Structure and properties of Gd3Ge4: the orthorhombic RE3Ge4 structures revisited (RE = Y, Tb-Tm)

The new binary compound Gd(3)Ge(4) has been synthesized and its structure has been determined from single-crystal X-ray diffraction. Gd(3)Ge(4) crystallizes in the orthorhombic space group Cmcm (No. 63) with unit cell parameters a = 4.0953(11) A, b = 10.735(3) A, c = 14.335(4) A, and Z = 4. Its structure can be described as corrugated layers of germanium atoms with gadolinium atoms enclosed between them. The bonding arrangement in Gd(3)Ge(4) can also be derived from that of the known compound GdGe (CrB type) through cleavage of the (infinity)(1)[Ge(2)] zigzag chains in GdGe and a subsequent insertion of an extra germanium atom between the resulting triangular fragments. Formally, these characteristics represent isotypism with the Er(3)Ge(4) type (Pearson's oC28). However, re-examination of the crystallography in the whole RE(3)Ge(4) series (RE = Y, Tb-Tm) revealed discrepancies and called into question the accuracy of the originally determined structures. This necessitated a new rationalization of the bonding, which is provided in the context of a comparative discussion concerning both the original and revised structure models, along with an analysis of the trends across the series. The temperature dependence of the magnetic susceptibility of Gd(3)Ge(4) shows that it is paramagnetic at room temperature and undergoes antiferromagnetic ordering below 29 K. Magnetization, resistivity, and calorimetry data for several other members of the RE(3)Ge(4) family are presented as well.     

Fabrication of silica-coated magnetic nanoparticles with highly photoluminescent lanthanide probes

Bi-functional nanoparticles (NPs) that consist of silica-coated magnetic cores and luminescent lanthanide (Ln) ions anchored on the silica surface via organic linker molecules are reported. Compared to individual Ln ions, the hybrid NPs show a drastically enhanced photoluminescence due to the efficient ligand-to-metal energy transfer in the Ln-loaded NPs: the new bi-functional NPs could be used in a variety of biological applications involving magnetic separation and optical detection.     

Lead Isotopic Constraints on the Provenance of Antarctic Dust and Atmospheric Circulation Patterns Prior to the Mid-Brunhes Event (~430 kyr ago)

A lead (Pb) isotopic record, covering the two oldest glacial–interglacial cycles (~572 to 801 kyr ago) characterized by lukewarm interglacials in the European Project for Ice Coring in Antarctica Dome C ice core, provides evidence for dust provenance in central East Antarctic ice prior to the Mid-Brunhes Event (MBE), ~430 kyr ago. Combined with published post-MBE data, distinct isotopic compositions, coupled with isotope mixing model results, suggest Patagonia/Tierra del Fuego (TdF) as the most important sources of dust during both pre-MBE and post-MBE cold and intermediate glacial periods. During interglacials, central-western Argentina emerges as a major contributor, resulting from reduced dust supply from Patagonia/TdF after the MBE, contrasting to the persistent dominance of dust from Patagonia/TdF before the MBE. The data also show a small fraction of volcanic Pb transferred from extra-Antarctic volcanoes during post-MBE interglacials, as opposed to abundant transfer prior to the MBE. These differences are most likely attributed to the enhanced wet removal efficiency with the hydrological cycle intensified over the Southern Ocean, associated with a poleward shift of the southern westerly winds (SWW) during warmer post-MBE interglacials, and vice versa during cooler pre-MBE ones. Our results highlight sensitive responses of the SWW and the associated atmospheric conditions to stepwise Antarctic warming.     

Low-Pressure Plasma Reactor with a Cylindrical Electrode for Eco-friendly Processing in the Semiconductor Industry

Thin film deposition processes emit large amounts of NF₃ and by-product particles, which are of great concerns in the semiconductor industry, from the environmental and economic points of view. With an objective to overcome these concerns, plasmas are generated from a cylindrical reactor placed before a vacuum pump. The discharge stability is evaluated by monitoring the changes in the plasma images with the pressure. By using a particle sampler and a particle trap, the size and quantity of the by-product particles are compared during plasma-on and plasma-off. The effects of adding O₂ and H₂O to the by-products of the NF₃ abatement process are investigated by analyzing the spectra obtained with a Fourier transform infrared spectroscopy. Further, the H₂O flow rate is optimized for the highest destruction and removal efficiency of NF₃. Finally, the applicability of our device to the after-treatment equipment is discussed.     

A Highly Stable and Magnetically Recyclable Nanocatalyst System: Mesoporous Silica Spheres Embedded with FeCo/Graphitic Shell Magnetic Nanoparticles and Pt Nanocatalysts

We have developed a highly stable and magnetically recyclable nanocatalyst system for alkene hydrogenation. The materials are composed of mesoporous silica spheres (MSS) embedded with FeCo/graphitic shell (FeCo/GC) magnetic nanoparticles and Pt nanocatalysts (Pt‐FeCo/GC@MSS). The Pt‐FeCo/GC@MSS have superparamagnetism at room temperature and show type IV isotherm typical for mesoporous silica, thereby ensuring a large enough inner space (surface area of 235.3 m² g^?1, pore volume of 0.165 cm³ g^?1, and pore diameter of 2.8 nm) to undergo catalytic reactions. We have shown that the Pt‐FeCo/GC@MSS system readily converts cyclohexene into cyclohexane, which is the only product isolated and Pt‐FeCo/GC@MSS can be seperated very quickly by an external magnetic field after the catalytic reaction is finished. We have demonstrated that the recycled Pt‐FeCo/GC@MSS can be reused further for the same hydrogenation reaction at least four times without loss in the initial catalytic activity.     

Vacancy ordering in SmGe2-x and GdGe2-x (x = 0.33): structure and properties of two Sm3Ge5 polymorphs and of Gd3Ge5

The crystal structures and the magnetic properties of three new binary rare-earth intermetallic phases are reported. alpha-Sm3Ge5 and beta-Sm3Ge5 and Gd3Ge5 have been prepared from the corresponding elements through high-temperature reactions using the flux-growth method. The structures of the three compounds have been established using single-crystal X-ray diffraction: alpha-Sm3Ge5 crystallizes with its own type in the hexagonal space group P2c (No. 190) with cell parameters a = 6.9238(11) A, c = 8.491(3) A, and Z = 2, whereas beta-Sm3Ge5 adopts the face-centered orthorhombic Y3Ge5 type with space group Fdd2 (No. 43) and with cell parameters a = 5.8281(6) A, b = 17.476(2) A, c = 13.785(2) A, and Z = 8. The orthorhombic Gd3Ge5 with cell parameters a = 5.784(2) A, b = 17.355(6) A, and c = 13.785(5) A is isostructural with beta-Sm3Ge5. The structures of the title compounds can be described as AlB(2) and alpha-ThSi2 derivatives with long-range ordering of the germanium vacancies. Temperature-dependent DC magnetization (5-300 K) measurements show evidence of antiferromagnetic ordering below ca. 30 and 10 K for alpha-Sm3Ge5 and beta-Sm3Ge5, respectively. Gd3Ge5 undergoes two successive magnetic transitions below ca. 15 and 11 K. The temperature dependence of the resistivity and heat capacity of Gd3Ge5 are discussed as well.     

Heterostructured nanohybrid of zinc oxide-montmorillonite clay

We have synthesized heterostructured zinc oxide-aluminosilicate nanohybrids through a hydrothermal reaction between the colloidal suspension of exfoliated montmorillonite nanosheets and the sol solution of zinc acetate. According to X-ray diffraction, N2 adsorption-desorption isotherm, and field emission-scanning electron microscopic analyses, it was found that the intercalation of zinc oxide nanoparticles expands the basal spacing of the host montmorillonite clay, and the crystallites of the nanohybrids are assembled to form a house-of-cards structure. From UV-vis spectroscopic investigation, it becomes certain that calcined nanohybrid contains two kinds of the zinc oxide species in the interlayer space of host lattice and in mesopores formed by the house-of-cards type stacking of the crystallites. Zn K-edge X-ray absorption near-edge structure/extended X-ray absorption fine structure analyses clearly demonstrate that guest species in the nanohybrids exist as nanocrystalline zinc oxides with wurzite-type structure.