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Technoeconomic Model and Pathway to <$2/kg Green Hydrogen Using Integrated Halide Perovskite Photoelectrochemical Cells

The cost of gray hydrogen produced via fossil fuel-based steam-methane reforming has led the U.S. Department of Energy to specify <$\$$2/kg H 2 as a target for commercially competitive green hydrogen generation methods. Integrated photoelectrochemical cells have been proposed as a solar-to-hydrogen conversion technology. In this paper we describe a technoeconomically feasible pathway to reaching <$\$$2/kg green H 2 using integrated photoelectrochemical cells with halide perovskite photoabsorbers, low-cost conductive barriers, and low precious metal-content catalysts in an aqueous, membrane-separated cell. A base-case solar-to-hydrogen conversion efficiency of 20%, stable lifetime of 10 years, and a combined electrocatalyst-plus-panel cost of $\$$50/m 2 enabled a levelized cost of hydrogen of $\$$2.43/kg, which dropped below $\$$2/kg with improved performance metrics including material cost, improvements in process design, or subsidies. We relate these metrics to lab-scale reports to recommend best research practices for scientists and funding agencies working at this intersection of photovoltaics, electrocatalysis, and surface science.

$1/kg↗

Mechanism of Methane Chemical Looping Combustion with Hematite Promoted with CeO 2

Chemical looping combustion (CLC) is a promising technology for fossil fuel combustion that produces sequestration-ready CO{sub 2} stream, reducing the energy penalty of CO{sub 2} separation from flue gases. An effective oxygen carrier for CLC will readily react with the fuel gas and will be reoxidized upon contact with oxygen. This study investigated the development of a CeO{sub 2}-promoted Fe{sub 2}O{sub 3}-hematite oxygen carrier suitable for the methane CLC process. Composition of CeO{sub 2} is between 5 and 25 wt % and is lower than what is generally used for supports in Fe{sub 2}O{sub 3} carrier preparations. The incorporation of CeO{sub 2} to the natural ore hematite strongly modifies the reduction behavior in comparison to that of CeO{sub 2} and hematite alone. Temperature-programmed reaction studies revealed that the addition of even 5 wt % CeO{sub 2} enhances the reaction capacity of the Fe{sub 2}O{sub 3} oxygen carrier by promoting the decomposition and partial oxidation of methane. Fixed-bed reactor data showed that the 5 wt % cerium oxides with 95 wt % iron oxide produce 2 times as much carbon dioxide in comparison to the sum of carbon dioxide produced when the oxides were tested separately. This effect is likely due to the reaction of CeO{sub 2} with methane forming intermediates, which are reactive for extracting oxygen from Fe{sub 2}O{sub 3} at a considerably faster rate than the rate of the direct reaction of Fe{sub 2}O{sub 3} with methane. These studies reveal that 5 wt % CeO{sub 2}/Fe{sub 2}O{sub 3} gives stable conversions over 15 reduction/oxidation cycles. Lab-scale reactor studies (pulsed mode) suggest the methane reacts initially with CeO{sub 2} lattice oxygen to form partial oxidation products (CO + H{sub 2}), which continue to react with oxygen from neighboring Fe{sub 2}O{sub 3}, leading to its complete oxidation to form CO{sub 2}. The reduced cerium oxide promotes the methane decomposition reaction to form C + H{sub 2}, which continue to react with Fe{sub 2}O{sub 3}/Fe{sub 3}O{sub 4} to form CO/CO{sub 2} and H{sub 2}O. This mechanism is supported by the characterization studies, which also suggest that the formation of carbonaceous intermediates may affect the reaction rate and selectivity of the oxygen carrier.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Multiple Mechanisms Mapped in Aryl Alkyl Ether Cleavage via Aqueous Electrocatalytic Hydrogenation over Skeletal Nickel

We present here detailed mechanistic studies of electrocatalytic hydrogenation (ECH) in aqueous solution over skeletal nickel cathodes to probe the various paths of reductive catalytic C–O bond cleavage among functionalized aryl ethers relevant to energy science. Heterogeneous catalytic hydrogenolysis of aryl ethers is important both in hydrodeoxygenation of fossil fuels and in upgrading of lignin from biomass. The presence or absence of simple functionalities such as carbonyl, hydroxyl, methyl, or methoxyl groups is known to cause dramatic shifts in reactivity and cleavage selectivity between sp3 C–O and sp2 C–O bonds. Specifically, reported hydrogenolysis studies with Ni and other catalysts have hinted at different cleavage mechanisms for the C–O ether bonds in α-keto and α-hydroxy β-O-4 type aryl ether linkages of lignin. Our new rate, selectivity, and isotopic labeling results from ECH reactions confirm that these aryl ethers undergo C–O cleavage via distinct paths. For the simple 2-phenoxy-1-phenylethane or its alcohol congener, 2-phenoxy-1-phenylethanol, the benzylic site is activated via Ni C–H insertion, followed by beta elimination of the phenoxide leaving group. But in the case of the ketone, 2-phenoxyacetophenone, the polarized carbonyl π system apparently binds directly with the electron rich Ni cathode surface without breaking the aromaticity of the neighboring phenyl ring, leading to rapid cleavage. Substituent steric and electronic perturbations across a broad range of β-O-4 type ethers create a hierarchy of cleavage rates that supports these mechanistic ideas while offering guidance to allow rational design of the catalytic method. Furthermore, on the basis of the new insights, the usage of cosolvent acetone is shown to enable control of product selectivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The development of molecular water oxidation catalysts

There is an urgent need to transition from fossil fuels to solar fuels $-$ not only to lower CO 2 emissions that cause global warming but also to ration fossil resources. Splitting H 2 O with sunlight emerges as a clean and sustainable energy conversion scheme that can afford practical technologies in the short-to-mid-term. A crucial component in such a device is a water oxidation catalyst (WOC). These artificial catalysts have been developed mainly over the past two decades, which is in contrast to nature’s WOCs, which have featured in its photosynthetic apparatus for more than a billion years. Recent times have seen the development of increasingly active molecular WOCs, the study of which affords an understanding of catalytic mechanisms and decomposition pathways. This Perspective offers a historical description of the landmark molecular WOCs, particularly ruthenium systems, that have guided research to our present degree of understanding.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Improving future travel demand projections: a pathway with an open science interdisciplinary approach

Transport accounts for 24% of global CO 2 emissions from fossil fuels. Governments face challenges in developing feasible and equitable mitigation strategies to reduce energy consumption and manage the transition to low-carbon transport systems. To meet the local and global transport emission reduction targets, policymakers need more realistic/sophisticated future projections of transport demand to better understand the speed and depth of the actions required to mitigate greenhouse gas emissions. In this paper, we argue that the lack of access to high-quality data on the current and historical travel demand and interdisciplinary research hinders transport planning and sustainable transitions toward low-carbon transport futures. We call for a greater interdisciplinary collaboration agenda across open data, data science, behaviour modelling, and policy analysis. These advancemets can reduce some of the major uncertainties and contribute to evidence-based solutions toward improving the sustainability performance of future transport systems. The paper also points to some needed efforts and directions to provide robust insights to policymakers. We provide examples of how these efforts could benefit from the International Transport Energy Modeling Open Data project and open science interdisciplinary collaborations.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

2012 wind technologies market report

Annual wind power capacity additions in the United States achieved record levels in 2012, motivated by the then-planned expiration of federal tax incentives at the end of 2012 and recent improvements in the cost and performance of wind power technology. At the same time, even with a short-term extension of federal tax incentives now in place, the U.S. wind power industry is facing uncertain times. It will take time to rebuild the project pipeline, ensuring a slow year for new capacity additions in 2013. Continued low natural gas prices, modest electricity demand growth, and limited near-term demand from state renewables portfolio standards (RPS) have also put a damper on industry growth expectations. In combination with global competition within the sector, these trends continue to impact the manufacturing supply chain. What these trends mean for the medium to longer term remains to be seen, dictated in part by future natural gas prices, fossil plant retirements, and policy decisions, although recent declines in the price of wind energy have boost ed the prospects for future growth

29 ENERGY PLANNING, POLICY, AND ECONOMY↗

Developing high-resolution spatial data of migration corridors for avian species of concern in regions of high potential wind development

The future of the US economy, our national security, and our environmental quality all depend on decreasing our reliance on foreign oil and on fossil fuels. An essential component of decreasing this reliance is the development of alternative energy sources. Wind power is among the most important alternative energy sources currently available, and the mid-Atlantic region is a primary focus for wind power development. In addition to being important to the development of wind power, the mid-Atlantic region holds a special responsibility for the conservation of the eastern North America's golden eagles (Aquila chrysaetos). This small population breeds in northeastern Canada, winters in the southern Appalachians, and nearly all of these birds pass through the mid-Atlantic region twice each year. Movement of these birds is not random and, particularly during spring and autumn, migrating golden eagles concentrate in a narrow 30-50 mile wide corridor in central Pennsylvania. Thus, because the fate of these rare birds may depend on responsible management of the habitat they use it is critical to use research to identify ways to mitigate prospective impacts on this and similar raptor species. The goal of this project was to develop high-resolution spatial risk maps showing migration corridors of and habitat use by eastern golden eagles in regions of high potential for wind development. To accomplish this, we first expanded existing models of raptor migration for the eastern USA to identify broad-scale migration patterns. We then used data from novel high-resolution tracking devices to discover routes of passage and detailed flight behavior of individual golden eagles throughout the eastern USA. Finally, we integrated these data and models to predict population-level migration patterns and individual eagle flight behavior on migration. We then used this information to build spatially explicit, probabilistic maps showing relative risk to birds from wind development. This project has numerous benefits to people and to wildlife, primarily because it will provide a framework for safer and less controversial development of wind power. Because golden eagles are an important "umbrella" for other raptors, this project benefits a suite of species that may be impacted by wind turbines. Finally this work is a recognized priority for central Appalachian states and it is explicitly called for in, and meets the goals of, numerous state wildlife conservation plans. The final product we created, a region-wide map of relative risk to eagles of development of wind power, has allowed us to make specific recommendations regarding siting and operation of and mitigation at wind facilities. This approach also serves as a model for other projects to protect eagles in other places and to conserve suites of species beyond raptors.

17 WIND ENERGY↗

Vertically-Aligned Carbon-Nanotubes Embedded in Ceramic Matrices for Hot Electrode Applications

The proposed is aimed to develop carbon nanotube-ceramic (CNT-C) composite structures, in which vertically aligned CNTs (VA-CNTs) are embedded in ceramic matrices for hot electrode applications in Magnetohydrodynamics (MHD) power systems, including four objectives: 1) Super growth of VA-CNT carpets; 2) Fabrication of CNT-boron nitride (CNT-BN) composite structures by chemical vapor infiltration; 3) Stability and resistance studies of the CNT-BN Composite structures; and 4) Thermionic emissions of the CNT-BN composite structures. The researchers will deploy water vapor-assisted chemical vapor deposition (CVD) method in the super growth of VA-CNT carpets on copper (Cu) with a maximum length up to 1 cm. Fabrication of the CNT-BN composite structures will be achieved by infiltrating gaseous boron precursors into the VA-CNTs followed by a universal heating, converting the precursors to solid BN crystals. Thermal stability and oxidation resistivity of the CNT-BN composite structures will be investigated using Thermogravimetric Analysis (TGA) and Differential thermal analysis (DTA) under an oxidation environment from room temperature to 3000 K. An oxy-acetylene flame will be employed to simulate the extreme environment in MHD channels for investigating the thermal and electrical conductivity, and corrosion and erosion resistance of the CNT-BN composite structures under the extreme conditions. Thermionic emission performance of the CNT-BN composite structures will be investigated to study the transport properties of the composite structures. If the CNT-BN composite does not perform as anticipated, selected ultra-high-temperature ceramics, such as titanium boride (TiB2), will be investigated as a backup candidate wrapping CNTs. Upon the successful completion of the propose research, CNT-C composite structures, such as CNT-BN and CNT-TiB2, will be developed for “hot” electrode applications. Fundamental understanding on the thermal and electrical transport properties of CNTs at high temperatures up to 3000 K will be established. Wrapping CNTs in ceramic matrices will isolate CNTs from the extreme environments in the MHD channels. The embedded CNTs will serve as conductive channels for heat and electricity transport. It is anticipated that the CNT-C composite structures would withstand the extreme environments in MHD channels and provide sufficient electrical and thermal conductivities for direct power extraction from seeded oxy-fuel combustion fluids. Successful development of the CNT-C composite structures will significant improve the reliability and promote the commercial applications of MHD generators, which are capable of large scale mass energy conversion at an unprecedented efficiency of 60% with reduced overall production of hazardous fossil fuel wastes.

01 COAL, LIGNITE, AND PEAT↗

An Overview of Significant Achievements in Ruthenium-Based Molecular Water Oxidation Catalysis

Fossil fuels (coal, oil, natural gas) are becoming increasingly disfavored as long-term energy options due to concerns of scarcity and environmental consequences (e.g., release of anthropogenic CO 2 ). Hydrogen gas, on the other hand, has gained popularity as a clean-burning fuel because the only byproduct from its reaction with O 2 is H 2 O. In recent decades, hydrogen derived from water splitting has been a topic of extensive research. The bottleneck of the water splitting reaction is the difficult water oxidation step (2H 2 O → O 2 + 4H + + 4e - ), which requires an effective and robust catalyst to overcome its high kinetic barrier. Research in water oxidation by molecular ruthenium catalysts enjoys a rich history spanning nearly 40 years. As the diversity of novel ligands continues to widen, the relationship between ligand geometry or electronics, and catalyst activity is undoubtedly becoming clearer. The present review highlights, in the authors’ opinion, some of the most impactful discoveries in the field and explores the evolution of ligand design that has led to the current state of the art.

14 SOLAR ENERGY↗

Method and apparatus for automated, modular, biomass power generation

Method and apparatus for generating a low tar, renewable fuel gas from biomass and using it in other energy conversion devices, many of which were designed for use with gaseous and liquid fossil fuels. An automated, downdraft gasifier incorporates extensive air injection into the char bed to maintain the conditions that promote the destruction of residual tars. The resulting fuel gas and entrained char and ash are cooled in a special heat exchanger, and then continuously cleaned in a filter prior to usage in standalone as well as networked power systems.

09 BIOMASS FUELS↗

Energy Literacy Essential Principle #7

Energy Literacy Essential Principle #7: The quality of life of individuals and societies is affected by energy choices.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Hydroelectric Power and Hydrogen Production Integration

Hydropower-based hydrogen production could introduce opportunities for new revenue streams for hydropower plants, including from energy storage and regeneration as well as from sale of the hydrogen product to external markets. Hydrogen-based energy storage and regeneration could also help support Idaho Power’s decarbonization goals by decreasing dependence on fossil-based peaking power plants. Additionally, integration of hydrogen production with hydropower generation could help address the issue of low dissolved oxygen river water conditions that commonly accompany hydropower plant operations by utilizing the oxygen byproduct from an electrolytic hydrogen production process as a resource for mitigation of low dissolved oxygen water conditions. Comprehensive techno-economic analysis of the hybrid hydroelectric and hydrogen energy storage system has revealed critical insights into the pathways and considerations for optimizing the economic value and environmental benefits of such systems. Among the three identified pathways of natural gas blending, regeneration, and direct sale of hydrogen, the direct sale of hydrogen emerges as the most profitable, particularly given the current pricing dynamics of hydrogen and electricity. However, as we anticipate a future grid characterized by higher renewable energy penetration, the landscape may evolve, featuring lower average electricity prices, heightened fluctuations, and more significant seasonal variations. Consequently, the attractiveness of electricity regeneration through hydrogen and the benefits of long-duration hydrogen storage are expected to increase substantially in such a dynamic energy scenario. The careful selection of component sizes within the hybrid system proves to be paramount for ensuring cost-effectiveness. Notably, the size of the hydrogen market has emerged as a critical determinant for the optimal size of the electrolyzer. Hydrogen storage should be sized to meet energy shifting requirements. The appropriate size of the fuel cell/microturbine generator hinges on the shape of electricity prices and the available revenue streams derived from participating in grid services. Striking the right balance among these components is essential for maximizing the overall efficiency and profitability of the hydrogen facility. Furthermore, the by-product of electrolysis, namely oxygen, introduces an additional dimension to the system's functionality. The oxygen generated can be effectively utilized for dissolved oxygen (DO) mitigation, particularly with larger electrolyzer sizes capable of satisfying the complete oxygen demand for this purpose. While the economic benefits derived from saved oxygen purchase costs may be relatively modest compared to other revenue streams, the environmental advantages of repurposing oxygen for DO mitigation could help Idaho Power meet their environmental obligations. In addition to the identified factors shaping the viability of hybrid hydrogen production and hydroelectric generation, it is noteworthy that the integration of hydrogen energy storage offers a unique advantage during unusually wet years. In such periods of increased water inflow, the hydrogen storage capacity serves as a valuable supplement to the reservoir. By utilizing hydrogen energy storage as a complementary reservoir, the system gains flexibility in reservoir management when dealing with fluctuations in water availability.

08 HYDROGEN↗

Coupling of the Electricity and Transportation Sectors - Part I: Sector Overviews

“Sector coupling” is a concept that addresses potential designs for the future power industry. Traditionally, the energy sectors, i.e., electricity supply, transport, and industry, have functioned largely independently from one another. Thus, the concept of sector coupling means that the electricity sector would become the central pillar of the energy system, supplying the other sectors – transportation and industry – with energy in various ways, a scheme described by the term “Power-to-X”. This report delves into the ambitious goal set by the United States to achieve net-zero emissions by 2050, with a pivotal milestone of making half of all passenger vehicles sold in America zero-emission by 2030. Central to achieving this objective is the electrification of the transportation sector, resulting in complex interactions between this sector and the electric industry. As electric vehicles become more prevalent, a shift in the dependency on electricity for vehicle charging emerges, alongside a reduction in the electricity demand associated with maintaining the fossil fuel supply chain. Both the electricity and fossil fuel have been identified as critical infrastructure sectors, the transportation sector's historical reliance on fossil fuels, and the mature supply chain supporting them are explored. This study emphasizes the existing sectoral coupling between the electric energy and transportation sectors, extending beyond vehicle charging to essential operations at refineries, pipeline facilities, storage, and fuel extraction. Recognizing the critical dependency of fossil fuel supply chain operations on the electric sector, this research underscores the need for a comprehensive view of the evolving dynamics between the transportation and electric sectors. This study has been split into two segments, Part-I provides an overview of the existing fossil fuel supply chain architecture and the electrical sector. We provide an in-depth analysis of the grid-transportation sectoral coupling, its interactions, the vulnerabilities and essential take-aways that would help us to address them and apply towards an electrified transportation sector in the future. We engaged with stakeholders to understand their expectations in enabling an electrified transportation. We accumulate the understandings from the current fossil fuel-based system in developing a risk matrix, by identifying all the threats and vulnerabilities and how would they apply to both the current and future transportation systems in Part-II of this report.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

RENEWABLE ENERGY AND ENVIRONMENTAL SUSTAINABILITY USING BIOMASS FROM DAIRY AND BEEF ANIMAL PRODUCTION

The Texas Panhandle is regarded as the "Cattle Feeding Capital of the World", producing 42% of the fed beef cattle in the United States within a 200-mile radius of Amarillo generating more than 5 million tons of feedlot manure /year. Apart from feedlots, the Bosque River Region in Erath County, just north of Waco, Texas with about 110,000 dairy cattle in over 250 dairies, produces 1.8 million tons of manure biomass (excreted plus bedding) per year. While the feedlot manure has been used extensively for irrigated and dry land crop production, most dairies, as well as other concentrated animal feeding operations (CAFO's), the dairy farms utilize large lagoon areas to store wet animal biomass. Water runoff from these lagoons has been held responsible for the increased concentration of phosphorus and other contaminates in the Bosque River which drains into Lake Waco—the primary source of potable water for Waco's 108,500 people. The concentrated animal feeding operations may lead to land, water, and air pollution if waste handling systems and storage and treatment structures are not properly managed. Manure-based biomass (MBB) has the potential to be a source of green energy at large coal-fired power plants and on smaller-scale combustion systems at or near confined animal feeding operations. Although MBB particularly cattle biomass (CB) is a low quality fuel with an inferior heat value compared to coal and other fossil fuels, the concentration of it at large animal feeding operations can make it a viable source of fuel. The overall objective of this interdisciplinary proposal is to develop environmentally benign technologies to convert low-value inventories of dairy and beef cattle biomass into renewable energy. Current research expands the suite of technologies by which cattle biomass (CB: manure, and premature mortalities) could serve as a renewable alternative to fossil fuel. The work falls into two broad categories of research and development. Category 1 – Renewable Energy Conversion. This category addressed mostly in volume I involves developing. Thermo-chemical conversion technologies including cofiring with coal, reburn to reduce nitrogen oxide (NO, N2O, NOx, etc.) and Hg emissions and gasification to produce low-BTU gas for on-site power production in order to extract energy from waste streams or renewable resources. Category 2 – Biomass Resource Technology. This category, addressed mostly in Volume II, deals with the efficient and cost-effective use of CB as a renewable energy source (e.g. through and via aqueous-phase, anaerobic digestion or biological gasification). The investigators formed an industrial advisory panel consisting fuel producers (feedlots and dairy farms) and fuel users (utilities), periodically met with them, and presented the research results; apart from serving as dissemination forum, the PIs used their critique to red-direct the research within the scope of the tasks. The final report for the 5 to 7 year project performed by an interdisciplinary team of 9 professors is arranged in three volumes: Vol. I (edited by Kalyan Annamalai) addressing thermo-chemical conversion and direct combustion under Category 1 and Vol. II and Vol. III ( edited by J M Sweeten) addressing biomass resource Technology under Category 2. Various tasks and sub-tasks addressed in Volume I were performed by the Department of Mechanical Engineering (a part of TEES; see Volume I), while other tasks and sub-tasks addressed in Volume II and IIII were conducted by Texas AgriLife Research at Amarillo; the TAMU Biological & Agricultural Engineering Department (BAEN) College Station; and West Texas A&M University (WTAMU) (Volumes II and III). The three volume report covers the following results: fuel properties of low ash and high ash CB (particularly DB) and MB (mortality biomass and coals, non-intrusive visible infrared (NVIR) spectroscopy techniques for ash determination, dairy energy use surveys at 14 dairies in Texas and California, cofiring of low quality CB with high quality coal, emission results and ash fouling behavior, using CB as reburn fuel for NOx and Hg reduction, gasification of fuels to produce low quality gases, modeling of reburn, pilot scale test results, synthesis of engineering characterization, geographical mapping, a transportation cost study to determine potential handling and transportation systems for co-firing with coal at regional coal-fired power plants, software analyses for the design of off-site manure, pre-processing and storage systems for a typical dairy farm or beef cattle feedlot, recursive production functions/systems models for both cattle feedlots, systems modeling, stocks and flows of energy involved in the CAFO system, feedback from an Industry Advisory Committee (IAC) to the investigators on project direction and task emphasis and economics of using CB as cofiring and reburn fuel.

09 BIOMASS FUELS↗

RENEWABLE ENERGY AND ENVIRONMENTAL SUSTAINABILITY USING BIOMASS FROM DAIRY AND BEEF ANIMAL PRODUCTION

The Texas Panhandle is regarded as the "Cattle Feeding Capital of the World", producing 42% of the fed beef cattle in the United States within a 200-mile radius of Amarillo generating more than 5 million tons of feedlot manure/year. Apart from feedlots, the Bosque River Region in Erath County, just north of Waco, Texas with about 110,000 dairy cattle in over 250 dairies, produces 1.8 million tons of manure biomass (excreted plus bedding) per year. While the feedlot manure has been used extensively for irrigated and dry land crop production, most dairies, as well as other concentrated animal feeding operations (CAFO's), the dairy farms utilize large lagoon areas to store wet animal biomass. Water runoff from these lagoons has been held responsible for the increased concentration of phosphorus and other contaminates in the Bosque River which drains into Lake Waco -- the primary source of potable water for Waco's 108,500 people. The concentrated animal feeding operations may lead to land, water, and air pollution if waste handling systems and storage and treatment structures are not properly managed. Manure-based biomass (MBB) has the potential to be a source of green energy at large coal-fired power plants and on smaller-scale combustion systems at or near confined animal feeding operations. Although MBB particularly cattle biomass (CB) is a low quality fuel with an inferior heat value compared to coal and other fossil fuels, the concentration of it at large animal feeding operations can make it a viable source of fuel. The overall objective of this interdisciplinary proposal is to develop environmentally benign technologies to convert low-value inventories of dairy and beef cattle biomass into renewable energy. Current research expands the suite of technologies by which cattle biomass (CB: manure, and premature mortalities) could serve as a renewable alternative to fossil fuel. The work falls into two broad categories of research and development. Category 1 -- Renewable Energy Conversion. This category addressed mostly in volume I involves developing. Thermo-chemical conversion technologies including cofiring with coal, reburn to reduce nitrogen oxide (NO, N2O, NOx, etc.) and Hg emissions and gasification to produce low-BTU gas for on-site power production in order to extract energy from waste streams or renewable resources. Category 2 -- Biomass Resource Technology. This category, addressed mostly in Volume II, deals with the efficient and cost-effective use of CB as a renewable energy source (e.g. through and via aqueous-phase, anaerobic digestion or biological gasification). The investigators formed an industrial advisory panel consisting fuel producers (feedlots and dairy farms) and fuel users (utilities), periodically met with them, and presented the research results; apart from serving as dissemination forum, the PIs used their critique to re-direct the research within the scope of the tasks. The final report for the 5 to 7 year project performed by an interdisciplinary team of 9 professors is arranged in three volumes: Vol. I (edited by Kalyan Annamalai) addressing thermo-chemical conversion and direct combustion under Category 1 and Vol. II and Vol. III ( edited by J M Sweeten) addressing biomass resource Technology under Category 2. Various tasks and sub-tasks addressed in Volume I were performed by the Department of Mechanical Engineering (a part of TEES; see Volume I), while other tasks and sub-tasks addressed in Volume II and IIII were conducted by Texas AgriLife Research at Amarillo; the TAMU Biological & Agricultural Engineering Department (BAEN) College Station; and West Texas A&M University (WTAMU) (Volumes II and III). The three volume report covers the following results: fuel properties of low ash and high ash CB (particularly DB) and MB (mortality biomass and coals, non-intrusive visible infrared (NVIR) spectroscopy techniques for ash determination, dairy energy use surveys at 14 dairies in Texas and California, cofiring of low quality CB with high quality coal, emission results and ash fouling behavior, using CB as reburn fuel for NOx and Hg reduction, gasification of fuels to produce low quality gases, modeling of reburn, pilot scale test results, synthesis of engineering characterization, geographical mapping, a transportation cost study to determine potential handling and transportation systems for co-firing with coal at regional coal-fired power plants, software analyses for the design of off-site manure, pre-processing and storage systems for a typical dairy farm or beef cattle feedlot, recursive production functions/systems models for both cattle feedlots, systems modeling, stocks and flows of energy involved in the CAFO system, feedback from an Industry Advisory Committee (IAC) to the investigators on project direction and task emphasis and economics of using CB as cofiring and reburn fuel.

01 COAL, LIGNITE, AND PEAT↗

Martian Magmatic-Driven Hydrothermal Sites: Potential Sources of Energy, Water, and Life

Magmatic-driven processes and impact events dominate the geologic record of Mars. Such recorded geologic activity coupled with significant evidence of past and present-day water/ice, above and below the martian surface, indicate that hydrothermal environments certainly existed in the past and may exist today. The identification of such environments, especially long-lived magmatic-driven hydrothermal environments, provides NASA with significant target sites for future sample return missions, since they (1) could favor the development and sustenance of life, (2) may comprise a large variety of exotic mineral assemblages, and (3) could potentially contain water/ice reservoirs for future Mars-related human activities. If life developed on Mars, the fossil record would presumably be at its greatest concentration and diversity in environments where long-term energy sources and water coexisted such as at sites where long-lived, magmatic-driven hydrothermal activity occurred. These assertions are supported by terrestrial analogs. Small, single-celled creatures (prokaryotes) are vitally important in the evolution of the Earth; these prokaryotes are environmentally tough and tolerant of environmental extremes of pH, temperature, salinity, and anoxic conditions found around hydrothermal vents. In addition, there is a great ability for bacteria to survive long periods of geologic time in extreme conditions, including high temperature hydrogen sulfide and sulfur erupted from Mount St. Helens volcano. Our team of investigators is conducting a geological investigation using multiple mission-derived datasets (e.g., existing geologic map data, MOC imagery, MOLA, TES image data, geophysical data, etc.) to identify prime target sites of hydrothermal activity for future hydrological, mineralogical, and biological investigations. The identification of these sites will enhance the probability of success for future missions to Mars.

Anderson, R. C.↗

Evaluation of Cryogenic Systems for Post Combustion CO2 Capture

Cryogenic capture of carbon dioxide from flue gas streams is one potential pathway to reduce the CO2 emissions from power plants and industrial sources. In this paper, a minimum energy analysis of idealized cryogenic carbon capture processes is performed. Parametric studies on this idealized process are quantified to study the effect of minimum capture temperature and simulated heat exchange approach temperatures. The theoretical and practical difficulties in approaching this ideal process are described and discussed. Finally, the Sustainable Energy Solutions External Cooling Loop Cryogenic Carbon Capture™ process is evaluated and compared to the idealized carbon-capture process.

20 FOSSIL-FUELED POWER PLANTS↗

Semiconductor-electrocatalyst contacts: theory, experiment, and applications to solar water photoelectrolysis

Semiconductor photoelectrodes coated with electrocatalysts are key components of photoelectrochemical (PEC) energy conversion and storage systems. Such systems could provide a way to convert the energy in sunlight directly into energy stored in a fuel like hydrogen gas to power our modern society without using fossil fuels. Despite an intense effort aimed at optimizing these materials, there has been little systematic work focused on the semiconductor-electrocatalyst (SC|EC) interface. The SC|EC interface is important because it is responsible for collecting the photoexcited electron-hole pairs generated in the semiconductor. During the performance period we initiated a fundamental effort to understand interfacial electron transfer between electrocatalysts and bulk semiconductors. We developed an experimental technique, dual-working-electrode (DWE) photoelectrochemistry, allowing for direct electrical measurement of the SC-EC interface in situ. We also developed the first theory of the SC|EC interface and applied the theory through numerical simulation to explain the measured interfacial charge transfer properties of the SC|EC junction. We discovered that porous, ion-permeable, redox-active catalysts such as Ni-(Fe) oxyhydroxides form so-called “adaptive” junctions where the effective interfacial barrier height for electron transfer depends on the charge state of the catalyst. This is in sharp contrast to interface properties of dense ion-impermeable catalysts, which we found form buried junctions that could be described by simple equivalent electrical circuits. These results elucidated a design principle for catalyzed photoelectrodes - high-performance photoelectrodes with direct SC|EC junctions use soft deposition techniques that yield ion-permeable catalysts. This work thus provides a foundation for the development of improved photoelectrodes that are practically relevant because they provide a mechanism to directly convert and store solar energy in the form of hydrogen gas, a renewable chemical fuel.

08 HYDROGEN↗