Uncovering The Role of Oxygen in Ni-Fe(OxHy) Electrocatalysts using In situ Soft X-ray Absorption Spectroscopy during the Oxygen Evolution Reaction.

In-situ X-ray absorption spectroscopy (XAS) at the oxygen K-edge was used to investigate the role of oxygen during the oxygen evolution reaction (OER) in an electrodeposited Ni-Fe(OxHy) electrocatalyst in alkaline pH. We show the rise of a pre-peak feature at 529 eV in the O K-edge spectra, correlated to the appearance of a shoulder at the Ni L3-edge and formation of oxidized Ni3+/4+-O. Then, for the first time, we track the spectral changes in a dynamic fashion in both the soft and hard X-ray regimes during cyclic voltammetry (in situ CV-XAS) to obtain a fine-tuned resolution of the potential-related changes. The pre-peak feature at the O K-edge likely signifies formation of an electron deficient oxygen site. The electrophilic oxygen species appears and disappears reversibly in correlation with the Ni2+ ↔ Ni3+/4+ process, and persists during OER catalysis as long the metal is oxidized. Our study provides new insight into OER electrocatalysis: Before onset of the O-O bond formation step, the catalytic oxyhydroxide has accumulated electron deficiencies by both, oxidation of transition metal ions and formation of partially oxidized oxygen sites.

Retraction: On the enzymatic activity of catalase: an iron L-edge X-ray absorption study of the active centre.

Retraction of 'On the enzymatic activity of catalase: an iron L-edge X-ray absorption study of the active centre' by Nora Bergmann et al., Phys. Chem. Chem. Phys., 2010, 12, 4827-4832.

An efficient laser vaporization source for chemically modified metal clusters characterized by thermodynamics and kinetics.

A laser vaporization cluster source that has a room for cluster aggregation and a reactor volume, each equipped with a pulsed valve, is presented for the efficient gas-phase production of chemically modified metal clusters. The performance of the cluster source is evaluated through the production of Ta and Ta oxide cluster cations, TaxOy+ (y ≥ 0). It is demonstrated that the cluster source produces TaxOy+ over a wide mass range, the metal-to-oxygen ratio of which can easily be controlled by changing the pulse duration that influences the amount of reactant O2 introduced into the cluster source. Reaction kinetic modeling shows that the generation of the oxides takes place under thermalized conditions at less than 300 K, whereas metal cluster cores are presumably created with excess heat. These characteristics are also advantageous to yield "reaction intermediates" of interest via reactions between clusters and reactive molecules in the cluster source, which may subsequently be mass selected for their reactivity measurements.

Single-Atom Au/NiFe Layered Double Hydroxide Electrocatalyst: Probing the Origin of Activity for Oxygen Evolution Reaction.

A fundamental understanding of the origin of oxygen evolution reaction (OER) activity of transition-metal-based electrocatalysts, especially for single precious metal atoms supported on layered double hydroxides (LDHs), is highly required for the design of efficient electrocatalysts toward further energy conversion technologies. Here, we aim toward single-atom Au supported on NiFe LDH (sAu/NiFe LDH) to clarify the activity origin of LDHs system and a 6-fold OER activity enhancement by 0.4 wt % sAu decoration. Combining with theoretical calculations, the active behavior of NiFe LDH results from the in situ generated NiFe oxyhydroxide from LDH during the OER process. With the presence of sAu, sAu/NiFe LDH possesses an overpotential of 0.21 V in contrast to the calculated result (0.18 V). We ascribe the excellent OER activity of sAu/NiFe LDH to the charge redistribution of active Fe as well as its surrounding atoms causing by the neighboring sAu on NiFe oxyhydroxide stabilized by interfacial CO32- and H2O interfacing with LDH.

Polymersomes at the solid-liquid interface: Dynamic morphological transformation and lubrication.

Polymersomes are hollow spheres self-assembled from amphiphilic block copolymers of certain molecular architecture. Whilst they have been widely studied for biomedical applications, relatively few studies have reported their interfacial properties. In particular, lubrication by polymersomes has not been previously reported. Here, interfacial properties of polymersomes self-assembled from poly(butadiene)-poly(ethylene oxide) (PBD-PEO; molecular weight 10,400 g mol-1) have been studied at both hydrophilic and hydrophobic surfaces. Their morphology at silica and mica surfaces was imaged with quantitative nanomechanical property mapping atomic force microscopy (QNM AFM), and friction and surface forces they mediate under confinement between two surfaces were studied using colloidal probe AFM (CP-AFM). We find that the polymersomes remained intact but adopted flattened conformation once adsorbed to mica, with a relatively low coverage. However, on silica these polymersomes were unstable, rupturing to form donut shaped residues or patchy bilayers. On a silica surface hydrophobized with a 19 nm polystyrene (PS) film, the polymer vesicles formed a more stable layer with a higher surface coverage as compared to the hydrophilic surface, and the interfacial structure also evolved over time. Moreover, friction was greatly reduced on hydrophobized silica surfaces in the presence of polymersomes, suggesting their potential as effective aqueous lubricants.

In situ XAS study of CoBi modified hematite photoanodes.

Solar water splitting is a potentially scalable method to store solar energy in the form of renewable hydrogen gas. In this study, we demonstrate that the photoelectrochemical (PEC) performance of hematite photoanodes can be improved by modification with the oxygen evolution catalyst CoBi. The current density at 1.23 V of the pristine hematite under one sun is 0.88 mA cm-2 and it increases to 1.12 mA cm-2 after CoBi modification (∼27% improvement). The presence of a CoBi cocatalayst layer is proposed to improve the oxygen evolution reaction (OER) kinetics and also to prevent electron-hole recombination at the surface via passivating surface defects as well as suppressing the tunneling of electrons from the hematite core, thus improving the photocurrents and resulting in a negative shift of photocurrent onset potentials. These effects of CoBi modification are supported by experimental data obtained by performing electrochemical impedance spectroscopy (EIS), PEC and incident photon-to-current efficiency (IPCE) measurements. To investigate the electronic structure of the CoBi cocatalyst deposited on hematite, XPS and in situ X-ray absorption spectroscopy (XAS) are employed. Co K-edge spectra at different potentials and light conditions are recorded. This makes the present work different from most of the previous studies. Using a quantitative analysis method, information on the mean oxidation state of Co in the CoBi film under applied potential and illumination is revealed. We also compare different methods for determining the oxidation state from the edge position and find that the integral method and half height methods are most suitable. In summary, the present work underlines the improvement of the semiconductor/cocatalyst interface of oxygen evolving photoanodes and strengthens the importance of in situ XAS spectroscopy when studying catalysts. This study is the first report so far combining the studies of the PEC performance of a CoBi modified hematite nanorod array photoanode and in situ XAS at the Co K-edge.

One-Pot Synthesis of Nickel-Modified Carbon Nitride Layers Toward Efficient Photoelectrochemical Cells.

A new method to significantly enhance the photoelectrochemical properties of phenyl-modified carbon nitride layers via the insertion of nickel ions into carbon nitride layers is reported. The nickel ions are embedded within the carbon nitride layers by manipulating the interaction of Ni ions and molten organic molecules at elevated temperature prior to their condensation. A detailed analysis of the chemical and photophysical properties suggests that the nickel ions dissolve in the molten molecules, leading to the homogeneous distribution of nickel atoms within the carbon nitride layers. We found that the nickel atoms can alter the growth mechanism of carbon nitride layers, resulting in extended light absorption, charge transfer properties, and the total photoelectrochemical performance. For the most photoactive electrode, the Ni ions have an oxidation state of 2.8, as confirmed by soft X-ray absorption spectroscopy. Furthermore, important parameters such as absorption coefficient, exciton lifetime, and diffusion length were studied in depth, providing substantial progress in our understanding of the photoelectrochemical properties of carbon nitride films. This work opens new opportunities for the growth of carbon nitride layers and similar materials on different surfaces and provides important progress in our understanding of the photophysical and photoelectrochemical properties of carbon nitride layers toward their implantation in photoelectronic and other devices.

Retraction: Charge transfer to solvent identified using dark channel fluorescence-yield L-edge spectroscopy.

This corrects the article DOI: 10.1038/nchem.807.

[Monitoring devices and their alarms: incident reports suggest problems with device knowledge]. / Umgang mit Patientenmonitoren und ihren Alarmen: Vorkommnismeldungen liefern Hinweise auf Probleme mit Gerätewissen.

Missing or false device alarms pose a risk in clinical practice. Publications from the United States suggest that alarm errors are not only caused by technical issues but to a considerable degree result from user-device interaction problems. To safely operate a medical device, users have to thoroughly understand both device behavior and device functioning. They also need to foresee the exact consequences of their interactions with the device. This can be challenging, especially if a device has multiple functions, is applied in various use contexts or networked with other devices - as is often the case with patient monitors. In this case, human error in operating a device may not necessarily be detected, but is experienced as device failure. If medical device failures occur in German hospitals that are associated with a risk to the patient, the user, or other persons, they have to be reported to the Federal Institute for Drugs and Medical Devices (Bundesinstitut für Arzneimittel und Medizinprodukte, BfArM). In the present study, we analyzed reports to the BfArM (received between 01/2009 and 12/2015) about loss or failure of the alarm function of patient monitors. It was found that the perceived 'faulty' behavior of the device was the device's intended behavior in almost half of these reports. Hence, the person who detected this fault was not sufficiently acquainted with the device and/or its configuration. Examples of knowledge deficits related to various aspects of device knowledge. Further studies are needed to find out whether these findings are suggestive of more general knowledge deficits among clinical staff and to explore the underlying reasons.

C=C π Bond Modified Graphitic Carbon Nitride Films for Enhanced Photoelectrochemical Cell Performance.

Applications of graphitic carbon nitride (g-CN) in photoelectrochemical and optoelectronic devices are still hindered due to the difficulties in synthesis of g-CN films with tunable chemical, physical and catalytic properties. Herein we present a general method to alter the electronic and photoelectrochemical properties of g-CN films by annealing. We found that N atoms can be removed from the g-CN networks after annealing treatment. Assisted by theoretical calculations, we confirm that upon appropriate N removal, the adjacent C atoms will form new C=C π bonds. Detailed calculations demonstrate that the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) are located at the structure unit with C=C π bonds and the electrons are more delocalized. Valence band X-ray photoelectron spectroscopy spectra together with optical absorption spectra unveil that the structure changes result in the alteration of the g-CN energy levels and position of band edges. Our results show that the photocurrent density of the annealed g-CN film is doubled compared with the pristine one, thanks to the better charge separation and transport within the film induced by the new C=C π bonds. An ultrathin TiO2 film (2.2 nm) is further deposited on the g-CN film as stabilizer and the photocurrent density is kept at 0.05 mA cm-2 at 1.23 V versus reversible hydrogen electrode after two-cycle stability assessment. This work enables the applications of g-CN films in many electronic and optoelectronic devices.

Correlating Oxygen Evolution Catalysts Activity and Electronic Structure by a High-Throughput Investigation of Ni1-y-zFeyCrzOx.

High-throughput characterization by soft X-ray absorption spectroscopy (XAS) and electrochemical characterization is used to establish a correlation between electronic structure and catalytic activity of oxygen evolution reaction (OER) catalysts. As a model system a quasi-ternary materials library of Ni1-y-zFeyCrzOx was synthesized by combinatorial reactive magnetron sputtering, characterized by XAS, and an automated scanning droplet cell. The presence of Cr was found to increase the OER activity in the investigated compositional range. The electronic structure of NiII and CrIII remains unchanged over the investigated composition spread. At the Fe L-edge a linear combination of two spectra was observed. These spectra were assigned to FeIII in Oh symmetry and FeIII in Td symmetry. The ratio of FeIII Oh to FeIII Td increases with the amount of Cr and a correlation between the presence of the FeIII Oh and a high OER activity is found.

A soft XAS transmission cell for operando studies.

A new cell for operando soft X-ray absorption spectroscopy in transmission mode is presented. Developed for investigations on solar water-splitting catalysts, the cell allows the study of solid films in direct contact with electrolyte solution while applying voltage and visible light. The design is optimized for fast sample exchange and the simultaneous measurement of fluorescence and transmission signal. The capability of the cell is presented on a manganese oxide (MnOx) film, where electronic structure changes are monitored during forward and backward potential changes. Detailed information about the varying contributions of several Mn oxidation states during this process was revealed.

Hydrophilic nanoparticles stabilising mesophase curvature at low concentration but disrupting mesophase order at higher concentrations.

Using high pressure small angle X-ray scattering (HP-SAXS), we have studied monoolein (MO) mesophases at 18 wt% hydration in the presence of 10 nm silica nanoparticles (NPs) at NP-lipid number ratios (ν) of 1 × 10(-6), 1 × 10(-5) and 1 × 10(-4) over the pressure range 1-2700 bar and temperature range 20-60 °C. In the absence of the silica NPs, the pressure-temperature (p-T) phase diagram of monoolein exhibited inverse bicontinuous cubic gyroid (Q), lamellar alpha (Lα), and lamellar crystalline (Lc) phases. The addition of the NPs significantly altered the p-T phase diagram, changing the pressure (p) and the temperature (T) at which the transitions between these mesophases occurred. In particular, a strong NP concentration effect on the mesophase behaviour was observed. At low NP concentration, the p-T region pervaded by the Q phase and the Lα-Q mixture increased, and we attribute this behaviour to the NPs forming clusters at the mesophase domain boundaries, encouraging transition to the mesophase with a higher curvature. At high NP concentrations, the Q phase was no longer observed in the p-T phase diagram. Instead, it was dominated by the lamellar (L) phases until the transition to a fluid isotropic (FI) phase at 60 °C at low pressure. We speculate that NPs formed aggregates with a "chain of pearls" structure at the mesophase domain boundaries, hindering transitions to the mesophases with higher curvatures. These observations were supported by small angle neutron scattering (SANS) and scanning electron microscopy (SEM). Our results have implications to nanocomposite materials and nanoparticle cellular entry where the interactions between NPs and organised lipid structures are an important consideration.

Charge Transfer Dynamics at Dye-Sensitized ZnO and TiO2 Interfaces Studied by Ultrafast XUV Photoelectron Spectroscopy.

Interfacial charge transfer from photoexcited ruthenium-based N3 dye molecules into ZnO thin films received controversial interpretations. To identify the physical origin for the delayed electron transfer in ZnO compared to TiO2, we probe directly the electronic structure at both dye-semiconductor interfaces by applying ultrafast XUV photoemission spectroscopy. In the range of pump-probe time delays between 0.5 to 1.0 ps, the transient signal of the intermediate states was compared, revealing a distinct difference in their electron binding energies of 0.4 eV. This finding strongly indicates the nature of the charge injection at the ZnO interface associated with the formation of an interfacial electron-cation complex. It further highlights that the energetic alignment between the dye donor and semiconductor acceptor states appears to be of minor importance for the injection kinetics and that the injection efficiency is dominated by the electronic coupling.

Influence of the Outer Ligands on Metal-to-Ligand Charge Transfer in Solvated Manganese Porphyrins.

Two manganese porphyrin complexes, manganese tetraphenylporphyrin chloride (MnTPP-Cl) and manganese octaethylporphyrin chloride (MnOEP-Cl), exhibit distinctive spectral features of metal-to-ligand charge-transfer (MLCT) when dissolved in dichloromethane, characterized by resonant inelastic X-ray scattering at the Mn L-edge and N K-edge. The metal-ligand orbital mixing that mediates the MLCT is analyzed with the help of density functional theory/restricted open-shell configuration interaction singles calculations. On the basis of experimental and theoretical analyses, the distinctive MLCT is argued to originate from alteration of the porphyrin outer ligands: phenyl groups in MnTPP-Cl and ethyl groups in MnOEP-Cl.

A human factors perspective on medical device alarms: problems with operating alarming devices and responding to device alarms.

Medical devices emit alarms when a problem with the device or with the patient needs to be addressed by healthcare personnel. At present, problems with device alarms are frequently discussed in the literature, the main message being that patient safety is compromised because device alarms are not as effective and safe as they should - and could - be. There is a general consensus that alarm-related hazards result, to a considerable degree, from the interactions of human users with the device. The present paper addresses key aspects of human perception and cognition that may relate to both operating alarming devices and responding to device alarms. Recent publications suggested solutions to alarm-related hazards associated with usage errors based on assumptions on the causal relations between, for example, alarm management and human perception, cognition, and responding. However, although there is face validity in many of these assumptions, future research should provide objective empirical evidence in order to deepen our understanding of the actual causal relationships, and hence improve and expand the possibilities for taking appropriate action.

Chemical bonding in aqueous ferrocyanide: experimental and theoretical X-ray spectroscopic study.

Resonant inelastic X-ray scattering (RIXS) and X-ray absorption (XA) experiments at the iron L- and nitrogen K-edge are combined with high-level first-principles restricted active space self-consistent field (RASSCF) calculations for a systematic investigation of the nature of the chemical bond in potassium ferrocyanide in aqueous solution. The atom- and site-specific RIXS excitations allow for direct observation of ligand-to-metal (Fe L-edge) and metal-to-ligand (N K-edge) charge-transfer bands and thereby evidence for strong σ-donation and π-backdonation. The effects are identified by comparing experimental and simulated spectra related to both the unoccupied and occupied molecular orbitals in solution.

Challenging perceptual tasks require more attention: the influence of task difficulty on the N1 effect of temporal orienting.

Both filter and resource models of attention suggest an influence of task difficulty on the size of early attention effects. As for temporal orienting, the idea that early effects are modulated by task difficulty has not been tested directly, so far. To fill this empirical gap, the present study used an auditory temporal-orienting task, in which two differently pitched pure tones served as targets. To manipulate perceptual difficulty, the pitch difference between the targets was either small or large. Temporal orienting enhanced the N1 component of the auditory event-related potential. This early, sensory effect tended to be larger in the more difficult condition, particularly over the frontal scalp. Notably, increasing task difficulty affected predominantly the processing of attended stimuli. Hence, temporal orienting may operate by increasing processing resources or gain settings for the attended time point - rather than by withdrawing resources from the unattended time point.

Probing ion-specific effects on aqueous acetate solutions: Ion pairing versus water structure modifications.

The effect of monovalent cations (Li(+), K(+), NH4 (+), Na(+)) on the water structure in aqueous chloride and acetate solutions was characterized by oxygen K-edge X-ray absorption spectroscopy (XAS), X-ray emission spectroscopy, and resonant inelastic X-ray scattering (RIXS) of a liquid microjet. We show ion- and counterion dependent effects on the emission spectra of the oxygen K-edge, which we attribute to modifications of the hydrogen bond network of water. For acetates, ion pairing with carboxylates was also probed selectively by XAS and RIXS. We correlate our experimental results to speciation data and to the salting-out properties of the cations.

Nature of the chemical bond of aqueous Fe2+ probed by soft X-ray spectroscopies and ab initio calculations.

Aqueous iron(II) chloride is studied by soft X-ray absorption, emission, and resonant inelastic Raman scattering techniques on the Fe L-edge and O K-edge using the liquid-jet technique. Soft X-ray spectroscopies allow in situ and atom-specific probing of the electronic structure of the aqueous complex and thus open the door for the investigation of chemical bonding and molecular orbital mixing. In this work, we combine theoretical ab initio restricted active space self-consistent field and local atomic multiplet calculations with experimental soft X-ray spectroscopic methods for a description of the local electronic structure of the aqueous ferrous ion complex. We demonstrate that the atomic iron valence final states dominate the resonant inelastic X-ray scattering spectra of the complex over the ligand-to-metal charge transfer transitions, which indicates a weak interaction of Fe(2+) ion with surrounding water molecules. Moreover, the oxygen K-edge also shows only minor changes due to the presence of Fe(2+) implying a small influence on the hydrogen-bond network of water.