arXiv subjects

Andrea M. Mingers

Publications and source records attributed to Andrea M. Mingers.

4 recordsLinked to original sources

arXiv2025

Controlling Metastability through Annealing of High-Entropy Nanoalloy Electrocatalysts to Boost Performance towards the Oxygen Evolution Reaction

Low-cost transition metal high-entropy nanoalloys are emerging as sustainable alternatives to platinum group electrocatalysts. Synthesis conditions of single-phase solid solutions can alter phase stability, causing surface composition changes that affect electrocatalytic performance. Here, we propose to exploit the metastability of carbon-doped Cantor alloy-based amorphous high-entropy alloy nanoparticles produced by nanosecond-pulsed laser synthesis in organic solvents. In situ electron microscopy reveals crystallization and partitioning of elements upon heating to 600 °C, forming heterostructured nanoparticles with reinforced carbon shells that exhibit a 5- to 7-fold enhancement of the electrocatalytic activity compared to the as-synthesized counterparts for the oxygen evolution reaction. We demonstrate the strategic utilization of phase metastability in high-entropy nanoalloys through post-synthesis annealing to enhance the electrochemical activity of laser-generated nanoparticles.

cond-mat.mtrl-sci↗

arXiv2025

Kinetics and direct imaging of electrochemically formed palladium hydride for efficient hydrogen evolution reaction

Active and reliable electrocatalysts are fundamental to renewable energy technologies. PdCoO2 has recently been recognized as a promising catalyst template for the hydrogen evolution reaction (HER) in acidic media thanks to the formation of active PdHx. In this article, we monitor the transformation of single PdCoO2 particles during HER, and confirm their almost complete transformation to PdHx with sub-millimeter depths and cracks throughout the particles. Using operando mass spectrometry, Co dissolution is observed under reductive potentials, leading to PdHx formation, whereas the dissolution partial current is found to be 0.1 % of the HER current. The formation of PdHx is confirmed through secondary ion mass spectrometry and quantitatively analyzed by atom probe tomography, enabled by isotope labelling of hydrogen using heavy water. Despite dry storage and high vacuum during sample preparations, an overall composition of PdD0.28 is measured for the PdHx sample, with separation between alpha- (D-poor) and beta- (D-rich) PdHx phases. The PdHx phase formed on PdCoO2 particles is stable for a wide electrochemical potential window, until Pd dissolution is observed at open circuit potentials. Our findings highlight the critical role of a templated growth method in obtaining stabilized PdHx, enabling efficient HER without the commonly slow activation processes observed in Pd. This offers insights into the design of more efficient electrocatalysts for renewable energy technologies.

physics.chem-ph↗

arXiv2024

Operando Insights on the Degradation Mechanisms of Rhenium-doped and Undoped Molybdenum Disulfide Nanocatalysts for Electrolyzer Applications

MoS2 nanostructures are promising catalysts for proton-exchange-membrane (PEM) electrolyzers to replace expensive noble metals. Their broadscale application demands high activity for the hydrogen evolution reaction (HER) as well as robust durability. Doping is commonly applied to enhance the HER activity of MoS2-based nanocatalysts, but the effect of dopants in the electrochemical and structural stability is yet to be discussed. Herein, we correlate operando electrochemical measurements to the structural evolution of the materials down to the nanometric scale by identical location electron microscopy and spectroscopy. The range of stable operation for MoS2 nanocatalysts with and without rhenium doping is experimentally defined. The responsible degradation mechanisms at first electrolyte contact, open circuit stabilization and HER conditions are experimentally identified and confirmed with the calculated Pourbaix diagram of Re-doped MoS2. Doping MoS2-based nanocatalysts is validated as a promising strategy for the continuous improvement of high performance and durable PEM electrolyzers.

physics.app-ph↗

arXiv2021

Different Photostability of BiVO4 in Near-pH-Neutral Electrolytes

Photoelectrochemical water splitting is a promising route to produce hydrogen from solar energy. However, corrosion of semiconducting photoelectrodes remains a fundamental challenge for their practical application. The stability of BiVO4, one of the best performing photoanode materials, is systematically examined here using an illuminated scanning flow cell to measure its dissolution operando. The dissolution rates of BiVO4 under illumination depend on the electrolyte and decrease in the order: borate (pH=9.3) > phosphate (pH=7.2) > citrate (pH=7.0). BiVO4 exhibits an inherent lack of stability during the oxygen evolution reaction (OER), while hole-scavenging citrate electrolyte offers kinetic protection. The dissolution of Bi peaks at different potentials than the dissolution of V in phosphate buffer, whereas both ions dissolve simultaneously in borate buffer. The life cycle of a 90 nm BiVO4 film is monitored during one hour of light-driven OER in borate buffer. The photocurrent and dissolution rates show independent trends with time, highlighting the importance to measure both quantities operando. Dissolution rates are correlated to the surface morphology and chemistry characterized using electron microscopy, X-ray photoelectron spectroscopy and atom probe tomography. These correlative measurements further the understanding on corrosion processes of photoelectrodes down to the nanoscopic scale to facilitate their future developments.

cond-mat.mtrl-sci↗