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1) To fully understand the chemical and microbial interactions in agricultural systems, it is essential that novel sensors be developed which can accurately measure such concentrations in both bulk fluids and at appropriate scales near the fluid/surface/microbe interface. A portion of this project is focused on the development of such advanced sensor systems, with application in renewable energy and safe foods systems (climate change, sustainable energy & safe food). <P>2) Access to rapid, easy-to-use, and inexpensive environmental diagnostics will provide tools to track the concentration of contaminants in traditional hunting and gathering grounds and to identify high-risk geographic regions and seasons. Farming communities have similar needs. This is a special concern regionally where migrants in Central Washington harvest fruit orchards and fields. Here, research that will enable the development of several such systems that will enable the inexpensive, accurate determination of chemical species concentrations. <P>3) Novel microelectrodes will be developed which will be used to understand the biologically catalyzed reactions occurring in the guts of wood-feeding termites. Such understanding will facilitate the development of biomimetic catalysts for the conversion of lignocellulosic materials to drop-in fuels and chemicals. <P>4) The ability to detect and isolate target organism from multiple sources (clinical specimens, food, water, environment, animals) is a foundational component of any disease control program. Research will focus on the development of a real-time biosensor to enable the rapid detection of low concentrations of hazardous microbes. <P>5) Within agricultural systems, electrical power is often needed at locations that are far from the traditional power transmission grid. Such situations require power to be generated at the point where it is needed. Fuel cells are an efficient technology which can be used for such generation. Fuel cells that use novel chemical catalysts may be able to efficiently convert transportable, renewable liquids to electricity and novel, biologically-catalyzed fuel cells may produce appropriate quantities of electrical power in remote locations, meeting agricultural and other needs for electricity. <P>6) Part of this project is focused on the development and demonstration of a technically feasible and economically attractive integrated process for the distributed conversion of biomass to compounds that can be readily dropped in existing refineries. This integrated process will provide a quantum change in how such conversions are accomplished, yet will compliment other efforts being undertaken by others. <P>7) Biofilms will naturally form and impact how contaminants move through the environment. Moreover, they also impact our ability to store foods and bio-based fuels and chemicals. This portion of the project will help us understand these phenomena such as how the positive impacts of biofilms can be enhanced, and their negative impacts can be limited.
Non-Technical Summary:<br/>
Our nation and, indeed, the world face the unprecedented challenges of creating a sustainable energy future and ensuring a safe food supply while also minimizing or reversing the impact of growing economies on the climate. In response to these challenges, the US Congress created the USDA National Institute of Food and Agriculture (NIFA), which is to use broad, systems-level research to address major societal needs. In 2010, NIFA articulated five thematic areas, of which this proposal will address three: climate change, sustainable energy, and food safety:(1) To address these needs, NIFA priorities include both fundamental and applied research. Here, as in the USDA enabling legislation, - Fundamental research means research that (i) increases knowledge or understanding of the fundamental aspects of phenomena and has the potential for broad application and (ii) has an effect on agriculture, food, nutrition, or the environment. - Applied research means research that includes expansion of the findings of fundamental research to uncover practical ways in which new knowledge can be advanced to benefit individuals and society. Further, research that addresses these national issues will also help advance production agriculture within Washington State, a fundamental goal of the WSU Agricultural Research Center. Catalysis, an essential technology for accelerating and directing the transformation of chemicals to higher value, more useful products, is key to the development of environmentally friendly, economical processes for the conversion of lignocellulosic agricultural materials and/or wastes to useful fuels, chemicals and electricity. Such understanding is, therefore, one of the steps needed to create a sustainable energy future by converting renewable materials to drop-in fuels and chemicals. Further catalytic conversion of carbon dioxide to liquid fuels using solar and electrical energy would enable carbon recycle into fuels, thus reducing its contribution to global climate change while also creating drop-in fuels that will reduce petroleum consumption. Efficient fuel cell systems that employ novel chemical and biological catalysts will provide electrical power needed for small operations, such as those found on farms. Moreover, biological catalysts underlie microbial growth in biofilms, the understanding of which is essential to safe foods. The challenge is to understand chemical and biological catalysts and to then apply these catalysts to yield the greatest benefit to society. To realize the full potential offered by new catalytic systems, a profound understanding of catalytic materials that enable the atom-by-atom construction of novel catalysts that function with molecular precision is needed. Moreover, tools and sensors that enable real-time, bulk-solution and spatially-resolved measurements of chemical concentrations and physical properties must be developed. Ultimately, these systems must be used in to address our needs for sustainable energy and safe food. Although this is a broad charge, we have the potential to address specific elements of these needs, and to integrate understanding to address the nation's needs.
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Approach:<br/>
Fundamental and applied studies will be conducted using the following techniques:
1. We will develop multi-scale computational models to facilitate the design of catalytic materials and reactor systems. For example, using ab initio quantum mechanics, we are able to examine the energetics of an adsorption system. To couple the quantum regime to the mesoscopic and the macroscopic regime, we will use coarse-grained methods such as lattice gas models, which are parameterized using density functional theory. Here Monte Carlo simulations are typically used to obtain the lowest free energy configuration at a given temperature and pressure for relatively large systems.
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2. Effective catalysts are needed to convert renewable, alternative materials to drop-in fuels and chemicals. We propose a unique combination of experiment and theory to enable the development of effective catalysts. Specifically, hydrogen produced in-situ via aqueous phase reforming (APR) of small and water soluble oxygenates from pyrolysis oil will used to perform hydrodeoxygenation of pyrolysis oils (hydrotreating). The effluent gas from such an integrated hydrogen production/hydrodeoxygenation process can be recycled to perform a mild hydro-pyrolysis to improve the pyrolysis oil stability and quality. ab initio quantum mechanical calculations and infrared spectroscopy experiments will be integrated with fast pyrolysis systems, enabling the development of a mild hydro-pyrolysis process without the requirement of a separate and external production of hydrogen.
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3. Electrons generated from renewable sources, such as wind and solar will enable CO2 reduction in a high-temperature Solid Oxide Electrolyzer (SOE), which is essentially a solid oxide fuel cell (SOFC) operated in reverse, into long chain hydrocarbons such as gasoline, diesel fuel or jet fuel. A combined theoretical and experimental approach will be used throughout.
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4. Ion-selective electrodes (ISEs) can be modified to create a potentiometric immunoassay by covalent attachment of a hapten to the ionophore and use of immunocompetition to modulate transmembrane ion flux. A dual ionophore system (di-ISE) will be developed to enable the measurement of very low concentrations of environmentally significant chemical species.
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5. Sediment microbial fuel cells (SMFCs) are considered an alternative renewable power source for remote environmental monitoring. Our goal is to develop a SMFC and a power management system (PMS) that enables the use of a SMFC to power a systems that consumer high power. This will be accomplished by developing new PMS technologies and a better understanding the role of biofilms in the SMFC. To ensure broad impact, we will work with the WSU Extension Energy Office to communicate research results to stakeholders. We will also publish results in peer-refereed journals, appropriately use press releases, and make presentations at local, regional, and national meetings.
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Progress:<br/>
2012/01 TO 2012/12<br/>
OUTPUTS: We have made much progress in the use of atomistic models of catalytic processes in energy applications: Specifically, (1) We have better understood how a bimetallic catalyst will interact with phenolic molecules. In particular, our group has found that palladium will always be enriched at the surface with palladium regardless of whether it is an impurity. (2) We have begun to study the electric field-induced reactions for the decomposition of methane on a Ni(111) surface. Our preliminary results show that the presence of a positive electric field hinders coke formation.
<br/>We have made significant progress on the development of an integrated system to thermochemically convert biomass to fuels. In the presence of representative pyrolysis gasses, our work indicates that Mn2O3-CeO2 is the most active. Through first principles calculations, advanced characterization and catalytic activity tests, we designed a highly active and selective catalyst by alloying Pd with Fe which showed four times higher yield to benzene compared with Fe. Effective production of H2 from small oxygenates of pyrolysis vapors via steam reforming is critical to maximize the hydrogen efficiency in biomass conversion to fuels via fast pyrolysis. We have recently elucidated that graphitized carbon supported Co nanoparticles is highly stable and selective for acetone steam reforming.
Catalysts are also foundational to the construction of solid oxide fuel cells (SOFC), which may provide on-demand electricity for on-farm or other distributed electrical needs. During this year, we investigated the performance of direct feed liquid fuel SOFCs using MoO2-based anodes, The MoO2-based anodes were found to be highly coke resistant and exhibited significantly improved long-term stability. We also have optimized the pore structure of MoO2-based SOFCs that can operate with a direct feed stream of a model liquid fuel mixture and produce a high initial power density of 3 W/cm2 at 750 degrees C.
<br/>In addition to the focus on SOFC's, a renewable, fuel cell system that is based on microbial catalysts is under development. Such a system will enable the generation of electricity in remote areas. This year we developed a sediment microbial fuel cell to power a submersible ultrasonic receiver that required the continuous operation of a real-time clock. Novel sensors which enable the measurement of low concentrations of chemicals and cells will facilitate the development of energy and safe food systems. Progress was made in improving the sensor platform. This year, problems in our original concept were identified and a potential solution was devised. We divided the membrane into two regions, one for each ion carrier and showed the system works. We simplified the original idea and are buying off-the-shelf polymers that link cholesterol with the binding molecule. The cholesterol has a strong affinity for the membrane, and the polymer is hydrophilic; so the coupled molecule will sit at the membrane surface with the binding site sticking out. When proteins or cells come by, they will bind, coat the surface, and "turn off" one ionophore, creating a voltage change. PARTICIPANTS: More than 15 PhD students and 5 postdoctoral research associates worked with the faculty team TARGET AUDIENCES: Students, engineers, scientists in academia and government, and practicing engineers and scientists in industry. PROJECT MODIFICATIONS: Nothing significant to report during this reporting period.
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IMPACT: Part of this project is focused on the development and demonstration of technically feasible and economically attractive catalysts that will reduce environmental impacts and enable the development of an integrated process for the distributed conversion of biomass to drop-in fuels and chemicals. Such an integrated process will provide a quantum change in the use of biomass for energy, yet will compliment efforts being undertaken by others. To accomplish these impacts, a fundamental understanding of catalysts and their role in processes, is needed. We have gained fundamental understanding in catalysis in the following areas: ketonization of acidic acids, condensation of oxygenates, hydrogen production from steam reforming of small oxgygnates, and hydrodeoxygenation of phenolics.
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We are developing coke resistant and sulfur tolerant MoO2-based nanoparticle catalysts by increasing our fundamental understanding of their catalytic, electrochemical and material properties. These nanoparticles can be applied to many important industrial applications where mitigating coking and sulfur poisoning are a huge technical challenge. If MoO2-based nanoparticles are successfully used as an alternative anode material for direct feed liquid fuel SOFC, a direct outcome will be a generation of an efficient electrical power from available liquid fuels including biofuels when the power grid is not available. We have trained our graduate and undergraduate students on several new methodologies for characterization of pure MoO2 and Ti-doped MoO2 nanoparticles. One of our graduate students spent an entire summer at Boeing's fuel cell laboratory (part of their Concept Center in Everett, WA) as a summer intern, assisting with a wide range of fuel cell projects. New concepts were devised that will facilitate the detection of microbial species and other large molecular weight environmental contaminants that are present in streams, ponds, or drinking water supplies. Anticipated applications include detection of food-borne pathogens, chlorinated hydrocarbon contaminants, and other water-borne environmental contaminants. The system also holds promise in the realm of detection of health-related toxins, pathogens, and various cell types, and therefore has application for animal health.
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During 2012, the team co-authored 37 peer-refereed manuscripts, several of which were invited review articles. One of the manuscripts was featured on the journal's cover page. The team also made numerous presentations at national and international meetings. One of the members (Wang) also served as co-chair of the American Chemical Society's Energy and Fuel Division and as a member of the editorial boards of six catalysis and energy related journals including ACS Catalysis, Catalysis Today, J. Nanomaterials, J. Energy Chemisty, and Energy Focus. Y. Wang was also invited by Department of Energy Secretary Chu to serve as the hydrogen panelist. In addition, members served as panelists for review panels, including the on-site review of the nano-center at the University of Oklahoma and on the scientific advisory board of a federally funded research Center.