Robert Lascola

Synthesis and Characterization of a Lithium-Doped Fullerane (Lix-C60-Hy) for Reversible Hydrogen Storage

Herein, we present a lithium-doped fullerane (Li(x)-C(60)-H(y)) that is capable of reversibly storing hydrogen through chemisorption at elevated temperatures and pressures. This system is unique in that hydrogen is closely associated with lithium and carbon upon rehydrogenation of the material and that the weight percent of H(2) stored in the material is intimately linked to the stoichiometric ratio of Li:C(60) in the material. Characterization of the material (IR, Raman, UV-vis, XRD, LDI-TOF-MS, and NMR) indicates that a lithium-doped fullerane is formed upon rehydrogenation in which the active hydrogen storage material is similar to a hydrogenated fullerene. Under optimized conditions, a lithium-doped fullerane with a Li:C(60) mole ratio of 6:1 can reversibly desorb up to 5 wt % H(2) with an onset temperature of ~270 °C, which is significantly less than the desorption temperature of hydrogenated fullerenes (C(60)H(x)) and pure lithium hydride (decomposition temperature 500-600 and 670 °C respectively). However, our Li(x)-C(60)-H(y) system does not suffer from the same drawbacks as typical hydrogenated fullerenes (high desorption T and release of hydrocarbons) because the fullerene cage remains mostly intact and is only slightly modified during multiple hydrogen desorption/absorption cycles. We also observed a reversible phase transition of C(60) in the material from face-centered cubic to body-centered cubic at high levels of hydrogenation.

Structure/Property Relations in Bulk Versus Solution Derived Proton Conducting Ceramics of the Form SrCe 0.95 Yb 0.05 O 3 With Applications in Membrane Separations

Membrane separations are a key enabling technology for future energy conversion devices. Ionic transport membranes must have both proton and electronic conductivity to function as hydrogen separation membranes without an external power supply. A technical obstacle to material modification by compositional changes is that the hydrogen flux through a dense membrane is a function of both the proton ionic conductivity and the electronic conductivity. An alternative way to modify the materials conductivity without changing the ratio of the chemical constituents is by altering the microstructure. In this study, SrCe0.95Yb0.05O3 was produced by conventional mixed oxide bulk ceramic techniques and chemical solution routes self-rising approaches using urea as the leavening agent. In conventional ceramic processing routes, the perovskite phase was observed to form at temperatures near 1300C, while solution techniques resulted in perovskite phase formation starting near 1000C with complete phase transformations occurring at 1100C. Thermogravimetric analysis (TGA) was conducted in various gas atmospheres resulting in bulk oxide route powders exhibiting a 0.6% weight loss at 800C under a nitrogen environment as compared to chemically derived powders which displayed weight losses on the order of 3.4%.The increase weight loss observed in chemically derived SrCe0.95Yb0.05O3 is correlated with an increase in the number of electron charge carriers and results in elevated electronic conduction. This study will report on the development structure property relations in the model proton conducting ceramic system SrCe0.95Yb0.05O3.

Isotopic hydrogen analysis via conventional and surface-enhanced fiber optic Raman spectroscopy

This report describes laboratory development and process plant applications of Raman spectroscopy for detection of hydrogen isotopes in the Tritium Facilities at the Savannah River Site (SRS), a U.S. Department of Energy complex. Raman spectroscopy provides a lower-cost, in situ alternative to mass spectrometry techniques currently employed at SRS. Using conventional Raman and fiber optics, we have measured, in the production facility glove boxes, process mixtures of protium and deuterium at various compositions and total pressures ranging from 1000 - 4000 torr, with detection limits ranging from 1-2% for as low as 3-second integration times. We are currently investigating fabrication techniques for SERS surfaces in order to measure trace (0.01-0.1%) amounts of one isotope in the presence of the other. These efforts have concentrated on surfaces containing palladium, which promotes hydrogen dissociation and forms metal hydride bonds, essentially providing a chemical enhancement mechanism.

Multifunctional Hybrid Fe2O3-Au Nanoparticles for Efficient Plasmonic Heating

One of the most widely used methods for manufacturing colloidal gold nanospherical particles involves the reduction of chloroauric acid (HAuCl4) to neutral gold Au(0) by reducing agents, such as sodium citrate or sodium borohydride. The extension of this method to decorate iron oxide or similar nanoparticles with gold nanoparticles to create multifunctional hybrid Fe2O3-Au nanoparticles is straightforward. This approach yields fairly good control over Au nanoparticle dimensions and loading onto Fe2O3. Additionally, the Au metal size, shape, and loading can easily be tuned by changing experimental parameters (e.g., reactant concentrations, reducing agents, surfactants, etc.). An advantage of this procedure is that the reaction can be done in air or water, and, in principle, is amenable to scaling up. The use of such optically tunable Fe2O3-Au nanoparticles for hyperthermia studies is an attractive option as it capitalizes on plasmonic heating of gold nanoparticles tuned to absorb light strongly in the VIS-NIR region. In addition to its plasmonic effects, nanoscale Au provides a unique surface for interesting chemistries and catalysis. The Fe2O3 material provides additional functionality due to its magnetic property. For example, an external magnetic field could be used to collect and recycle the hybrid Fe2O3-Au nanoparticles after a catalytic experiment, or alternatively, the magnetic Fe2O3 can be used for hyperthermia studies through magnetic heat induction. The photothermal experiment described in this report measures bulk temperature change and nanoparticle solution mass loss as functions of time using infrared thermocouples and a balance, respectively. The ease of sample preparation and the use of readily available equipment are distinct advantages of this technique. A caveat is that these photothermal measurements assess the bulk solution temperature and not the surface of the nanoparticle where the heat is transduced and the temperature is likely to be higher.

Advanced Gas Sensors Using SERS‐Activated Waveguides

This contribution describes progress towards the development and testing of a functionalized capillary that will provide detection of low‐concentration gas‐phase analytes through SERS. Measurement inside a waveguide allows interrogation of a large surface area, potentially overcoming the short distance dependence of the SERS effect.The possible use of Raman spectroscopy for gas detection is attractive for IR‐inactive molecules or scenarios where infrared technology is inconvenient. However, the weakness of Raman scattering limits the use of the technique to situations where low detection limits are not required or large gas pressures are present.With surface‐enhanced Raman spectroscopy (SERS), signal enhancements of 106 are often claimed, and higher values are seen in specific instances. However, most of the examples of SERS analysis are on liquid‐phase samples, where the molecular density is high, usually combined with some sort of sample concentration at the surface. Neither of these factors is present ...

A Piecewise Local Partial Least Squares (PLS) Method for the Quantitative Analysis of Plutonium Nitrate Solutions

We have developed a piecewise local (PL) partial least squares (PLS) analysis method for total plutonium measurements by absorption spectroscopy in nitric acid-based nuclear material processing streams. Instead of using a single PLS model that covers all expected solution conditions, the method selects one of several local models based on an assessment of solution absorbance, acidity, and Pu oxidation state distribution. The local models match the global model for accuracy against the calibration set, but were observed in several instances to be more robust to variations associated with measurements in the process. The improvements are attributed to the relative parsimony of the local models. Not all of the sources of spectral variation are uniformly present at each part of the calibration range. Thus, the global model is locally overfitting and susceptible to increased variance when presented with new samples. A second set of models quantifies the relative concentrations of Pu(III), (IV), and (VI). Standards containing a mixture of these species were not at equilibrium due to a disproportionation reaction. Therefore, a separate principal component analysis is used to estimate of the concentrations of the individual oxidation states in these standards in the absence of independent confirmatory analysis. The PL analysis approach is generalizable to other systems where the analysis of chemically complicated systems can be aided by rational division of the overall range of solution conditions into simpler sub-regions.