Chad L. Staiger

Synthesis of an ionic liquid with an iron coordination cation

An iron-based ionic liquid, Fe((OHCH(2)CH(2))(2)NH)(6)(CF(3)SO(3))(3), is synthesized in a single-step complexation reaction. Infrared and Raman data suggest NH(CH(2)CH(2)OH)(2) primarily coordinates to Fe(iii) through alcohol groups. The compound has T(g) and T(d) values of -64 degrees C and 260 degrees C, respectively. Cyclic voltammetry reveals quasi-reversible Fe(iii)/Fe(ii) reduction waves.

DFT-based force field development for noble gas adsorption in metal organic frameworks

Density Functional Theory (DFT) based force fields (FFs) for Ar and Xe adsorption in six metal–organic frameworks were developed using three DFT functionals (PBE-D2, vdW-DF, vdW-DF2) in periodic systems. These force fields include van der Waals (vdW) and polarization terms, and the effect of the latter was shown to be small. Using our DFT-derived and standard (UFF) FFs in grand canonical Monte Carlo simulations, adsorption isotherms and heats of adsorption were calculated and compared with experiment. In most of the cases, it was possible to accurately predict adsorption isotherms using one of the DFT-derived FFs. Still, among the DFT functionals investigated, no single DFT functional could accurately describe all of the adsorbate-framework interactions. On average, performance of UFF and PBE-D2 based FFs to predict experimental isotherms were at a similar quality, still, UFF was slightly superior. Although vdW-DF2 based FFs predicted experimental isotherms almost perfectly for ZIF-8 and HKUST-1 up to 20 bar, their average performance was less than that of PBE-D2 based FFs. Nevertheless, the overall performance of UFF, PBE-D2 and vDW-DF2 FFs was similar. Lastly, vdW-DF based FFs always over-predicted experiments.

Impacts of Humidity and Temperature on the Performance of Transparent Conducting Zinc Oxide

The impact of humidity and temperature on a zinc oxide based transparent conducting oxide (TCO) was assessed under accelerated aging conditions. An in situ electroanalytical method was used to monitor the electrical properties for a conducting zinc oxide under controlled atmospheric (humidity, temperature and irradiation) conditions. A review of thin film photovoltaic (PV) literature has shown one major failure mode of cells/modules is associated with the ingress of water into modules in the field. Water contamination has been shown to degrade the performance of the TCO in addition to corroding interconnects and other conductive metals/materials associated with the module. Water ingress is particularly problematic in flexible thin film PV modules since traditional encapsulates such as poly(ethyl vinyl acetate) (EVA) have high water vapor transmission rates. The accelerated aging studies of the zinc oxide based TCOs will allow acceleration factors and kinetic parameters to be determined for reliability purposes.

Reimagining liquid transportation fuels : sunshine to petrol.

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 projects end, we had demonstrated solar-driven conversion of CO{sub 2} to CO, a key energetic synthetic fuel intermediate, at 1.7% efficiency.

Bio micro fuel cell grand challenge final report.

Christopher Apblett, Kent Schubert, Bruce Kelley, Andrew Walker, Blake Simmons, Ted Borek, Stephen Meserole, Todd Alam, Brian Cherry, Greg Roberts, Jim Novak, Jim Hudgens, Dave Peterson, Jason Podgorski, Susan Brozik, Jeb Flemming, Stan Kravitz, David Ingersoll, Steve Eisenbies, Randy Shul, Sarah Rich, Carrie Schmidt, Mike Beggans, Jeanne Sergeant, Chris Cornelius, Cy Fujimoto, Micheal Hickner, Swapnil Chabra, Suzanne Ma, Joanne Volponi, Micheal Kelly, Kevin Zavadil, Chad Staiger, Patricia Dolan, Monica Manginell, Jason Harper, Dan Doughty, Steve Casalnuovo

Organosilicon-based electrolytes for long-life lithium primary batteries

This report describes advances in electrolytes for lithium primary battery systems. Electrolytes were synthesized that utilize organosilane materials that include anion binding agent functionality. Numerous materials were synthesized and tested in lithium carbon monofluoride battery systems for conductivity, impedance, and capacity. Resulting electrolytes were shown to be completely non-flammable and showed promise as co-solvents for electrolyte systems, due to low dielectric strength.

Summary report : universal fuel processor.

The United States produces only about 1/3 of the more than 20 million barrels of petroleum that it consumes daily. Oil imports into the country are roughly equivalent to the amount consumed in the transportation sector. Hence the nation in general, and the transportation sector in particular, is vulnerable to supply disruptions and price shocks. The situation is anticipated to worsen as the competition for limited global supplies increases and oil-rich nations become increasingly willing to manipulate the markets for this resource as a means to achieve political ends. The goal of this project was the development and improvement of technologies and the knowledge base necessary to produce and qualify a universal fuel from diverse feedstocks readily available in North America and elsewhere (e.g. petroleum, natural gas, coal, biomass) as a prudent and positive step towards mitigating this vulnerability. Three major focus areas, feedstock transformation, fuel formulation, and fuel characterization, were identified and each was addressed. The specific activities summarized herein were identified in consultation with industry to set the stage for collaboration. Two activities were undertaken in the area of feedstock transformation. The first activity focused on understanding the chemistry and operation of autothermal reforming, with an emphasis on understanding, and therefore preventing, soot formation. The second activity was focused on improving the economics of oxygen production, particularly for smaller operations, by integrating membrane separations with pressure swing adsorption. In the fuel formulation area, the chemistry of converting small molecules readily produced from syngas directly to fuels was examined. Consistent with the advice from industry, this activity avoided working on improving known approaches, giving it an exploratory flavor. Finally, the fuel characterization task focused on providing a direct and quantifiable comparison of diesel fuel and JP-8.

Photo-control of nanointeractions.

The manipulation of physical interactions between structural moieties on the molecular scale is a fundamental hurdle in the realization and operation of nanostructured materials and high surface area microsystem architectures. These include such nano-interaction-based phenomena as self-assembly, fluid flow, and interfacial tribology. The proposed research utilizes photosensitive molecular structures to tune such interactions reversibly. This new material strategy provides optical actuation of nano-interactions impacting behavior on both the nano- and macroscales and with potential to impact directed nanostructure formation, microfluidic rheology, and tribological control.