Superstructure of Fe5-xGeTe2 Determined by Te K-Edge Extended X-ray Absorption Fine Structure and Te Kα X-ray Fluorescence Holography.

The local structure of the two-dimensional van der Waals material, Fe5-xGeTe2, which exhibits unique structural/magnetic phase transitions, was investigated by Te K-edge extended X-ray absorption fine structure (EXAFS) and Te Kα X-ray fluorescence holography (XFH) over a wide temperature range. The formation of a trimer of Te atoms at low temperatures has been fully explored using these methods. An increase in the Te-Fe distance at approximately 150 K was suggested by EXAFS and presumably indicates the formation of a Te trimer. Moreover, XFH displayed clear atomic images of Te atoms. Additionally, the distance between the Te atoms shortened, as confirmed from the atomic images reconstructed from XFH, indicating the formation of a trimer of Te atoms, i.e., a charge-ordered superstructure. Furthermore, Te Kα XFH provided unambiguous atomic images of Fe atoms occupying the Fe1 site; the images were not clearly observed in the Ge Kα XFH that was previously reported because of the low occupancy of Fe and Ge atoms. In this study, EXAFS and XFH clearly showed the local structure around the Te atom; in particular, the formation of Te trimers caused by charge-ordered phase transitions was clearly confirmed. The charge-ordered phase transition is fully discussed based on the structural variation at low temperatures, as established from EXAFS and XFH.

Interfacial Structure of Pt(110) Electrode during Hydrogen Evolution Reaction in Alkaline Solutions.

In alkaline solutions, interfacial cations affect the hydrogen evolution reaction (HER) activity of platinum electrodes. However, the effects of cations on the HER activity have not been previously investigated based on interfacial structures. In situ surface X-ray diffraction was performed on Pt(110), of which the HER activity is the highest in the low-index planes of Pt, at hydrogen evolution potentials in alkaline solutions, and revealed the interfacial structure of alkali metal cations (Li+ and Cs+). The interfacial structure of the Pt(110) electrode changed reversibly depending on the electrode potential. In the LiOH solution, where the HER activity was higher, the densely packed water layer in the electrical double layer acted as a hydrogen supplier. In the CsOH solution, where the HER activity was lower, the Cs+ cations were aligned in the missing rows of the 1 × 2 reconstructed Pt(110) surface, suggesting that the Cs+ hindered water from accessing the surface, resulting in a lower HER activity.

Tailoring the active site for the oxygen evolution reaction on a Pt electrode.

Highly active electrocatalysts for the oxygen evolution reaction (OER) are essential to improve the efficiency of water electrolysis. The properties of OER active sites on single-crystal Pt electrodes were examined herein. The OER is markedly enhanced by repeated oxidative and reductive potential cycles on the Pt(111) surface. The OER activity on Pt(111) is nine times higher in the third cycle than that before the potential cycles. OER activation by potential cycling depends on the (111) terrace width, with wider (111) terraces significantly enhancing the OER. The oxidation/reduction of the Pt(111) surface produces atomic-sized vacancies on the terraces that activate the OER. Structural analysis using X-ray diffraction reveals that the active sites formed by potential cycling are defects in the second subsurface Pt layer. Potential cycling induces the bowl-shaped roughening of the electrode surface, wherein high-coordination number Pt atoms at the bottom of the cavities activate the OER.

Energy-resolved beam-monitoring system for undulator radiation using scattering from a chemical-vapor-deposition diamond film.

With low-emittance synchrotron radiation rings, introducing accurate x-ray beams to a sample is difficult, and ensuring that the direction of the undulator beam is stable is essential. However, measuring the centroid of the undulator photon beam at the beamline front-end (FE) is difficult because the soft x-ray radiation is contaminated by the bending magnets upstream and downstream of the undulator. The x-ray beam position monitors (XBPMs), based on the interaction with the halo of undulator radiation, cannot estimate the centroid of the beam, and they cannot eliminate the effects of the bending magnets. To solve this problem, we have developed an energy-resolved beam-monitoring system for undulator radiation with the scattering from a diamond thin film deposited by chemical vapor deposition (CVD) in this study. An undulator x-ray beam is irradiated onto this film, and its elastic and Compton scattering are observed through a 50 µm-diameter pinhole. A beam spot is detected through a pinhole camera system using a direct-detection-type charge-coupled device camera with energy resolution. The peak of the first-order harmonic of the undulator radiation is selectively visualized to measure the centroid of the undulator radiation, as well as the spectrum. The proposed system using a CVD diamond film can provide accurate position information for a photon beam exiting the FE.

A middle energy-bandwidth X-ray monochromator for high-flux synchrotron diffraction: revisiting asymmetrically cut silicon crystals.

To supply the growing demand for high photon flux in synchrotron science including surface diffraction, a middle energy-bandwidth monochromator covering the 10-4 to 10-3 range has been adapted by applying an asymmetric diffraction geometry to a cryogenically cooled silicon 111 double-crystal monochromator used as a standard for the undulator source at SPring-8. The asymmetric geometry provides a great advantage with its ability to configure flux gains over a wide energy range by simply changing the asymmetry angle, while the angular divergence of the exit beam remains unchanged. A monolithic design with three faces has been employed, having one symmetrically cut and another two asymmetrically cut surfaces relative to the same atomic plane, maintaining cooling efficiency and the capability of quickly changing the reflection surface. With the asymmetric geometry, an X-ray flux greater than 1014 photons s-1 was available around 12 keV. A maximum gain of 2.5 was obtained relative to the standard symmetric condition.

Facile preparation of hybrid thin films composed of spin-crossover nanoparticles and carbon nanotubes for electrical memory devices.

In this study, organic solvent-dispersible nanoparticles of an FeII-1,2,4-triazole spin-crossover complex were synthesized. On mixing the suspension of the spin-crossover nanoparticles with a solution of single-walled carbon nanotubes (SWCNTs), the nanoparticles were strongly adsorbed on the hydrophobic SWCNT bundles, resulting in hybrid network structures. Variable temperature DC electrical conductivity measurements of the hybrid network thin films demonstrated that the conductivities of the composite films were switched by the spin transition of the nanoparticles.

Effect of hydrophobic cations on the oxygen reduction reaction on single‒crystal platinum electrodes.

Highly active catalysts for the oxygen reduction reaction are essential for the widespread and economically viable use of polymer electrolyte fuel cells. Here we report the oxygen reduction reaction activities of single‒crystal platinum electrodes in acidic solutions containing tetraalkylammonium cations with different alkyl chain lengths. The high hydrophobicity of a tetraalkylammonium cation with a longer alkyl chain enhances the oxygen reduction reaction activity. The activity on Pt(111) in the presence of tetra‒n‒hexylammonium cation is eight times as high as that without this cation, which is comparable to the activities on Pt3Co(111) and Pt3Ni(111) electrodes. Hydrophobic cations and their hydration shells destabilize the adsorbed hydroxide and adsorbed water. The hydrophobic characteristics of non‒specifically adsorbed cations can prevent the adsorption of poisoning species on the platinum electrode and form a highly efficient interface for the oxygen reduction reaction.

Air/Liquid Interfacial Nanoassembly of Molecular Building Blocks into Preferentially Oriented Porous Organic Nanosheet Crystals via Hydrogen Bonding.

Nanosheets with highly regulated nanopores are ultimately thin functional materials for diverse applications including molecular separation and detection, catalysis, and energy conversion and storage. However, their availability has hitherto been restricted to layered parent materials, covalently bonded sheets, which are layered via relatively weak electrostatic interactions. Here, we report a rational bottom-up methodology that enables nanosheet creation beyond the layered systems. We employ the air/liquid interface to assemble a triphenylbenzene derivative into perfectly oriented highly crystalline noncovalent-bonded organic nanosheets under ambient conditions. Each molecular building unit connects laterally by hydrogen bonding, endowing the nanosheets with size- and position-regulated permanent nanoporosity, as established by in situ synchrotron X-ray surface crystallography and gas sorption measurements. Notably, the nanosheets are constructed specifically by interfacial synthesis, which suppresses the intrinsic complex interpenetrated structure of the bulk crystal. Moreover, they possess exceptional long-term and thermal stability and are easily transferrable to numerous substrates without loss of structural integrity. Our work shows the power of interfacial synthesis using a suitably chosen molecular component to create two-dimensional (2D) nanoassemblies not accessible by conventional bulk crystal exfoliation techniques.

Real-time observation of interfacial ions during electrocrystallization.

Understanding the electrocrystallization mechanisms of metal cations is of importance for many industrial and scientific fields. We have determined the transitional structures during underpotential deposition (upd) of various metal cations on Au(111) electrode using time-resolved surface X-ray diffraction and step-scan IR spectroscopy. At the initial stage of upd, a characteristic intensity transient appears in the time-resolved crystal truncation rod depending on metal cations. Metal cations with relatively high coordination energies of hydration water are deposited in two steps: first, the hydrated metal cations approached the surface and are metastably located at the outer Helmholtz plane, then they are deposited via the destruction of the hydration shell. However, Tl+ and Ag+, which have low hydration energy, are rapidly adsorbed on Au(111) electrode without any metastable states of dehydration. Therefore, the deposition rate is strongly related to the coordination energy of the hydration water. Metal cations strongly interacting with the counter coadsorbed anions such as Cu2+ in sulfuric acid causes the deposition rate to be slower because of the formation of complexes.

Interfacial Structure of PtNi Surface Alloy on Pt(111) Electrode for Oxygen Reduction Reaction.

The interfacial structure and activity for the oxygen reduction reaction (ORR) were investigated on a PtNi surface alloy on a Pt(111) electrode (PtNi/Pt(111)). The PtNi surface alloy was prepared by thermal annealing of Ni2+ modified on Pt(111) at 573-803 K. After optimizing the alloying temperature and the amount of added Ni, the ORR current density of PtNi/Pt(111) at 0.9 V (reversible hydrogen electrode) is enhanced 9.5 times compared with that of Pt(111), and the activity is decreased by 24% after 1000 potential cycles. The atomic composition and subsurface structure of PtNi/Pt(111) were determined by in situ infrared reflection-absorption spectroscopy and X-ray diffraction. The surface contains a (111)-oriented Pt-skin and the subsurface of the 2nd-5th layers of the PtNi alloy contains less than 11% Ni atoms. The layer spacings of the surface alloy layers are slightly expanded compared with those of bare Pt(111). Homogeneous alloying with a small amount of Ni in the subsurface layers achieves the high ORR activity and durability.

New x-ray pink-beam profile monitor system for the SPring-8 beamline front-end.

A new beam profile monitoring system for the small X-ray beam exiting from the SPring-8 front-end was developed and tested at BL13XU. This system is intended as a screen monitor and also as a position monitor even at beam currents of 100 mA by using photoluminescence of a chemical vapor deposition-grown diamond film. To cope with the challenge that the spatial distribution of the photoluminescence in the vertical direction is too flat to detect the beam centroid within a limited narrow aperture, a filter was installed that absorbs the fundamental harmonic concentrated in the beam center, which resulted in "de-flattening" of the vertical distribution. For the measurement, the filter crossed the photon beam vertically at high speed to withstand the intense heat flux of the undulator pink-beam. A transient thermal analysis, which can simulate the movement of the irradiation position with time, was conducted to determine the appropriate configuration and the required moving speed of the filter to avoid accidental melting. In a demonstration experiment, the vertically separated beam profile could be successfully observed for a 0.8 × 0.8 mm(2) beam shaped by an XY slit and with a fundamental energy of 18.48 keV. The vertical beam centroid could be detected with a resolution of less than 0.1 mm.

Large-aperture two-dimensional x-ray refractive mosaic lenses.

Lenses with high numerical aperture are required for images with very high spatial resolution, which is difficult to realize in the x-ray range because of low-refraction-index decrement and relatively high absorption of x-rays in the material. However, such an aperture can be realized by means of a mosaic lens, as shown in this work.

Direct Estimation of the Surface Location of Immobilized Functional Groups for Concerted Catalysis Using a Probe Molecule.

The location of active sites during concerted catalysis by a metal complex and tertiary amine on a SiO2 surface is discussed based on the interaction between the functionalized SiO2 surface and a probe molecule, p-formyl phenylboronic acid. The interactions of the probe molecule with the surface functionalities, diamine ligand, and tertiary amine, were analyzed by FT-IR and solid-state (13)C and (11)B MAS NMR. For the catalyst exhibiting high 1,4-addition activity, the diamine ligand and tertiary amine base exist in closer proximity than in the catalyst with low activity.

Thin films of spin-crossover coordination polymers with large thermal hysteresis loops prepared by nanoparticle spin coating.

This communication describes the synthesis of spin-crossover nanoparticles, which can disperse in various organic solvents without an excess amount of surfactants. The nanoparticles form homogeneous thin films on substrates by spin coating. The films show abrupt spin transitions with large thermal hysteresis loops.

Effect of non-specifically adsorbed ions on the surface oxidation of Pt(111).

The oxidation processes of a Pt(111) electrode in alkaline electrolytes depend on non-specifically adsorbed ions according to in situ X-ray diffraction and infrared spectroscopic measurements. In an aqueous solution of LiOH, an OHad adlayer is formed in the first oxidation step of the Pt(111) electrode as a result of the strong interaction between Li(+) and OHad , whereas Pt oxidation proceeds without OHad formation in CsOH solution. Structural analysis by X-ray diffraction indicates that Li(+) is strongly protective against surface roughening caused by subsurface oxidation. Although Cs(+) is situated near the Pt surface, the weak protective effect of Cs(+) results in irreversible surface roughening due to subsurface oxidation.