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A giant magnetoresistance effect (~46% at 20 K under 7 T) and anomalous magnetic properties were found in a highly epitaxial double perovskite LaBaCo2O5.5+δ (LBCO) thin film on (001) MgO. Aberration-corrected Electron Microscopy and related analytical techniques were employed to understand the nature of these unusual physical properties. The as-grown film is epitaxial with the c-axis of the LBCO structure lying in the film plane and with an interface relationship given by (100)LBCO || (001)MgO and [001]LBCO || [100]MgO or [010]MgO. Orderly oxygen vacancies were observed by line profile electron energy loss spectroscopy and by atomic resolution imaging. Especially, oxygen vacancy and nanodomain structures were found to have a crucial effect on the electronic transport and magnetic properties. [ABSTRACT FROM AUTHOR]

Electrolyzers operate over a range of temperatures; hence, it is crucial to design electrocatalysts that do not compromise the product distribution unless temperature can promote selectivity. This work reports a synthetic approach based on electrospinning to produce NiO:SnO 2 nanofibers (NFs) for selectively reducing CO 2 to formate above room temperature. The NFs comprise compact but disjoined NiO and SnO 2 nanocrystals identified with STEM. The results are attributed to the segregation of NiO and SnO 2 confirmed with XRD. The NFs are evaluated for the CO 2 reduction reaction (CO 2 RR) over various temperatures (25, 30, 35, and 40 °C). The highest faradaic efficiencies to formate (FE HCOO - ) are reached by NiO:SnO 2 NFs containing 50% of NiO and 50% SnO 2 (NiOSnO50NF), and 25% of NiO and 75% SnO 2 (NiOSnO75NF), at an electroreduction temperature of 40 °C. At 40 °C, product distribution is assessed with in situ differential electrochemical mass spectrometry (DEMS), recognizing methane and other species, like formate, hydrogen, and carbon monoxide, identified in an electrochemical flow cell. XPS and EELS unveiled the FE HCOO - variations due to a synergistic effect between Ni and Sn. DFT-based calculations reveal the superior thermodynamic stability of Ni-containing SnO 2 systems towards CO 2 RR over the pure oxide systems. Furthermore, computational surface Pourbaix diagrams showed that the presence of Ni as a surface dopant increases the reduction of the SnO 2 surface and enables the production of formate. Our results highlight the synergy between NiO and SnO 2 , which can promote the electroreduction of CO 2 at temperatures above room temperature., Competing Interests: The authors declare no competing interests., (This journal is © The Royal Society of Chemistry.)

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.

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 Mežica 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 (PbMoO 4 ), 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., (© 2024. The Author(s).)

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 V RHE 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 V RHE ) 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 V RHE rather than 0.6-0.95 V RHE . 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., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

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 (BaZrO 3 , CaZrO 3 , and SrZrO 3 ) 3D structures shaped in the form of octet-truss lattices, gyroids, or inspired architectures like sodalite zeolite, and C 60 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 BaZrO 3 , CaZrO 3 , and SrZrO 3 . 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., (© 2024 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

In the present work, we report on a synergistic relationship between platinum nanoparticles and a titanium oxynitride support (TiO x N y /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 TiO x N y /C support. In particular, according to the generated strain maps obtained via scanning transmission electron microscopy (STEM), the Pt-TiO x N y /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-TiO x N y /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-TiO x N y /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-TiO x N y /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 TiO x N y origin., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

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., Competing Interests: There are no conflicts to declare., (This journal is © the Partner Organisations.)

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., (© 2023 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

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 H 2 /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 ( R pt ) 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.

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 m 2 g -1 vs. >70 m 2 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., Competing Interests: The authors declare no competing financial interest., (This journal is © The Royal Society of Chemistry.)

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., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

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., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

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 cm 2 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., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Photocatalytic H 2 generation by water splitting is a promising alternative for producing renewable fuels. This work synthesized a new type of Ta 2 O 5 /SrZrO 3 heterostructure with Ru and Cu (RuO 2 /Cu x O/Ta 2 O 5 /SrZrO 3 ) using solid-state chemistry methods to achieve a high H 2 production of 5164 μmol g -1 h -1 under simulated solar light, 39 times higher than that produced using SrZrO 3 . The heterostructure performance is compared with other Ta 2 O 5 /SrZrO 3 heterostructure compositions loaded with RuO 2 , Cu x O, or Pt. Cu x O is used to showcase the usage of less costly cocatalysts to produce H 2 . The photocatalytic activity toward H 2 by the RuO 2 /Cu x O/Ta 2 O 5 /SrZrO 3 heterostructure remains the highest, followed by RuO 2 /Ta 2 O 5 /SrZrO 3 > Cu x O/Ta 2 O 5 /SrZrO 3 > Pt/Ta 2 O 5 /SrZrO 3 > Ta 2 O 5 /SrZrO 3 > SrZrO 3 . Band gap tunability and high optical absorbance in the visible region are more prominent for the heterostructures containing cocatalysts (RuO 2 or Cu x O) and are even higher for the binary catalyst (RuO 2 /Cu x O). The presence of the binary catalyst is observed to impact the charge carrier transport in Ta 2 O 5 /SrZrO 3 , improving the solar to hydrogen conversion efficiency. The results represent a valuable contribution to the design of SrZrO 3 -based heterostructures for photocatalytic H 2 production by solar water splitting.

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 ∼0.45 V RHE , TAP is protonated and its conductivity is improved, which enables supported Pt to run hydrogen reactions. At potentials corresponding to Pt oxidation/reduction (>∼0.45 V RHE ), 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 HClO 4 electrolyte, 3000 voltammetric scans, 1 V/s, 0.05-1.4 V RHE ). 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., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

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., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

A fast and facile pulse combustion (PC) method that allows for the continuous production of multigram quantities of high-metal-loaded and highly uniform supported metallic nanoparticles (SMNPs) is presented. Namely, various metal on carbon (M/C) composites have been prepared by using only three feedstock components: water, metal-salt, and the supporting material. The present approach can be elegantly utilized also for numerous other applications in electrocatalysis, heterogeneous catalysis, and sensors. In this study, the PC-prepared M/C composites were used as metal precursors for the Pt NPs deposition using double passivation with the galvanic displacement method (DP method). Lastly, by using thin-film rotating disc electrode (TF-RDE) and gas-diffusion electrode (GDE) methodologies, we show that the synergistic effects of combining PC technology with the DP method enable production of superior intermetallic Pt-M electrocatalysts with an improved oxygen reduction reaction (ORR) performance when compared to a commercial Pt-Co electrocatalyst for proton exchange membrane fuel cells (PEMFCs) application., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

Combining the abundance and inexpensiveness of their constituent elements with their atomic dispersion, atomically dispersed Fe-N-C catalysts represent the most promising alternative to precious-metal-based materials in proton exchange membrane (PEM) fuel cells. Due to the high temperatures involved in their synthesis and the sensitivity of Fe ions toward carbothermal reduction, current synthetic methods are intrinsically limited in type and amount of the desired, catalytically active Fe-N 4 sites, and high active site densities have been out of reach (dilemma of Fe-N-C catalysts). We herein identify a paradigm change in the synthesis of Fe-N-C catalysts arising from the developments of other M-N-C single-atom catalysts. Supported by DFT calculations we propose fundamental principles for the synthesis of M-N-C materials. We further exploit the proposed principles in a novel synthetic strategy to surpass the dilemma of Fe-N-C catalysts. The selective formation of tetrapyrrolic Zn-N 4 sites in a tailor-made Zn-N-C material is utilized as an active-site imprint for the preparation of a corresponding Fe-N-C catalyst. By successive low- and high-temperature ion exchange reactions, we obtain a phase-pure Fe-N-C catalyst, with a high loading of atomically dispersed Fe (>3 wt %). Moreover, the catalyst is entirely composed of tetrapyrrolic Fe-N 4 sites. The density of tetrapyrrolic Fe-N 4 sites is more than six times as high as for previously reported tetrapyrrolic single-site Fe-N-C fuel cell catalysts.

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., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

Co-axial electrospinning was applied for the structuring of non-woven webs of TiO 2 nanofibers loaded with Ag, Au, and CuO nanoparticles. The composite layers were tested in an electrochromic half-cell assembly. A clear correlation between the nanoparticle composition and electrochromic effect in the nanofibrous composite is observed: TiO 2 loaded with Ag reveals a black-brown color, Au shows a dark-blue color, and CuO shows a dark-green color. For electrochromic applications, the Au/TiO 2 layer is the most promising choice, with a color modulation time of 6 s, transmittance modulation of 40%, coloration efficiency of 20 cm 2 /C, areal capacitance of 300 F/cm 2 , and cyclic stability of over 1000 cycles in an 18 h period. In this study, an unexplored path for the rational design of TiO 2 -based electrochromic device is offered with unique color-switching and optical efficiency gained by the fibrous layer. It is also foreseen that co-axial electrospinning can be an alternative nanofabrication technique for smart colored windows., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

Achieving highly active and stable oxygen reduction reaction performance at low platinum-group-metal loadings remains one of the grand challenges in the proton-exchange membrane fuel cells community. Currently, state-of-the-art electrocatalysts are high-surface-area-carbon-supported nanoalloys of platinum with different transition metals (Cu, Ni, Fe, and Co). Despite years of focused research, the established structure-property relationships are not able to explain and predict the electrochemical performance and behavior of the real nanoparticulate systems. In the first part of this work, we reveal the complexity of commercially available platinum-based electrocatalysts and their electrochemical behavior. In the second part, we introduce a bottom-up approach where atomically resolved properties, structural changes, and strain analysis are recorded as well as analyzed on an individual nanoparticle before and after electrochemical conditions (e.g. high current density). Our methodology offers a new level of understanding of structure-stability relationships of practically viable nanoparticulate systems., Competing Interests: The authors declare no competing interests., (© 2021 The Author(s).)

The development of affordable, low-iridium-loading, scalable, active, and stable catalysts for the oxygen-evolution reaction (OER) is a requirement for the commercialization of proton-exchange membrane water electrolyzers (PEMWEs). However, the synthesis of high-performance OER catalysts with minimal use of the rare and expensive element Ir is very challenging and requires the identification of electrically conductive and stable high-surface-area support materials. We developed a synthesis procedure for the production of large quantities of a nanocomposite powder containing titanium oxynitride (TiON x ) and Ir. The catalysts were synthesized with an anodic oxidation process followed by detachment, milling, thermal treatment, and the deposition of Ir nanoparticles. The anodization time was varied to grow three different types of nanotubular structures exhibiting different lengths and wall thicknesses and thus a variety of properties. A comparison of milled samples with different degrees of nanotubular clustering and morphology retention, but with identical chemical compositions and Ir nanoparticle size distributions and dispersions, revealed that the nanotubular support morphology is the determining factor governing the catalyst's OER activity and stability. Our study is supported by various state-of-the-art materials' characterization techniques, like X-ray photoelectron spectroscopy, scanning and transmission electron microscopies, X-ray powder diffraction and absorption spectroscopy, and electrochemical cyclic voltammetry. Anodic oxidation proved to be a very suitable way to produce high-surface-area powder-type catalysts as the produced material greatly outperformed the IrO 2 benchmarks as well as the Ir-supported samples on morphologically different TiON x from previous studies. The highest activity was achieved for the sample prepared with 3 h of anodization, which had the most appropriate morphology for the effective removal of oxygen bubbles., Competing Interests: The authors declare no competing financial interest., (© 2020 American Chemical Society.)

Electrochemical stability of a commercial Au/C catalyst in an acidic electrolyte has been investigated by an accelerated stress test (AST), which consisted of 10,000 voltammetric scans (1 V/s) in the potential range between 0.58 and 1.41 V RHE . Loss of Au electrochemical surface area (ESA) during the AST pointed out to the degradation of Au/C. Coupling of an electrochemical flow cell with ICP-MS showed that only a minor amount of gold is dissolved despite the substantial loss of gold ESA during the AST (∼35% of initial value remains at the end of the AST). According to the electrochemical mass spectrometry experiments, carbon corrosion occurs during the AST but to a minor extent. By using identical location scanning electron microscopy and identical location transmission electron microscopy, it was possible to discern that the dissolution of small Au particles (<5 nm) within the polydisperse Au/C sample is the main degradation mechanism. The mass of such particles gives only a minor contribution to the overall Au mass of the polydisperse sample while giving a major contribution to the overall ESA, which explains a significant loss of ESA and minor loss of mass during the AST. The addition of low amounts of chloride anions (10 -4 M) substantially promoted the degradation of gold nanoparticles. At an even higher concentration of chlorides (10 -2 M), the dissolution of gold was rather effective, which is useful from the recycling point of view when rapid leaching of gold is desirable., Competing Interests: The authors declare no competing financial interest., (© 2021 American Chemical Society.)

In this paper, we present the results of a multi-analytical characterization of a glaucophane sample collected in the Piedmont region of northwestern Italy. Investigation methods included optical microscopy, powder X-ray diffraction, Fourier-transform infrared spectroscopy, μ-Raman spectroscopy, Mössbauer spectroscopy, electron probe microanalysis, environmental scanning electron microscopy and energy-dispersive X-ray spectroscopy, and scanning/transmission electron microscopy combined with energy-dispersive X-ray spectroscopy and electron energy-loss spectroscopy. In addition to the crystal-chemical characterization of the sample from the mesoscale to the near-atomic scale, we have also conducted an extended study on the morphology and dimensions of the mineral particles. The main finding is that studying the same particle population at different magnifications yields different results for mineral habit, dimensions, and dimensional distributions. As glaucophane may occur as an elongate mineral particle (e.g., asbestiform glaucophane occurrences in California and Nevada), the observed discrepancies therefore need to be considered when assessing potential breathability of such particles, with implications for future regulations on elongate mineral particles. While the sample preparation and particle counting methods are not directly investigated in this work, our findings suggest that different magnifications should be used when characterizing an elongate mineral particle population, irrespective of whether or not it contains asbestiform material. These results further reveal the need for developing improved regulation for elongate mineral particles. We thus propose a simple methodology to merge the datasets collected at different magnifications to provide a more complete description and a better risk evaluation of the studied particle population., Competing Interests: Competing interests. The authors declare that they have no conflict of interest.

Carbon-based nanofibers decorated with metallic nanoparticles (NPs) as hierarchically structured electrodes offer significant opportunities for use in low-temperature fuel cells, electrolyzers, flow and air batteries, and electrochemical sensors. We present a facile and scalable method for preparing nanostructured electrodes composed of Pt NPs on graphitized carbon nanofibers. Electrospinning directly addresses the issues related to large-scale production of Pt-based fuel cell electrocatalysts. Through precursors containing polyacrylonitrile and Pt salt electrospinning along with an annealing protocol, we obtain approximately 180 nm thick graphitized nanofibers decorated with approximately 5 nm Pt NPs. By in situ annealing scanning transmission electron microscopy, we qualitatively resolve and quantitatively analyze the unique dynamics of Pt NP formation and movement. Interestingly, by very efficient thermal-induced segregation of all Pt from the inside to the surface of the nanofibers, we increase overall Pt utilization as electrocatalysis is a surface phenomenon. The obtained nanomaterials are also investigated by spatially resolved Raman spectroscopy, highlighting the higher structural order in nanofibers upon doping with Pt precursors. The rationalization of the observed phenomena of segregation and ordering mechanisms in complex carbon-based nanostructured systems is critically important for the effective utilization of all metal-containing catalysts, such as electrochemical oxygen reduction reactions, among many other applications., Competing Interests: The authors declare no competing financial interest.

Single-atom catalysts (SACs) have quickly emerged as a new class of catalytic materials. When confronted with classical carbon-supported nanoparticulated catalysts (Pt/C), SACs are often claimed to have superior electrocatalytic properties, e.g., stability. In this study, we critically assess this statement by investigating S-doped carbon-supported Pt SACs as a representative example of noble-metal-based SACs. We use a set of complementary techniques, which includes online inductively coupled plasma mass spectrometry (online ICP-MS), identical location transmission electron microscopy (IL-TEM), and X-ray photoelectron spectroscopy (XPS). It is shown by online ICP-MS that the dissolution behavior of as-synthesized Pt SACs is significantly different from that of metallic Pt/C. Moreover, Pt SACs are, indeed, confirmed to be more stable toward Pt dissolution. When cycled to potentials of up to 1.5 V RHE , however, the dissolution profiles of Pt SACs and Pt/C become similar. IL-TEM and XPS show that this transition is due to morphological and chemical changes caused by cycling. The latter, in turn, is a consequence of the relatively poor stability of S ligands. As monitored by online ICP-MS and XPS, significant amounts of sulfur leave the catalyst during oxidation. Hence, in case catalysts with improved stability in the anodic potential region are desired, more robust supports and ligands must be developed.

Preparation of large quantities of high-performance supported Pt-alloy electrocatalysts is crucial for the faster development and implementation of low-temperature proton exchange membrane fuel cells (PEMFCs). One of the prospective nanofabrication synthesis methods is based on the galvanic displacement (GD) reaction. A facile, highly reproducible, gram scale, water-based double passivation GD method is now presented for the synthesis of carbon-supported Pt-M nanoparticles (M=Cu, Ni, Co). It offers great flexibility over the catalyst design, such as the choice of the sacrificial metal (M), variation of the chemical composition of alloy, variation of total metal loading (Pt+M) on carbon support, or even variation of the carbon support itself. The obtained Pt-alloy catalysts are several times more active compared to a Pt reference and exhibits better stability during accelerated degradation tests performed at 60 °C., (© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Catalytic properties of advanced functional materials are determined by their surface and near-surface atomic structure, composition, morphology, defects, compressive and tensile stresses, etc; also known as a structure-activity relationship. The catalysts structural properties are dynamically changing as they perform via complex phenomenon dependent on the reaction conditions. In turn, not just the structural features but even more importantly, catalytic characteristics of nanoparticles get altered. Definitive conclusions about these phenomena are not possible with imaging of random nanoparticles with unknown atomic structure history. Using a contemporary PtCu-alloy electrocatalyst as a model system, a unique approach allowing unprecedented insight into the morphological dynamics on the atomic-scale caused by the process of dealloying is presented. Observing the detailed structure and morphology of the same nanoparticle at different stages of electrochemical treatment reveals new insights into atomic-scale processes such as size, faceting, strain and porosity development. Furthermore, based on precise atomically resolved microscopy data, Kinetic Monte Carlo (KMC) simulations provide further feedback into the physical parameters governing electrochemically induced structural dynamics. This work introduces a unique approach toward observation and understanding of nanoparticles dynamic changes on the atomic level and paves the way for an understanding of the structure-stability relationship.

Herein, we report for the first time the successful preparation of a gold(III) nitrate [Au(NO 3 ) 3 ] water-based precursor for use in a bottom-up ultrasonic spray pyrolysis (USP) process. Due to its limited solubility in water, the precursor was prepared under reflux conditions with nitric acid (HNO 3 ) as the solvent and ammonium hydroxide (NH 4 OH) as a neutralizer. This precursor enabled the USP synthesis of gold nanoparticles (AuNPs) and the in situ formation of low concentrations of NO 2 - and NO 3 - ions, which were caught directly in deionized water in a collection system. These ions were proven to act as stabilizers for the AuNPs. Investigations showed that the AuNPs were monodispersed and spherically shaped with a size distribution over three groups: the first contained 5.3 % AuNPs with diameters (2  r ) <15 nm, the second contained 82.5 % AuNPs with 2  r between 15 and 200 nm, and the third contained 12.2 % AuNPs with 2  r >200 nm. UV/Vis spectroscopy revealed the maximum absorbance band of the AuNPs at λ =528 nm. Additionally, scanning transmission electron microscopy (STEM) observations of the smallest AuNPs (2  r <5 nm) revealed atomically resolved coalescence phenomena induced by interaction with the electron beam. Four stages of the particle-growth process were distinguished: 1) movement and rotation of the AuNPs; 2) necking mechanism; 3) orientated attachment at matching facets; 4) reshaping of the AuNPs by surface diffusion. This provided important insight into the formation/synthesis process of the AuNPs.

Iridium-based particles, regarded as the most promising proton exchange membrane electrolyzer electrocatalysts, were investigated by transmission electron microscopy and by coupling of an electrochemical flow cell (EFC) with online inductively coupled plasma mass spectrometry. Additionally, studies using a thin-film rotating disc electrode, identical location transmission and scanning electron microscopy, as well as X-ray absorption spectroscopy have been performed. Extremely sensitive online time-and potential-resolved electrochemical dissolution profiles revealed that Ir particles dissolve well below oxygen evolution reaction (OER) potentials, presumably induced by Ir surface oxidation and reduction processes, also referred to as transient dissolution. Overall, thermally prepared rutile-type IrO 2 particles are substantially more stable and less active in comparison to as-prepared metallic and electrochemically pretreated (E-Ir) analogues. Interestingly, under OER-relevant conditions, E-Ir particles exhibit superior stability and activity owing to the altered corrosion mechanism, where the formation of unstable Ir(>IV) species is hindered. Due to the enhanced and lasting OER performance, electrochemically pre-oxidized E-Ir particles may be considered as the electrocatalyst of choice for an improved low-temperature electrochemical hydrogen production device, namely a proton exchange membrane electrolyzer.

The dissolution of different platinum-based nanoparticles deposited on a commercial high-surface area carbon (HSAC) support in thin catalyst films is investigated using a highly sensitive electrochemical flow cell (EFC) coupled to an inductively coupled plasma mass spectrometer (ICP-MS). The previously reported particle-size-dependent dissolution of Pt is confirmed on selected industrial samples with a mean Pt particle size ranging from 1 to 4.8 nm. This trend is significantly altered when a catalyst is diluted by the addition of HSAC. This indicates that the intrinsic dissolution properties are masked by local oversaturation phenomena, the so-called confinement effect. Furthermore, by replacing the standard HSAC support with a support having an order of magnitude higher specific surface area (a micro- and mesoporous nitrogen-doped high surface area carbon, HSANDC), Pt dissolution is reduced even further. This is due to the so-called non-intrinsic confinement and entrapment effects of the (large amount of) micropores and small mesopores doped with N atoms. The observed more effective Pt re-deposition is presumably induced by local Pt oversaturation and the presence of nitrogen nucleation sites. Overall, our study demonstrates the high importance and beneficial effects of porosity, loading and N doping of the carbon support on the Pt stability in the catalyst layer.

Using off-axis electron holography under Lorentz microscopy conditions to experimentally determine the magnetization distribution in individual cobalt (Co) nanowires, and scanning precession-electron diffraction to obtain their crystalline orientation phase map, allowed us to directly visualize with high accuracy the effect of crystallographic texture on the magnetization of nanowires. The influence of grain boundaries and disorientations on the magnetic structure is correlated on the basis of micromagnetic analysis in order to establish the detailed relationship between magnetic and crystalline structure. This approach demonstrates the applicability of the method employed and provides further understanding on the effect of crystalline structure on magnetic properties at the nanometric scale.

The synthesis of rebar graphene on Cu substrates is described using functionalized boron nitride nanotubes (BNNTs) that were annealed or subjected to chemical vapor deposition (CVD) growth of graphene. Characterization shows that the BNNTs partially unzip and form a reinforcing bar (rebar) network within the graphene layer that enhances the mechanical strength through covalent bonds. The rebar graphene is transferrable to other substrates without polymer assistance. The optical transmittance and conductivity of the hybrid rebar graphene film was tested, and a field effect transistor was fabricated to explore its electrical properties. This method of synthesizing 2D hybrid graphene/BN structures should enable the hybridization of various 1D nanotube and 2D layered structures with enhanced mechanical properties.

Bimetallic nanoparticles like Cu-Ni are particularly attractive due to their magnetic and catalytic properties; however, their properties depend strongly on the structure of the alloy i.e. mixed, core-shell or Janus. To predict the alloy structure, this paper investigates the size and shape effects as well as the surface segregation effect on the Cu-Ni phase diagram. Phase maps have been plotted to determine the mixing/demixing behavior of this alloy according the particle shape. Cu-Ni nanoalloy can form a mixed particle or a Janus one depending on the synthesis temperature. Surface segregation is also considered and reveals a nickel surface-enrichment. Finally, this paper provides a useful roadmap for experimentalists.

The cost effective synthesis and patterning of carbon nanomaterials is a challenge in electronic and energy storage devices. Here we report a one-step, scalable approach for producing and patterning porous graphene films with three-dimensional networks from commercial polymer films using a CO 2 infrared laser. The sp 3 -carbon atoms are photothermally converted to sp 2 -carbon atoms by pulsed laser irradiation. The resulting laser-induced graphene (LIG) exhibits high electrical conductivity. The LIG can be readily patterned to interdigitated electrodes for in-plane microsupercapacitors with specific capacitances of >4 mF cm -2 and power densities of ~9 mW cm -2 . Theoretical calculations partially suggest that enhanced capacitance may result from LIG's unusual ultra-polycrystalline lattice of pentagon-heptagon structures. Combined with the advantage of one-step processing of LIG in air from commercial polymer sheets, which would allow the employment of a roll-to-roll manufacturing process, this technique provides a rapid route to polymer-written electronic and energy storage devices.