Oxygen evolution on alpha-lead dioxide electrodes in methanesulfonic acid

The corrosion behavior of aged and annealed sample of 18 Ni 250 grade maraging steel was investigated in varied conditions of concentration and temperature of sulphuric acid medium, using electrochemical techniques like Tafel polarization and electrochemical impedance spectroscopy (EIS).The results obtained from both the techniques are in good agreement.These results have shown increase in corrosion rate of aged specimen with increase in concentration and temperature of sulphuric acid.With increase in concentration of sulphuric acid from 0.025 M to 0.25 M the corrosion rate of annealed sample was found to increase, but there after in 0.5 M, 0.75 M and 1 M, the rate of corrosion decreases, indicating passivation of alloy surface at higher concentration of sulphuric acid.The corrosion rate of aged specimen was found to be higher than that of the annealed specimen.Similar observations are revealed by SEM images.The thermodynamic parameters like activation energy, enthalpy of activation and entropy of activation were calculated.

Effective control of anodic gas evolving processes like, e.g. oxygen evolution and chlorine evolution is important from both fundamental as well as of applied point of view. The oxygen evolution process is of crucial importance in steering the water electrolysis needed for renewable energy storage. The chlorine evolution then is at core of chlor–alkali and chlorate applications. Both electrode processes take part at similar potentials and also are catalyzed by the same type of materials. It is generally known that kinetic hindrances of four electron oxygen evolution are not only limiting possible deployment of water electrolyzers in replacement of fossil fuels, but also are responsible for kinetic preference of chlorine evolution as prevailing anodic reaction in chloride containing solutions. An effective control of the catalyst selectivity in these competing reactions can be seen as the key enabler of the use of brackish or even sea water electrolytic hydrogen production. This workshop will discuss the selectivity tendencies of Ru based oxides in parallel chlorine and oxygen evolution reactions. on identification of key catalyst parameters needed to steer selectively gas evolving reaction on Ru oxides substituted with Mn and Ti prepared by the spray freeze freeze drying approach and their behavior in parallel oxygen and chlorine evolution reactions. The selectivity of these single phase materials with rutile structure based on RRDE and DEMS measurements will be rationalized in terms of chemical composition, local structure and prevailing mechanism of the oxygen evolving process. It will be shown that the overall electrocatalytic activity of Ru oxides increases with increasing content of the substituting transition metal. The increasing presence of Ti and Mn has, however an opposite effect on the selectivity. While the presence of Ti in substituted materials supports the selectivity towards CER the presence of Mn leads to an increase the selectivity towards oxygen evolution in acidic chloride containing solutions. The analysis of reaction orders for both competing reactions with respect to chloride concentration indicates that the overall selectivity is in fact controlled by the oxygen evolution process regardless of the chemical composition. The high selectivity towards oxygen evolution reaction coincides with low tendency of prepared phases to evolve oxygen via lattice oxygen activation (LOER). The experimental behaviour is further discussed from the theoretical point of view by DFT analysis of the reactivity of the Ru-Me-O surfaces where Me stands for Ti, Mn and Ni respectively.

Photodeposited IrO2 on TiO2 support as a catalyst for oxygen evolution reaction

Ni-(Ebonex-supported Ir) composite coatings as electrocatalysts for alkaline water electrolysis. Part II: Oxygen evolution

Designing cost-effective and highly efficient electrocatalysts for water splitting is a significant challenge. We have systematically investigated a series of quasi-2D oxides, LaSrMn0.5M0.5O4 (M = Co, Ni, Cu, Zn), to enhance the electrocatalytic properties of the two half-reactions of water-splitting, namely oxygen and hydrogen evolution reactions (OER and HER). The four materials are isostructural, as confirmed by Rietveld refinements with X-ray diffraction. The oxygen contents and metal valence states were determined by iodometric titrations and X-ray photoelectron spectroscopy. Electrical conductivity measurements in a wide range of temperatures revealed semiconducting behavior for all four materials. Electrocatalytic properties were studied for both half-reactions of water-splitting, namely, oxygen-evolution and hydrogen-evolution reactions (OER and HER). For the four materials, the trends in both OER and HER were the same, which also matched the trend in electrical conductivities. Among them, LaSrMn0.5Co0.5O4 showed the best bifunctional electrocatalytic activity for both OER and HER, which may be attributed to its higher electrical conductivity and favorable electron configuration.

Anion exchange membrane water electrolysis (AEM-WE) stands out as a promising method for hydrogen production from renewable energy sources. Unlike proton exchange membrane water electrolysis (PEM-WE), AEM-WE offers the advantage of nonprecious metal catalysts due to mild alkaline conditions, while still enabling a compact cell design and operation under differential pressure. Remarkable performances of AEM-electrolysis cells have been demonstrated in literature, achieving current densities of up to 7.68 A·cm−2 [1], surpassing the record current density of PEM-WE at 6 A·cm−2 [2], both measured at 80 °C and 2 V. However, challenges related to efficiency and stability persist and demand effective solutions to unlock the full potential of AEM-WE. In order to achieve this, cell components, particularly the membrane, catalysts, and electrode structure have to be improved and advanced measurement techniques have to be applied.Different measurement tools serve to characterize, separate, and quantify the dynamic processes inherent in AEM-WE. Electrochemical impedance spectroscopy (EIS) serves as a valuable non-destructive, in-situ diagnostic tool for electrochemical cells, enabling the differentiation of various phenomena based on their respective relaxation times. Moreover, EIS enables the quantification of loss mechanisms thereby facilitating a targeted optimization of electrolysis components and the identification of weaknesses limiting long-time stability.Despite its utility, the broad use of EIS is hindered by its complex interpretation. The widely applied approach of fitting equivalent circuit models (ECMs) aims to extract quantitative data from the semi-circular shapes observed in Nyquist plots. However, the assumption of a physico-chemical meaningful ECM is challenging without prior knowledge of the number, size, and time constants of appearing loss mechanisms. Furthermore, the potential for multiple ECMs to fit one and the same experimental result introduces ambiguity, leading to potential misinterpretations of data.An alternative approach to analyse EIS spectra involves converting the measured data into the time (τ) domain and characterize the different mechanisms based on their characteristic relaxation times. The distribution of relaxation times (DRT) analysis has already been applied across diverse electrochemical systems, spanning from solid oxide fuel cells (SO-FC) and PEM fuel cells (PEM-FC) to PEM water electrolysis and AEM fuel cells (AEM-FC). However, to the best of the authors’ knowledge, DRT analysis of AEM-WE is still absent in literature.In this study we present a thorough investigation of an AEM-WE single-cell, employing a combination of electrochemical impedance spectroscopy (EIS) and the equivalent circuit model (ECM). Notably, we demonstrate the distribution of relaxation times (DRT) analysis at AEM-WE cells for the first time, utilizing a reversible hydrogen electrode (RHE) as a reference. Through half-cell EIS measurements and subsequent DRT spectra analysis, anodic and cathodic half-cell reactions are clearly identified and quantified. The DRT analysis differentiates five loss mechanisms within the AEM-WE system, encompassing the hydrogen evolution reaction, the oxygen evolution reaction, and ionic transport losses within the catalyst layers. By systematically varying operating parameters, we successfully attribute DRT peaks to their respective physicochemical origins. These findings provide valuable insights into the electrochemical processes within the AEM-WE single-cell, significantly advancing our understanding of underlying mechanisms.In fig. 1, we investigate the degradation of AEM-WE single cells through long-term experiments. Periodic EIS measurements enable an in-operando analysis of catalyst degradation. The impedance data is analysed using ECM and DRT. Ohmic contributions resulting from electric and ionic charge transport are distinguished from polarisation resistances arising from electrochemical reactions. A catalyst degradation is observable in fig 1b & c, where the low frequency resistance (LFR) in the Nyquist plot and the DRT peak area increases over time. However, fig. 1b also reveals the reduction of the high frequency resistance (HFR) resulting in an overall performance increase and voltage decrease.[1] N. Chen, S. Y. Paek, J. Y. Lee, J. H. Park, S. Y. Lee, Y. M. Lee, High-performance anion exchange membrane water electrolyzers with a current density of 7.68 a cm −2 and a durability of 1000 hours, Energy & Environmental Science 14 (12) (2021) 6338–6348. doi:10.1039/D1EE02642A.[2] M. Braig, R. Zeis, Distribution of relaxation times analysis of electrochemical hydrogen pump impedance spectra, Journal of Power Sources 576 (2023) 233203. doi:10.1016/j.jpowsour.2023.233203. Figure 1

<strong class="journal-contentHeaderColor">Abstract.</strong> Understanding chemical processes leading to the formation of atmospheric aerosol particles is crucial to improve our capabilities in predicting the future climate. However, those mechanisms are still inadequately characterized, especially in polar regions. In this study, we report observations of neutral and charged aerosol precursor molecules and chemical cluster composition (qualitatively and quantitatively), as well as air ions and aerosol particle number concentrations and size distributions from the Marambio research station (64<span class="inline-formula">^∘</span>15<span class="inline-formula">^′</span> S, 56<span class="inline-formula">^∘</span>38<span class="inline-formula">^′</span> W), located north of the Antarctic Peninsula. We conducted measurements during the austral summer, between 15 January and 25 February 2018. The scope of this study is to characterize new particle formation (NPF) event parameters and connect our observations of gas-phase compounds with the formation of secondary aerosols to resolve the nucleation mechanisms at the molecular scale. NPF occurred on 40 % of measurement days. All NPF events were observed during days with high solar radiation, mostly with above-freezing temperatures and with low relative humidity. The averaged formation rate for 3 nm particles (<span class="inline-formula"><i>J</i>₃</span>) was 0.686 cm<span class="inline-formula">^−3</span> s<span class="inline-formula">^−1</span>, and the average particle growth rate (GR<span class="inline-formula">_{3.8–12 nm}</span>) was 4.2 nm h<span class="inline-formula">^−1</span>. Analysis of neutral aerosol precursor molecules showed measurable concentrations of iodic acid (IA), sulfuric acid (SA), and methane sulfonic acid (MSA) throughout the entire measurement period with significant increase in MSA and SA concentrations during NPF events. We highlight SA as a key contributor to NPF processes, while IA and MSA likely only contribute to particle growth. Mechanistically, anion clusters containing ammonia and/or dimethylamine (DMA) and SA were identified, suggesting significant concentration of ammonia and DMA as well. Those species are likely contributing to NPF events since SA alone is not sufficient to explain observed nucleation rates. Here, we provide evidence of the marine origin of the measured chemical precursors and discuss their potential contribution to the aerosol phase.

Highly efficient photocatalysts of the type M x O y @MIL‐125(Ti) (M x O y = MnO 2 , Fe 2 O 3 , Co 3 O 4 , NiO and CuO) have been prepared by in‐situ incorporation of pre synthesized metal oxide nanoparticles into MIL‐125(Ti) through hydrothermal method. The synthesized samples have been characterized by Powder X‐ray diffraction, Raman spectroscopy, Scanning Electron Microscopy, Energy Dispersive X‐ray Spectrometry, Elemental Mapping, UV‐Vis spectrophotometry andN 2 ‐adsorption Isotherm. The photoelectrochemical properties for oxygen evolution reaction and hydrogen evolution reaction have been studied by Cyclic voltammetry and Linear sweep voltammetry analysis in 2 M aq. KOH electrolyte and stability for constant current generation of these samples is observed by Chronoamperometric measurements. These studies indicate that metal oxide nanoparticles have been successfully incorporated into MIL‐125(Ti), which enhance the efficient absorption of visible light and improve the oxygen evolution and hydrogen evolution reaction activity during water splitting. Furthermore, from linear sweep voltammetry results at 1mVs −1 scan rate it is observed that M x O y @MIL‐125(Ti) samples have lower onset potential and higher current density as compared to pure MIL‐125(Ti). CuO@MIL‐125(Ti)/NF exhibited highest current density, lowest onset potential and better oxygen evolution reaction and hydrogen evolution reaction activity as compared to all other synthesized samples.

Developing efficient and earth-abundant electrocatalysts for electrochemical water splitting is greatly desired due to growing energy demands. Herein, we develop a promising hierarchical nickel-iron-copper nitride electrode that is fabricated via a three-step process, starting with a hydrothermal synthesis of nickel-iron hydroxide on nickel foam and followed by the direct growth of copper metal-organic frameworks and, finally, low temperature ammonization. This approach yields a material that is an efficient catalyst for both the oxygen evolution reaction and the hydrogen evolution reaction. The as-fabricated heterostructured nickel-iron-copper nitride electrode exhibits an excellent activity with an overpotential of only 121 mV for the oxygen evolution reaction and an even a lower overpotential of 33 mV for the hydrogen evolution reaction. Additionally, this structure displays strong long-term stability with only a negligible increase in potential after 500 cycles of uninterrupted cyclic voltammetry testing. To the best of our knowledge, this as-prepared hierarchical nickel-iron-copper nitride is one of the most promising alternatives for the electrochemical oxygen and hydrogen evolution reactions.

Tantalum-based electrocatalysts prepared by a microemulsion method for the oxygen reduction and evolution reactions

The properties of activated titanium anodes, RuO2-TiO2/Ti and RuO2--TiO2-IrO2/Ti, prepared from oxide sols by the sol-gel procedure, are reviewed. RuO2 and TiO2 sols were synthesized by forced hydrolysis of the corresponding chlorides in acid medium. The morphology of the prepared sols was investigated by transmission electron microscopy. The chemical composition of the RuO2 sol was determined by X-ray diffraction and thermogravimetric analysis. The loss of electrocatalytic activity of a RuO2-TiO2/Ti anode during an accelerated stability test was investigated by examination of the changes in the electrochemical characteristics in the potential region of the chlorine and oxygen evolution reaction, as well as on the open circuit potential. These electrochemical characteristics were investigated by cyclic voltammetry, electrochemical impedance spectroscopy and polarization measurements. The changes in electrochemical characteristics of the anode prepared by the sol-gel procedure were compared to the changes registered for an anode prepared by the traditional thermal decomposition of metal chlorides. The comparison indicated that the main cause for the activity loss of the sol-gel prepared anode was the electrochemical dissolution of RuO2, while in the case of thermally prepared anode the loss was mainly caused by the formation of an insulating TiO2 layer in the coating/Ti substrate interphase. The results of an accelerated stability test on RuO2-TiO2/Ti and RuO2--TiO2-IrO2/Ti anodes showed that the ternary coating is considerably more stable than the binary one, which is the consequence of the greater stability of IrO2 in comparison to RuO2.

The material design of highly active catalysts for energy storage applications (e.g., metal-air batteries and fuel cells) is crucial for solving global energy problems. The oxygen evolution reaction (OER) and the oxygen reduction reaction (ORR) is used for charging and discharging rechargeable metal-air batteries, respectively. Although precious metal-based catalysts facilitate these reactions, the kinetics of the OER and ORR are rather sluggish due to their multistep electron transfer. It is therefore important to explore the mechanism of the OER and ORR to discover the key factors for highly active catalysts. As demonstrated by Suntivich et al. (2011)[1],[2], when the number of electrons in the eg orbital is close to unity for transition metals, perovskite oxides exhibit maximum OER and ORR activities. In other words, Mn3+ (t2g 3 eg 1 for both surface and bulk), Co3+ (t2g 5 eg 1 for surface), and Ni3+ (t2g 6 eg 1 for both surface and bulk) become OER and ORR active sites for Mn3+, Co3+ and Ni3+ based compounds . However, LaMnO3 exhibits a significantly lower specific OER activity[3] compared with LaCoO3 and LaNiO3 (~6% of LaNiO3 at 1.8 V vs. RHE). Also, Mn3O4 exhibits a low specific OER activity[4] (40% of Mn2O3 at 1.8 V vs. RHE) similar to LaMnO3. It is therefore important to explore what causes degradation of the OER activity of Mn3+-based (t2g 3 eg 1) compounds to improve their catalytic activity. We attempt to improve the performance of Mn3+-based oxides by controlling the degradation factors of their OER activities. To directly compare the OER activities of Mn3+-based oxides containing more than two cation sites, Mn3+ concentrations at the octahedral site and their initial crystal structures were maintained. Mn3-x Co x O4 (0 ≤ x < 1), a series of tetragonally distorted spinel compounds, satisfies this condition, as their octahedral sites remain occupied by only Mn3+ ions . For Mn3+-based oxides with a single cation site, Mn3+ was directly substituted by Co3+.We systematically studied the OER and ORR performances of Mn3+-based oxides by Co3+-substitution. Nanoparticles were prepared for the evaluation of catalytic activity to minimize the influence of geometric factors. Electrochemical measurements were conducted using a rotating ring disk electrode rotator (RRDE-3A, BAS Inc., Japan) at 1600 rpm, in combination with a bipotentiostat (ALS Co., Ltd, Japan). In addition, a Pt wire counter electrode, and an Hg/HgO reference electrode (International Chemistry Co., Ltd., Japan) filled with 0.10 M KOH (Nacalai Tesque, Inc., Japan) were used. Electrochemical measurements were conducted with O2 saturation (30 min bubbling O2 gas through the solution) at ~25 °C, where the equilibrium potential of the O2/H2O redox couple was fixed at 0.304 V vs. Hg/HgO (or 1.23 V vs. RHE). During OER current density measurements for each sample, the potential of the sample-modified GC was controlled from 0.3-0.9 V vs. Hg/HgO (1.226-1.826 V vs. RHE) at 10 mV/s. For all measurements, the OER current density was iR-corrected (R = ~43 Ω) using the measured solution resistance, and capacitance-corrected by averaging the anodic and cathodic scans to remove the influence of the current related to the formation of an electrical double layer. With an increase in Co content, signicant improvements in the OER and ORR activities were observed for Mn3+-based oxides. For example, Mn2.1Co0.9O4 exhibited a high specific OER activity (1700 % of Mn3O4 at 1.76 V vs. RHE) and a long-term stability over 100 cycles [5]. The OER activities of Mn3+-based oxides increased linearly with the suppression of the Jahn–Teller distortion. We examined whether the electronic state of Mn3+ changes in favor of enhancing the OER and ORR activities. When the Jahn-Teller distortion of Mn3+O6 octahedra is suppressed due to the increase in Co content, the splitting of the Mn3+ eg orbitals becomes smaller and the electron occupying the Mn3+ eg orbital shifts to a higher energy level. Thus, the overlap of the antibonding Mn3+ eg orbitals with the O 2p orbitals of the oxygen adsorbate becomes stronger. The OER and ORR activities of Mn3+-based oxides should therefore be enhanced due to the stronger binding of OER intermediates to the catalytic surface. We therefore conclude that the suppression of Jahn–Teller distortion enhances the OER and ORR activities of Mn3+-based oxides. Our result suggests a future application of Mn3+-based oxides as bifunctional catalysts for metal-air batteries. [1] J. Suntivich et al., Science, 2011, 334, 1383. [2] J. Suntivich et al., Nature Chemistry, 2011, 3, 546. [3] B. Han et al., Phys. Chem. Chem. Phys., 2015, 17, 22576. [4] A. Ramirez et al., J. Phys. Chem. C, 2014, 118, 14073. [5] S. Hirai et al., RSC Adv., 2016, 6, 2019.

Three-dimensional hierarchically porous iridium oxide-nitrogen doped carbon hybrid: An efficient bifunctional catalyst for oxygen evolution and hydrogen evolution reaction in acid

The effect of the crystallographic form of MnO2 on the kinetics of oxygen reduction and evolution reaction

Designing bifunctional catalysts for oxygen reduction/evolution reactions for high efficiency and long lifetime