Berry curvature contributions of kagome-lattice fragments in amorphous Fe-Sn thin films.

Amorphous semiconductors are widely applied to electronic and energy-conversion devices owing to their high performance and simple fabrication processes. The topological concept of the Berry curvature is generally ill-defined in amorphous solids, due to the absence of long-range crystalline order. Here, we demonstrate that the Berry curvature in the short-range crystalline order of kagome-lattice fragments effectively contributes to the anomalous electrical and magneto-thermoelectric properties in Fe-Sn amorphous films. The Fe-Sn films on glass substrates exhibit large anomalous Hall and Nernst effects comparable to those of the single crystals of topological semimetals Fe3Sn2 and Fe3Sn. With modelling, we reveal that the Berry curvature contribution in the amorphous state likely originates from randomly distributed kagome-lattice fragments. This microscopic interpretation sheds light on the topology of amorphous materials, which may lead to the realization of functional topological amorphous electronic devices.

Oxidation-induced nanolite crystallization triggered the 2021 eruption of Fukutoku-Oka-no-Ba, Japan.

Nanometer-sized crystals (nanolites) play an important role in controlling eruptions by affecting the viscosity of magmas and inducing bubble nucleation. We present detailed microscopic and nanoscopic petrographic analyses of nanolite-bearing and nanolite-free pumice from the 2021 eruption of Fukutoku-Oka-no-Ba, Japan. The nanolite mineral assemblage includes biotite, which is absent from the phenocryst mineral assemblage, and magnetite and clinopyroxene, which are observed as phenocrysts. The boundary between the nanolite-bearing brown glass and nanolite-free colorless glass is either sharp or gradational, and the sharp boundaries also appear sharp under the transmitted electron microscope. X-ray absorption fine structure (XAFS) analysis of the volcanic glass revealed that the nanolite-free colorless glass records an oxygen fugacity of QFM + 0.98 (log units), whereas the nanolite-bearing brown glass records a higher apparent oxygen fugacity (~ QFM + 2). Thermodynamic modelling using MELTS indicates that higher oxygen fugacities increase the liquidus temperature and thus induced the crystallization of magnetite nanolites. The hydrous nanolite mineral assemblage and glass oxygen fugacity estimates suggest that an oxidizing fluid supplied by a hot mafic magma induced nanolite crystallization in the magma reservoir, before the magma fragmentation. The oxidation-induced nanolite crystallization then enhanced heterogeneous bubble nucleation, resulting in convection in the magma reservoir and triggering the eruption.

Boosted Activity of Cobalt Catalysts for Ammonia Synthesis with BaAl2O4-xHy Electrides.

Electrides are promising support materials to promote transition metal catalysts for ammonia synthesis due to their strong electron-donating ability. Cobalt (Co) is an alternative non-noble metal catalyst to ruthenium in ammonia synthesis; however, it is difficult to achieve acceptable activity at low temperatures due to the weak Co-N interaction. Here, we report a novel oxyhydride electride, BaAl2O4-xHy, that can significantly promote ammonia synthesis over Co (500 mmol gCo-1 h-1 at 340 °C and 0.90 MPa) with a very low activation energy (49.6 kJ mol-1; 260-360 °C), which outperforms the state-of-the-art Co-based catalysts, being comparable to the latest Ru catalyst at 300 °C. BaAl2O4-xHy with a stuffed tridymite structure has interstitial cage sites where anionic electrons are accommodated. The surface of BaAl2O4-xHy with very low work functions (1.7-2.6 eV) can donate electrons strongly to Co, which largely facilitates N2 reduction into ammonia with the aid of the lattice H- ions. The stuffed tridymite structure of BaAl2O4-xHy with a three-dimensional AlO4-based tetrahedral framework has great chemical stability and protects the accommodated electrons and H- ions from oxidation, leading to robustness toward the ambient atmosphere and good reusability, which is a significant advantage over the reported hydride-based catalysts.

Realization of Stacked-Ring Aromaticity in a Water-Soluble Micellar Capsule.

Stacked-ring aromaticity arising from the close stacking of antiaromatic π-systems has recently received considerable attention. Here, we realize stacked-ring aromaticity via a rational supramolecular approach. A nanocapsule composed of bent polyaromatic amphiphiles was employed to encapsulate several antiaromatic norcorrole Ni(II) complexes (NCs) in water. The resulting micellar capsules display high stability toward heating and concentration change. The encapsulation resulted in the appearance of a broad absorption band in the near-infrared region, which is characteristic of norcorroles with close face-to-face stacking. Importantly, a meso-isopropyl NC, which does not exhibit π-stacking even in a concentrated solution or the crystalline phase, adopted π-stacking with stacked-ring aromaticity in the supramolecular micellar capsule.

Approach to Chemically Durable Nickel and Cobalt Lanthanum-Nitride-Based Catalysts for Ammonia Synthesis.

Metal nitride complexes have recently been proposed as an efficient noble-metal-free catalyst for ammonia synthesis utilizing a dual active site concept. However, their high sensitivity to air and moisture has restricted potential applications. We report that their chemical sensitivity can be improved by introducing Al into the LaN lattice, thereby forming La-Al metallic bonds (La-Al-N). The catalytic activity and mechanism of the resulting TM/La-Al-N (TM=Ni, Co) are comparable to the previously reported TM/LaN catalyst. Notably, the catalytic activity did not degrade after exposure to air and moisture. Kinetic analysis and isotopic experiment showed that La-Al-N is responsible for N2 absorption and activation despite substantial Al being introduced into its lattice because the local coordination of the lattice N remained largely unchanged. These findings show the effectiveness of metallic bond formation, which can support the chemical stability of rare-earth nitrides with retention of catalytic functionality.

Structure of Atomically Dispersed Pt in a SnO2 Thin Film under Reaction Conditions: Origin of Its High Performance in Micro Electromechanical System Gas Sensor Catalysis.

A battery-driven micro electromechanical system (MEMS) gas sensor has been developed for household safety when using natural gas. The heart of the MEMS gas sensor is a 7.5 at % Pt-SnO2 thin film catalyst deposited on the SnO2 sensor layer. The catalyst enhances the sensitivity to methane, though its structure under working conditions is unclear. In this study, in situ XAFS was applied to a 7.5 at % Pt-SnO2 catalyst layer deposited on a Si substrate, and we demonstrated that atomically dispersed Pt maintains its lattice position in SnO2 with a small loss of surrounding lattice oxygen in the presence of 1% CH4 and a more reducing gas of 1% H2 at the reaction temperature (703 K), i.e., no Pt aggregation is observed. The lost oxygen is easily recovered by re-oxidation by air. This work has revealed that the atomically dispersed Pt in the SnO2 lattice is the active structure and it is stable even under reaction conditions, which guarantees a long lifetime for the gas sensor.

Synergistic Effects of Earth-Abundant Metal-Metal Oxide Enable Reductive Amination of Carbonyls at 50 °C.

Reductive amination of carbonyls to primary amines is of importance to the synthesis of fine chemicals; however, this reaction with heterogeneous catalysts containing earth-abundant metals under mild conditions remains scarce. Here, we show that the nickel catalyst with mixed oxidation states enables such synthesis of primary amines under low temperature (50 °C) and H2 pressure (0.9 MPa). The catalyst shows activity in both water and toluene. The high activity likely results from the formation of small (ca. 4.6 nm) partially oxidized nickel nanoparticles (NPs) homogeneously anchored onto the silica and their synergistic effect. Detailed characterizations indicate stabilization of NPs through strong metal support interaction via electron donation from the metal to support. We identify that the support endowed with an amphoteric nature shows better performance. This strategy of making small metal-metal oxide NPs will open an avenue toward the rational development of efficient catalysts that would allow for other organic transformations under mild reaction conditions.

Conceptual design of the Hybrid Ring with superconducting linac.

The Hybrid Ring with a superconducting-linac injector as a highly flexible synchrotron radiation source to enable new experimental techniques and enhance many existing ones is proposed. It is designed to be operated with the coexistence of the storage (SR) bunches characterized by the performance of the storage ring, and the single-pass (SP) bunches characterized by the performance of the superconducting linac. Unique experiments can be performed by simultaneous use of the SR and SP beams, in addition to research with various experimental techniques utilizing the versatile SR beam and research in the field of ultrafast dynamics utilizing the ultrashort pulse of the SP beam. The extendability of the Hybrid Ring will allow it to be developed into a synchrotron radiation complex.

Femtosecond Charge Density Modulations in Photoexcited CuWO4.

Copper tungstate (CuWO4) is an important semiconductor with a sophisticated and debatable electronic structure that has a direct impact on its chemistry. Using the PAL-XFEL source, we study the electronic dynamics of photoexcited CuWO4. The Cu L3 X-ray absorption spectrum shifts to lower energy upon photoexcitation, which implies that the photoexcitation process from the oxygen valence band to the tungsten conduction band effectively increases the charge density on the Cu atoms. The decay time of this spectral change is 400 fs indicating that the increased charge density exists only for a very short time and relaxes electronically. The initial increased charge density gives rise to a structural change on a time scale longer than 200 ps.

A surface sensitive hard X-ray spectroscopic method applied to observe the surface layer reduction reaction of Co oxide to Co metal.

A simple and easy surface sensitive spectroscopic method using hard X-rays has been developed and applied to observe the surface oxide reduction reaction. The method named TREXS, Total REflection X-ray Spectroscopy, records the total reflection of incident X-rays at sample surfaces. The surface reduction reaction of Co oxide (Co3O4) to Co metal was successfully observed by in situ TREXS measurements with a surface sensitivity of ∼2 nm. The in situ TREXS measurements were performed under H2 flow of N2 balanced atmospheric pressure with increasing temperature. This method, in situ TREXS, will be a suitable and powerful tool to observe a variety of surface chemical reactions and consequently to understand catalytic processes under realistic operating conditions.

Nanoscale crack initiation and propagation in carbon fiber/epoxy composites using synchrotron: 3D image data.

Crack initiation and propagation in carbon fiber-reinforced plastic (CFRP) was observed in situ under the application of an opening load using nanoscopic synchrotron radiation X-ray computed tomography (nanoscopic SR X-CT) at a high spatial resolution of ∼50 nm. Two datasets of reconstructed and segmented images were produced in typical regions, namely in the thin and thick epoxy regions where the resin thickness between the adjacent carbon fibers was small and large, respectively. This novel study presents the first non-destructive three-dimensional (3D) visualization of resin deformation behavior around crack tips, and provides a valuable and unique insight for the future design of CFRPs.

Stable single platinum atoms trapped in sub-nanometer cavities in 12CaO·7Al2O3 for chemoselective hydrogenation of nitroarenes.

Single-atom catalysts (SACs) have attracted significant attention because they exhibit unique catalytic performance due to their ideal structure. However, maintaining atomically dispersed metal under high temperature, while achieving high catalytic activity remains a formidable challenge. In this work, we stabilize single platinum atoms within sub-nanometer surface cavities in well-defined 12CaO·7Al2O3 (C12A7) crystals through theoretical prediction and experimental process. This approach utilizes the interaction of isolated metal anions with the positively charged surface cavities of C12A7, which allows for severe reduction conditions up to 600 °C. The resulting catalyst is stable and highly active toward the selective hydrogenation of nitroarenes with a much higher turnover frequency (up to 25772 h-1) than well-studied Pt-based catalysts. The high activity and selectivity result from the formation of stable trapped single Pt atoms, which leads to heterolytic cleavage of hydrogen molecules in a reaction that involves the nitro group being selectively adsorbed on C12A7 surface.

Thermochemical formation of dioxins promoted by chromium chloride: In situ Cr- and Cl-XAFS analysis.

Chromium is commonly found in the flue gases and ashes of Municipal Solid Waste Incineration. It has been reported as an active catalyst for the formation of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/F) during de novo tests, yet its specific mode of action has remained unclear. This study aims to identify the effects of chromium chloride on the formation of PCDD/F and other chloro-aromatics and to elucidate the underlying reaction mechanisms. A series of de novo tests, conducted over a wide range of temperature (from 250 to 550 °C) and for four different oxygen contents (0, 5, 10, 20 %), confirmed the promoting effect of CrCl3 on the PCDD/F formation. In situ X-ray Absorption Fine Structure (XAFS) spectroscopy was applied to investigate the behavior of CrCl3 during heating, describing the entire picture of CrCl3-promoted formation pathways of dioxins. The effect of oxygen was studied by measuring XAFS spectra on samples heated at different oxygen concentrations. According to these spectra, chromium compounds play two key roles during dioxins formation: (a) chlorinating carbon, using chlorine derived from conversion of CrCl3 into Cr2O3, and further oxidation to Cr(VI), and (b) facilitating oxidative destruction of the carbon matrix, while reducing Cr(VI) to Cr2O3.

Photoinduced anisotropic distortion as the electron trapping site of tungsten trioxide by ultrafast W L1-edge X-ray absorption spectroscopy with full potential multiple scattering calculations.

Understanding the excited state of photocatalysts is significant to improve their activity for water splitting reaction. X-ray absorption fine structure (XAFS) spectroscopy in X-ray free electron lasers (XFEL) is a powerful method to address dynamic changes in electronic states and structures of photocatalysts in the excited state in ultrafast short time scales. The ultrafast atomic-scale local structural change in photoexcited WO3 was observed by W L1 edge XAFS spectroscopy using an XFEL. An anisotropic local distortion around the W atom could reproduce well the spectral features at a delay time of 100 ps after photoexcitation based on full potential multiple scattering calculations. The distortion involved the movement of W to shrink the shortest W-O bonds and elongate the longest one. The movement of the W atom could be explained by the filling of the dxy and dzx orbitals, which were originally located at the bottom of the conduction band with photoexcited electrons.

Direct observation of the electronic states of photoexcited hematite with ultrafast 2p3d X-ray absorption spectroscopy and resonant inelastic X-ray scattering.

Hematite, α-Fe2O3, is an important semiconductor for photoelectrochemical water splitting. Its low charge carrier mobility and the presence of midgap states provide favourable conditions for electron-hole recombination, hence affecting the semiconductor's photoelectrochemical efficiency. The nature of the excited state and charge carrier transport in hematite is strongly debated. In order to further understand the fundamental properties of the hematite photoexcited state, we conducted femtosecond 2p (L3) X-ray absorption (XAS) and 2p3d resonant inelastic scattering (RIXS) measurements on hematite thin-films at the Pohang Accelerator Laboratory X-ray Free Electron Laser (PAL-XFEL). The observed spectral changes and kinetic processes are in agreement with previous 3p XAS reports. The potential additional information that could be acquired from 2p3d RIXS experiments is also discussed.

Palladium-bearing intermetallic electride as an efficient and stable catalyst for Suzuki cross-coupling reactions.

Suzuki cross-coupling reactions catalyzed by palladium are powerful tools for the synthesis of functional organic compounds. Excellent catalytic activity and stability require negatively charged Pd species and the avoidance of metal leaching or clustering in a heterogeneous system. Here we report a Pd-based electride material, Y3Pd2, in which active Pd atoms are incorporated in a lattice together with Y. As evidenced from detailed characterization and density functional theory (DFT) calculations, Y3Pd2 realizes negatively charged Pd species, a low work function and a high carrier density, which are expected to be beneficial for the efficient Suzuki coupling reaction of activated aryl halides with various coupling partners under mild conditions. The catalytic activity of Y3Pd2 is ten times higher than that of pure Pd and the activation energy is lower by nearly 35%. The Y3Pd2 intermetallic electride catalyst also exhibited extremely good catalytic stability during long-term coupling reactions.

Low-Temperature Synthesis of Perovskite Oxynitride-Hydrides as Ammonia Synthesis Catalysts.

Mixed anionic materials such as oxyhydrides and oxynitrides have recently attracted significant attention due to their unique properties, such as fast hydride ion conduction, enhanced ferroelectrics, and catalytic activity. However, high temperature (≥800 °C) and/or complicated processes are required for the synthesis of these compounds. Here we report that a novel perovskite oxynitride-hydride, BaCeO3-xNyHz, can be directly synthesized by the reaction of CeO2 with Ba(NH2)2 at low temperatures (300-600 °C). BaCeO3-xNyHz, with and without transition metal nanoparticles, functions as an efficient catalyst for ammonia synthesis through the lattice N3- and H- ion-mediated Mars-van Krevelen mechanism, while ammonia synthesis occurs over conventional catalysts through a Langmuir-Hinshelwood mechanism with high energy barriers (85-121 kJ mol-1). As a consequence, the unique reaction mechanism leads to enhancement of the activity of BaCeO3-based catalysts by a factor of 8-218 and lowers the activation energy (46-62 kJ mol-1) for ammonia synthesis. Furthermore, isotopic experiments reveal that this catalyst shifts the rate-determining step for ammonia synthesis from N2 dissociation to N-H bond formation.

In situ TREXS Observation of Surface Reduction Reaction of NiO Film with ∼2 nm Surface Sensitivity.

X-ray absorption fine structure (XAFS) spectroscopy is one of the most widely used methods at synchrotron radiation facilities. XAFS gives us information on chemical states and local structures. Fundamentally, XAFS is bulk sensitive, not surface sensitive. If a surface sensitive XAFS method was available, surface chemical reactions can be observed under realistic conditions. Here, we report the development and present status of a type of surface sensitive x-ray spectroscopy, which is named total reflection x-ray spectroscopy, TREXS.

Finding Degradation Trigger Sites of Structural Materials for Airplanes Using X-Ray Microscopy.

Macroscopic properties of carbon fiber-reinforced plastic (CFRP) and environmental barrier coating (EBC), widely used for airplanes, can be deteriorated by local cracks or degradation ("trigger sites"). We have tried to find these trigger sites using x-ray microscopy (XM), which can provide the 2D or 3D images of the chemical states and microstructures. Crack initiation in CFRP was observed in a non-destructive manner in multi-scales (nm-mm). 3D chemical-state mapping of Yb in EBC was achieved with high resolution (<50 nm). In addition to XM, in-situ observations at high temperatures were conducted for obtaining complementary information. X-ray absorption spectroscopy (XAS) and x-ray diffraction (XRD) analysis were performed simultaneously up to 1773 K. Dynamic XAS with short time-resolution (<10 ns) was conducted to investigate changes in the local structure of metal. These approaches can help us identify degradation trigger sites in the materials.

Large Oblate Hemispheroidal Ruthenium Particles Supported on Calcium Amide as Efficient Catalysts for Ammonia Decomposition.

Ammonia decomposition is an important technology for extracting hydrogen from ammonia toward the realization of a hydrogen economy. Herein, it is reported that large oblate hemispheroidal Ru particles on Ca(NH2 )2 function as efficient catalysts for ammonia decomposition. The turnover frequency of Ru/Ca(NH2 )2 increased by two orders of magnitude when the Ru particle size was increased from 1.5 to 8.4 nm. More than 90 % ammonia decomposition was achieved over Ru/Ca(NH2 )2 with large oblate hemispheroidal Ru particles at 360 °C, which is comparable to that of alkali-promoted Ru catalysts with small Ru particle sizes. XAFS analyses revealed that Ru particles are immobilized on Ca(NH2 )2 by Ru-N bonds formed at the metal/support interface, which lead to oblate hemispheroidal Ru particles. Such a strong metal-support interaction in Ru/Ca(NH2 )2 is also substantiated by DFT calculations. The high activity of Ru/Ca(NH2 )2 with large Ru particles primarily originates from the shape and appropriate size of the Ru particles with a high density of active sites rather than the electron-donating ability of Ca(NH2 )2 .