Reusable magnetic mixture of CuFe2O4-Fe2O3 and TiO2 for photocatalytic degradation of pesticides in water.

Photocatalysis is a promising treatment method to remove pollutants from water. TiO2-P25 is a commercially available model photocatalyst, which very efficiently degrades organic pollutants under UVA light exposure. However, the collection and the recovery of TiO2-P25 from cleaned water poses significant difficulties, severely limiting its usability. To address this challenge, we have prepared a sintered mixture of TiO2-P25 nanomaterials and magnetic CuFe2O4-Fe2O3 nanocomposites. The mixture material was shown to contain spinel ferrite, hematite and maghemite structures, copper predominantly in Cu2+ and iron predominantly in Fe3+ state. The CuFe2O4-Fe2O3 and TiO2-P25 mixture demonstrated magnetic collectability from processed water and photocatalytic activity, which was evidenced through the successful photodegradation of the herbicide 2,4-D. Our findings suggest that the sintered mixture of CuFe2O4-Fe2O3 and TiO2-P25 holds a promise for improving photocatalytic water treatment, with the potential to overcome current photocatalyst recovery issues.

Impact of Ge Doping on Structural and Magnetic Ordering in RMnxGa3 and R4Mn1-xGa12-yGey (R = Tb, Dy; x ≤ 0.25, y ≈ 1.0-3.3).

Single crystals of RMnxGa3 and their new quaternary derivatives R4Mn1-xGa12-yGey (R = Tb, Dy, x ≤ 0.25, y ≈ 1.0-3.3) were grown from a Ga flux. The compounds are derivatives of cubic RGa3 phases, with Mn atoms filling the Ga6 voids. RMnxGa3 formally adopts a cubic ABO3 perovskite structure, in which the presence of Mn atoms results in a shift of the neighboring Ga atoms from their ideal position. A partial substitution of Ga by Ge leads to a higher Mn content, resulting in structural ordering of the latter and the formation of the superstructure phases R4Mn1-xGa12-yGey, which can be formally described in the Y4PdGa12 structure type. The presence of Mn vacancies, which was observed for R = Tb, and Ga/Ge mixing lead to a noticeable deviation from the idealized structure. The compounds contain two magnetic sublattices: the R sublattice, which orders antiferromagnetically near 20 K, and the Mn sublattice, which orders ferromagnetically at TC = 125-225 K with the Ge doping resulting in higher TC. The two sublattices are not independent, as the Mn sublattice induces partial ferromagnetic ordering of the rare earth atoms below TC, at least for the Ge-doped phases. Near TN, both magnetic susceptibility and heat capacity reveal complex behavior, indicating changes in magnetic structures below TN.

Bonding and Suppression of a Magnetic Phase Transition in EuMn2P2.

Electrons in solids often adopt complex patterns of chemical bonding driven by the competition between energy gains from covalency and delocalization, and energy costs of double occupation to satisfy Pauli exclusion, with multiple intermediate states in the transition between highly localized, and magnetic, and delocalized, and nonmagnetic limits. Herein, we report a chemical pressure-driven transition from a proper Mn magnetic ordering phase transition to a Mn magnetic phase crossover in EuMn2P2 the limiting end member of the EuMn2X2 (X = Sb, As, P) family of layered materials. This loss of a magnetic ordering occurs despite EuMn2P2 remaining an insulator at all temperatures, and with a phase transition to long-range Eu antiferromagnetic order at TN ≈ 17 K. The absence of a Mn magnetic phase transition contrasts with the formation of long-range Mn order at T ≈ 130 K in isoelectronic EuMn2Sb2 and EuMn2As2. Temperature-dependent specific heat and 31P NMR measurements provide evidence for the development of short-range Mn magnetic correlations from T ≈ 250-100 K, interpreted as a precursor to covalent bond formation. Density functional theory calculations demonstrate an unusual sensitivity of the band structure to the details of the imposed Mn and Eu magnetic order, with an antiferromagnetic Mn arrangement required to recapitulate an insulating state. Our results imply a picture in which long-range Mn magnetic order is suppressed by chemical pressure, but that antiferromagnetic correlations persist, narrowing bands and producing an insulating state.

Memory Effects in Nanolaminates of Hafnium and Iron Oxide Films Structured by Atomic Layer Deposition.

HfO2 and Fe2O3 thin films and laminated stacks were grown by atomic layer deposition at 350 °C from hafnium tetrachloride, ferrocene, and ozone. Nonlinear, saturating, and hysteretic magnetization was recorded in the films. Magnetization was expectedly dominated by increasing the content of Fe2O3. However, coercive force could also be enhanced by the choice of appropriate ratios of HfO2 and Fe2O3 in nanolaminated structures. Saturation magnetization was observed in the measurement temperature range of 5-350 K, decreasing towards higher temperatures and increasing with the films' thicknesses and crystal growth. Coercive force tended to increase with a decrease in the thickness of crystallized layers. The films containing insulating HfO2 layers grown alternately with magnetic Fe2O3 exhibited abilities to both switch resistively and magnetize at room temperature. Resistive switching was unipolar in all the oxides mounted between Ti and TiN electrodes.

Cubic Iron Core-Shell Nanoparticles Functionalized to Obtain High-Performance MRI Contrast Agents.

Nanoparticles with SiO2 coating were synthesized to have a cubic iron core. These were found to have saturation magnetization very close to the highest possible value of any iron-containing nanoparticles and the bulk iron saturation magnetization. The in vitro toxicology studies show that they are highly biocompatible and possess better MRI contrast agent potential than iron oxide NPs.

Mechanical and Magnetic Properties of Double Layered Nanostructures of Tin and Zirconium Oxides Grown by Atomic Layer Deposition.

Double layered stacks of ZrO2 and SnO2 films, aiming at the synthesis of thin magnetic and elastic material layers, were grown by atomic layer deposition to thicknesses in the range of 20-25 nm at 300 °C from ZrCl4, SnI4, H2O, and O3 as precursors. The as-deposited nanostructures consisted of a metastable tetragonal polymorph of ZrO2, and a stable tetragonal phase of SnO2, with complementary minor reflections from the orthorhombic polymorph of SnO2. The hardness and elastic modulus of the stacks depended on the order of the constituent oxide films, reaching 15 and 171 GPa, respectively, in the case of top SnO2 layers. Nonlinear saturative magnetization could be induced in the stacks with coercive fields up to 130 Oe.

Atomic layer deposited nanolaminates of zirconium oxide and manganese oxide from manganese(III)acetylacetonate and ozone.

Atomic layer deposition method was used to grow thin films consisting of ZrO2and MnOxlayers. Magnetic and electric properties were studied of films deposited at 300 °C. Some deposition characteristics of the manganese(III)acetylacetonate and ozone process were investigated, such as the dependence of growth rate on the deposition temperature and film crystallinity. All films were partly crystalline in their as-deposited state. Zirconium oxide contained cubic and tetragonal phases of ZrO2, while the manganese oxide was shown to consist of cubic Mn2O3and tetragonal Mn3O4phases. All the films exhibited nonlinear saturative magnetization with hysteresis, as well as resistive switching characteristics.

Atomic layer deposition of superparamagnetic ruthenium-doped iron oxide thin film.

Due to the several applications of biosensors, such as magnetic hyperthermia and magnetic resonance imaging, the use of superparamagnetic nanoparticles or thin films for preparing biosensors has increased greatly. We report herein on a strategy to fabricate a nanostructure composed of superparamagnetic thin films. Ruthenium-doped iron oxide thin films were deposited by using atomic layer deposition at 270 and 360 °C. FeCl3 and Ru(EtCp)2 were used as metal precursors and H2O/O2 as the oxygen precursor. Doping with ruthenium helps to lower the formation temperature of hematite (α-Fe2O3). Ruthenium content was changed from 0.42 at% up to 29.7 at%. Ru-doped films had a nano-crystallized structure of hematite with nanocrystal sizes from 4.4 up to 7.8 nm. Magnetization at room temperature was studied in iron oxide and Ru-doped iron oxide films. A new finding is a demonstration that in a Ru-doped iron oxide thin film superparamagnetic behavior of nanocrystalline materials (α-Fe2O3) is observed with the maximum magnetic coercive force H c of 3 kOe. Increasing Ru content increased crystallite size of hematite and resulted in a lower blocking temperature.

Atomic layer deposition and properties of ZrO2/Fe2O3 thin films.

Thin solid films consisting of ZrO2 and Fe2O3 were grown by atomic layer deposition (ALD) at 400 °C. Metastable phases of ZrO2 were stabilized by Fe2O3 doping. The number of alternating ZrO2 and Fe2O3 deposition cycles were varied in order to achieve films with different cation ratios. The influence of annealing on the composition and structure of the thin films was investigated. Additionally, the influence of composition and structure on electrical and magnetic properties was studied. Several samples exhibited a measurable saturation magnetization and most of the samples exhibited a charge polarization. Both phenomena were observed in the sample with a Zr/Fe atomic ratio of 2.0.

Magnetic and Electrical Performance of Atomic Layer Deposited Iron Erbium Oxide Thin Films.

Mixed films of a high-permittivity oxide, Er2O3, and a magnetic material, Fe2O3, were grown by atomic layer deposition on silicon and titanium nitride at 375 °C using erbium diketonate, ferrocene, and ozone as precursors. Crystalline phases of erbium and iron oxides were formed. Growth into three-dimensional trenched structures was demonstrated. A structure deposited using tens to hundreds subsequent cycles for both constituent metal oxide layers promoted both charge polarization and saturative magnetization compared to those in the more homogeneously mixed films.

Nonfrustrated interlayer order and its relevance to the Bose-Einstein condensation of magnons in BaCuSi2O6.

Han purple (BaCuSi2O6) is not only an ancient pigment, but also a valuable model material for studying Bose-Einstein condensation of magnons in high magnetic fields. Using precise low-temperature structural data and extensive density-functional calculations, we elucidate magnetic couplings in this compound. The resulting magnetic model comprises two types of nonequivalent spin dimers, in excellent agreement with the Cu63,65 nuclear magnetic resonance data. We further argue that leading interdimer couplings connect the upper site of one dimer to the bottom site of the contiguous dimer, and not the upper-to-upper and bottom-to-bottom sites, as assumed previously. This finding is verified by inelastic neutron scattering data and implies the lack of frustration between the layers of spin dimers in BaCuSi2O6, thus challenging existing theories of the two-dimensional-like Bose-Einstein condensation of magnons in this compound.

High resolution 11B NMR of magnesium diboride using cryogenic magic angle spinning.

Static and magic-angle spinning (11)B nuclear magnetic resonance (NMR) data at 4.7 T and 8.5 T have been obtained under cryogenic conditions on a diluted sample of magnesium diboride powder in the normal and superconducting state. The data provide accurate information on the magnetic shift and longitudinal relaxation time down to a temperature of 8 K, with a resolution improvement over the entire temperature range. The onset of superconductivity is unaffected by the sample rotation, as revealed by a steep variation of the magnetic shift just below the critical temperature.

Solid-state NMR spectroscopy of molecular hydrogen trapped inside an open-cage fullerene.

Solid-state 1H experiments were performed an open-cage fullerene hosting molecular hydrogen. The anisotropy of the molecular hydrogen rotation was studied by double-quantum magic-angle-spinning NMR. The time scale of the molecular hydrogen rotation was estimated by spin-lattice relaxation measurements as a function of temperature.