Rough Electrode Research Articles

Enhancing Ice Nucleation: The Role of Surface Roughness in Electrofreezing Using Laser Shock Processed Al6061 T6 Electrodes

The present study investigates the impact of the electrode surface roughness on the electrofreezing of water. This research focuses on how the electrode microstructure induced by a laser treatment affects the nucleation and growth of ice crystals under controlled electric fields. For this, electrofreezing experiments of deionized water over electrodes with varying surface roughnesses and crystalline textures were conducted. The electrodes of the Al6061 T6 alloy were microstructured via the Laser Shock Processing (LSP) method. For this purpose, the pulse densities during the LSP process were varied (900, 1600, and 2500 pulses/cm2). The increase in pulse density was correlated to the microstructural features and average roughness of the LSP-treated Al6061 alloy. A wave-like microstructure was induced upon the LSP treatment, with roughnesses between 3.5 and 6 µm at the selected pulse densities. The results indicate that electrode roughness significantly influences the electrofreezing process. Rougher electrodes were found to increase the nucleation temperature, suggesting enhanced ice nucleation activity. These findings are attributed to the increased electric field concentration at the asperities of the rough surfaces and the (111) planes of the Al6061 alloy, which may facilitate the alignment of water molecules and the formation of critical ice nuclei.

A study on the repeatability of electroformed electrochemical gas driven micro-pump, using the surface roughness of cathode electrodes

ABSTRACT The objective of this paper was to analyse the effect of the surface roughness of a deposited copper cathode on repeatability for the discharge flow rate of an electroformed micro-pump. For this purpose, a measurement set-up was assembled using a glass gauge with a threshold sensor. Each test cathode was fitted into the micro-pump and the flow rate was measured three times. The value of the standard deviation of the measured flow rate was calculated as a criterion for the repeatability of the prepared micro pump. Finally, the covariance value and correlation coefficient between each surface roughness parameter and standard deviation of flow rate were calculated and compared. The results demonstrated that the Rz surface roughness parameter has the strongest relation with micro-pump flow rate repeatability using covariance analysis. Also, the auto-correlation length (ACL) that can describe the surface roughness using a correlation function has the most linear relation among all surface roughness parameters with a flow rate based on correlation analysis. SEM analysis and hydrogen bubble illustration were also reported.

Directly patterned ITO nanoparticle-based transparent electrode using co-solvent-based aerosol jet printing for transparent thin film heaters

High-performance transparent thin film heaters (TFHs) employing cost-effective nanoparticle-based transparent electrodes have attracted significant attention for applications in multifunctional smart windows. This study demonstrates the fabrication of high-performance TFHs featuring directly patterned Sn-doped In2O3 (ITO) nanoparticle electrodes using a methanol and ethylene glycol co-solvent-based aerosol jet printing (AJP) process. Our method utilizes a co-solvent ITO nanoparticle solution, blending methanol and ethylene glycol, to improve the surface uniformity and roughness of the AJP-processed ITO nanoparticle electrodes. The optimization of these electrodes was assessed using the figure of merit (FoM=T10/Rsh) value, derived from the transparency and sheet resistance of the electrodes. As a result of the AJP process and post-annealing optimization, the directly patterned ITO nanoparticle electrodes exhibited a high FoM value of 16.1 Ω−1, attributed to a high optical transmittance of 90.6 % and low sheet resistance of 23.20 Ω/sq. These optimized ITO nanoparticle electrodes were subsequently applied to TFHs through precise patterning of ITO electrodes via AJP. The ITO nanoparticle-based TFHs, benefiting from superior conductivity and precise AJP patterning, demonstrated a saturation temperature of 118.2 °C when subjected to a voltage of 9 V. Thermal stability and uniformity tests showed a temperature deviation of less than 5 %, validating the reliability of the TFHs. The performance of the AJP-processed ITO nanoparticle-based TFHs highlights the feasibility of cost-effective transparent TFHs for multifunctional smart windows, showing potential applications in electric vehicles and next-generation smart buildings.

Review of Cathode Plasma Electrolysis Treatment: Progress, Applications, and Advancements in Metal Coating Preparation.

Cathodic plasma electrolytic treatment (CPET) is an emerging surface modification and coating preparation technology. By utilizing plasma discharge induced through electrolysis and the cooling impact of electrolyte, metal cleaning, saturation, and coating preparation are efficiently achieved. In this review, the principle, application, and development of the CPET process are briefly summarized based on the past literature. Detailed insights are provided into the influence of electrolyte parameters (pH, metal salt concentration, and temperature), electrical parameters (voltage, duty cycle, and frequency), and process parameters (electrode area ratio, material, roughness, and deposition time) on plasma discharge and coating formation for metal coatings. The interaction mechanism between plasma and material surfaces is also investigated. Recommendations and future research avenues are suggested to propel CPET and its practical implementations. This review is expected to provide assistance and inspiration for researchers engaged in CPET.

Mechanism of overscreening breakdown by molecular-scale electrode surface morphology in asymmetric ionic liquids

The interfacial nature of the electric double layer (EDL) assumes that electrode surface morphology significantly impacts the EDL properties. Since molecular-scale roughness modifies the structure of EDL, it is expected to disturb the overscreening effect and alter differential capacitance (DC). In this paper, we present a model that describes EDL near atomically rough electrodes with account for short-range electrostatic correlations. We provide numerical and analytical solutions for the analysis of conditions for the overscreening breakdown and DC shift estimation. Our findings reveal that electrode surface structure leads to DC decrease and can both break or enhance overscreening depending on the relation of surface roughness to electrostatic correlation length and ion size asymmetry.

Improving the roughness of copper working electrode through electroless deposition for carbon dioxide reduction reaction

Electrocatalytic CO2 conversion into usable fuels (CO, CH4, C2H4, and HCOOH) is a promising approach to mitigate the greenhouse effect and the energy deficit. Herein, we employ the wet etching process to significantly enhance the surface roughness of the copper foil, followed by deposition of Cu particles on the surface-etched copper foil (Cu NPs/Cu foil) for electrochemical CO2 reduction. FESEM and AFM results confirms the morphology and roughness changes. Introducing glycine to the electrolyte increase the Faraday efficiency (FE) of the resulting products. Upon adding 5 × 10−5 mM glycine significantly improves the FEs 10.1 % CO, 8.7 % CH4, 11.7 % C2H4, and 44.5 % HCOOH, with 75.0 % as C1 and C2 compounds. Concurrently, hydrogen production decreases to 20.2 % at a potential of –1.4 V utilizing roughened Cu NPs/Cu foil as a catalyst. These results shed light on the factors contributing to increased hydrocarbons and formic acid production with enhanced surface roughness of Cu foil.

Enhancement effect of Mo electrodes on the ignition characteristics of HAN-based gel propellant fuel and its combustion mechanisms

Hydroxylammonium nitrate (HAN) serves as a monopropellant fuel, renowned for its low toxicity and high-performance in space propulsion systems. HAN-based gel propellant may offer additional advantages, including long-term stability and excellent throttling capabilities. To better understand the ignition performance and combustion characteristics of this gel propellant, we prepared HAN-based gel propellant, and monitored its decomposition products using thermogravimetry (TG), Fourier Transform Infrared Spectroscopy (FTIR) and mass spectrometry (MS). Electrode materials of Mo, Cu, Ti and SUS 304 were fabricated to investigated their impact on ignition performance. It was found that the Mo electrode exhibited the shortest ignition delay time (ti) compared to Cu, Ti, and SUS 304. Meanwhile, the role of surface roughness of Mo electrode on the ignition delaytime (ti) and the ignition energy (Qi) were also studied. Our results revealed that, as the voltage increased from 100 V to 200 V, the fine-surfaced Mo electrode demonstrated a lower sensitivity to changes in ti compared to the rough-surfaced electrode. Additionally, the Qi of the rough-surfaced electrode decreased from 43.5 J to 16.7 J, while the Qi of the fine-surfaced electrode decreased from 52.5 J to 17.6 J. Combining a thermocouple, the combustion wave structure of the gel propellant was divided into pre-heating zone, condensed phase, electro chemical reaction zone, microexplosion-gases mixing zone and flame zone. Finally, the combustion model of HAN-based gel propellant was inferred to explain its combustion mechanism.

Ion beam irradiation induced modification of PPy/ZnO nanocomposite thin films for supercapacitor applications

Thin films of Polypyrrole/Zinc Oxide (PPy/ZnO) nanocomposite were fabricated using electrodeposition and subjected to 100 MeV Ag10+ ion beam irradiation at various fluences ranging from 1.0 × 1010 to 1.0 × 1012 ions cm-2. We characterized the well-synthesized PPy/ZnO nanocomposite thin films and examined the modification induced by irradiation using XRD, Raman, FTIR, FESEM-EDS, and AFM techniques. FESEM and AFM images reveal that PPy/ZnO exhibits a cauliflower-like nanosphere structure. An increase in roughness indicates a larger surface area of the electrode, which improves capacitive performance at 1.0 × 1010 ions cm-2, enhancing ion transport from the electrode surface to the bulk. The damage tracks formed by highly energetic ions along their path may contribute to more charge storage by increasing the roughness of the nanocomposite thin film electrodes for energy storage applications. We evaluated the electrochemical performance of thin films using CV, EIS, and GCD measurements. Electrochemical studies reveal enhanced capacitive properties up to 1.0 × 1010 ions cm-2 fluence and decrease at higher fluences. The irradiated nanocomposites achieve a higher specific capacitance of 323.11 F g-1, and the fabricated device shows cyclic stability of 86 %, a remarkable power density (P) of 0.72 kW kg-1, and an energy density (Ep) of 6.32 Wh kg-1.

Trading Off Initial PEM Fuel Cell Performance versus Voltage Cycling Durability for Different Carbon Support Morphologies

Tailored design of carbon supports and their pore morphologies is crucial to achieve the ambitious durability and performance targets for future proton exchange membrane fuel cells (PEMFCs). We compared platinum catalysts supported on solid Vulcan carbon, porous Ketjenblack carbon, and accessible porous modified Ketjenblack carbon in a voltage cycling-based accelerated stress test (AST) with frequent intermittent characterizations. We derived how catalyst morphologies affect cell performance and electrochemical properties (electrode roughness factor, ORR activity, oxygen transport resistances) at beginning-of-life (BoL) and in various states of degradation up to 200,000 voltage cycles. We confirmed the enhanced Pt surface area retention of porous carbon-supported catalysts, ascribed to well-shielded Pt particles in internal pores, but find that this comes at the expense of lower initial high current density performance already at BoL. Accessible porous carbon-supported catalysts with wider pores mostly retain those durability benefits while, simultaneously, maximizing H2/air performance at all current densities due to improved oxygen transport. We also tracked changes in catalyst accessibility throughout voltage cycling by analyzing local oxygen transport resistances and relative humidity-dependent platinum utilization. We propose that catalysts with porous carbon supports undergo oxidative pore opening, followed by continuous migration of internal Pt particles to the external carbon surface.

Size-dependent electrochemistry of laser-induced graphene electrodes

Laser-induced graphene (LIG) electrodes have become popular for electrochemical sensor fabrication due to their simplicity for batch production without the use of reagents. The high surface area and favorable electrocatalytic properties also enable the design of small electrochemical devices while retaining the desired electrochemical performance. In this work, we systematically investigated the effect of LIG working electrode size, from 0.8 mm to 4.0 mm diameter, on their electrochemical properties, since it has been widely assumed that the electrochemistry of LIG electrodes is independent of size above the microelectrode size regime. The background and faradaic current from cyclic voltammetry (CV) of an outer-sphere redox probe [Ru(NH3)6]3+ showed that smaller LIG electrodes had a higher electrode roughness factor and electroactive surface ratio than those of the larger electrodes. Moreover, CV of the surface-sensitive redox probes [Fe(CN)6]3– and dopamine revealed that smaller electrodes exhibited better electrocatalytic properties, with enhanced electron transfer kinetics. Scanning electron microscopy, Raman spectroscopy, and X-ray photoelectron spectroscopy showed that the physical and chemical surface structure were different at the electrode center versus the edges, so the electrochemical properties of the smaller electrodes were improved by having rougher surface, more density of the graphitic edge planes, and more oxide-containing groups. The difference could be explained by the different photothermal reaction time from the laser scribing process that causes different stable carbon morphology to form on the polymer surface. Our results give a new insight on relationships between surface structure and electrochemistry of LIG electrodes and are useful for designing miniaturized electrochemical devices.

Manufacturing of TiO2, Al2O3 and Y2O3 Ceramic Nanotubes for Application as Electrodes for Printable Electrochemical Sensors

This paper describes the process to obtain ceramic nanotubes from titanium dioxide, alumina and yttrium oxide by a feasible, replicable and reliable technology, including three stages, starting from an electrospinning process of poly(methyl methacrylate) solutions. A minimum diameter of 0.3 μm was considered optimal for PMMA nanofibers in order to maintain the structural stability of covered fibers, which, after ceramic film deposition, leads to a fiber diameter of 0.5–0.6 μm. After a chemical and physical analysis of the stages of obtaining ceramic nanotubes, in all cases, uniform deposition of a ceramic film on PMMA fibers and, finally, a uniform structure of ceramic nanotubes were noted. The technological purpose was to use such nanotubes as ingredients in screen-printing inks for electrochemical sensors, because no study directly targeted the subject of ceramic nanotube applications for printed electronics to date. The printing technology was analyzed in terms of the ink deposition process, printed electrode roughness vs. type of ceramic nanotubes, derived inks, thermal curing of the electrodes and the conductivity of electrodes on different support (rigid and flexible) at different curing temperatures. The experimental inks containing ceramic nanotubes can be considered feasible for printed electronics, because they offer fast curing at low temperatures, reasonable conductivity vs. electrode length, good printability on both ceramic or plastic (flexible) supports and good adhesion to surface after curing.

Robustly and Intrinsically Stretchable Ionic Gel-Based Moisture-Enabled Power Generator with High Human Body Conformality.

Direct harvesting of energy from moist air will be a promising route to supply electricity for booming wearable and distributed electronics, with the recent rapid development of the moisture-enabled electricity generator (MEG). However, the easy spatial distortion of rigid MEG materials under severe deformation extremely inconveniences the human body with intense physical activity, seriously hindering the desirable applications. Here, an intrinsically stretchable moisture-enabled electricity generator (s-MEG) is developed based on a well-fabricated stretchable functional ionic gel (SIG) with a flexible double-network structure and reversible cross-linking interactions, demonstrating stable electricity output performance even when stretched up to 150% strain and high human body conformality. This SIG exhibits ultrahigh tensile strain (∼600%), and a 1 cm × 1 cm SIG film-based s-MEG can generate a voltage of ∼0.4 V and a current of ∼5.7 μA when absorbing water from humidity air. Based on the strong adhesion and the excellent interface combination of SIG and rough fabric electrodes induced by the fabrication process, s-MEG is able to realize bending or twisting deformation and shows outstanding electricity output stability with ∼90% performance retention after 5000 cycles of bending tests. By connecting s-MEG units in series or parallel, an integrated device of "moisture-powered wristband" is developed to wear on the wrist of humans and drive a flexible sensor for tracking finger motions. Additionally, a comfortable "moisture-powered sheath" based on s-MEGs is created, which can be worn like clothing on human arms to generate energy while walking and flexing the elbow, which is promising in the field of wearable electronics.

Nucleation of Pitting and Evolution of Stripping on Lithium-Metal Anodes.

The stripping reaction of lithium (Li) will greatly impact the cyclability and safety of Li-metal batteries. However, Li pits' nucleation and growth, the origin of uneven stripping, are still poorly understood. In this study, we analyze the nucleation mechanism of Li pits and their morphology evolution with a large population and electrode area (>0.45 cm2). We elucidate the dependence of the pit size and density on the current density and overpotential, which are aligned with classical nucleation theory. With a confocal laser scanning microscope, we reveal the preferential stripping on certain crystal grains and a new stripping mode between pure pitting and stripping without pitting. Descriptors like circularity and the aspect ratio (R) of the pit radius to depth are used to quantify the evolution of Li pits in three dimensions. As the pits grow, growth predominates along the through-planedirection, surpassing the expanding rate in the in-plane direction. After analyzing more than 1000 pits at each condition, we validate that the overpotential is inversely related to the pit radius and exponentially related to the rate of nucleation. With this established nucleation-overpotential relationship, we can better understand and predict the evolution of the surface area and roughness of Li electrodes under different stripping conditions. The knowledge and methodology developed in this work will significantly benefit Li-metal batteries' charging/discharging profile design and the assessment of large-scale Li-metal foils.

Limitations in the electrochemical analysis of voltage transients.

Objective. Chronopotentiometric voltage transients (VTs) are used to assess the performance of bionic electrodes. The data obtained from VTs are used to define the safe operating conditions of clinical devices. Various approaches to analysing VTs have been reported, and a number of limitations in the accuracy of the measurements in relation to electrode size have been noted previously.Approach. The impact of electronic hardware and electrode configuration on VTs is discussed.Main results. The slew rate, rise time, sample time, minimum pulse length and waveform averaging characteristics of the electronic hardware, and electrode configuration will impact on VT measurement accuracy. Subsequently, activation and polarisation voltage measurements, and the definition of safe stimulation levels can be affected by the electronic hardware and electrode configuration.Significance. This article has identified some limitations in the previous literature related to the measurement and reporting of VTs and subsequent analysis of access and polarisation voltages. Furthermore, the commonly used Shannon plot used to define safe stimulation protocols does not correct for uncompensated resistance, account for electrode roughness or changes in electrode configuration. The creation of a safe stimulation plot which has been corrected for uncompensated resistance would generate more widely applicable stimulation guidelines for clinical devices used in different anatomical locations such as endovascular neural interfaces.

Machining characteristics in ultrasonic vibration-assisted powder-mixed electrical discharge machining of TiN ceramics

This study aims to investigate the application and machining characteristics of brittle conductive ceramics using ultrasonic vibration-assisted powder-mixed electrical discharge machining (UV-PMEDM) technology. Titanium nitride (TiN) ceramics are widely used in aerospace, biomedicine, and electronics due to their excellent properties. However, the conventional mechanical machining methods of these materials result in severe tool wear, high costs, and low efficiency. Although electrical discharge machining (EDM) can overcome some limitations, it typically exhibits a low material removal rate and poor surface quality. This study utilizes the UV-PMEDM technology to process TiN ceramics. Single-factor experiments are conducted to analyze the effects of processing parameters, including ultrasonic amplitude, powder concentration, pulse-on time, and pulse-off time, on the material removal rate, surface roughness, and relative electrode wear rate, which indicate the EDM processing performance. With the assistance of ultrasonic vibration and mixed powders, the material removal rate of TiN ceramics using UV-PMEDM reaches 0.50 mm3/min, while maintaining a relative electrode wear rate below 1 % and surface roughness lower than 4.2 μm. The synergistic combination of ultrasonic vibration and mixed powders significantly enhances the processing efficiency and reduces surface roughness of TiN ceramics. These findings contribute to a better understanding of machining strategies for brittle conductive ceramics.

Trade-Off between Rough and Smooth Electrode Surfaces toward Stable Zn Stripping/Plating in Aqueous Electrolytes.

The effects of surface roughness on the performance of the Zn metal anode in aqueous electrolytes are investigated by experiments and computational simulations. Smooth surfaces can homogenize the nucleation and growth of Zn, which helps to form a flat Zn anode under high current density. In spite of these advantages, the whole surface of the smooth electrode serves as the reactive contact area for parasitic reactions, generating severe hydrogen evolution, corrosion, and byproduct formation, which seriously hinder the long-term cycle stability of the Zn anode. To trade off this double-sided effect, we identify a medium degree of surface roughness that could stabilize the Zn anode for 1000 h cycling at 1.0 mAh cm-2. The electrode also enabled stable cycling for 800 h at a high current density of 5.0 mAh cm-2. This naked Zn metal anode with optimized surface roughness holds great promise for direct use in aqueous zinc ion batteries.

Dynamically blocking leakage current in molecular tunneling junctions.

Molecular tunneling junctions based on self-assembled monolayers (SAMs) have demonstrated rectifying characteristics at the nanoscale that can hardly be achieved using traditional approaches. However, defects in SAMs result in high leakage when applying bias. The poor performance of molecular diodes compared to silicon or thin-film devices limits their further development. In this study, we show that incorporating "mixed backbones" with flexible-rigid structures into molecular junctions can dynamically block tunneling currents, which is difficult to realize using non-molecular technology. Our idea is achieved by the interaction between interfacial dipole moments and electric field, triggering structured packing in SAMs. Efficient blocking of leakage by more than an order of magnitude leads to a significant enhancement of the rectification ratio to the initial value. The rearrangement of supramolecular structures has also been verified through electrochemistry and electroluminescence measurements. Moreover, the enhanced rectification is extended to various challenging environments, including endurance measurements, bending of electrodes, and rough electrodes, thus demonstrating the feasibility of the dynamic behavior of molecules for practical electronic applications.

The effect of interface heterogeneity on zinc metal anode cyclability.

Zinc metal batteries (ZMBs) are promising candidates for low-cost, intrinsically safe, and environmentally friendly energy storage systems. However, the anode is plagued with problems such as the parasitic hydrogen evolution reaction, surface passivation, corrosion, and a rough metal electrode morphology that is prone to short circuits. One strategy to overcome these issues is understanding surface processes to facilitate more homogeneous electrodeposition of zinc by guiding the alignment of electrodeposited zinc. Using Scanning Electrochemical Microscopy (SECM), the charge transport rate on zinc metal anodes was mapped, demonstrating that manipulating electrolyte concentration can influence zinc electrodeposition and solid electrolyte interphase (SEI) formation in ZMBs. Using XPS and Raman spectroscopy, it is demonstrated that an SEI is formed on zinc electrodes at neutral pH, composed primarily of a Zn4(OH)6SO4·xH2O species, its formation being attributed to local pH increases at the interface. This work shows that more extended high-rate cycling can be achieved using a 1 M ZnSO4 electrolyte and that these systems have a reduced tendency for soft shorts. The improved cyclability in 1 M ZnSO4 was attributed to a more homogeneous and conductive interface formed, rather than the bulk electrolyte properties. This experimental methodology for studying metal battery electrodes is transferable to lithium metal and anode-free batteries, and other sustainable battery chemistries such as sodium, magnesium, and calcium.

High DC-Bias Stability and Reliability in BaTiO3-Based Multilayer Ceramic Capacitors: The Role of the Core-Shell Structure and the Electrode.

With the miniaturization of multilayer ceramic capacitors (MLCCs) and the increase of the electric field on a single dielectric layer, dielectric constant DC-bias stability and reliability have gradually aroused attention in the advanced electronics industry. In this study, MLCCs with outstanding DC-bias stability and reliability were prepared by using dielectric ceramic optimization and electrode optimization strategies. The effect of the Dy-Y doping concentration on the microstructure, dielectric properties, and reliability of BaTiO3-based ceramics was investigated. The shell ratio and effective shell doping concentration of the core-shell structure in ceramic grains play important roles in defects and electrical performances. The ceramic with appropriate doping contents shows a dielectric constant of 1800 and a dielectric constant change rate of -17% under a DC field of 4 kV/mm, which was fabricated into prototype MLCCs with different Ni electrodes. MLCCs exhibit outstanding DC-bias stability with a -28% degradation in the dielectric constant under a DC field of 4 kV/mm while possessing a dielectric constant of 2300 and satisfying the EIA X7S specification. Additionally, it was discovered that MLCCs prepared by using fine-size Ni particle electrodes have low electrode roughness and high interfacial Schottky barriers, resulting in better reliability. This study provides promising candidate materials and theoretical references for high-end and high DC-bias stability MLCCs.

Insights into the Complex Oxidation Behaviour of Aqueous H3PO3 through in Situ P K- Edge XANES

High-temperature electrolyte membrane fuel cells (HT-PEMFCs) using H3PO4-doped membranes are an enticing choice for electrochemical energy sources at elevated temperatures [1]. Yet, one of the challenges concerning these systems is the reduction of H3PO4 to lower valency phosphorus compounds, such as H3PO3, during operation [2,3,4]. H3PO3 can strongly adsorb on the Pt catalysts, hence poisoning it and thereby lowering the fuel cell performance [5,6]. Interestingly, the presence of Pt may, under certain conditions, catalyze the chemical (re-)oxidation of aqueous H3PO3 back to H3PO4, illustrating the complexity of the H3POx – Pt interaction. Therefore, to optimize the performance of HT-PEMFCs by rational design of the catalyst/electrolyte interface, further insight into H3PO3 oxidation behaviour and Pt/H3PO3 interaction under conditions relevant to HT-PEMFCs operation is required.In this study, in situ P K- edge XANES (x-ray absorption near edge structure) spectroscopy was conducted to shed light on the oxidation behaviour of aqueous H3PO3 by investigating the impact of (i) different temperatures (25°C vs 75°C), (ii) varying electrode roughness (flat planar Pt vs rough Pt black), (iii) different electrode potentials (open circuit potentials vs more positive potentials [+0.8, +0.9, and +1.0 VRHE]), and (iv) varying molar concentrations of H3PO3 (0.1 , 1 , and 5 mol dm-3). Initially, XANES coupled with electrochemical characterization (e.g. OCP, cyclic voltammetry) of the system was performed under different radiation doses (i.e.: photon fluxes, exposure time) to determine the effect of radiolysis and/or radiation damage during experiments that may lead to misinterpretations of XANES results. Under high radiation dose, we find evidence of H2 presence in the vicinity of the Pt electrode, likely generated by water radiolysis. We have developed experimental procedures to suppress these undesirable effects during the collection of the XANES data, enabling an accurate determination of H3PO3 oxidation behaviour and minimizing the radiolysis contribution to the process. It was found that higher temperature facilitates the oxidation of aqueous H3PO3 to H3PO4, presumably because H3PO3 exists in the thermodynamically preferred “active” pyramidal form at elevated temperatures, which is more prone to react with H2O, forming H3PO4 and H2. In aqueous H3PO3 solutions with higher H2O contents, also more pronounced oxidation of H3PO3 is observed, indicating that oxidation of H3PO3 to H3PO4 in aqueous solutions proceeds via the presence of H2O. The experiments using rough Pt black electrodes additionally hint at the observation of electrochemical oxidation of H3PO3 to H3PO4 during the application of positive potentials. This work provides insights into the underlying chemical processes that occur at conditions relevant for HT-PEMFCs operation and thus it paves the way for possible strategies to mitigate H3PO3 poisoning of the Pt electrode during operation.