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Using angular resolved X-ray Photoelectron Spectroscopy (XPS), Magneto Optic Kerr Effect (MOKE) and X-ray Absorption Spectroscopy (XAS), we characterize the structural and magnetic evolution upon annealing of two thin Co films (8 and 9 Monolayers) deposited on Ir(111). The XAS data collected in the near Co K edge region (XANES), interpreted with ab-initio simulations, show that intermixing takes place at the Co-Ir interface. Using a linear combination analysis, we follow the intermixing during the thermally driven diffusion process. At 500 °C, the interface between Co and Ir(111) roughens slightly, but no alloy formation is detected. At 600 °C, the Co film loses integrity and MOKE data show a rearrangement of the magnetic domains. Annealing to higher temperatures results in CoxIr1- x alloy formation and Ir segregation on the surface. [ABSTRACT FROM AUTHOR]

A new tomographic reconstruction algorithm is presented, termed direct least‐squares reconstruction (DLSR), which solves the well known parallax problem in X‐ray‐scattering‐based experiments. The parallax artefact arises from relatively large samples where X‐rays, scattered from a scattering angle 2gθ, arrive at multiple detector elements. This phenomenon leads to loss of physico‐chemical information associated with diffraction peak shape and position (i.e. altering the calculated crystallite size and lattice parameter values, respectively) and is currently the major barrier to investigating samples and devices at the centimetre level (scale‐up problem). The accuracy of the DLSR algorithm has been tested against simulated and experimental X‐ray diffraction computed tomography data using the TOPAS software. [ABSTRACT FROM AUTHOR]

High-energy X-ray surface diffraction in transmission geometry is combined with a microfluidic thin layer flow cell for in situ studies of the local structure of electrodeposited epitaxial films. The capabilities of this approach are illustrated using Bi films on Au(100) single crystals as an example. We demonstrate that the local film thickness, the strain, and the orientation of the deposits' crystallites can be mapped with a spatial resolution of a few micrometers. The high heterogeneity of the Bi films provides deposits with a wide range of structural properties, allowing to establish correlations between the different parameters as a function of the local thickness. [ABSTRACT FROM AUTHOR]

Thin Co films intercalated between a Graphene capping layer and the Ir(111) surface are of interest for spintronics applications due to their peculiar magnetic properties and to their chemical stability. The structure, and then the magnetic properties, of the Co films depend on the intercalation process which is strongly influenced by the temperature, total amount of Cobalt and quality of the capping Graphene layer. In order to identify and disentangle the effects of these contributions, we report on the structural characterisation of four Co films as a function of thickness, annealing temperature, and Graphene capping. From the structural point of view, the deposition of Co on a hot Ir substrate mimics quite well the intercalation process proving the validity of the colander model describing the Graphene role during the process. [ABSTRACT FROM AUTHOR]

Germanene is a single layer allotrope of Ge, with a honeycomb structure similar to graphene. This report concerns the electrochemical formation of germanene in a pH 4.5 solution. The studies were performed using in situ Electrochemical Scanning Tunneling Microscopy (EC-STM), voltammetry, coulometry, surface X-ray diffraction (SXRD) and Raman spectroscopy to study germanene electrodeposition on Au(111) terraces. The deposition of Ge is kinetically slow and stops after 2-3 monolayers. EC-STM revealed a honeycomb (HC) structure with a rhombic unit cell, 0.44 ± 0.02 nm on a side, very close to that predicted for germanene in the literature. Ideally the HC structure is a continuous sheet, with six Ge atoms around each hole. However, only small domains, surrounded by defects, of this structure were observed in this study. The small coherence length and multiple rotations domains made direct observation with surface X-ray diffraction difficult. Raman spectroscopy was used to investigate the multi-layer Ge deposits. A peak near 290 cm-1, predicted to correspond to germanene, was observed on one particular area of the sample, while the rest resembled amorphous germanium. Electrochemical studies of germanene showed limited stability when exposed to oxygen. [ABSTRACT FROM AUTHOR]

The electrochemical formation and dissolution of the oxygen reduction reaction (ORR) PtZn catalyst on Pt(1 1 1) surface is followed by in-situ X-ray diffraction (XRD) and X-ray reflectivity (XRR) measurements. When the crystalline Pt surface is polarized to sufficiently negative potential values, with respect to an Ag/AgCl|KCl reference electrode, the electrodeposited zinc atoms diffuse into the bulk and characteristic features are observed in the X-ray patterns. The surface structure and composition during deposition and dissolution is determined from analysis of XRR curves and measurements of crystal truncation rods. Thin Zn-rich surface layer is present during the alloy formation while a Zn-depleted layer forms during dissolution. [ABSTRACT FROM AUTHOR]

The in-vitro susceptibility of Mycoplasma pneumoniae to clarithromycin, a new macrolide, was compared with that to erythromycin. A broth microdilution assay was used to evaluate 30 clinical isolates collected over a 15 year period from four countries (United States, Australia, Denmark and Japan). Clarithromycin inhibited the growth of all M. pneumoniae strains at low concentrations (≤ 0.008 mg/l) similarly to erythromycin (≤ 0.008 mg/l).In 120 outpatients with radiographically confirmed community acquired pneumonia (mean age 46-2 years), M. pneumoniae was detected culturally and/or serologically by ELISA and immunoblotting in 13% of patients, thus confirming the continued importance of this organism as a respiratory pathogen. M. pneumoniae isolates from these patients were shown to be equally susceptible to clarithromycin (≤ 0.008 mg/l) and erythromycin (≤ 0.008 mg/l). Both clarithromycin and erythromycin were effective in the treatment of community-acquired pneumonia. There were no statistically significant or clinically important differences between the two treatment groups with respect to clinical or radiographic resolution of disease or improvement in signs and symptoms. While the number of clinically evaluable patients with M. pneumoniae infections was small, both macrolides seemed equally effective. [ABSTRACT FROM PUBLISHER]

Various transport and storage conditions for the recovery of Helicobacter pylori from gastric biopsies were evaluated. Gastric mucosal biopsies from 16 Helicobacter pylori-infected patients were stored in cysteine-Albimi medium containing 20 % glycerol in a refrigerator (4°C) for 1 and 2 weeks and in a −20°C laboratory freezer for 4 and 12 weeks. Two clinical isolates were stored in saline, Stuart's transport media, cysteine-Albimi broth with 20 % glycerol, brucella broth with 20 % glycerol and skim milk with 17 % glycerol at room temperature, 4°C, −20°C and −70°C. Storage at 4°C for 1 and 2 weeks resulted in Helicobacter pylori recovery from 81 % and 19 % of biopsies, respectively. Storage at −20°C yielded Helicobacter pylori recovery in 100 % and 57 % after 4 and 12 weeks, respectively. At room temperature after 6 h, the Helicobacter pylori titer was reduced. The best storage media for frozen isolates were skim milk/glycerol, brucella broth/glycerol and cysteine-Albimi/glycerol (in descending order). Recovery was better at −70°C than −20°C. [ABSTRACT FROM AUTHOR]

The thermal stability and the structural evolution of graphene grown on Fe(110) has been studied upon annealing in ultra-high vacuum conditions (UHV, P ≤ 10 −9 mbar) and in the presence of gaseous ethylene at a pressure of ∼10 −6 mbar by grazing incidence X-ray diffraction. It was observed that upon annealing at temperatures below 630 °C, graphene on Fe is thermally stable. Exposure to ethylene at these temperatures promotes the formation of graphene while inhibiting its deterioration. Annealing graphene/Fe(110) at temperatures above 630 °C results in a fast degradation of graphene followed by carburization of the sample, that is the irreversible formation of various iron carbides, with the most common phases being Fe 3 C (cementite) and Fe 7 C 3 (Eckström-Adcock carbide). Annealing of the carburized sample does not result in the formation of a detectable graphitic structure. [ABSTRACT FROM AUTHOR]

• The Co local structure and magnetic response are closely related in Gr/Co/Ir systems. • Upon intercalation, Co local structure is isotropic. • Annealing effects on the intercalated Co depend on the film thickness. • Annealed thick films (10 MLs) retain local structural isotropy and show lower PMA. • Annealed thin films (5 MLs) present local scale anisotropy and enhanced PMA. The local atomic structure and the magnetic response of Co films intercalated between Graphene and Ir(111) were investigated combining polarized X-ray Absorption Spectroscopy at the Co K edge with Magneto-Optic Kerr Effect. The structural and magnetic evolution upon a 500 ° C annealing was evaluated as a function of the film thickness. After the thermal treatment, our thick film (10 monolayers) presented a lower perpendicular magnetic anisotropy (PMA) as well as a reduced average structural disorder. On the other hand, in our thin film (5 monolayers), the annealing enhanced the perpendicular magnetic response and induced a local anisotropy by stretching the Co-Co bonds in the film plane and compressing those outside the plane. Our finding emphasizes the close relationship between the local structure of Co within the film and its magnetic properties. [ABSTRACT FROM AUTHOR]

We investigate K-shell ionization of N2 at 40 keV photon energy. Using a cold target recoil ion momentum spectroscopy reaction microscope, we determine the vector momenta of the photoelectron, the Auger electron, and both N+ fragments. These fully differential data show that the dissociation process of the N22+ ion is significantly modified not only by the recoil momentum of the photoelectron but also by the photon momentum and the momentum of the emitted Auger electron. We find that the recoil energy introduced by the photon and the photoelectron momentum is partitioned with a ratio of approximately 30:70 between the Auger electron and fragment ion kinetic energies, respectively. We also observe that the photon momentum induces an additional rotation of the molecular ion. [ABSTRACT FROM AUTHOR]

The structure of the quasicrystalline approximant Al13Co4(100) has been determined by surface x-ray diffraction (SXRD) and complementary density-functional-theory (DFT) calculations. Thanks to the use of a two-dimensional pixel detector, which speeds up the data acquisition enormously, an exceptionally large set of experimental data, consisting of 124 crystal truncation rods, has been collected and used to refine this complex structure of large unit cell and low symmetry. Various models were considered for the SXRD analysis. The best fit is consistent with a surface termination at the puckered type of planes but with a depletion of the protruding Co atoms. The surface energy of the determined surface model was calculated using DFT, and it takes a rather low value of 1.09J/m². The results for the atomic relaxation of surface planes found by SXRD or DFT were in excellent agreement. This work opens up additional perspectives for the comprehension of related quasicrystalline surfaces. [ABSTRACT FROM AUTHOR]

Understanding the structure of nanoparticles under (electro)catalytic operating conditions is crucial for uncovering structure-property relationships. By combining operando X-ray total scattering and pair distribution function analysis with operando small-angle X-ray scattering (SAXS), we obtained comprehensive structural information on ultrasmall (<3 nm) iridium nanoparticles and tracked their changes during oxygen evolution reaction (OER) in acid. When subjected to electrochemical conditions at reducing potentials, the metallic Ir nanoparticles are found to be decahedral. The iridium oxide formed in the electrochemical oxidation contains small rutile-like clusters composed of edge- and corner-connected [IrO 6 ] octahedra of a very confined range. These rutile domains are smaller than 1 nm. Combined with complementary SAXS data analysis to extract the particle size, we find that the OER-active iridium oxide phase lacks crystalline order. Additionally, we observe an iridium oxide contraction under OER conditions, which is confirmed by operando X-ray absorption spectroscopy. Our results highlight the need for multitechnique operando studies for a complete understanding of the electrochemically formed Ir oxide active in OER.

A free-standing and compact reaction cell for combined in situ/operando x-ray spectroscopy, scattering, and imaging measurements at high pressures and high temperatures is described. The cell permits measurements under realistic operating conditions (up to 50 bar and 1000 °C), under static and flow conditions (up to 100 ml/min), over a wide range of hard x-ray energies, variable detection modes (transmission, fluorescence, and scattering), and at all angles of rotation. An operando XAS, x-ray fluorescence, x-ray computed tomography, and x-ray diffraction computed tomography case study on the reduction of a heterogeneous catalyst is presented to illustrate the performance of the reaction cell., (© 2024 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).)

Advanced in situ analyses are indispensable for comprehending the catalyst aging mechanisms of Pt-based PEM fuel cell cathode materials, particularly during accelerated stress tests (ASTs). In this study, a combination of in situ small-angle and wide-angle X-ray scattering (SAXS & WAXS) techniques were employed to establish correlations between structural parameters (crystal phase, quantity, and size) of a highly active skeleton-PtCo (sk-PtCo) catalyst and their degradation cycles within the potential range of the start-up/shut-down (SUSD) conditions. Despite the complex case of the sk-PtCo catalyst comprising two distinct fcc alloy phases, our complementary techniques enabled in situ monitoring of structural changes in each crystal phase in detail. Remarkably, the in situ WAXS measurements uncover two primary catalyst aging processes, namely the cobalt depletion (regime I) followed by the crystallite growth via Ostwald ripening and/or particle coalescence (regime II). Additionally, in situ SAXS data reveal a continuous size growth over the AST. The Pt-enriched shell thickening based on the Co depletion within the first 100 SUSD cycles and particle growth induced by additional potential cycles were also collaborated by ex situ STEM-EELS. Overall, our work shows a comprehensive aging model for the sk-PtCo catalyst probed by complementary in situ WAXS and SAXS techniques., (© 2024 The Authors. ChemSusChem published by Wiley-VCH GmbH.)

X-ray diffraction/scattering computed tomography (XRS-CT) was used to create two-dimensional images, with 20 μm resolution, of passivated Co/TiO 2 /Mn Fischer-Tropsch catalyst extrudates postreaction after 300 h on stream under industrially relevant conditions. This combination of scattering techniques provided insights into both the spatial variation of the different cobalt phases and the influence that increasing Mn loading has on this. It also demonstrated the presence of a wax coating throughout the extrudate and its capacity to preserve the Co/Mn species in their state in the reactor. Correlating these findings with catalytic performance highlights the crucial phases and active sites within Fischer-Tropsch catalysts required for understanding the tunability of the product distribution between saturated hydrocarbons or oxygenate and olefin products. In particular, a Mn loading of 3 wt % led to an optimum equilibrium between the amount of hexagonal close-packed Co and Co 2 C phases resulting in maximum oxygenate selectivity. XRS-CT revealed Co 2 C to be located on the extrudates' periphery, while metallic Co phases were more prevalent toward the center, possibly due to a lower [CO] ratio there. Reduction at 450 °C of a 10 wt % Mn sample resulted in MnTiO 3 formation, which inhibited carbide formation and alcohol selectivity. It is suggested that small MnO particles promote Co carburization by decreasing the CO dissociation barrier, and the Co 2 C phase promotes CO nondissociative adsorption leading to increased oxygenate selectivity. This study highlights the influence of Mn on the catalyst structure and function and the importance of studying catalysts under industrially relevant reaction times., Competing Interests: The authors declare the following competing financial interest(s): Andrew M. Beale is a co-owner of Finden Ltd., (© 2024 The Authors. Published by American Chemical Society.)

A carbon paper-based gas diffusion electrode (GDE) is used with a bismuth(III) subcarbonate active catalyst phase for the electrochemical reduction of CO 2 in a gas/electrolyte flow-by configuration electrolyser at high current density. It is demonstrated that in this configuration, the gas and catholyte phases recombine to form K 2 CO 3 /KHCO 3 precipitates to an extent that after electrolyses, vast amount of K + ions is found by EDX mapping in the entire GDE structure. The fact that the entirety of the GDE gets wetted during electrolysis should, however, not be interpreted as a sign of flooding of the catalyst layer, since electrolyte perspiring through the GDE can largely be removed with the outflow gas, and the efficiency of electrolysis (toward the selective production of formate) can thus be maintained high for several hours. For a full spatial scale quantitative monitoring of electrolyte penetration into the GDE, (relying on K + ions as tracer) the method of inductively coupled plasma-mass spectrometry (ICP-MS) assisted energy dispersive X-ray (EDX) tomography is introduced. This new, cheap and robust tomography of non-uniform aspect ratio has a large planar span that comprises the entire GDE surface area and a submicrometer depth resolution, hence it can provide quantitative information about the amount and distribution of K + remnants inside the GDE structure, in three dimensions., (© 2024 The Author(s). Small Methods published by Wiley‐VCH GmbH.)

We experimentally study the influence of the binding energy on nondipole effects in K-shell single-photon ionization of atoms at high photon energies. We find that for each ionization event, as expected by momentum conservation, the photon momentum is transferred almost fully to the recoiling ion. The momentum distribution of the electrons becomes asymmetrically deformed along the photon propagation direction with a mean value of 8/(5c)(E&#95;{γ}-I&#95;{P}) confirming an almost 100 year old prediction by Sommerfeld and Schur [Ann. Phys. (N.Y.) 396, 409 (1930)10.1002/andp.19303960402]. The emission direction of the photoions results from competition between the forward-directed photon momentum and the backward-directed recoil imparted by the photoelectron. Which of the two counteracting effects prevails depends on the binding energy of the emitted electron. As an example, we show that at 20 keV photon energy, Ne^{+} and Ar^{+} photoions are pushed backward towards the radiation source, while Kr^{+} photoions are emitted forward along the light propagation direction.

Ni-rich layered oxides LiNi 1- x - y Mn x Co y O 2 (NMC811, x = 0.1 and y = 0.1) are considered promising cathode materials in lithium-ion batteries (LiBs) due to their high energy density. However, those suffer a severe capacity loss upon cycling at high delithiated states. The loss of performance over time can be retarded by Zr doping. Herein, a small amount of Zr is added to NMC811 material via two alternative pathways: during the formation of the transition metal (TM) hydroxide precursor at the co-precipitation step (0.1%-Zr-cp) and during the lithiation at the solid-state synthesis step (0.1%-Zr-ss). In this work, the crystallographic Zr uptake in both 0.1%-Zr-ss and 0.1%-Zr-cp is determined and quantified through synchrotron X-ray diffraction and X-ray absorption spectroscopy. We prove that the inclusion of Zr in the TM site for 0.1%-Zr-cp leads to an improvement of both specific capacity (156 vs 149 mAh/g) and capacity retention (85 vs 82%) upon 100 cycles compared to 0.1%-Zr-ss where the Zr does not diffuse into the active material and forms only an extra phase separated from the NMC811 particles.

Electrochemical and electrocatalytic processes are of key importance for the transition to a sustainable energy supply as well as for a wide variety of other technologically relevant fields. Further development of these processes requires in-depth understanding of the atomic, nano, and micro scale structure of the materials and interfaces in electrochemical devices under reaction conditions. We here provide a comprehensive review of in situ and operando studies by X-ray scattering methods, which are powerful and highly versatile tools to provide such understanding. We discuss the application of X-ray scattering to a wide variety of electrochemical systems, ranging from metal and oxide single crystals to nanoparticles and even full devices. We show how structural data on bulk phases, electrode-electrolyte interfaces, and nanoscale morphology can be obtained and describe recent developments that provide highly local information and insight into the composition and electronic structure. These X-ray scattering studies yield insights into the structure in the double layer potential range as well as into the structural evolution during electrocatalytic processes and phase formation reactions, such as nucleation and growth during electrodeposition and dissolution, the formation of passive films, corrosion processes, and the electrochemical intercalation into battery materials.

Li-ion battery cathode active materials obtained from different sources or preparation methods often exhibit broadly divergent performance and stability despite no obvious differences in morphology, purity, and crystallinity. We show how state-of-the-art, commercial, nominally single crystalline LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC-622) particles possess extensive internal nanostructure even in the pristine state. Scanning X-ray diffraction microscopy reveals the presence of interlayer strain gradients, and crystal bending is attributed to oxygen vacancies. Phase contrast X-ray nano-tomography reveals two different kinds of particles, welded/aggregated, and single crystal like, and emphasizes the intra- and interparticle heterogeneities from the nano- to the microscale. It also detects within the imaging resolution (100 nm) substantial quantities of nanovoids hidden inside the bulk of two-thirds of the overall studied particles (around 3000), with an average value of 12.5% v per particle and a mean size of 148 nm. The powerful combination of both techniques helps prescreening and quantifying the defective nature of cathode material and thus anticipating their performance in electrode assembly/battery testing.

Lithiation dynamics and phase transition mechanisms in most battery cathode materials remain poorly understood, because of the challenge in differentiating inter- and intra-particle heterogeneity. In this work, the structural evolution inside Li 1-x Mn 1.5 Ni 0.5 O 4 single crystals during electrochemical delithiation is directly resolved with operando X-ray nanodiffraction microscopy. Metastable domains of solid-solution intermediates do not appear associated with the reaction front between the lithiated and delithiated phases, as predicted by current phase transition theory. Instead, unusually persistent strain gradients inside the single crystals suggest that the shape and size of solid solution domains are instead templated by lattice defects, which guide the entire delithiation process. Morphology, strain distributions, and tilt boundaries reveal that the (Ni 2+ /Ni 3+ ) and (Ni 3+ /Ni 4+ ) phase transitions proceed through different mechanisms, offering solutions for reducing structural degradation in high voltage spinel active materials towards commercially useful durability. Dynamic lattice domain reorientation during cycling are found to be the cause for formation of permanent tilt boundaries with their angular deviation increasing during continuous cycling., (© 2023. The Author(s).)

The catalytic oxidation of CO and CH 4 can be strongly influenced by the structures of oxide phases that form on metallic catalysts during reaction. Here, we show that an epitaxial PdO(100) structure forms at temperatures above 600 K during the oxidation of Pd(100) by gaseous O atoms as well as exposure to O 2 -rich mixtures at millibar partial pressures. The oxidation of Pd(100) by gaseous O atoms preferentially generates an epitaxial, multilayer PdO(101) structure at 500 K, but initiating Pd(100) oxidation above 600 K causes an epitaxial PdO(100) structure to grow concurrently with PdO(101) and produces a thicker and rougher oxide. We present evidence that this change in the oxidation behavior is caused by a temperature-induced change in the stability of small PdO domains that initiate oxidation. Our discovery of the epitaxial PdO(100) structure may be significant for developing relationships among oxide structure, catalytic activity, and reaction conditions for applications of oxidation catalysis.

The degradation of Pt-containing oxygen reduction catalysts for fuel cell applications is strongly linked to the electrochemical surface oxidation and reduction of Pt. Here, we study the surface restructuring and Pt dissolution mechanisms during oxidation/reduction for the case of Pt(100) in 0.1 M HClO 4 by combining operando high-energy surface X-ray diffraction, online mass spectrometry, and density functional theory. Our atomic-scale structural studies reveal that anodic dissolution, detected during oxidation, and cathodic dissolution, observed during the subsequent reduction, are linked to two different oxide phases. Anodic dissolution occurs predominantly during nucleation and growth of the first, stripe-like oxide. Cathodic dissolution is linked to a second, amorphous Pt oxide phase that resembles bulk PtO 2 and starts to grow when the coverage of the stripe-like oxide saturates. In addition, we find the amount of surface restructuring after an oxidation/reduction cycle to be potential-independent after the stripe-like oxide has reached its saturation coverage., (© 2023 The Authors. Angewandte Chemie International Edition published by Wiley-VCH GmbH.)

The first step of electrochemical surface oxidation is extraction of a metal atom from its lattice site to a location in a growing oxide. Here we show by fast simultaneous electrochemical and in situ high-energy surface X-ray diffraction measurements that the initial extraction of Pt atoms from Pt(111) is a fast, potential-driven process, whereas charge transfer for the related formation of adsorbed oxygen-containing species occurs on a much slower time scale and is evidently uncoupled from the extraction process. It is concluded that potential plays a key independent role in electrochemical surface oxidation.

The mobility of 79 Se, a fission product of 235 U and long-lived radioisotope, is an important parameter in the safety assessment of radioactive nuclear waste disposal systems. Nonradioactive selenium is also an important contaminant of drainage waters from black shale mountains and coal mines. Highly mobile and soluble in its high oxidation states, selenate (Se( VI )O 4 2- ) and selenite (Se( IV )O 3 2- ) oxyanions can interact with magnetite, a mineral present in anoxic natural environments and in steel corrosion products, thereby being reduced and consequently immobilized by forming low-solubility solids. Here, we investigated the sorption and reduction capacity of synthetic nanomagnetite toward Se(VI) at neutral and acidic pH, under reducing, oxygen-free conditions. The additional presence of Fe( II ) aq , released during magnetite dissolution at pH 5, has an effect on the reduction kinetics. X-ray absorption spectroscopy analyses revealed that, at pH 5, trigonal gray Se(0) formed and that sorbed Se(IV) complexes remained on the nanoparticle surface during longer reaction times. The Se(0) nanowires grew during the reaction, which points to a complex transport mechanism of reduced species or to active reduction sites at the tip of the Se(0) nanowires. The concomitant uptake of aqueous Fe(II) and Se(VI) ions is interpreted as a consequence of small pH oscillations that result from the Se(VI) reduction, leading to a re-adsorption of aqueous Fe(II) onto the magnetite, renewing its reducing capacity. This effect is not observed at pH 7, where we observed only the formation of Se(0) with slow kinetics due to the formation of an oxidized maghemite layer. This indicates that the presence of aqueous Fe(II) may be an important factor to be considered when examining the environmental reactivity of magnetite.

Recently proposed bimetallic octahedral Pt-Ni electrocatalysts for the oxygen reduction reaction (ORR) in proton exchange membrane fuel cell (PEMFC) cathodes suffer from particle instabilities in the form of Ni corrosion and shape degradation. Advanced trimetallic Pt-based electrocatalysts have contributed to their catalytic performance and stability. In this work, we propose and analyse a novel quaternary octahedral (oh-)Pt nanoalloy concept with two distinct metals serving as stabilizing surface dopants. An efficient solvothermal one-pot strategy was developed for the preparation of shape-controlled oh-PtNi catalysts doped with Rh and Mo in its surface. The as-prepared quaternary octahedral PtNi(RhMo) catalysts showed exceptionally high ORR performance accompanied by improved activity and shape integrity after stability tests compared to previously reported bi- and tri-metallic systems. Synthesis, performance characteristics and degradation behaviour are investigated targeting deeper understanding for catalyst system improvement strategies. A number of different operando and on-line analysis techniques were employed to monitor the structural and elemental evolution, including identical location scanning transmission electron microscopy and energy dispersive X-ray analysis (IL-STEM-EDX), operando wide angle X-ray spectroscopy (WAXS), and on-line scanning flow cell inductively coupled plasma mass spectrometry (SFC-ICP-MS). Our studies show that doping PtNi octahedral catalysts with small amounts of Rh and Mo suppresses detrimental Pt diffusion and thus offers an attractive new family of shaped Pt alloy catalysts for deployment in PEMFC cathode layers., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

Cathode catalyst layers of proton exchange membrane fuel cells (PEMFCs) typically consist of carbon-supported platinum catalysts with varying weight ratios of proton-conducting ionomers. N-Doping of carbon support materials is proposed to enhance the performance and durability of the cathode layer under operating conditions in a PEMFC. However, a detailed understanding of the contributing N-moieties is missing. Here, we report the successful synthesis and fuel cell implementation of Pt electrocatalysts supported on N-doped carbons, with a focus on the analysis of the N-induced effect on catalyst performance and durability. A customized fluidized bed reduction reactor was used to synthesize highly monodisperse Pt nanoparticles deposited on N-doped carbons (N-C), the catalytic oxygen reduction reaction activity and stability of which matched those of state-of-the-art PEMFC catalysts. Operando high-energy X-ray diffraction experiments were conducted using a fourth generation storage ring; the light of extreme brilliance and coherence allows investigating the impact of N-doping on the degradation behavior of the Pt/N-C catalysts. Tests in liquid electrolytes were compared with tests in membrane electrode assemblies in single-cell PEMFCs. Our analysis refines earlier views on the subject of N-doped carbon catalyst supports: it provides evidence that heteroatom doping and thus the incorporation of defects into the carbon backbone do not mitigate the carbon corrosion during high-potential cycling (1-1.5 V) and, however, can promote the cell performance under usual PEMFC operating conditions (0.6-0.9 V).

Co oxides and oxyhydroxides have been studied extensively in the past as promising electrocatalysts for the oxygen evolution reaction (OER) in neutral to alkaline media. Earlier studies showed the formation of an ultrathin CoO x (OH) y skin layer on Co 3 O 4 at potentials above 1.15 V vs reversible hydrogen electrode (RHE), but the precise influence of this skin layer on the OER reactivity is still under debate. We present here a systematic study of epitaxial spinel-type Co 3 O 4 films with defined (111) orientation, prepared on different substrates by electrodeposition or physical vapor deposition. The OER overpotential of these samples may vary up to 120 mV, corresponding to two orders of magnitude differences in current density, which cannot be accounted for by differences in the electrochemically active surface area. We demonstrate by a careful analysis of operando surface X-ray diffraction measurements that these differences are clearly correlated with the average thickness of the skin layer. The OER reactivity increases with the amount of formed skin layer, indicating that the entire three-dimensional skin layer is an OER-active interphase. Furthermore, a scaling relationship between the reaction centers in the skin layer and the OER activity is established. It suggests that two lattice sites are involved in the OER mechanism., Competing Interests: The authors declare no competing financial interest., (© 2022 The Authors. Published by American Chemical Society.)

Protein adsorption to surfaces is at the heart of numerous technological and bioanalytical applications, but sometimes, it is also associated with medical risks. To deepen our insights into processes involving layers of surface-adsorbed proteins, high-resolution structural information is essential. Here, we use standing-wave X-ray fluorescence (SWXF) in combination with an optimized liquid-cell setup to investigate the underwater conformation of the random-coiled phosphoprotein β-casein adsorbed to hydrophilic and hydrophobized solid surfaces. The orientation of the protein, as determined through the distributions of sulfur and phosphorus, is found to be sensitive to the chemical nature of the substrate. While no preferred orientations are observed on hydrophobized surfaces, on hydrophilic Al oxide, β-casein is adsorbed as a diblock copolymer with the phosphorylated domain I attached to the surface. Our results demonstrate that targeting biologically relevant chemical elements with SWXF enables a detailed investigation of biomolecular layers under near-physiological conditions.

The theoretical design of effective metal electrocatalysts for energy conversion and storage devices relies greatly on supposed unilateral effects of catalysts structure on electrocatalyzed reactions. Here, by using high-energy X-ray diffraction from the new Extremely Brilliant Source of the European Synchrotron Radiation Facility (ESRF-EBS) on device-relevant Pd and Pt nanocatalysts during cyclic voltammetry experiments in liquid electrolytes, we reveal the near ubiquitous feedback from various electrochemical processes on nanocatalyst strain. Beyond challenging and extending the current understanding of practical nanocatalysts behavior in electrochemical environment, the reported electrochemical strain provides experimental access to nanocatalysts absorption and adsorption trends (i.e., reactivity and stability descriptors) operando . The ease and power in monitoring such key catalyst properties at new and future beamlines is foreseen to provide a discovery platform toward the study of nanocatalysts encompassing a large variety of applications, from model environments to the device level.

In this mini-review we compare two prototypical metal foam electrocatalysts applied to the transformation of CO₂ into value-added products ( e.g. alcohols on Cu foams and formate on Bi foams). A substantial improvement in the catalyst performance is typically achieved through thermal annealing of the as-deposited foam materials, followed by the electro-reduction of the pre-formed oxidic precursors prior or during the actual CO₂ electrolysis. Utilizing highly insightful and sensitive complementary operando analytical techniques (XAS, XRD, and Raman spectroscopy) we demonstrate that this catalyst pre-activation process is entirely accomplished in case of the oxidized Cu foams prior to the formation of hydrocarbons and alcohols from the CO₂. The actually active catalyst is therefore the metallic Cu derived from the precursor by means of oxide electro-reduction. Conversely, in their oxidic form, the Cu-based foam catalysts are inactive towards the CO₂ reduction reaction (denoted ec-CO₂ RR). Oxidized Bi foams can be regarded as an excellent counter example to the above-mentioned Cu case as both metallic and the thermally derived oxidic Bi foams are highly active towards ec-CO₂ RR (formate production). Indeed, operando Raman spectroscopy reveals that CO₂ electrolysis occurs upon its embedment into the oxidic Bi₂O₃ foam precursor, which itself undergoes partial transformation into an active sub-carbonate phase. The potential-dependent transition of sub-carbonates/oxides into the corresponding metallic Bi foam dictates the characteristic changes of the ec-CO₂ RR pathway. Identical location (IL) microscopic inspection of the catalyst materials, e.g. by means of scanning electron microscopy, demonstrates substantial morphological alterations on the nm length scale on the material surface as consequence of the sub-carbonate formation and the potential-driven oxide reduction into the metallic Bi foam. The foam morphology on a mesoscopic length scale (macroporosity) remains, by contrast, fully unaffected by these phase transitions.

The addition of molten alkali metal salts drastically accelerates the kinetics of CO 2 capture by MgO through the formation of MgCO 3 However, the growth mechanism, the nature of MgCO 3 formation, and the exact role of the molten alkali metal salts on the CO 2 capture process remain elusive, holding back the development of more-effective MgO-based CO 2 sorbents. Here, we unveil the growth mechanism of MgCO 3 under practically relevant conditions using a well-defined, yet representative, model system that is a MgO(100) single crystal coated with NaNO 3 The model system is interrogated by in situ X-ray reflectometry coupled with grazing incidence X-ray diffraction, scanning electron microscopy, and high-resolution transmission electron microscopy. When bare MgO(100) is exposed to a flow of CO 2 , a noncrystalline surface carbonate layer of ca. 7-Å thickness forms. In contrast, when MgO(100) is coated with NaNO 3 , MgCO 3 crystals nucleate and grow. These crystals have a preferential orientation with respect to the MgO(100) substrate, and form at the interface between MgO(100) and the molten NaNO 3 MgCO 3 grows epitaxially with respect to MgO(100), and the lattice mismatch between MgCO 3 and MgO is relaxed through lattice misfit dislocations. Pyramid-shaped pits on the surface of MgO, in proximity to and below the MgCO 3 crystals, point to the etching of surface MgO, providing dissolved [Mg 2+ …O 2- ] ionic pairs for MgCO 3 growth. Our studies highlight the importance of combining X-rays and electron microscopy techniques to provide atomic to micrometer scale insight into the changes occurring at complex interfaces under reactive conditions., Competing Interests: The authors declare no competing interest.

In this study, we investigate the effect of thermal treatment/calcination on the stability and activity of a Na-Mn-W/SiO 2 catalyst for the oxidative coupling of methane. The catalyst performance and characterisation measurements suggest that the W species are directly involved in the catalyst active site responsible for CH 4 conversion. Under operating conditions, the active components, present in the form of a Na-W-O-Mn molten state, are highly mobile and volatile. By varying the parameters of the calcination protocol, it was shown that these molten components can be partially stabilised, resulting in a catalyst with lower activity (due to loss of surface area) but higher stability even for long duration OCM reaction experiments.