with 0.02 mol L−1 sodium molybdate, a deposition current density of 600 mA cm−2, without electrode rotation. Respective samples combined a favorable Ni:Mo ratio comprising 56 wt% Mo content with increased surface area and low oxygen content.
Various aqueous citrate electrolyte compositions for the Ni-Mo electrodeposition are explored in order to deposit Ni-Mo alloys with Mo-content ranging from 40 wt% to 65 wt% to find an alloy composition with superior catalytic activity towards the hydrogen evolution reaction (HER). The depositions were performed on copper substrates mounted onto a rotating disc electrode (RDE) and were investigated via scanning electron microscopy (SEM), X-ray fluorescence (XRF) and X-ray diffraction (XRD) methods as well as linear sweep voltammetry (LSV) and impedance spectroscopy. Kinetic parameters were calculated via Tafel analysis. Partial deposition current densities and current efficiencies were determined by correlating XRF measurements with gravimetric results. The variation of the electrolyte composition and deposition parameters enabled the deposition of alloys with Mo-content over the range of 40-65 wt%. An increase in Mo-content in deposited alloys was recorded with an increase in rotation speed of the RDE. Current efficiency of the deposition was in the magnitude of <1%, which is characteristic for the deposition of alloys with high Mo-content. The calculated kinetic parameters were used to determine the Mo-content with the highest catalytic activity for use in the HER.

