Publications

The oxidative dehydrogenation (ODH) reactions for the formation of two important organic feedstocks ethylene and propylene are of great interest because of the potential in capital and energy savings associated with these reactions. Theoretically, ODH can achieve high conversions of the starting materials (ethane and propane) at lower temperatures than conventional dehydrogenation reactions. The important focus in our study of ODH catalysts is the development of a structure-property relationship for catalyst with respect to selectivity, so as to avoid the more thermodynamically favorable combustion reaction. Catalysts for the ODH reaction generally consist of mixed metal oxides. Since for the most selective catalyst lattice oxygen is known to participate in the reaction, catalysts are sought with surface oxygen atoms that are labile enough to perform dehydrogenation, but not so plentiful or weakly bound as to promote complete combustion. Also, catalysts must be able to replenish surface oxygen by transport from the bulk. Perovskite materials are candidates to fulfill these requirements. We are studying BaCeO3 perovskites doped with elements such as Ca, Mg, and Sr. During the ODH of the alkanes at high temperatures, the perovskite structure is not retained and a mixture of carbonates and oxides is formed, as revealed by XRD. While the Ca doped materials showed enhanced total combustion activity below 600°C, they only showed enhanced alkene production at 700°C. Bulk structural and surface changes, as monitored by powder X-ray diffraction, and X-ray photoelectron spectroscopy are being correlated with activity in order to understand the factors affecting catalyst performance, and to modify catalyst formulations to improve conversion and selectivity.

The goal is the development of materials that are highly sensitive and selective for chid chemicals and biochemical (such as insecticides, herbicides, proteins, and nerve agents) to be used as sensors, catalysts and separations membranes. Molecular modeling methods are being used to tailor chiral molecular recognition sites with high affinity and selectivity for specified agents. The work focuses on both silicate and non-silicate materials modified with chirally-pure fictional groups for the catalysis or separations of enantiomerically-pure molecules. Surfactant and quaternary amine templating is being used to synthesize porous frameworks, containing mesopores of 30 to 100 angstroms. Computer molecukw modeling methods are being used in the design of these materials, especially in the chid surface- modi~ing agents. Molecular modeling is also being used to predict the catalytic and separations selectivities of the modified mesoporous materials. The ability to design and synthesize tailored asymmetric molecular recognition sites for sensor coatings allows a broader range of chemicals to be sensed with the desired high sensitivity and selectivity. Initial experiments target the selective sensing of small molecule gases and non-toxic model neural compounds. Further efforts will address designing sensors that greatly extend the variety of resolvable chemical species and forming a predictive, model-based method for developing advanced sensors.

Our research is focused on developing inorganic molecular sieve membranes for light gas separations such as hydrogen recovery and natural gas purification, and organic molecular separations, such as chiral enantiomers. We focus on zinc phosphates because of the ease in crystallization of new phases and the wide range of pore sizes and shapes obtained. With our hybrid systems of zinc phosphate crystalline phases templated by amine molecules, we are interested in better understanding the association of the template molecules to the inorganic phase, and how the organic transfers its size, shape, and (in some cases) chirality to the bulk. Furthermore, the new porous phases can also be synthesized as thin films on metal oxide substrates. These films allow us to make membranes from our organic/inorganic hybrid systems, suitable for diffusion experiments. Characterization techniques for both the bulk phases and the thin films include powder X-ray diffraction, TGA, Scanning Electron Micrograph (SEM) and Electron Dispersive Spectrometry (EDS).

Work was done for developing biomimetic oxidation catalysts. Two classes of metalloporphyrin catalysts were studied. The first class of catalysts studied were a novel series of highly substituted metalloporphyrins, the fluorinated iron dodecaphenylporphyrins. These homogeneous metalloporphyrin catalysts were screened for activity as catalysts in the oxidation of hydrocarbons by dioxygen. Results are discussed with respect to catalyst structural features. The second type of catalysts studied were heterogeneous catalysts consisting of metalloporphyrins applied to inorganic supports. Preliminary catalytic testing results with these materials are presented.

A sodium silicotitanate (TAM5) of ideal composition Na{sub 3}Si{sub 2}Ti{sub 4}O{sub 13}(OH) {center_dot} 4H{sub 2}O (jointly developed by Sandia and Texas A and M) is synthesized hydrothermally in highly alkaline media. The material selectively removes cesium cations from solutions containing up to 5.7 M Na{sup +} and for a pH range of less than 1 to greater than 14. The crystal structure of TAM5 has been refined from X-ray powder data by Rietveld refinement, using the mineral Sitinakite as a model. The compound is tetragonal. The titanium and niobium atoms occur in clusters of four and are octahedrally coordinated by oxygen atoms. These clusters are held together by tetrahedral linkages to the silicon atoms. The framework forms a three dimensional structure that has potential accessibility to the three cation sites (two in the cages, one in the framework wall) from three directions. However, the sodium cation that sits in the wall is tightly held due to octahedral bonding from a combination of framework and water oxygen atoms. Furthermore, that site is too small for cations greater in size than sodium. In a concurrent report, extensive monovalent and divalent cation exchange studies are presented, with analyses including structure refinement, elemental analyses and thermal stability of both powder and UOP engineered forms.

A new inorganic ion exchange material, called SNL-1, has been prepared at Sandia National Laboratories. Development samples of SNL-1 have been determined to have high selectivity for the adsorption of Sr from highly acidic solutions (1 M HNO3). This paper presents results obtained for the material in batch ion exchange tests conducted at various solution pH values and in the presence of a number of competing cations. Results from a continuous flow column ion exchange experiment are also presented.

This report summarizes research on the aging of Class I components in environments representative of nuclear power plants. It discusses Class IE equipment used in nuclear power plants, typical environments encountered by Class IE components, and aging techniques used to qualify this equipment. General discussions of radiation chemistry of polymers and accelerated aging techniques are also included. Based on the inadequacies of present aging techniques for Class IE equipment, a proposal for an experimental program on electrical cables is presented. One of the main purposes of the proposed work is to obtain relevant data in two areas of particular concern--the effect of radiation dose rate on polymer degradation, and the importance of synergism for combined thermal and radiation environments. A new model that allows combined environment accelerated aging to be carried out is introduced, and it is shown how the experimental data to be generated can be used to test this model.