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Neurogenesis is the process by which new brain cells are formed. This crucial event emerges during embryonic life and proceeds in adulthood, and it could be influenced by environmental pollution. Non-combustion-derived magnetite represents a portion of the coarse particulate matter (PM) contributing to air and water pollution in urban settings. Studies on humans have reported that magnetite and other iron oxides have significant damaging effects at a central level, where these particles accumulate and promote oxidative stress. Similarly, magnetite nanoparticles can cross the placenta and damage the embryo brain during development, but the impact on neurogenesis is still unknown. Furthermore, an abnormal Fe cation concentration in cells and tissues might promote reactive oxygen species (ROS) generation and has been associated with multiple neurodegenerative conditions. In the present study, we used zebrafish as an in vivo system to analyze the specific effects of magnetite on embryonic neurogenesis. First, we characterized magnetite using mineralogical and spectroscopic analyses. Embryos treated with magnetite at sub-lethal concentrations showed a dose-response increase in ROS in the brain, which was accompanied by a massive decrease in antioxidant genes (sod2, cat, gsr, and nrf2). In addition, a higher number of apoptotic cells was observed in embryos treated with magnetite. Next, interestingly, embryos exposed to magnetite displayed a decrease in neural staminal progenitors (nestin, sox2, and pcna markers) and a neuronal marker (elavl3). Finally, we observed significative increases in apoeb (specific microglia marker) and interleukin-1b (il1b), confirming a status of inflammation in the brain embryos treated with magnetite. Our study represents the very first in vivo evidence concerning the effects of magnetite on brain development.
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Embrião não Mamífero , Óxido Ferroso-Férrico , Neurogênese , Peixe-Zebra , Animais , Peixe-Zebra/embriologia , Neurogênese/efeitos dos fármacos , Embrião não Mamífero/efeitos dos fármacos , Embrião não Mamífero/metabolismo , Espécies Reativas de Oxigênio/metabolismo , Estresse Oxidativo/efeitos dos fármacos , Encéfalo/metabolismo , Encéfalo/efeitos dos fármacos , Encéfalo/embriologia , Apoptose/efeitos dos fármacos , Nanopartículas de Magnetita/química , Nanopartículas de Magnetita/toxicidadeRESUMO
In this study, we introduce a novel approach using correlative analysis techniques to unravel detailed insights into the environmental influences on crystal growth. Tabular and bipyramidal wulfenite samples from the Mezica mine in north-eastern Slovenia were analysed to combine the morphological aspects of crystal growth with the atomic-resolution reconstruction of the positions of lead (Pb) and molybdenum (Mo) atoms in the parent crystal lattice. These combined data also allow us to present the formation mechanism that enables the development of bipyramidal or tabular morphologies in wulfenite. The bipyramidal and tabular crystals are chemically pure wulfenite (PbMoO4), as confirmed by various advanced diffraction and spectroscopy techniques. However, each habit includes multiple inclusions, mostly consisting of carbonates, Pb-Fe oxides, Pb oxides and, more rarely, Pb vanadate (descloizite). The differences in the morphologies can be attributed to compositional changes during precipitation from a meteoric solution and thus, we propose a growth mechanism consisting of three different phases of growth. This innovative approach emphasises the importance of understanding the origin of crystal habits, as can help to decipher how external influences can affect the crystal structure and its surface, leading to the dissolution of preferred surfaces and the selective release of Pb and Mo.
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A current trend in the investigation of state-of-the-art Pt-alloys as proton exchange membrane fuel cell (PEMFC) electrocatalysts is to study their long-term stability as a bottleneck for their full commercialization. Although many parameters have been appropriately addressed, there are still certain issues that must be considered. Here, the stability of an experimental Pt-Co/C electrocatalyst is investigated by high-temperature accelerated degradation tests (HT-ADTs) in a high-temperature disk electrode (HT-DE) setup, allowing the imitation of close-to-real operational conditions in terms of temperature (60 °C). Although the US Department of Energy (DoE) protocol has been chosen as the basis of the study (30,000 trapezoidal wave cycling steps between 0.6 and 0.95 VRHE with a 3 s hold time at both the lower potential limit (LPL) and the upper potential limit (UPL)), this works demonstrates that limiting both the LPL and UPL (from 0.6-0.95 to 0.7-0.85 VRHE) can dramatically reduce the degradation rate of state-of-the-art Pt-alloy electrocatalysts. This has been additionally confirmed with the use of an electrochemical flow cell coupled to inductively coupled plasma mass spectrometry (EFC-ICP-MS), which enables real-time monitoring of the dissolution mechanisms of Pt and Co. In line with the HT-DE methodology observations, a dramatic decrease in the total dissolution of Pt and Co has once again been observed upon narrowing the potential window to 0.7-0.85 VRHE rather than 0.6-0.95 VRHE. Additionally, the effect of the potential hold time at both LPL and UPL on metal dissolution has also been investigated. The findings demonstrate that the dissolution rate of both metals is proportional to the hold time at UPL regardless of the applied potential window, whereas the hold time at the LPL does not appear to be as detrimental to the stability of metals.
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In the present work, we report on a synergistic relationship between platinum nanoparticles and a titanium oxynitride support (TiOxNy/C) in the context of oxygen reduction reaction (ORR) catalysis. As demonstrated herein, this composite configuration results in significantly improved electrocatalytic activity toward the ORR relative to platinum dispersed on carbon support (Pt/C) at high overpotentials. Specifically, the ORR performance was assessed under an elevated mass transport regime using the modified floating electrode configuration, which enabled us to pursue the reaction closer to PEMFC-relevant current densities. A comprehensive investigation attributes the ORR performance increase to a strong interaction between platinum and the TiOxNy/C support. In particular, according to the generated strain maps obtained via scanning transmission electron microscopy (STEM), the Pt-TiOxNy/C analogue exhibits a more localized strain in Pt nanoparticles in comparison to that in the Pt/C sample. The altered Pt structure could explain the measured ORR activity trend via the d-band theory, which lowers the platinum surface coverage with ORR intermediates. In terms of the Pt particle size effect, our observation presents an anomaly as the Pt-TiOxNy/C analogue, despite having almost two times smaller nanoparticles (2.9 nm) compared to the Pt/C benchmark (4.8 nm), manifests higher specific activity. This provides a promising strategy to further lower the Pt loading and increase the ECSA without sacrificing the catalytic activity under fuel cell-relevant potentials. Apart from the ORR, the platinum-TiOxNy/C interaction is of a sufficient magnitude not to follow the typical particle size effect also in the context of other reactions such as CO stripping, hydrogen oxidation reaction, and water discharge. The trend for the latter is ascribed to the lower oxophilicity of Pt-based on electrochemical surface coverage analysis. Namely, a lower surface coverage with oxygenated species is found for the Pt-TiOxNy/C analogue. Further insights were provided by performing a detailed STEM characterization via the identical location mode (IL-STEM) in particular, via 4DSTEM acquisition. This disclosed that Pt particles are partially encapsulated within a thin layer of TiOxNy origin.
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Platinum-based fuel cell electrocatalysts are structured on a nano level in order to extend their active surface area and maximize the utilization of precious and scarce platinum. Their performance is dictated by the atomic arrangement of their surface layers atoms via structure-property relationships. Transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM) are the preferred methods for characterizing these catalysts, due to their capacity to achieve local atomic-level resolutions. Size, morphology, strain and local composition are just some of the properties of Pt-based nanostructures that can be obtained by (S)TEM. Furthermore, advanced methods of (S)TEM are able to provide insights into the quasi-in situ, in situ or even operando stability of these nanostructures. In this review, we present state-of-the-art applications of (S)TEM in the investigation and interpretation of structure-activity and structure-stability relationships.
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3D ceramic architectures are captivating geometrical features with an immense demand in optics. In this work, an additive manufacturing (AM) approach for printing alkaline-earth perovskite 3D microarchitectures is developed. The approach enables custom-made photoresists suited for two-photon lithography, permitting the production of alkaline-earth perovskite (BaZrO3 , CaZrO3 , and SrZrO3 ) 3D structures shaped in the form of octet-truss lattices, gyroids, or inspired architectures like sodalite zeolite, and C60 buckyballs with micrometric and nanometric feature sizes. Alkaline-earth perovskite morphological, structural, and chemical characteristics are studied. The optical properties of such perovskite architectures are investigated using cathodoluminescence and wide-field photoluminescence emission to estimate the lifetime rate and defects in BaZrO3 , CaZrO3 , and SrZrO3 . From a broad perspective, this AM methodology facilitates the production of 3D-structured mixed oxides. These findings are the first steps toward dimensionally refined high-refractive-index ceramics for micro-optics and other terrains like (photo/electro)catalysis.
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In the past, platinum-copper catalysts have proven to be highly active for the oxygen reduction reaction (ORR), but transferring the high activities measured in thin-film rotating disk electrodes (TF-RDEs) to high-performing membrane electrode assemblies (MEAs) has proven difficult due to stability issues during operation. High initial performance can be achieved. However, fast performance decay on a timescale of 24 h is induced by repeated voltage load steps with H2/air supplied. This performance decay is accelerated if high relative humidity (>60% RH) is set for a prolonged time and low voltages are applied during polarization. The reasons and possible solutions for this issue have been investigated by means of electrochemical impedance spectroscopy and distribution of relaxation time analysis (EIS-DRT). The affected electrochemical sub-processes have been identified by comparing the PtCu electrocatalyst with commercial Pt/C benchmark materials in homemade catalyst-coated membranes (CCMs). The proton transport resistance (Rpt) increased by a factor of ~2 compared to the benchmark materials. These results provide important insight into the challenges encountered with the de-alloyed PtCu/KB electrocatalyst during cell break-in and operation. This provides a basis for improvements in the catalysts' design and break-in procedures for the highly attractive PtCu/KB catalyst system.
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Hysteresis is a general phenomenon regularly observed in various materials. Usually, hysteretic behavior is an intrinsic property that cannot be circumvented in the nonequilibrium operation of the system. Herein, it is shown that, at least with regard to the hysteretic behavior of phase-separating battery materials, it is possible to enter (deeply) the hysteretic loop at finite battery currents. This newly observed electric response of the electrode, which is inherent to phase-separating materials, is related to its microscopic origin arising from a (significant) share of the active material residing in an intraparticle phase-separated state. This intriguing observation is further generalized by revealing that a phase-separating material can feature (significantly) different chemical potentials at the same bulk lithiation level and temperature when exposed to the same finite current and external voltage hysteresis. Therefore, the intraparticle phase-separated state significantly affects the DC and AC characteristics of the battery. The experimental evidence for entering the intraparticle phase-separated state is supported by thermodynamic reasoning and advanced modeling. The current findings will help advance the understanding, control, diagnostics, and monitoring of batteries composed of phase-separating materials while also providing pertinent motivation for the enhancement of battery design and performance.
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The design of catalysts with stable and finely dispersed platinum or platinum alloy nanoparticles on the carbon support is key in controlling the performance of proton exchange membrane (PEM) fuel cells. In the present work, an intermetallic PtCo/C catalyst is synthesized via double-passivation galvanic displacement. TEM and XRD confirm a significantly narrowed particle size distribution for the catalyst particles compared to commercial benchmark catalysts (Umicore PtCo/C). Only about 10% of the mass fraction of PtCo particles show a diameter larger than 8 nm, whereas this is up to or even more than 35% for the reference systems. This directly results in a considerable increase in electrochemically active surface area (96 m2 g-1 vs. >70 m2 g-1), which confirms the more efficient usage of precious catalyst metal in the novel catalyst. Single-cell tests validate this finding by improved PEM fuel cell performance. Reducing the cathode catalyst loading from 0.4 mg cm-2 to 0.25 mg cm-2 resulted in a power density drop at an application-relevant 0.7 V of only 4% for the novel catalyst, compared to the 10% and 20% for the commercial benchmarks reference catalysts.
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Water electrolysis powered by renewables is regarded as the feasible route for the production of hydrogen, obtained at the cathode side through electrochemical hydrogen evolution reaction (HER). Herein, we present a rational strategy to improve the overall HER catalytic performance of Pt, which is known as the best monometallic catalyst for this reaction, by supporting it on a conductive titanium oxynitride (TiON x ) dispersed over reduced graphene oxide nanoribbons. Characterization of the Pt/TiON x composite revealed the presence of small Pt particles with diameters between 2 and 3 nm, which are well dispersed over the TiON x support. The Pt/TiON x nanocomposite exhibited improved HER activity and stability with respect to the Pt/C benchmark in an acid electrolyte, which was ascribed to the strong metal-support interaction (SMSI) triggered between the TiON x support and grafted Pt nanoparticles. SMSI between TiON x and Pt was evidenced by X-ray photoelectron spectroscopy (XPS) through a shift of the binding energies of the characteristic Pt 4f photoelectron lines with respect to Pt/C. Density functional theory (DFT) calculations confirmed the strong interaction between Pt nanoparticles and the TiON x support. This strong interaction improves the stability of Pt nanoparticles and weakens the binding of chemisorbed H atoms thereon. Both of these effects may result in enhanced HER activity.
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The lack of efficient and durable proton exchange membrane fuel cell electrocatalysts for the oxygen reduction reaction is still restraining the present hydrogen technology. Graphene-based carbon materials have emerged as a potential solution to replace the existing carbon black (CB) supports; however, their potential was never fully exploited as a commercial solution because of their more demanding properties. Here, a unique and industrially scalable synthesis of platinum-based electrocatalysts on graphene derivative (GD) supports is presented. With an innovative approach, highly homogeneous as well as high metal loaded platinum-alloy (up to 60 wt %) intermetallic catalysts on GDs are achieved. Accelerated degradation tests show enhanced durability when compared to the CB-supported analogues including the commercial benchmark. Additionally, in combination with X-ray photoelectron spectroscopy Auger characterization and Raman spectroscopy, a clear connection between the sp 2 content and structural defects in carbon materials with the catalyst durability is observed. Advanced gas diffusion electrode results show that the GD-supported catalysts exhibit excellent mass activities and possess the properties necessary to reach high currents if utilized correctly. We show record-high peak power densities in comparison to the prior best literature on platinum-based GD-supported materials which is promising information for future application.
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Pt-alloy (Pt-M) nanoparticles (NPs) with less-expensive 3d transition metals (M = Ni, Cu, Co) supported on high-surface-area carbon supports are currently the state-of-the-art (SoA) solution to reach the production phase in proton exchange membrane fuel cells (PEMFCs). However, while Pt-M electrocatalysts show promise in terms of increased activity for oxygen reduction reaction (ORR) and, thus, cost reductions from the significantly lower use of expensive and rare Pt, key challenges in terms of synthesis, activation, and stability remain to unlock their true potential. This work systematically tackles them with a combination of electrocatalyst synthesis and characterization methodologies including thin-film rotating disc electrodes (TF-RDEs), an electrochemical flow cell linked to an inductively coupled plasma mass spectrometer (EFC-ICP-MS), and testing in 50 cm2 membrane electrode assemblies (MEAs). In the first part of the present work, we highlight the crucial importance of the chemical activation (dealloying) step on the performance of Pt-M electrocatalysts in the MEA at high current densities (HCDs). In addition, we provide the scientific community with a preliminary and facile method of distinguishing between a "poorly" and "adequately" dealloyed (activated) Pt-alloy electrocatalyst using a much simpler and affordable TF-RDE methodology using the well-known CO-stripping process. Since the transition-metal cations can also be introduced in a PEMFC due to the degradation of the Pt-M NPs, the second part of the work focuses on presenting clear evidence on the direct impact of the lower voltage limit (LVL) on the stability of Pt-M electrocatalysts. The data suggests that in addition to intrinsic improvements in stability, significant improvements in the PEMFC lifetime can also be obtained via the correct MEA design and applied limits of operation, namely, restricting not just the upper but equally important also the lower operation voltage.
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Photocatalytic H2 generation by water splitting is a promising alternative for producing renewable fuels. This work synthesized a new type of Ta2O5/SrZrO3 heterostructure with Ru and Cu (RuO2/CuxO/Ta2O5/SrZrO3) using solid-state chemistry methods to achieve a high H2 production of 5164 µmol g-1 h-1 under simulated solar light, 39 times higher than that produced using SrZrO3. The heterostructure performance is compared with other Ta2O5/SrZrO3 heterostructure compositions loaded with RuO2, CuxO, or Pt. CuxO is used to showcase the usage of less costly cocatalysts to produce H2. The photocatalytic activity toward H2 by the RuO2/CuxO/Ta2O5/SrZrO3 heterostructure remains the highest, followed by RuO2/Ta2O5/SrZrO3 > CuxO/Ta2O5/SrZrO3 > Pt/Ta2O5/SrZrO3 > Ta2O5/SrZrO3 > SrZrO3. Band gap tunability and high optical absorbance in the visible region are more prominent for the heterostructures containing cocatalysts (RuO2 or CuxO) and are even higher for the binary catalyst (RuO2/CuxO). The presence of the binary catalyst is observed to impact the charge carrier transport in Ta2O5/SrZrO3, improving the solar to hydrogen conversion efficiency. The results represent a valuable contribution to the design of SrZrO3-based heterostructures for photocatalytic H2 production by solar water splitting.
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Avocado bronze mite (ABM), Oligonychus punicae Hirst (Trombidiformes: Tetranychidae) has potential for development in several plant species of agricultural importance. ABM is one of the most economically important pests in avocado cultivars, causing major damage to fruit and defoliation. At present, the control of ABM depends mainly on agrochemicals. Therefore, it is necessary to find alternatives to agrochemicals that can help minimize environmental impact and health risks for humans and mammals. The aim of this research was to assess the effect of different concentrations (5, 10, 50, 100, 250, 500, 1000 µg/mL) of ethanolic powdered extract of M. tamaulipana leaves against adult ABM females. The different concentrations of M. tamaulipana extract did not cause mortality of O. punicae. Females treated with 5 and 1000 µg/mL of the extract showed a decrease in the number of eggs laid per female at 24 (5.17 and 1.27), 48 (5.07 and 1.17), and 72 h (4.97 and 0.80), compared to the control treatment (5.20, 6.60 and 6.87), respectively, which led to a reduction in the growth rate. Percentage of feeding damage decreased with the increasing concentration of the extract. The ethanolic powdered extract of M. tamaulipana leaf has potential to control O. punicae.
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At least 59 maize races (Zea mays L.) have been registered in Mexico. The feeding damage caused by insects and mites to maize crops generates up to ~30% of maize yield losses. Spider-mite-resistant plants are needed. The red spider mite, Tetranychus merganser Boudreaux (Acari: Tetranychidae), is distributed in the United States, China, Mexico, and Thailand. It is considered a potential pest in Mexican agriculture. The aim of this study was to evaluate the resistance mechanisms (antixenosis and antibiosis) of 11 native maize populations, representative of each race of maize grown in Tamaulipas, Mexico, to T. merganser under laboratory conditions. The aim was also to obtain information on the chemical composition and some morphological characteristics of these maize races and to identify resistant maize races for incorporation into a breeding program. Antixenosis was assessed by non-preference for oviposition and feeding. Antibiosis was measured by growth rate (ri). The presence of secondary metabolites in the 11 maize races were different. In the 11 maize races, quantitative analysis of total phenol concentration, total flavonoid concentration, and antioxidant capacity were significantly different. The multivariate analysis of variance showed that there is evidence of antixenosis noted by maize race differences in egg laying and percentage feeding damage but not of antibiosis noted by growth rate. Red spider mites laid significantly more eggs on the Celaya (24 h: 25.67 ± 17.04, 48 h: 42.67 ± 26.86, 72 h: 49.33 ± 28.54) race than on Raton (24 h: 7.00 ± 5.00, 48 h: 12.67 ± 8.02, 72 h: 14.67 ± 9.29) and Elotes Occidentales × Tuxpeño (24 h: 9.67 ± 5.85, 48 h: 15.33 ± 10.69, 72 h: 17.67 ± 10.97) races. However, the growth rate and mortality of T. merganser in the 11 corn races were similar. The Vandeño (24 h: 11.67 ± 2.89, 48 h: 27.67 ± 7.64, 72 h: 30.00 ± 18.03) and Tabloncillo × Tuxpeño (24 h: 18.33 ± 7.64, 48 h: 25.00 ± 8.66, 72 h: 25.00 ± 8.66) races were the most resistant to red spider mite damage, whereas the most susceptible race was Celaya (24 h: 26.67 ± 15.28, 48 h: 48.33 ± 29.30, 72 h: 65.00 ± 30.00). Further analysis by PCA at 24, 48, and 72 h found the Celaya race positively correlated to growth rate and oviposition of T. merganser and to a lesser extent with the percentage of feeding damage, suggesting that the Celaya race was most susceptible to T. merganser. At 24 h, the Vandeño race was most resistant, given a negative correlation to growth rate and oviposition by T. merganser. The PCA at 48 and 72 h noted the Elotes Occidentales × Tuxpeño race was most resistant to red spider mite, with negative relationships to growth rate and oviposition and, to a lesser extent, to feeding damage. This resistance is due to the differences in both its morphological characteristics and the secondary metabolites present in their leaves.
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BACKGROUND: Repetitive peripheral nerve sensory stimulation (RPSS) is a potential add-on intervention to motor training for rehabilitation of upper limb paresis after stroke. Benefits of RPSS were reported in subjects in the chronic phase after stroke, but there is limited information about the effects of this intervention within the 1st weeks or months. The primary goal of this study is to compare, in a head-to-head proof-of-principle study, the impact of a single session of suprasensory vs. subsensory RPSS on the upper limb motor performance and learning in subjects at different phases after stroke subacute and chronic phases and mild upper limb motor impairments after stroke. In addition, we examine the effects of RPSS on brain perfusion, functional imaging activation, and γ-aminobutyric acid (GABA) levels. Subjects with mild upper limb motor impairments will be tested with MRI and clinical assessment either at an early (7 days to 3 months post-stroke) or at a chronic (>6 months) stage after stroke. METHODS: In this multicenter, randomized, parallel-group, proof-of-principle clinical trial with blinded assessment of outcomes, we compare the effects of one session of suprasensory or subsensory RPSS in patients with ischemic or hemorrhagic stroke and upper limb paresis. Clinical assessment and MRI will be performed only once in each subject (either at an early or at a chronic stage). The primary outcome is the change in performance in the Jebsen-Taylor test. Secondary outcomes: hand strength, cerebral blood flow assessed with arterial spin labeling, changes in the blood oxygenation level-dependent (BOLD) effect in ipsilesional and contralesional primary motor cortex (M1) on the left and the right hemispheres assessed with functional MRI (fMRI) during a finger-tapping task performed with the paretic hand, and changes in GABA levels in ipsilesional and contralesional M1 evaluated with spectroscopy. The changes in outcomes will be compared in four groups: suprasensory, early; subsensory, early; suprasensory, chronic; and subsensory, chronic. DISCUSSION: The results of this study are relevant to inform future clinical trials to tailor RPSS to patients more likely to benefit from this intervention. TRIAL REGISTRATION: NCT03956407.
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Degradation of carbon-supported Pt nanocatalysts in fuel cells and electrolyzers hinders widespread commercialization of these green technologies. Transition between oxidized and reduced states of Pt during fast potential spikes triggers significant Pt dissolution. Therefore, designing Pt-based catalysts able to withstand such conditions is of critical importance. We report here on a strategy to suppress Pt dissolution by using an organic matrix tris(aza)pentacene (TAP) as an alternative support material for Pt. The major benefit of TAP is its potential-dependent conductivity in aqueous media, which was directly evidenced by electrochemical impedance spectroscopy. At potentials below â¼0.45 VRHE, TAP is protonated and its conductivity is improved, which enables supported Pt to run hydrogen reactions. At potentials corresponding to Pt oxidation/reduction (>â¼0.45 VRHE), TAP is deprotonated and its conductivity is restricted. Tunable conductivity of TAP enhanced the durability of the Pt/TAP with respect to Pt/C when these two materials were subjected to the same degradation protocol (0.1 M HClO4 electrolyte, 3000 voltammetric scans, 1 V/s, 0.05-1.4 VRHE). The exceptional stability of Pt/TAP composite on a nanoscale level was confirmed by identical location TEM imaging before and after the used degradation protocol. Suppression of transient Pt dissolution from Pt/TAP with respect to the Pt/C benchmark was directly measured in a setup consisting of an electrochemical flow cell connected to inductively coupled plasma-mass spectrometry.
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The present research provides a study of carbon-supported intermetallic Pt-alloy electrocatalysts and assesses their stability against metal dissolution in relation to the operating temperature and the potential window using two advanced electrochemical methodologies: (i) the in-house designed high-temperature disk electrode (HT-DE) methodology as well as (ii) a modification of the electrochemical flow cell coupled to an inductively coupled plasma mass spectrometer (EFC-ICP-MS) methodology, allowing for highly sensitive time- and potential-resolved measurements of metal dissolution. While the rate of carbon corrosion follows the Arrhenius law and increases exponentially with temperature, the findings of the present study contradict the generally accepted hypothesis that the kinetics of Pt and subsequently the less noble metal dissolution are supposed to be for the most part unaffected by temperature. On the contrary, clear evidence is presented that in addition to the importance of the voltage/potential window, the temperature is one of the most critical parameters governing the stability of Pt and thus, in the case of Pt-alloy electrocatalysts, also the ability of the nanoparticles (NPs) to retain the less noble metal. Lastly, but also very importantly, results indicate that the rate of Pt redeposition significantly increases with temperature, which has been the main reason why mechanistic interpretation of the temperature-dependent kinetics related to the stability of Pt remained highly speculative until now.
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The production of hydrogen via a proton-exchange membrane water electrolyzer (PEM-WE) is directly dependent on the rational design of electrocatalysts for the anodic oxygen evolution reaction (OER), which is the bottleneck of the process. Here, we present a smart design strategy for enhancing Ir utilization and stabilization. We showcase it on a catalyst, where Ir nanoparticles are efficiently anchored on a conductive support titanium oxynitride (TiON x ) dispersed over carbon-based Ketjen Black and covered by a thin layer of copper (Ir/CuTiON x /C), which gets removed in the preconditioning step. Electrochemical OER activity, stability, and structural changes were compared to the Ir-based catalyst, where Ir nanoparticles without Cu are deposited on the same support (Ir/TiON x /C). To study the effect of the sacrificial less-noble metal layer on the catalytic performance of the synthesized material, characterization methods, namely X-ray powder diffraction, X-ray photoemission spectroscopy, and identical location transmission electron microscopy were employed and complemented with scanning flow cell coupled to an inductively coupled plasma mass spectrometer, which allowed studying the online dissolution during the catalytic reaction. Utilization of these advanced methods revealed that the sacrificial Cu layer positively affects both Ir OER mass activity and its durability, which was assessed via S-number, a recently reported stability metric. Improved activity of Cu analogue was ascribed to the higher surface area of smaller Ir nanoparticles, which are better stabilized through a strong metal-support interaction (SMSI) effect.