Correction to "Structural Effects of FeN Active Sites Surrounded by Fourteen-Membered Ring Ligands on Oxygen Reduction Reaction Activity and Durability".

[This corrects the article DOI: 10.1021/acscatal.4c01122.

Transient Kinetic QXAFS Approach for Understanding the RDE-MEA Gap in Fuel Cell (Oxygen Reduction Reaction) Performances of Pt-Based Electrocatalysts.

There is a large gap between the performances indicated by rotating disk electrode (RDE) results in acidic media and the actual performances obtained in membrane-electrode assemblies (MEAs) composed of the same electrocatalysts. It is unclear whether the intrinsic kinetic reactivity of the available surface Pt sites of Pt-based cathode electrocatalysts is similar or different at RDE and in MEA. To address this, we used an operando element-selective time-resolved Pt L-edge quick X-ray absorption fine structure (QXAFS) technique to determine transient response profiles and rate constants, , , and , corresponding to changes in the oxidation states [white line (WL) intensity] and local structures (coordination numbers of Pt-O and Pt-Pt bonds) at Pt sites for nine representative Pt-based cathode electrocatalysts under transient voltage operations, aiming to understand the oxygen reduction reaction (ORR) performance gap between RDE and MEA.

Hydrogen isotope separation at exceptionally high temperature using an unsaturated organometallic complex.

A new approach for hydrogen isotope separation using an unsaturated organometallic complex was proposed. Adsorption measurements of [Mn(dppe)(CO)(N)](BArF) (Mn-dppe) (dppe = 1,2-bis(diphenylphosphino)ethane, BArF = B[CH(3,5-CF)]) using H and D revealed a significant difference in the adsorption enthalpy of H/D at much higher room temperatures than in previous studies, with D molecules being more strongly adsorbed on unsaturated metal sites. Mixed gas adsorption isotherms were calculated at each temperature using IAST, and it was predicted that D uptake was much larger than H uptake.

QXAFS study of CO and H adsorption on Pt in [PtAu(PPh)]-H[PMoO] solid.

The adsorption behaviors of H and CO molecules in crown-motif [PtAu(PPh)]-H[PMoO] (PtAu8-PMo12) solids were investigated by quick-scan X-ray absorption fine structure (QXAFS) measurements with a time resolution of 0.1 s. The electronic state of Pt in PtAu8-PMo12 was drastically changed by the adsorption of H and CO molecules because of the formation of Pt-H/Pt-CO interactions.

Atomically dispersed hexavalent iridium oxide from MnO reduction for oxygen evolution catalysis.

Hexavalent iridium (Ir) oxide is predicted to be more active and stable than any other iridium oxide for the oxygen evolution reaction in acid; however, its experimental realization remains challenging. In this work, we report the synthesis, characterization, and application of atomically dispersed Ir oxide (Ir-) for proton exchange membrane (PEM) water electrolysis. The Ir- was synthesized by oxidatively substituting the ligands of potassium hexachloroiridate(IV) (KIrCl) with manganese oxide (MnO).

3D X-ray imaging of water distribution in each layer of a membrane electrode assembly of a polymer electrolyte fuel cell.

3D computed tomography imaging with statistical analysis successfully revealed the water accumulation and drainage characteristics in the stacked gas diffusion layers (GDLs) and membrane electrode assembly (MEA) of a polymer electrolyte fuel cell. Efficient water drainage at the interface between the cathode GDL and MEA was confirmed upon supplying oxygen to the cathode.

Application of transition-edge sensors for micro-X-ray fluorescence measurements and micro-X-ray absorption near edge structure spectroscopy: a case study of uranium speciation in biotite obtained from a uranium mine.

In this study, we successfully applied a transition-edge sensor (TES) spectrometer as a detector for microbeam X-ray measurements from a synchrotron X-ray light source in the hard X-ray region to determine uranium (U) distribution at the micro-scale and its chemical species in biotite obtained from a U mine. It is difficult to separate the fluorescent X-ray of the U Lα line at 13.615 keV from that of the Rb Kα line at 13.

Subnanometric Osmium Clusters Confined on Palladium Metallenes for Enhanced Hydrogen Evolution and Oxygen Reduction Catalysis.

Highly efficient, cost-effective, and durable electrocatalysts, capable of accelerating sluggish reaction kinetics and attaining high performance, are essential for developing sustainable energy technologies but remain a great challenge. Here, we leverage a facile heterostructure design strategy to construct atomically thin Os@Pd metallenes, with atomic-scale Os nanoclusters of varying geometries confined on the surface layer of the Pd lattice, which exhibit excellent bifunctional properties for catalyzing both hydrogen evolution (HER) and oxygen reduction reactions (ORR). Importantly, Os@Pd metallenes manifest a low η overpotential of only 11 mV in 1.

Three-Dimensional Visualization of Adsorption Distribution in a Single Crystalline Particle of a Metal-Organic Framework.

Many unique adsorption properties of metal-organic frameworks (MOFs) have been revealed by diffraction crystallography, visualizing their vacant and guest-loaded crystal structures at the molecular scale. However, it has been challenging to see the spatial distribution of the adsorption behaviors throughout a single MOF particle in a transient equilibrium state. Here, we report three-dimensional (3D) visualization of molecular adsorption behaviors in a single crystalline particle of a MOF by X-ray absorption fine structure spectroscopy combined with computed tomography for the first time.

5D Analysis of Capacity Degradation in Battery Electrodes Enabled by Operando CT-XANES.

For devices encountering long-term stability challenges, a precise evaluation of degradation is of paramount importance. However, methods for comprehensively elucidating the degradation mechanisms in devices, particularly those undergoing dynamic chemical and mechanical changes during operation, such as batteries, are limited. Here, a method is presented using operando computed tomography combined with X-ray absorption near-edge structure spectroscopy (CT-XANES) that can directly track the evolution of the 3D distribution of the local capacity loss in battery electrodes during (dis)charge cycles, thereby enabling a five-dimensional (the 3D spatial coordinates, time, and chemical state) analysis of the degradation.

Oxidation and phase transfer of individual Cr-doped dendritic FeO particles visualized by full-field nano-XAFS spectroimaging.

Iron oxides with various compositions and polymorphs have been widely used as compounds that require reversible redox properties, such as catalysts. However, partial decomposition during phase transitions often causes irreversible degradation of the redox properties of iron oxides. Cr doping into the crystalline framework of iron oxide dendrites improves the stability of the structural transformation of iron oxides.

High-sensitive XANES analysis at Ce L-edge for Ce in bauxites using transition-edge sensors: Implications for Ti-rich geological samples.

Accurate determination of cerium (Ce) valence state is important for interpreting the Ce anomaly in geological archives for (paleo)redox reconstruction. However, the routine application of Ce L-edge X-ray absorption near-edge structure (XANES) spectroscopy for detecting trace Ce in geological samples can often be restricted by coexisting titanium (Ti) due to the proximity of their fluorescence emission lines. Therefore, the signal-to-noise ratio of Ce L-edge XANES spectra may not be sufficiently high for high-quality spectroscopic analysis.

Pd-PdO Nanodomains on Amorphous Ru Metallene Oxide for High-Performance Multifunctional Electrocatalysis.

Developing highly efficient multifunctional electrocatalysts is crucial for future sustainable energy  pursuits, but remains a great challenge. Herein, a facile synthetic strategy is used to confine atomically thin Pd-PdO nanodomains to amorphous Ru metallene oxide (RuO ). The as-synthesized electrocatalyst (Pd RuOx-0.

Synthesis of catalysts with fine platinum particles supported by high-surface-area activated carbons and optimization of their catalytic activities for polymer electrolyte fuel cells.

Herein, we demonstrated that carbon-supported platinum (Pt/C) is a low-cost and high-performance electrocatalyst for polymer electrolyte fuel cells (PEFCs). The ethanol reduction method was used to prepare the Pt/C catalyst, which was realized by an effective matching of the carbon support and optimization of the Pt content for preparing a membrane electrode assembly (MEA). For this, the synthesis of Pt/C catalysts with different Pt loadings was performed on two different carbons (KB1600 and KB800) as new support materials.

Imaging of Ce Radical Scavengers in a Practical Polymer Electrolyte Fuel Cell by 3D Fluorescence CT-XAFS and Depth-Profiling Nano-XAFS-SEM/EDS Techniques.

There is little information on the spatial distribution, migration, and valence of Ce species doped as an efficient radical scavenger in a practical polymer electrolyte fuel cell (PEFC) for commercial fuel cell vehicles (FCVs) closely related to a severe reliability issue for long-term PEFC operation. An three-dimensional fluorescence computed tomography-X-ray absorption fine structure (CT-XAFS) imaging technique and an same-view nano-XAFS-scanning electron microscopy (SEM)/energy-dispersive spectrometry (EDS) combination technique were applied for the first time to perform spatial visualization and depth-profiling analysis of Ce radical scavengers in a practical PEFC of Toyota MIRAI FCV under PEFC operating conditions. Using these techniques, we successfully visualized and analyzed the domain, density, valence, and migration of Ce scavengers that were heterogeneously distributed in the components of PEFC, such as anode microporous layer, anode catalyst layer, polymer electrolyte membrane (PEM), cathode catalyst layer, and cathode microporous layer.

Sulfur poisoning of Pt and PtCo anode and cathode catalysts in polymer electrolyte fuel cells studied by operando near ambient pressure hard X-ray photoelectron spectroscopy.

We have investigated the S adsorption behaviours on Pt (average particle diameter of ∼2.6 nm) and PtCo (∼3.0 nm) anode and cathode electrode catalysts in polymer electrolyte fuel cells (PEFCs) under working conditions for the fresh state just after the aging process and also the degraded state after accelerated degradation tests (ADT), by studying near ambient pressure hard X-ray photoelectron spectroscopy (HAXPES).

Broadband high-energy resolution hard x-ray spectroscopy using transition edge sensors at SPring-8.

We have succeeded in operating a transition-edge sensor (TES) spectrometer and evaluating its performance at the SPring-8 synchrotron x-ray light source. The TES spectrometer consists of a 240 pixel National Institute of Standards and Technology (NIST) TES system, and 220 pixels are operated simultaneously with an energy resolution of 4 eV at 6 keV at a rate of ∼1 c/s pixel. The tolerance for high count rates is evaluated in terms of energy resolution and live time fraction, leading to an empirical compromise of ∼2 × 10 c/s (all pixels) with an energy resolution of 5 eV at 6 keV.

Reversible structural transformation and redox properties of Cr-loaded iron oxide dendrites studied by XANES spectroscopy.

Cr-Loaded iron oxide with a dendritic crystalline structure was synthesized and the reversible crystalline phase transition during redox cycling of the iron oxide was investigated. X-ray diffraction and transmission electron microscopy analyses revealed that Cr was well dispersed and loaded in the iron oxide dendrite crystals, whose lattice constant was dependent on the Cr loading. Temperature-programmed oxidation and reduction experiments revealed the reversible redox properties of the Cr-loaded iron oxide dendrites, whose redox temperature was found to be lower than that of Cr-free iron oxide dendrites.

Surface Freezing of Cetyltrimethylammonium Chloride-Hexadecanol Mixed Adsorbed Film at Dodecane-Water Interface.

The surface freezing transition of a mixed adsorbed film containing cetyltrimethylammonium chloride (CTAC) and -hexadecanol (C16OH) was utilized at the dodecane-water interface to control the stability of oil-in-water (O/W) emulsions. The corresponding surface frozen and surface liquid mixed adsorbed films were characterized using interfacial tensiometry and X-ray reflectometry. The emulsion samples prepared in the temperature range of the surface frozen and surface liquid phases showed a clear difference in their stability: the emulsion volume decreased continuously right after the emulsification in the surface liquid region, while it remained constant or decreased at a much slower rate in the surface frozen region.

Condensed Film Formation and Molecular Packing in Cationic Surfactant-Cholesterol and Zwitterionic Surfactant-Cholesterol Systems at the Hexane/Water Interface.

A condensed film formation of surfactants with a charged head group at the oil/water interface was achieved by mixing surfactants of different geometric shapes to control molecular packing at the interface. The adsorbed films of mixed tetradecyltrimethylammonium bromide (C14TAB)-cholesterol (Chol) and tetradecylphosphocholine (C14PC)-Chol systems at the hexane/water interface were examined by interfacial tension and X-ray reflectivity measurements. The interfacial tension versus Chol concentration curves have break points because of the expanded-condensed phase transition of the adsorbed film.

Periodic Elastic Motion in a Self-Assembled Monolayer under Spontaneous Oscillations of Surface Tension: Molecules in a Scrum Push Back a Marangoni Flow.

Regularly recurring phenomena are a common and important part of life. Such rhythmic behaviors are often seen in nonliving systems under far-from-equilibrium conditions. The study of simple nonliving systems provides clues for improving our understanding of the origin of biological rhythms.

Visualization and understanding of the degradation behaviors of a PEFC Pt/C cathode electrocatalyst using a multi-analysis system combining time-resolved quick XAFS, three-dimensional XAFS-CT, and same-view nano-XAFS/STEM-EDS techniques.

We developed a multi-analysis system that can measure in situ time-resolved quick XAFS (QXAFS) and in situ three-dimensional XAFS-CT spatial imaging in the same area of a cathode electrocatalyst layer in a membrane-electrode assembly (MEA) of a polymer electrolyte fuel cell (PEFC) at the BL36XU beamline of SPring-8. The multi-analysis system also achieves ex situ two-dimensional nano-XAFS/STEM-EDS same-view measurements of a sliced MEA fabricated from a given place in the XAFS-CT imaged area at high spatial resolutions under a water-vapor saturated N atmosphere using a same-view SiN membrane cell. In this study, we applied the combination method of time-resolved QXAFS/3D XAFS-CT/2D nano-XAFS/STEM-EDS for the first time for the visualization analysis of the anode-gas exchange (AGEX) (simulation of the start-up/shut-down of PEFC vehicles) degradation process of a PEFC MEA Pt/C cathode.

Model building analysis - a novel method for statistical evaluation of Pt L-edge EXAFS data to unravel the structure of Pt-alloy nanoparticles for the oxygen reduction reaction on highly oriented pyrolytic graphite.

Extended X-ray absorption fine structure (EXAFS) is a powerful tool to determine the local structure in Pt nanoparticles (NP) on carbon supports, active catalysts for fuel cells. Highly oriented pyrolytic graphite (HOPG) covered with Pt NP gives samples with flat surfaces that allow application of surface science techniques. However, the low concentration of Pt makes it difficult to obtain good quality EXAFS data.

3D Imaging and Quantification of Inhomogeneous Electrochemical Reactions in Composite Battery Electrodes.

The performances of electrochemical systems such as solid-state batteries (SSBs) can be severely hindered by the three-dimensional (3D) and mesoscopically inhomogeneous electrochemical reactions that take place in the electrodes. However, the majority of existing methods for analyzing such inhomogeneous reactions are restricted to one- or two-dimensional observations. Herein, we performed 3D imaging of the mesoscopically inhomogeneous electrochemical reaction in a composite SSB electrode using hard X-ray computed-tomography with X-ray absorption near edge structure spectroscopy (CT-XANES).