ABSTRACT
Deep eutectic solvents are a new class of green solvents that are being explored as an alternative for used nuclear fuel and critical material recycling. However, there is a paucity of knowledge regarding metal behavior in them. This paper explores the underlying chemistry of rare-earth elements in choline chloride-based deep eutectic solvents by using a multi-technique spectroscopic methodology. Results show that speciation is highly dependent on the choice of the hydrogen-bond donor. Collected EXAFS data showed Ln3+ coordination with ethylene glycol and urea in their respective solvents and coordination with chloride in the lactic acid system. Generalized coordination environments were determined to be [LnL4-5], [LnL7-10], and [LnL5-6] in the ethylene glycol, urea, and lactic acid systems, respectively. Collected UV/vis spectra for Nd3+ and Er3+ showed variations with changing solvents, showing that Ln-Cl interactions do not dominate in these systems. Luminescence studies were consistent, showing varying emission spectra with varying solvent systems. The shortest luminescent lifetimes were observed in the choline chloride-ethylene glycol deep eutectic solvent, suggesting coordination through O-H groups. Combining all collected data allowed Eu3+ coordination geometries to be assigned.
ABSTRACT
A large change is observed in the magnetic properties of amorphous Fe-Zr thin films sputtered at different Ar pressures. The change depends on the composition of the alloys and at compositions near 60 at.% Fe, for example, the magnetisation measured at 10 kOe increases 30-fold with an increase in the Ar pressure from 2 to 10 mTorr. The magnetic properties are well explained by a combination of two phenomena-superparamagnetism and spin glass behaviours-and the large change is partly related to the number density of a magnetically correlated region. Examinations of the microstructure by X-ray diffraction, transmission electron microscopy, and X-ray absorption fine structure spectroscopy reveal no appreciable difference in it as a function of the Ar pressure. This indicates that even a very slight change in the microstructure can greatly affect the magnetic properties of amorphous Fe-Zr thin films, thereby opening up the possibility of employing the magnetic properties of amorphous alloys for the characterisation of amorphous microstructures.
ABSTRACT
A microprobe system has been installed on the nanoprobe/XAFS beamline (BL8C) at PLS-II, South Korea. Owing to the reproducible switch of the gap of the in-vacuum undulator (IVU), the intense and brilliant hard X-ray beam of an IVU can be used in X-ray fluorescence (XRF) and X-ray absorption fine-structure (XAFS) experiments. For high-spatial-resolution microprobe experiments a Kirkpatrick-Baez mirror system has been used to focus the millimeter-sized X-ray beam to a micrometer-sized beam. The performance of this system was examined by a combination of micro-XRF imaging and micro-XAFS of a beetle wing. These results indicate that the microprobe system of the BL8C can be used to obtain the distributions of trace elements and chemical and structural information of complex materials.
ABSTRACT
The oxygen evolution reaction (OER) is considered a major bottleneck in the overall water electrolysis process. In this work, highly active manganese oxide nano-catalysts were synthesized via hot injection. Facile surface treatment generated Mn(III) species on monodisperse 10 nm MnO nanocrystals (NCs). Size dependency of MnO NCs on OER activity was also investigated. Surprisingly, the partially oxidized MnO NCs only required 530 mV @ 5 mA cm(-2) under near neutral conditions.
ABSTRACT
An in-vacuum undulator (IVU) with a tapered configuration was installed in the 8C nanoprobe/XAFS beamlime (BL8C) of the Pohang Light Source in Korea for hard X-ray nanoprobe and X-ray absorption fine-structure (XAFS) experiments. It has been operated in planar mode for the nanoprobe experiments, while gap-scan and tapered modes have been used alternatively for XAFS experiments. To examine the features of the BL8C IVU for XAFS experiments, spectral distributions were obtained theoretically and experimentally as functions of the gap and gap taper. Beam profiles at a cross section of the X-ray beam were acquired using a slit to visualize the intensity distributions which depend on the gap, degree of tapering and harmonic energies. To demonstrate the effect of tapering around the lower limit of the third-harmonic energy, V K-edge XAFS spectra were obtained in each mode. Owing to the large X-ray intensity variation around this energy, XAFS spectra of the planar and gap-scan modes show considerable spectral distortions in comparison with the tapered mode. This indicates that the tapered mode, owing to the smooth X-ray intensity profile at the expense of the highest and most stable intensity, can be an alternative for XAFS experiments where the gap-scan mode gives a considerable intensity variation; it is also suitable for quick-XAFS scanning.
ABSTRACT
The development of a water oxidation catalyst has been a demanding challenge in realizing water splitting systems. The asymmetric geometry and flexible ligation of the biological Mn4CaO5 cluster are important properties for the function of photosystem II, and these properties can be applied to the design of new inorganic water oxidation catalysts. We identified a new crystal structure, Mn3(PO4)2·3H2O, that precipitates spontaneously in aqueous solution at room temperature and demonstrated its high catalytic performance under neutral conditions. The bulky phosphate polyhedron induces a less-ordered Mn geometry in Mn3(PO4)2·3H2O. Computational analysis indicated that the structural flexibility in Mn3(PO4)2·3H2O could stabilize the Jahn-Teller-distorted Mn(III) and thus facilitate Mn(II) oxidation. This study provides valuable insights into the interplay between atomic structure and catalytic activity.
