Publications

Abstract not provided.

Abstract not provided.

Abstract not provided.

A systematic investigation of the effects of linker polarizability on the adsorption properties of weakly interacting gases (N 2, Ar, Kr, and Xe) is reported. Experimental and simulated adsorption properties were measured for a complete isoreticular series of monohalogenated metal-organic frameworks (MOFs). Variations on IRMOF-2, in which one linker hydrogen is replaced with -F, -Cl, -Br, or -I, comprise the series. Both experimental and simulated results indicate that increasing linker polarizability correlates with increased gas uptake. Evidence of increased adsorbate interaction with increased linker polarizability is also observed in the Kr/N 2, Xe/N 2, and Xe/Kr selectivity data and in isosteric heats of adsorption. Unexpectedly, comparison between simulated and experimental isotherms reveals that the agreement between the two improves with the size of the adsorbate, with essentially identical results for Xe. This is apparently due to the creation of regions inaccessible to any of the noble gases as a result of halogen functionalization. Simulated adsorption isotherms are also reported for radon, which is difficult to measure experimentally due to its radioactivity. © 2012 American Chemical Society.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Abstract not provided.

Two of the most daunting problems facing humankind in the twenty-first century are energy security and climate change. This report summarizes work accomplished towards addressing these problems through the execution of a Grand Challenge LDRD project (FY09-11). The vision of Sunshine to Petrol is captured in one deceptively simple chemical equation: Solar Energy + xCO{sub 2} + (x+1)H{sub 2}O {yields} C{sub x}H{sub 2x+2}(liquid fuel) + (1.5x+.5)O{sub 2} Practical implementation of this equation may seem far-fetched, since it effectively describes the use of solar energy to reverse combustion. However, it is also representative of the photosynthetic processes responsible for much of life on earth and, as such, summarizes the biomass approach to fuels production. It is our contention that an alternative approach, one that is not limited by efficiency of photosynthesis and more directly leads to a liquid fuel, is desirable. The development of a process that efficiently, cost effectively, and sustainably reenergizes thermodynamically spent feedstocks to create reactive fuel intermediates would be an unparalleled achievement and is the key challenge that must be surmounted to solve the intertwined problems of accelerating energy demand and climate change. We proposed that the direct thermochemical conversion of CO{sub 2} and H{sub 2}O to CO and H{sub 2}, which are the universal building blocks for synthetic fuels, serve as the basis for this revolutionary process. To realize this concept, we addressed complex chemical, materials science, and engineering problems associated with thermochemical heat engines and the crucial metal-oxide working-materials deployed therein. By project's end, we had demonstrated solar-driven conversion of CO{sub 2} to CO, a key energetic synthetic fuel intermediate, at 1.7% efficiency.

Abstract not provided.

Metal organic framework (MOF) materials are a class of hybrid organic-inorganic crystalline materials whose pore structures and chemical properties can be tailored by the selection of component chemical moieties. Many MOFs have extraordinary intrinsic surface areas, capable of adsorbing large quantities of other chemicals, such as volatile organic compounds or moisture. Upon absorption of guest molecules, many MOFs undergo reversible changes in the dimensions of their unit cells. These properties suggest several routes to chemical sensing in which the transduction mechanisms are: 1) the stress induced at an interface between a flexible MOF layer and a static microcantilever fabricated with a built-in piezoresistive stress sensor; 2) the change in the resonant frequency of an oscillating microcantilever induced by mass adsorption; and 3) the change in the resonant frequency of a acoustic sensor, such as a surface acoustic wave (SAW) sensor through changes in mass loading and film moduli. This paper focuses on humidity sensing by SAWs coated with Cu 3(BTC) 2 (HKUST-1) over a very broad concentration range. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000. © 2011 Materials Research Society.

Abstract not provided.

Abstract not provided.

Abstract not provided.