Understanding the Interplay of Vacancy, Cation, and Charge Ordering in the Tunable Sc2VO5+δ Defect Fluorite System.

We report the synthesis, structure, and redox behavior of the cation-ordered tetragonal Sc2VO5+δ defect fluorite superstructure previously thought to be the oxygen precise A3+2B4+O5 phase. Four synthesis routes in oxidative, reductive, and inert atmospheres are demonstrated. Ex situ and in situ powder X-ray and neutron diffraction analyses reveal vanadium disproportionation reactions. The structure-reaction map illustrates the oxygen-dependent competition between the tetragonal cation and anion ordered Sc2VO5+δ and the disordered cubic Sc2VO5+δ' (δ < δ' ≤ 0.5) phases as a function of temperature. Oxidation states and oxide stoichiometries were determined with DC magnetometry and XANES experiments. The tetragonal cation ordered Sc2VO5+δ phase with δ = -0.15(2) for as-synthesized samples reveals vanadium charge ordering. V3+ and V4+ cations occupy octahedral sites, whereas V5+ predominantly occupies a tetrahedral site. The paramagnetic 8g{V3+/4+}4 clusters are isolated by diamagnetic 2cV5+ cations. At temperatures below 500 °C the 8g{V3+/4+}4 clusters can be topotactically fine-tuned with varying V3+/V4+ ratios. Above 600 °C the tetragonal structure oxidizes to the cubic Sc2VO5+δ' fluorite phase-its disordered competitor. The investigation of the cation- and anion-ordered Sc-V-O phases, their formation, and thermal stability is important for the design of low-temperature solid state oxide ion conductors and vacancy structures.

Investigation of Factors That Affect the Oxidation State of Ce in the Garnet-Type Structure.

Oxide materials that adopt the garnet-type structure (X3A2B3O12) have received attention for a wide variety of applications, one of which is as potential wasteforms for the sequestration of radioactive actinide elements. The actinides are able to be accommodated in the eight-coordinate X site of the garnet structure. This study focuses on the investigation of Ce substitution into the X site as a surrogate for Pu because of their similar chemical properties. This is accomplished through analysis of the Y3- zCe zAlFe4O12 (0.05 ⩽ z ⩽ 0.20) materials. The effects of the Ce concentration, oxidation state of the Ce in the starting materials, annealing environment, and cooling rate on the local structure and Ce and Fe oxidation states were investigated through analysis of the powder X-ray diffraction patterns and Ce L3-edge and Fe K-edge X-ray absorption spectroscopy (XANES) spectra. Analysis of Ce L3-edge XANES spectra indicated that Ce was present as both 3+ and 4+ oxidation states, the ratios of which depended on the synthetic conditions. The largest concentration of Ce4+ was observed when the materials were postannealed at 800 °C following synthesis of the materials at 1400 °C. Variations in the Ce oxidation state are the result of the temperature-dependent Ce3+/Ce4+ redox couple, with Ce4+ being favored at lower temperatures. Analysis of the Fe K-edge spectra indicated that Fe was only present in the 3+ oxidation state and the Fe coordination number increased with increasing concentration of Ce4+, which is necessary to charge balance the system. The materials in this study can be described as an oxygen-intercalated garnet-type structure with the formula Y3- zCe zAlFe4O12+δ.

A one-step synthesis of rare-earth phosphate-borosilicate glass composites.

A new 1-step method for synthesizing glass-ceramic composites consisting of rare earth phosphates (REPO4) dispersed in borosilicate glass (BG) is reported herein as an alternative to the 2-step approach that is traditionally used. The effect of annealing time and annealing temperature on the formation of the 1-step glass-ceramic composites was investigated. Backscattered electron images and energy dispersive X-ray maps were collected to observe the morphology and chemical distribution in the glass-ceramic composites. X-ray diffraction was used to study the long-range order and X-ray absorption near edge spectroscopy was used to study the local environment of La, Y, P and Si. All analyses showed glass-ceramic composites made by the 1 and 2-step methods were similar to each other except for the Si L2,3-edge XANES spectra, which showed a slight change between the glass-ceramic composite materials made by the different synthesis methods. Xenotime-type phosphates (YPO4) were observed to be more soluble in the borosilicate glass than the monazite-type phosphates (LaPO4). This was attributed to the difference in the field strength of the rare-earth ions as a result of the difference in the ionic radii. Glass-ceramic composites made by the 1-step method were shown to form in 1 day at 1100 °C and in 3 days at 1000 °C without a significant change in glass or ceramic composition compared to the 1-step composite synthesized at 1100 °C for 3 days.

Construction of a Semiconductor-Biological Interface for Solar Energy Conversion: p-Doped Silicon/Photosystem I/Zinc Oxide.

The interface between photoactive biological materials with two distinct semiconducting electrodes is challenging both to develop and analyze. Building off of our previous work using films of photosystem I (PSI) on p-doped silicon, we have deposited a crystalline zinc oxide (ZnO) anode using confined-plume chemical deposition (CPCD). We demonstrate the ability of CPCD to deposit crystalline ZnO without damage to the PSI biomaterial. Using electrochemical techniques, we were able to probe this complex semiconductor-biological interface. Finally, as a proof of concept, a solid-state photovoltaic device consisting of p-doped silicon, PSI, ZnO, and ITO was constructed and evaluated.

Nanodiamond nanofluids for enhanced thermal conductivity.

Deaggregation of oxidized ultradispersed diamond (UDD) in dimethylsulfoxide followed by reaction with glycidol monomer, purification via aqueous dialysis, and dispersion in ethylene glycol (EG) base fluid affords nanodiamond (ND)-poly(glycidol) polymer brush:EG nanofluids exhibiting 12% thermal conductivity enhancement at a ND loading of 0.9 vol %. Deaggregation of UDD in the presence of oleic acid/octane followed by dispersion in light mineral oil and evaporative removal of octane gives ND·oleic acid:mineral oil dispersions exhibiting 11% thermal conductivity enhancement at a ND loading of 1.9 vol %. Average particle sizes of ND additives, determined by dynamic light scattering, are, respectively, ca. 11 nm (in H2O) and 18 nm (in toluene). Observed thermal conductivity enhancements outperform enhancement effects calculated using Maxwell's effective medium approximation by 2- to 4-fold. Covalent ND surface modification gives 2-fold greater thermal conductivity enhancement than ND surface modification via hydrogen-bonding interactions at similar concentrations. Stable, static ND:mineral oil dispersions are reported for the first time.