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.

Mechanical and Optical Properties of Cr2O3 Thin Films Grown by Atomic Layer Deposition Method Using Cr(thd)3 and Ozone.

Cr2O3 thin films were grown on a Si (1 0 0) substrate using Cr(thd)3 and O3 by atomic layer deposition (ALD) at substrate temperatures (TG) from 200 to 300 °C. X-ray amorphous films were deposited at a TG ≤ 225 °C, whereas at higher temperatures (TG ≥ 250 °C), the eskolaite phase was observed in the films. The growth rate of the films increased from 0.003 to 0.01 nm/cycle by increasing TG from 200 to 275 °C. The relatively low growth rate of Cr(thd)3-O3 makes it appropriate for the ALD of precisely controllable solid solution-type ternary-component thin films. The Ti-doped Cr2O3 film showed higher hardness (16.7 GPa) compared with that of the undoped film (12.8 GPa) with similar thickness. The band gap values of the pure Cr2O3 corresponding to the indirect transition model showed no dependence on TG; however, doping the Cr2O3 with Ti decreased its band gap energy value from 3.1 to 2.2 eV.

Hardness, Modulus, and Refractive Index of Plasma-Assisted Atomic-Layer-Deposited Hafnium Oxide Thin Films Doped with Aluminum Oxide.

Coatings with tunable refractive index and high mechanical resilience are useful in optical systems. In this work, thin films of HfO2 doped with Al2O3 were deposited on silicon at 300 °C by using plasma-enhanced atomic layer deposition (PE-ALD). The mainly amorphous 60-80 nm thick films consisted Al in the range of 2 to 26 at.%. The refractive indexes varied from 1.69 to 2.08 at the wavelength of 632 nm, and they consistently depended on the composition. The differences were higher in the UV spectral region. At the same time, the hardness of the films was from 12-15 GPa; the modulus was in the range of 160-180 GPa; and the mechanical properties did not have a good correlation with the deposited compositions. The deposition conditions, element contents, and refractive indexes at respective wavelengths were correlated. The results indicated that it is possible to tune optical properties and retain mechanical properties of atomic layer-deposited thin films of HfO2 with Al2O3 as doping oxide. Such films could be used as mechanically resilient and optically tunable coatings in, for instance, micro- or nano-electromechanical systems or transparent displays.

Nanoindentation of Chromium Oxide Possessing Superior Hardness among Atomic-Layer-Deposited Oxides.

Chromium (III) oxide is a technologically interesting material with attractive chemical, catalytic, magnetic and mechanical properties. It can be produced by different chemical and physical methods, for instance, by metal-organic chemical vapor deposition, thermal decomposition of chromium nitrate Cr(NO3)3 or ammonium dichromate (NH4)2Cr2O7, magnetron sputtering and atomic layer deposition. The latter method was used in the current work to deposit Cr2O3 thin films with thicknesses from 28 to 400 nm at deposition temperatures from 330 to 465 °C. The phase composition, crystallite size, hardness and modulus of elasticity were measured. The deposited Cr2O3 thin films had different structures from X-ray amorphous to crystalline α-Cr2O3 (eskolaite) structures. The averaged hardness of the films on SiO2 glass substrate varied from 12 to 22 GPa and the moduli were in the range of 76-180 GPa, as determined by nanoindentation. Lower values included some influence from a softer deposition substrate. The results indicate that Cr2O3 could be a promising material as a mechanically protective thin film applicable, for instance, in micro-electromechanical devices.

Solution Structure and Conformational Flexibility in the Active State of the Orange Carotenoid Protein: Part I. Small-Angle Scattering.

Orange carotenoid proteins (OCPs) are photoswitchable macromolecules playing an important role in nonphotochemical quenching of excess energy in cyanobacterial light harvesting. Upon absorption of a blue photon (450-500 nm), OCPs undergo a structural change from the ground state OCPO to the active state OCPR, but high-resolution structures of the active state OCPR are not yet available. Here, we use small-angle scattering methods combined with simulation tools to determine low-resolution structures of the active state at low protein concentrations via two approaches: first, directly by in situ illumination of wild-type OCP achieving a turnover to the active state of >90% and second, by using the mutant OCPW288A anticipated to mimic the active state structure. Data fits assuming the shape of an ellipsoid yield three ellipsoidal radii of about 9, 29, and 51 ± 1 Å, in the case of the ground state OCPO. In the active state, however, the molecule becomes somewhat narrower with the two smaller radii being 9 and only 19 ± 3 Å, while the third dimension of the ellipsoid is significantly elongated to 85-92 ± 5 Å. Reconstitutions of the active state structure corroborate that OCPR is significantly elongated compared to the ground state OCPO and characterized by a separation of the N-terminal and C-terminal domains with unfolded N-terminal extension. By direct comparison of small-angle scattering data, we directly show that the mutant OCPW288A can be used as a structural analogue of the active state OCPR. The small-angle experiments are repeated for OCPO and the mutant OCPW288A at high protein concentrations of 50-65 mg/mL required for neutron spectroscopy investigating the molecular dynamics of OCP (see accompanying paper). The results reveal that the OCPO and OCPW288A samples for dynamics experiments are preferentially dimeric and widely resemble the structures of the ground and active states of OCP, respectively. This enables us to properly characterize the molecular dynamics of both states of OCP in the accompanying paper.

Functionalization of Titanium Alloy Surface by Graphene Nanoplatelets and Metal Oxides: Corrosion Inhibition.

Corrosion inhibition of metallic substrates is an important and crucial step for great economical as well as environmental savings. In this paper, we introduce an extra thin effective corrosion inhibitive material having layered structure designed for protection and functionalization of Ti Grade 5 alloy substrates. The coating consists of a first layer made of thin graphene nanoplatelets, on top of which a multilayer Al2O3 and TiO2 films is applied by low-temperature atomic layer deposition. The amorphous structure of the metal oxide films was confirmed by micro-Raman and X-ray diffraction analysis. Corrosion inhibition ability of the prepared coatings was analyzed by open circuit potential, potentiodynamic plot and by voltammetric analysis, in aqueous potassium bromide solution. The open circuit potential of the graphene-metal oxide coated substrate showed much passive nature than bare substrate or graphene coated or only metal oxide coated substrates. The localized corrosion potential of the graphene-metal oxide coated, only metal oxide coated, and bare substrates were found 5.5, 3.0, and 1.1 V, respectively. In addition, corrosion current density values of the graphene-metal oxide and only metal oxide coated substrates showed much more passive nature than the bare and graphene coated substrates. Long immersion test in the salt solution further clarified the effective corrosion inhibition of the graphene-metal oxide coated substrate. The analyzed results reflect that the graphene-metal oxide films can be used to prepare better and effective corrosion inhibition coatings for the Ti Grade 5 alloy to increase their lifetime.

Structures of polynuclear complexes of palladium(II) and platinum(II) formed by slow hydrolysis in acidic aqueous solution.

The aqua ions of palladium(II) and platinum(II) undergo extremely slow hydrolysis in strongly acidic aqueous solution, resulting in polynuclear complexes. The size and structures of these species have been determined by EXAFS and small angle X-ray scattering, SAXS. For palladium(II), the EXAFS data show that the Pd-O and Pd···Pd distances are identical to those of crystalline palladium(II) oxide, but the intensities of the Pd···Pd distances in the Fourier transform at 3.04 and 3.42 Å are significantly lower compared to those of crystalline PdO. Furthermore, no Pd···Pd distances beyond 4 Å are observed. These observations strongly indicate that the polynuclear palladium(II) complexes are oxido- and hydroxido-bridged species with the same core structure as solid palladium(II) oxide. Based on the number of Pd···Pd distances, as derived from the EXAFS data, their size can be estimated to be approximately two unit cells, or ca. 1.0 nm(3). For platinum(II), EXAFS data of the polynuclear species formed in the slow hydrolysis process show Pt-O and Pt···Pt distances identical to those of amorphous platinum(II) oxide, precipitating from the solution studied. The Pt···Pt distances are somewhat different from those reported for crystalline platinum(II) oxide. The polynuclear platinum(II) complexes have a similar structure to the palladium ones, but they are somewhat larger, with an estimated diameter of 1.5-3.0 nm. It has not been possible to precipitate any of these species by ultracentrifugation. They are detectable by SAXS, indicating diameters between 0.7 and 2 nm, in excellent agreement with the EXAFS observations. The number of oxido- relative to hydroxido bridges will increase with increasing size of the complex. The charge of the complexes will remain about the same, +4, at growth, with approximate formulas [Pd10O4(OH)8(H2O)12](4+) and [Pt14O8(OH)8(H2O)12](4+) for complexes with a size of 2 and 3 unit cells of the corresponding solid metal oxide, respectively. Their high ionic charge in acidic aqueous solution will result in a stabilizing hydration shell.

Alkoxide-based precursors for direct drawing of metal oxide micro- and nanofibres.

The invention of electrospinning has solved the problem of producing micro- and nanoscaled metal oxide fibres in bulk quantities. However, until now no methods have been available for preparing a single nanofibre of a metal oxide. In this work, the direct drawing method was successfully applied to produce metal oxide (SnO2, TiO2, ZrO2, HfO2 and CeO2) fibres with a high aspect ratio (up to 10 000) and a diameter as small as 200 nm. The sol-gel processing includes consumption of precursors obtained from alkoxides by aqueous or non-aqueous polymerization. Shear thinning of the precursors enables pulling a material into a fibre. This rheological behaviour can be explained by sliding of particles owing to external forces. Transmission (propagation) of light along microscaled fibres and their excellent surface morphology suggest that metal oxide nanofibres can be directly drawn from sol precursors for use in integrated photonic systems.