Metal organic frameworks (MOF) are a recently discovered class of nanoporous, defect-free crystalline materials that enable rational design and exploration of porous materials at the molecular level. MOFs have tunable monolithic pore sizes and cavity environments due to their crystalline nature, yielding properties exceeding those of most other porous materials. These include: the lowest known density (91% free space); highest surface area; tunable photoluminescence; selective molecular adsorption; and methane sorption rivaling gas cylinders. These properties are achieved by coupling inorganic metal complexes such as ZnO4 with tunable organic ligands that serve as struts, allowing facile manipulation of pore size and surface area through reactant selection. MOFs thus provide a discovery platform for generating both new understanding of chemistry in confined spaces and novel sensors and devices based on their unique properties. At the outset of this project in FY06, virtually nothing was known about how to couple MOFs to substrates and the science of MOF properties and how to tune them was in its infancy. An integrated approach was needed to establish the required knowledge base for nanoscale design and develop methodologies integrate MOFs with other materials. This report summarizes the key accomplishments of this project, which include creation of a new class of radiation detection materials based on MOFs, luminescent MOFs for chemical detection, use of MOFs as templates to create nanoparticles of hydrogen storage materials, MOF coatings for stress-based chemical detection using microcantilevers, and "flexible" force fields that account for structural changes in MOFs that occur upon molecular adsorption/desorption. Eight journal articles, twenty presentations at scientific conferences, and two patent applications resulted from the work. The project created a basis for continuing development of MOFs for many Sandia applications and succeeded in securing $2.75 M in funding from outside agencies to continue the research. 3
Sandia National Laboratories (SNL) is evaluating the potential of an innovative approach for splitting water into hydrogen and oxygen using two-step thermochemical cycles. Thermochemical cycles are heat engines that utilize high-temperature heat to produce chemical work. Like their mechanical work-producing counterparts, their efficiency depends on operating temperature and on the irreversibility of their internal processes. With this in mind, we have invented innovative design concepts for two-step solar-driven thermochemical heat engines based on iron oxide and iron oxide mixed with other metal oxides (ferrites). The design concepts utilize two sets of moving beds of ferrite reactant material in close proximity and moving in opposite directions to overcome a major impediment to achieving high efficiency--thermal recuperation between solids in efficient counter-current arrangements. They also provide inherent separation of the product hydrogen and oxygen and are an excellent match with high-concentration solar flux. However, they also impose unique requirements on the ferrite reactants and materials of construction as well as an understanding of the chemical and cycle thermodynamics. In this report the Counter-Rotating-Ring Receiver/Reactor/Recuperator (CR5) solar thermochemical heat engine and its basic operating principals are described. Preliminary thermal efficiency estimates are presented and discussed. Our ferrite reactant material development activities, thermodynamic studies, test results, and prototype hardware development are also presented.
We have synthesized and tested new highly fluorescent metal organic framework (MOF) materials based on stilbene dicarboxylic acid as a linker. The crystal structure and porosity of the product are dependent on synthetic conditions and choice of solvent and a low-density cubic form has been identified by x-ray diffraction. In this work we report experiments demonstrating scintillation properties of these crystals. Bright proton-induced luminescence with large shifts relative to the fluorescence excitation spectra were recorded, peaking near 475 nm. Tolerance to fast proton radiation was evaluated by monitoring this radio-luminescence to absorbed doses of several hundred MRAD.
Atmospheric pressure chemical vapor deposition (APCVD) of tin oxide is a very important manufacturing technique used in the production of low-emissivity glass. It is also the primary method used to provide wear-resistant coatings on glass containers. The complexity of these systems, which involve chemical reactions in both the gas phase and on the deposition surface, as well as complex fluid dynamics, makes process optimization and design of new coating reactors a very difficult task. In 2001 the U.S. Dept. of Energy Industrial Technologies Program Glass Industry of the Future Team funded a project to address the need for more accurate data concerning the tin oxide APCVD process. This report presents a case study of on-line APCVD using organometallic precursors, which are the primary reactants used in industrial coating processes. Research staff at Sandia National Laboratories in Livermore, CA, and the PPG Industries Glass Technology Center in Pittsburgh, PA collaborated to produce this work. In this report, we describe a detailed investigation of the factors controlling the growth of tin oxide films. The report begins with a discussion of the basic elements of the deposition chemistry, including gas-phase thermochemistry of tin species and mechanisms of chemical reactions involved in the decomposition of tin precursors. These results provide the basis for experimental investigations in which tin oxide growth rates were measured as a function of all major process variables. The experiments focused on growth from monobutyltintrichloride (MBTC) since this is one of the two primary precursors used industrially. There are almost no reliable growth-rate data available for this precursor. Robust models describing the growth rate as a function of these variables are derived from modeling of these data. Finally, the results are used to conduct computational fluid dynamic simulations of both pilot- and full-scale coating reactors. As a result, general conclusions are reached concerning the factors affecting the growth rate in on-line APCVD reactors. In addition, a substantial body of data was generated that can be used to model many different industrial tin oxide coating processes. These data include the most extensive compilation of thermochemistry for gas-phase tin-containing species as well as kinetic expressions describing tin oxide growth rates over a wide range of temperatures, pressures, and reactant concentrations.
This report summarizes the results of a five-year effort to understand the mechanisms and develop models that predict the corrosion of refractories in oxygen-fuel glass-melting furnaces. Thermodynamic data for the Si-O-(Na or K) and Al-O-(Na or K) systems are reported, allowing equilibrium calculations to be performed to evaluate corrosion of silica- and alumina-based refractories under typical furnace operating conditions. A detailed analysis of processes contributing to corrosion is also presented. Using this analysis, a model of the corrosion process was developed and used to predict corrosion rates in an actual industrial glass furnace. The rate-limiting process is most likely the transport of NaOH(gas) through the mass-transport boundary layer from the furnace atmosphere to the crown surface. Corrosion rates predicted on this basis are in better agreement with observation than those produced by any other mechanism, although the absolute values are highly sensitive to the crown temperature and the NaOH(gas) concentration at equilibrium and at the edge of the boundary layer. Finally, the project explored the development of excimer laser induced fragmentation (ELIF) fluorescence spectroscopy for the detection of gas-phase alkali hydroxides (e.g., NaOH) that are predicted to be the key species causing accelerated corrosion in these furnaces. The development of ELIF and the construction of field-portable instrumentation for glass furnace applications are reported and the method is shown to be effective in industrial settings.
The thermochemistry of the transition-metal fluorides and chlorides MF{sub n} and MCl{sub n} (M = Cr, Mn, Fe; n = 1, 2) has been characterized by high-level ab initio electronic structure methods. Geometries and harmonic vibrational frequencies were computed at the B3LYP level of theory using triple-{zeta} basis sets including diffuse and polarization functions. Heats of formation were computed from isogyric reaction energies at the CCSD(T) level using high-quality basis sets, including corrections for core-valence correlation and scalar relativistic effects. To investigate the possible linearity of the ground states of CrCl{sub 2} and CrF{sub 2}, we performed geometry optimizations for these species at the CCSD(T) level using large basis sets. In both cases, a bent ({sup 5}B{sub 2}) minimum structure was located, but the bent structure is only slightly below the linear form, which was found to be a transition state. For all of the investigated halides, polynomial fits were carried out for the heat capacity and the standard enthalpy and entropy in the 300-3000 K temperature range.