Synthesis and properties of titanomagnetite (Fe(3-x)Ti(x)O4) nanoparticles: a tunable solid-state Fe(II/III) redox system.

Titanomagnetite (Fe(3-x)Ti(x)O(4)) nanoparticles were synthesized by room temperature aqueous precipitation, in which Ti(IV) replaces Fe(III) and is charge compensated by conversion of Fe(III) to Fe(II) in the unit cell. A comprehensive suite of tools was used to probe composition, structure, and magnetic properties down to site-occupancy level, emphasizing distribution and accessibility of Fe(II) as a function of x. Synthesis of nanoparticles in the range 0≤x≤0.6 was attempted; Ti, total Fe and Fe(II) content were verified by chemical analysis. TEM indicated homogeneous spherical 9-12 nm particles. µ-XRD and Mössbauer spectroscopy on anoxic aqueous suspensions verified the inverse spinel structure and Ti(IV) incorporation in the unit cell up to x≤0.38, based on Fe(II)/Fe(III) ratio deduced from the unit cell edge and Mössbauer spectra. Nanoparticles with a higher value of x possessed a minor amorphous secondary Fe(II)/Ti(IV) phase. XANES/EXAFS indicated Ti(IV) incorporation in the octahedral sublattice (B-site) and proportional increases in Fe(II)/Fe(III) ratio. XA/XMCD indicated that increases arise from increasing B-site Fe(II), and that these charge-balancing equivalents segregate to those B-sites near particle surfaces. Dissolution studies showed that this segregation persists after release of Fe(II) into solution, in amounts systematically proportional to x and thus the Fe(II)/Fe(III) ratio. A mechanistic reaction model was developed entailing mobile B-site Fe(II) supplying a highly interactive surface phase that undergoes interfacial electron transfer with oxidants in solution, sustained by outward Fe(II) migration from particle interiors and concurrent inward migration of charge-balancing cationic vacancies in a ratio of 3:1.

Reduction of Tc(VII) by Fe(II) sorbed on Al (hydr)oxides.

Under oxic conditions, Tc exists as the soluble, weakly sorbing pertechnetate [TcO4-] anion. The reduced form of technetium, Tc(IV), is stable in anoxic environments and is sparingly soluble as TcO2 x nH2O(s). Here we investigate the heterogeneous reduction of Tc(VII) by Fe(II) adsorbed on Al (hydr)oxides [diaspore (alpha-AlOOH) and corundum (alpha-Al2O3)]. Experiments were performed to study the kinetics of Tc(VII) reduction, examine changes in Fe surface speciation during Tc(VII) reduction (Mössbauer spectroscopy), and identify the nature of Tc(IV)-containing reaction products (X-ray absorption spectroscopy). We found that Tc(VII) was completely reduced by adsorbed Fe(II) within 11 (diaspore suspension) and 4 days (corundum suspension). Mössbauer measurements revealed thatthe Fe(II) signal became less intense with Tc(VII) reduction and was accompanied by an increase in the intensity of the Fe(III) doublet and magnetically ordered Fe(III) sextet signals. Tc-EXAFS spectroscopy revealed that the final heterogeneous redox product on corundum was similar to Tc(IV) oxyhydroxide, TcO2 x nH2O.

A short working distance multiple crystal x-ray spectrometer.

For x-ray spot sizes of a few tens of microns or smaller, a millimeter-sized flat analyzer crystal placed approximately 1 cm from the sample will exhibit high energy resolution while subtending a collection solid angle comparable to that of a typical spherically bent crystal analyzer (SBCA) at much larger working distances. Based on this observation and a nonfocusing geometry for the analyzer optic, we have constructed and tested a short working distance (SWD) multicrystal x-ray spectrometer. This prototype instrument has a maximum effective collection solid angle of 0.14 sr, comparable to that of 17 SBCA at 1 m working distance. We find good agreement with prior work for measurements of the Mn Kbeta x-ray emission and resonant inelastic x-ray scattering for MnO, and also for measurements of the x-ray absorption near-edge structure for Dy metal using Lalpha(2) partial-fluorescence yield detection. We discuss future applications at third- and fourth-generation light sources. For concentrated samples, the extremely large collection angle of SWD spectrometers will permit collection of high-resolution x-ray emission spectra with a single pulse of the Linac Coherent Light Source. The range of applications of SWD spectrometers and traditional multi-SBCA instruments has some overlap, but also is significantly complementary.

Structural observations of time dependent oscillatory behavior of CuIICl2 solutions measured via extended X-ray absorption fine structure.

Cell surface ECTO-NOX proteins exhibit a clock-related, temperature-independent entrainable pattern of periodic (24 min) oscillations in the rate of oxidation of NAD(P)H. Aqueous solutions of copper salts also oxidize NAD(P)H with a similar temperature-independent pattern. For both, five maxima are observed, two of which are separated by 6 min and the remaining three are separated by 4.5 min. In D2O, the pattern is retained but the period length is proportionately increased to 30 min in direct relationship to the 30 h circadian day observed with D2O-grown organisms. With copper solutions, periodic changes in redox potential correlate precisely with the periodic changes in the rates of NAD(P)H oxidation. Consequently, the local environment of the Cu2+ ion in copper chloride solutions was investigated by X-ray absorption spectroscopy. Detailed extended X-ray absorption fine structure (EXAFS) analyses revealed a pattern of oscillations closely resembling those of the copper-catalyzed oxidation of NADH. With CuCl2 in D2O, a pattern with a period length of 30 min was observed. The findings suggest a regular pattern of distortion in the axial and/or equatorial oxygen atoms of the coordinated water molecules which correlate with redox potential changes sufficient to oxidize NADH. A metastable equilibrium condition in the ratio of ortho to para nuclear spin orientation of the water associated hydrogen atoms would be kinetically consistent with a 24-30 min timeframe. The temperature independence of the biological clock can thus be understood as the consequence of a physical rather than a chemical basis for the timing events.

Negligible magnetism in excellent structural quality Cr(x)Ti(1-x)O(2) anatase: contrast with high-T(C) ferromagnetism in structurally defective Cr(x)Ti(1-x)O(2).

We reexamine the mechanism of ferromagnetism in doped TiO(2) anatase, using epitaxial Cr:TiO(2) with excellent structural quality as a model system. In contrast to highly oriented but defective Cr:TiO(2) (approximately 0.5 micro(b)/Cr), these structurally superior single crystal films exhibit negligible ferromagnetism. Similar results were obtained for Co:TiO(2). We show for the first time that charge-compensating oxygen vacancies alone, as predicted by F-center mediated exchange, are not sufficient to activate ferromagnetism. Instead, the onset of ferromagnetism correlates with the presence of structural defects.

Intrinsic ferromagnetism in insulating cobalt doped anatase TiO2.

Using complementary experiments we show that the room temperature ferromagnetism observed in anatase Co:TiO(2) films is not carrier mediated, but coexists with the dielectric state. TEM and x-ray absorption spectroscopy reveal a solid solution of Co in anatase, where Co is not metallic but in the +2 state substituting for Ti. Measurements at 300 K yield a M(S) of 1.1 mu(B)/Co atom, while all films are highly insulating. The evidence of intrinsic ferromagnetism in the dielectric ground state of Co:TiO(2) leads to new considerations for the origin of ferromagnetism in transition metal doped oxides.

Analytical electron microscopy study of high Tc superconductor YBa2Cu3O7.

The high Tc superconducting material YBa2Cu3O7 shows a complex relationship between microstructure and oxygen content, which are controlled by length of heat treatment, atmosphere, and quench rate. An AEM investigation studying changes in the oxygen near edge features was undertaken. Electron energy loss spectroscopy (EELS) measurements have the important advantage that they can be made on single crystal grains, allowing orientation-dependent studies. Both ion-milled and crushed samples with varying O2 content were analyzed. The structure of YBaCu3O7 was determined by neutron diffraction to be orthorhombic with distinct Cu-O chains along the b-axis as well as Cu-O planes in the a-b plane. Therefore, by looking for a crystallographic dependence of the oxygen K-edge one might be able to distinguish inequivalent oxygen atoms by their core level binding energy and correlate site occupancy with varying O2 content. The EELS results on the oxygen K-edge are strongly dependent on oxygen content, most noticeably when the c-axis is parallel to the electron beam.

X-ray filter assembly for fluorescence measurements of x-ray absorption fine structure.

Fluorescence detection, in principle, permits the detection of the extended x-ray absorption fine structure (EXAFS) of more dilute atoms than can be obtained in absorption. To take advantage of this it is necessary, in practice, to eliminate the background that normally accompanies the fluorescence signal. We describe an x-ray filter assembly that accomplishes this purpose. The unique characteristic of the assembly is a slit system that minimizes the fluorescence background from the filter. The theory of the slit assembly is presented and is found to agree with measurements made on the Fe EXAFS of a dilute sample. The filter assembly has a better effective counting rate in this case than that of a crystal monochromator design.