The transport and deposition of uranium under hydrothermal conditions in the Earth’s crust has been a subject of ongoing study but is yet to be completely understood. In addition, there is little known about the fate of nuclear waste, consisting of uranium from spent fuel and other radioactive materials, upon storage in repositories or in nuclear reactor facilities. Because the nuclear waste often comes in contact with aqueous fluids in storage environments, studies of uranyl complexation with chloride and other ligands in aqueous media, to high temperature and pressure conditions, are needed. The primary purpose of this study was to investigate the speciation of aqueous uranyl (VI) chloride complexes, in solutions having a 0.05 M uranyl concentration and [Cl] concentrations ranging from 0.2 M to 6 M, under hydrothermal conditions. The aqueous uranyl chloride complexes in the samples were studied using Raman spectroscopy and the hydrothermal diamond anvil cell (HDAC), at temperatures up to 500 °C and pressures up to ~ 0.5 GPa. The uranyl bond stretching band feature occurring in the ~810 to 870 cm-1 region was fitted using the Voigt peak shape to determine the speciation of the equilibrium uranyl chloride complexes present in the samples. As expected, the n integer value of the UO2Cln+2-n complex species increases with the increase in temperature and chloride concentration, generally trending toward charge neutrality at high temperatures.

The mixed-valence oxide Co3O4 nanoparticles, having the normal spinel structure, possess large surface area, active-site surface adsorption properties, and fast ion diffusivities. Consequently, they are widely used in lithium-ion batteries, as well as for gas sensing and heterogeneous catalysis applications. In our research, we use a two-step method to synthesize Co3O4–based core-shell nanoparticles (CSNs). Cobalt oxide (Co3O4) nanoparticles were successfully synthesized using a wet synthesis method employing KOH and cobalt acetate. Manganese was incorporated into the Co3O4 structure to synthesize inverted Co3O4@MnxCo3-xO4 CSNs using a hydrothermal method. By adjustment of pH value, we obtained two different morphologies of CSNs, one resulting in pseudo-spherical and octahedron-shaped nanoparticles (PS type) whereas the second type predominantly have a nanoplate (NP type) morphology. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and x-ray photoelectron spectroscopy (XPS) have been performed in order to determine the morphological and structural properties of our CSNs, whereas the magnetic properties have been characterized using a superconducting quantum interference device (SQUID) magnetometer. XRD and TEM results show that the CSNs have the same spinel crystal structure throughout the core and shell with an average particle size of ∼19.8 nm. Our Co3O4 nanoparticles, as measured prior to CSN formation, are shown to be antiferromagnetic (AFM) in nature as shown by the magnetization data. Our SQUID data indicate that the core-shell nanoparticles have both AFM (due to the Co3O4 core) and ferrimagnetic properties (of the shell) with a coercivity field of 300 Oe and 150 Oe at 5 K for the PS and NP samples, respectively. The magnetization vs temperature data show a spin order-disorder transition at ∼33 K and a superparamagnetic blocking temperature of ∼90 K for both batches.

We report on the exploration of perpendicular exchange bias in iron platinum/nickel oxide (FePt/NiO) bilayer thin films grown using pulsed laser deposition (PLD) on MgO (100) substrates. Exchange bias is an important property for giant magnetoresistance, and, as such has promise for applications in spin valves, magnetic sensors and magnetic random access memory. The magnetic L10 phase of FePt is known for having high perpendicular magnetic anisotropy, tunable coercivity/grain size and large magnetic storage density. The FePt layer was first deposited directly on MgO, followed by the deposition of the NiO layer on top of the FePt layer. The coercivity of the L10 FePt layer was tuned during growth to form a hard or soft magnetic layer. The FePt/NiO thin films grown for this study exhibit perpendicular exchange bias at 5K, as quantified using our SQUID measurements. XRD confirms parallel plane ordering between the MgO (200), FePt (002) and NiO (111) atomic planes while cross sectional TEM confirms the epitaxial growth of L10-FePt(001)<100>//MgO(100)<001> and the preferential growth of NiO on top of the FePt. Films of only FePt were grown to examine the surface architecture of the ferromagnetic layer and thus the interface of the FePt/NiO bilayer. The results from our XRD, TEM and magnetometry characterization of the FePt films and FePt/NiO bilayer thin films will be discussed.

Magnetic core–shell nanoparticles (CSNs) have potential applications in spintronic devices, drug delivery systems, and magnetic random access memory. By use of our hydrothermal nano-phase epitaxy method, we have accomplished synthesis of novel, well-ordered α-Cr2O3@α-Mn0.35Cr1.65O2.94 inverted CSNs. XRD and TEM analyses show a core–shell structure with corundum phase throughout the core and shell with a minimal amount of interface defects. TEM-EDX and XPS data show Mn having the +2 oxidation state in the shell of the CSNs. Magnetization measurements at 5 K show a weak coercivity (H C) value of 8 Oe and an exchange bias field (H E) of 293 Oe. Ab initio calculations show that Mn incorporation in α-Cr2O3 results in narrowing of the energy band gap, substantiated by UV–Vis measurements, and half metallic behavior in case of Mn(III) substitution. Our calculations substantiate that Mn substitution in α-Cr2O3 results in a combination of antiferromagnetic and weak ferrimagnetic character of our CSNs.

Periodic mesoporous materials possess high surface to volume ratio and nano-scale sized pores, making them potential candidates for heterogeneous catalysis, ion exchange, gas sensing and other applications. In this study, we use in situ small angle x-ray scattering (SAXS) and molecular dynamics (MD) simulations to investigate the mechanical and hydrothermal stability properties of periodic mesoporous SBA-15 silica and SBA-15 type aluminosilica (Al-SBA-15) to extreme conditions. The mesoporous SBA-15 silica and Al-SBA-15 aluminosilica possess amorphous frameworks and have similar pore size distribution (pore size ∼9-10 nm). The in situ SAXS measurements were made at the B1 beamline, at the Cornell High Energy Synchrotron Source (CHESS). The mesoporous SBA-15 silica and Al-SBA-15 aluminosilica specimens were loaded in a diamond anvil cell (DAC) for pressure measurements, and, separately, with water in the DAC for hydrothermal measurements to high P-T conditions (to 255 °C and ∼ 114 MPa). Analyses of the pressure-dependent SAXS data show that the mesoporous Al-SBA-15 aluminosilica is substantially more mechanically stable than the SBA-15 silica. Hydrothermal measurements show a small net swelling of the framework at elevated P-T conditions, due to dissolution of water into the pore walls. Under elevated P-T conditions, the Al-SBA-15 aluminosilica shows significantly greater hydrothermal stability than the SBA-15 silica. Our MD simulations show that the bulk modulus value of periodic mesoporous SBA-15 silica varies exponentially with percentage porosity. Molecular dynamics simulations are being made in order to better understand how the pore architecture and the chemical composition of the host structure govern the stability properties of the mesoporous materials.

Group 6 transition metal oxide thin films are in large demand for photocatalysis, heterogeneous catalysis, fuel cell, battery and electronic applications. Pulsed laser deposition offers an inexpensive method for the preparation of nanostructured thin films that may be suitable for heterogeneous catalysis. We have synthesized molybdenum oxide thin films using two types of pulsed laser deposition (PLD). The first method utilizes femtosecond laser-based PLD (f-PLD) while the second method uses an excimer (nanosecond) laser-based PLD (n-PLD). The PLD films have been deposited using f-PLD and, separately, n-PLD on glass and silicon substrates and subsequently annealed to 450 °C for up to 20 hours in air using a Linkam stage. SEM, XRD and Raman spectroscopic characterization shows that the f-PLD films are substantially more textured and partially crystalline prior to annealing whereas the n-PLD-grown thin films are much smoother and predominantly amorphous. A 3-dimensional nano-crystalline structure is evident in the post-annealed f-PLD synthesized thin films, which is desirable for catalytic applications. XPS elemental analysis shows that the stoichiometry of the f-PLD and n-PLD thin films is consistent with the presence of MoO2 and MoO3. Our results are discussed in terms of thin film growth models suitable for f-PLD vs n-PLD.

Nanostructured anatase TiO2 is a promising material for gas sensing and photocatalysis. In order to modify its catalytic properties, the lanthanide (Ln) ions Eu3+, Gd3+, Nd3+ and Yb3+ were precipitated on the surface of TiO2 nanoparticles (NPs) by hydrothermal treatment. Results from Raman spectroscopy and X-ray diffraction (XRD) measurements show that the anatase structure of the TiO2 nanoparticles was preserved after hydrothermal treatment. SEM and TEM show a heterogeneous distribution in size and a nanocrystallite morphology of the TiO2 NPs (∼ 14 nm in size) and EDX confirmed the presence of the Ln-ion surface doping after hydrothermal treatment. An increase in photoluminescence (PL) was observed for the Ln-surface-doped TiO2 NPs when measurements were made in forming gas (5% H2 + 95% Ar) at 520 °C. In contrast, the PL measurements made at room temperature did not show any noticeable difference in forming gas or in ambient air. Our temperature-dependent PL results obtained in different gas environments are consistent with modification of oxygen-vacancies and hole-defects due to a combination of hydrothermal treatment and surface Ln-doping.

A hydrothermal reactor has been used for surface doping of anatase TiO2 nanoparticles (∼ 13 nm across) with Eu3+ ions in aqueous fluids to 370 °C and ∼20 MPa. XRD and Raman measurements made both before and after hydrothermal treatment with Eu show that the anatase structure of the TiO2 nanoparticles (NPs) is preserved. SEM imaging, combined with XRD indicates that the size and overall morphology of the TiO2 nanoparticles is preserved subsequent to hydrothermal treatment in the presence of Eu. The photoluminescence occurring in the 400 to ∼700 nm range of the (as prepared) Eu surface-doped TiO2 NPs are red-shifted by ∼ 50 nm and reduced in intensity relative to the photoluminescence of TiO2 NPs.

In situ x-ray absorption spectroscopy (XAS) measurements were made on Fe3O4 nanoparticles in supercritical aqueous fluids to 500 °C in order to study their reactivity with Co2+ aqua ions and to investigate the structural properties of the reacted nanoparticles. The analyses of the x-ray absorption near edge structure (XANES) of XAS indicate that reactivity of Fe3O4 nanoparticles with Co2+ ions is minimal to 200 °C but becomes significant in the 250–500 °C temperature range. XANES and angular momentum projected density of states (l-DOS) calculations were carried out using the FEFF8.2 code and analyses were made using multi-peak fitting to determine the origin of the features exhibited in the spectra.

We have measured polarization-dependent Fe K-edge XAFS spectra from an epitaxially-grown Al/Fe/Al/ZnSe/GaAs(001) sample using synchrotron radiation. The Fourier-transformed XAFS spectra were fit up to four coordination shells simultaneously using theoretical spectra generated with FEFF 6. Our results reveal a small tetragonal distortion of the bcc α-Fe film lattice towards a contraction in the film growth direction (c=2.863 Å and a=2.874 Å; bulk a=2.867 Å). The anomalous tetragonal distortion is consistent with a model involving substantial interdifussion of Fe and Al, leading to Fe1−xAlx alloy formation localized in the interface regions.

In this paper, we discuss the use of x-ray absorption fine structure (XAFS) techniques for the determination of structure of metal complexes in fluid inclusions heated to elevated temperatures. Analysis of Zn K-edge XAFS spectra measured from a single hypersaline fluid inclusion in quartz shows that the ZnCl42- complex is dominant at all temperatures up to and including 430 °C. The Zn-Cl bond length was found to decrease uniformly with temperature, up to nearly 2% at 430 °C in comparison to the value at 25 °C. The Zn-Cl mean-square relative displacement increased linearly with temperature, from a value of 0.0043 Å2 at 25 °C to 0.0089 Å2 at 430 °C.