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At least 127 records · Page 7

Center for direct catalytic conversion of biomass to biofuels (Final Technical Report)

Lignocellulosic biomass has only one-third the energy density of crude oil and lacks petroleum’s versatility as a feedstock for fuels and chemicals. Since 2009, the Center for direct Catalytic Conversion of Biomass to Biofuels (C3Bio) has recognized the potential of chemical catalysis and fast-pyrolysis to overcome such limitations by transforming the main components of biomass (cellulose, xylan, and lignin) from grasses and trees directly to liquid hydrocarbons and aromatic co-products. In 2014, C3Bio proposed to develop critical systems-level understanding of how biomass structural complexity at molecular, nanoscale, and mesoscale levels impacts the yields and selectivities of desired products from catalytic and pyrolytic transformations. Our long-term goal was to gain unprecedented control of effective routing of carbon: we aimed to specify both the structures within, and the reaction products from, lignocellulosic biomass. Enabled by the EFRC high-risk, high-reward approach to grand challenge science, our interdisciplinary team of plant biologists, chemists, and chemical engineers disrupted the conventional paradigm of the cellulosic biorefinery into a new future of “no carbon left behind” - the full utilization of carbon from plant cell walls in energy-dense fuels.

09 BIOMASS FUELS↗

DOE Energy Frontier Research Centers Center for Direct Catalytic Conversion of Biomass to Biofuels (C3Bio)

New capabilities to predict, design and control the chemistries of carbon could answer a global imperative to transition from fossil-based to sustainable transportation fuels. While the use of inexpensive hydrocarbons has been an unparalleled achievement and enabler of economic prosperity for many nations, singular dependence upon crude oil has given rise to systemic vulnerabilities in climate, energy, economic, and national security. Lignocellulosic biomass, a renewable and carbon-neutral resource, has the potential to displace an estimated annual equivalent of three billion barrels of oil in the U.S. alone (National Research Council 2009, U. S. Department of Energy, 2011). However, biomass has only one-third the energy density of crude oil (Agrawal and Singh 2009, Richard 2010) and lacks petroleum’s versatility as a feedstock for fuels and chemicals. These limitations keep biomass conversion below the efficiency level needed for strategic impact while the scientific challenge of routing carbon from one molecular context to another remains unmet. In 2009, the Center for Direct Catalytic Conversion of Biomass to Biofuels (C3Bio) recognized the potential of chemical catalysis and fast pyrolysis to overcome such limitations by transforming the main components of biomass (cellulose, xylan, and lignin) from grasses and trees directly to liquid hydrocarbons and aromatic co-products. Enabled by the EFRC high-risk, high-reward approach to grand challenge science, C3Bio researchers have been key national players in disrupting the conventional paradigm of the cellulosic biorefinery into a new future of “no carbon left behind”—the full utilization of carbon from plant cell walls in energy-dense fuels (Fig. 1). We identified catalytic and fast-pyrolytic pathways that utilize cellulose, xylan and, most significantly, lignin. We developed catalytic processes that deoxygenate and transform monomers and isolated polymers into useful products and tested their use with intact biomass. We gained control of lignin synthesis within plants and initiated tailoring biomass to its end-use through the tools of plant molecular biology and genetic engineering. C3Bio breakthroughs have increased the energy density of biomass-derived substrates via catalytic and pyrolytic conversions into products such as benzoquinones, furfural and hydroxymethylfurfural, levoglucosan and levulinic acid, methoxypropylphenols and propylbenzene. Such advances in biomass conversion would not have been possible without simultaneous advances in analytical instrumentation and methodologies, and imaging technologies and applications. The legacy science developed by C3Bio enables design and control strategies for achieving a targeted product portfolio of fuel and chemical feedstocks from a diverse range of native and tailored biomass. Our research provides the knowledge base required for a bio-economy with product streams as diverse in functionality as those of the petrochemical industry. Coupling targeted computational modeling with experimentation, we achieved: (1) fundamental understanding of biopolymers and cell wall architecture assembly, (2) discovery of new chemistries that allow the development of highly selective pathways to fuels and desirable chemicals, and (3) an integrated systems-level understanding to control catalytic and pyrolytic pathways.

09 BIOMASS FUELS↗

Electronic tuning of the transport properties of off-stoichiometric Pb{sub x}Sn{sub 1−x}Te thermoelectric alloys by Bi{sub 2}Te{sub 3} doping

The recent energy demands affected by the dilution of conventional energy resources and the growing awareness of environmental considerations had motivated many researchers to seek for novel renewable energy conversion methods. Thermoelectric direct conversion of thermal into electrical energies is such a method, in which common compositions include IV-VI semiconducting compounds (e.g., PbTe and SnTe) and their alloys. For approaching practical thermoelectric devices, the current research is focused on electronic optimization of off-stoichiometric p-type Pb{sub x}Sn{sub 1−x}Te alloys by tuning of Bi{sub 2}Te{sub 3} doping and/or SnTe alloying levels, while avoiding the less mechanically favorable Na dopant. It was shown that upon such doping/alloying, higher ZTs, compared to those of previously reported undoped Pb{sub 0.5}Sn{sub 0.5}Te alloy, were obtained at temperatures lower than 210–340 °C, depending of the exact doping/alloying level. It was demonstrated that upon optimal grading of the carrier concentration, a maximal thermoelectric efficiency enhancement of ∼38%, compared to that of an undoped material, is expected.

30 DIRECT ENERGY CONVERSION↗

Direct Energy Conversion for Low Specific Mass In-Space Power and Propulsion

"Changing the game" in space exploration involves changing the paradigm for the human exploration of the Solar System, e.g, changing the human exploration of Mars from a three-year epic event to an annual expedition. For the purposes of this assessment an "annual expedition" capability is defined as an in-space power & propulsion system which, with launch mass limits as defined in NASA s Mars Architecture 5.0, enables sending a crew to Mars and returning them after a 30-day surface stay within one year, irrespective of planetary alignment. In this work the authors intend to show that obtaining this capability requires the development of an in-space power & propulsion system with an end-to-end specific mass considerably less than 3 kg/kWe. A first order energy balance analysis reveals that the technologies required to create a system with this specific mass include direct energy conversion and nuclear sources that release energy in the form of charged particle beams. This paper lays out this first order approximation and details these conclusions.

Scott, John H.↗

Fate of phosphorus in Everglades agricultural soils after fertilizer application

Land use changes, agricultural drainage and conventional cultivation of winter vegetables and sugarcane cropping in the Everglades Agricultural Area (EAA) may alter soil conditions and organic matter decomposition and ultimately influence the fate of phosphorus (P). Theses agricultural practices promote soil subsidence, reduce the soil depth to bedrock limestone and increase the potential for incorporation of limestone into the root zone of crops. The incorporation of limestone into surface soil has significantly increased soil pH which in turns causes greater fixation of P fertilizer into unavailable forms for plant growth. Additional P fertilization is thus required to satisfy crop nutrient requirements in plant-available P form. It is important to determine how the mixing of bedrock limestone into soils influences the behavior of P fertilizers after their application. To accomplish this task, P fertilizers were applied to (1) typical cultivated soils and to (2) soils that have never been fertilized or extensively tilled. The changes in P concentrations over time were then compared between the two land uses, with differences being attributable to the impacts of cultivation practices. The P distribution in soil varied between land uses, with sugarcane having more P in inorganic pools while the uncultivated soil had more in organic pools. Water-soluble P concentrations in soil increased with increasing fertilizer application rates for all sampling times and both land uses. However, concentrations in uncultivated soil increased proportionally to P-fertilized soil due to organic P mineralization. At all sampling times, plant-available P concentrations remained higher for uncultivated than sugarcane soil. Lower P concentrations for sugarcane were related to adsorption by mineral components (e.g. limestone). Cultivated soils have higher calcium concentrations resulting from incorporation of bedrock limestone into soil by tillage, which increased pH and fostered sequestration of plant-available P into stable calcium-bound P pools. This greater P retention for sugarcane was reflected in the greater proportion of P in inorganic pools compared to uncultivated soils. Some lands within the EAA, including wetlands and seasonally-flooded prairies, are being reclaimed for water quality purposes. However, long-term effects of fertilization and cropping practices described in this document indicate that direct conversion from active farming, such as from sugarcane production directly to wetlands, may be problematic due to the changes in nutrient dynamics that may occur. The shift directly to wetlands may, in fact, release considerable amounts of P into the Everglades, thwarting the intent of the land use change. The inorganic P component in sugarcane soils may lead to the regeneration of soluble P in frequently flooded land uses such as wetlands. While most of the inorganic P pools are unavailable to sugarcane, the direct conversion of sugarcane soils to wetlands may facilitate P release. Here, reclamation of sugarcane fields for environment uses would benefit by an intermediate step to allow for a short duration of seasonal flooding allowing for P conversion from inorganic to organic forms. Prolonged flooding of organic soils previously used for intensive agriculture is not recommended.

54 ENVIRONMENTAL SCIENCES↗

Engineering PdAu/CeO 2 Alloy/Oxide Interfaces for Selective Methane‐to‐Methanol Conversion with Water

The direct conversion of methane-to-methanol remains a critical challenge in methane valorization. In this study, we unveil the crucial role of PdAu/CeO 2 catalysts in enabling selective methane transformation under mild conditions, using only water as the sole oxidant. Through a combination of experimental techniques, including XPS and catalytic testing, alongside density functional theory (DFT) calculations, we demonstrate that a Pd 0.3 Au 0.7 /CeO 2 catalyst, which predominantly exposes isolated Pd atoms, achieves remarkable methanol selectivity (∼80%) at 500 K with a 1:1 methane-to-water ratio. While Pd/CeO 2 efficiently activates methane, its tendency for overreaction leads to complete methanol decomposition, thereby limiting selectivity. Alloying Pd with Au on ceria mitigates this over-reactivity, preventing methanol degradation while maintaining sufficient catalytic activity. The PdAu/CeO 2 composite exhibits a synergistic effect: Pd in contact with the ceria support facilitates methane activation and water dissociation, while Au fine-tunes reactivity to promote methanol formation. DFT calculations confirm that isolated Pd sites at the PdAu/CeO 2 interface play a key role in balancing activity and selectivity. This work underscores the importance of alloy/oxide interfaces in controlling selective methane conversion with water and offers valuable insights for designing highly efficient catalysts for methanol synthesis.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Thermoelectric Energy Conversion: Future Directions and Technology Development Needs

This viewgraph presentation reviews the process of thermoelectric energy conversion along with key technology needs and challenges. The topics include: 1) The Case for Thermoelectrics; 2) Advances in Thermoelectrics: Investment Needed; 3) Current U.S. Investment (FY07); 4) Increasing Thermoelectric Materials Conversion Efficiency Key Science Needs and Challenges; 5) Developing Advanced TE Components & Systems Key Technology Needs and Challenges; 6) Thermoelectrics; 7) 200W Class Lightweight Portable Thermoelectric Generator; 8) Hybrid Absorption Cooling/TE Power Cogeneration System; 9) Major Opportunities in Energy Industry; 10) Automobile Waste Heat Recovery; 11) Thermoelectrics at JPL; 12) Recent Advances at JPL in Thermoelectric Converter Component Technologies; 13) Thermoelectrics Background on Power Generation and Cooling Operational Modes; 14) Thermoelectric Power Generation; and 15) Thermoelectric Cooling.

theromelectric↗

Novel aqueous amine looping approach for the direct capture, conversion and storage of CO 2 to produce magnesium carbonate

Designing novel integrated chemical pathways for the capture, conversion, and storage of CO 2 is a crucial need for advancing sustainable energy conversion. The accelerated conversion of CO 2 to water-insoluble and stable magnesium carbonate is a thermodynamically downhill route for permanently storing CO 2 . However, a practical constraint of carbon mineralization is the slow kinetics at low CO 2 concentrations. In this study, we investigate a direct integrated mineralization approach, whereby CO 2 , amine solvents (such as monoethanolamine, MEA), water and alkaline Mg-bearing solids are reacted in a slurry reaction environment. About 70% conversion of magnesium oxide to magnesium carbonate was achieved at 50 °C after 3 hours. The looping of amine-bearing solvents between the CO 2 loaded and release states, facilitates the accelerated conversion of magnesium-bearing oxides to magnesium carbonate. Hydrated magnesium carbonate and magnesium hydroxide phases were noted when less than complete conversion of magnesium oxide was achieved. The morphological features were determined using in operando ultra-small and small angle X-ray scattering (USAXS/SAXS) and grazing incidence-small angle X-ray scattering (GI-SAXS) measurements. The proposed pathway is an adaptive, low temperature, single-step approach for the direct capture, conversion and storage of CO 2 . By demonstrating the effectiveness of aqueous alkaline amine looping approach for the accelerated carbon mineralization of MgO, we aim to expand this approach to include heterogeneous alkaline industrial residues such as coal fly ash and steel slag and naturally occurring minerals such as magnesium silicate and calcium silicate.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The theory of an auto-resonant field emission cathode relativistic electron accelerator for high efficiency microwave to direct current power conversion

A novel method of microwave power conversion to direct current is discussed that relies on a modification of well known resonant linear relativistic electron accelerator techniques. An analysis is presented that shows how, by establishing a 'slow' electromagnetic field in a waveguide, electrons liberated from an array of field emission cathodes, are resonantly accelerated to several times their rest energy, thus establishing an electric current over a large potential difference. Such an approach is not limited to the relatively low frequencies that characterize the operation of rectennas, and can, with appropriate waveguide and slow wave structure design, be employed in the 300 to 600 GHz range where much smaller transmitting and receiving antennas are needed.

Manning, Robert M.↗

Formation of the Radiation Conditions by the Nuclear Reactor of a Power Facility with Direct Energy Conversion

Computational and design studies of the arrangement of an autonomous power unit with a nuclear reaction in a sparsely populated location characterized by weak soil are presented. A variant of a possible arrangement of the reactor taking account of the requirements of the facility is shown. The radioactive emission around the reactor and the distribution of heat emission in the soil, for picking and determining the number of cooling elements, are calculated. A technical solution that provides for the installation of a nuclear reactor in soft ground is proposed.

22 GENERAL STUDIES OF NUCLEAR REACTORS↗

Direct Catalytic Conversion of Ethanol to C 5+ Ketones: Role of Pd–Zn Alloy on Catalytic Activity and Stability

Abstract Ethanol can be used as a platform molecule for synthesizing valuable chemicals and fuel precursors. Direct synthesis of C 5+ ketones, building blocks for lubricants and hydrocarbon fuels, from ethanol was achieved over a stable Pd‐promoted ZnO‐ZrO 2 catalyst. The sequence of reaction steps involved in the C 5+ ketone formation from ethanol was determined. The key reaction steps were found to be the in situ generation of the acetone intermediate and the cross‐aldol condensation between the reaction intermediates acetaldehyde and acetone. The formation of a Pd–Zn alloy in situ was identified to be the critical factor in maintaining high yield to the C 5+ ketones and the stability of the catalyst. A yield of >70 % to C 5+ ketones was achieved over a 0.1 % Pd‐ZnO‐ZrO 2 mixed oxide catalyst, and the catalyst was demonstrated to be stable beyond 2000 hours on stream without any catalyst deactivation.

Subramaniam, Senthil↗

Growth and device processing of hexagonal boron nitride epilayers for thermal neutron and deep ultraviolet detectors

Solid-state neutron detectors with high performance are highly sought after for the detection of fissile materials. However, direct-conversion neutron detectors based on semiconductors with a measureable efficiency have not been realized. We report here the first successful demonstration of a direct-conversion semiconductor neutron detector with an overall detection efficiency for thermal neutrons of 4% and a charge collection efficiency as high as 83%. The detector is based on a 2.7 μm thick {sup 10}B-enriched hexagonal boron nitride (h-BN) epitaxial layer. The results represent a significant step towards the realization of practical neutron detectors based on h-BN epilayers. Neutron detectors based on h-BN are expected to possess all the advantages of semiconductor devices including wafer-scale processing, compact size, light weight, and ability to integrate with other functional devices.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Space Photovoltaic Research and Technology, 1989

Remarkable progress on a wide variety of approaches in space photovoltaics, for both near and far term applications is reported. Papers were presented in a variety of technical areas, including multi-junction cell technology, GaAs and InP cells, system studies, cell and array development, and non-solar direct conversion. Five workshops were held to discuss the following topics: mechanical versus monolithic multi-junction cells; strategy in space flight experiments; non-solar direct conversion; indium phosphide cells; and space cell theory and modeling.

Source record↗

Rational Design of Mixed-Metal Oxides for Chemical Looping Combustion of Coal via Coupled Computational-Experimental Studies

Energy and global climate change are two grand challenges to the modern society. An urgent need exists for development of clean and efficient energy conversion processes. The chemical looping strategy, which utilizes regenerable oxygen carriers (OCs) to indirectly convert carbonaceous fuels via redox reactions, is considered to be one of the more promising approaches for CO2 capture by the U.S. Department of Energy (USDOE). To date, most long-term chemical looping operations were conducted using gaseous fuels, even though direct conversion of coal is more desirable from both economics and CO2 capture viewpoints. The main challenges for direct coal conversion reside in the stringent requirements on oxygen carrier performances. In addition, coal char and volatile compounds are more challenging to convert than gaseous fuels. A promising approach for direct conversion of coal is the so called chemical looping with oxygen uncoupling (CLOU) technique. In the CLOU process, a metal oxide that decomposes at the looping temperature, and releases oxygen to the gas phase is used as the OC. The overarching objective of this project was to discover the fundamental principles for rational design and optimization of oxygen carriers (OC) in coal chemical looping combustion (CLC) processes. It directly addresses Topic Area B of the funding opportunity announcement (FOA) in terms of “predictive description of the phase behavior and mechanical properties” of “mixed metal oxide” based OCs and rational development of new OC materials with superior functionality. This was achieved through studies exploring i) iron-containing mixed-oxide composites as oxygen carriers for CLOU, ii) Ca1-xAxMnO3-δ (A = Sr and Ba) as oxygen carriers for CLOU, iii) CaMn1-xBxO3-δ (B=Al, V, Fe, Co, and Ni) as oxygen carrier for CLOU and iv) vacancy creation energy in Mn-containing perovskites as an indicator chemical looping with oxygen uncoupling.

20 FOSSIL-FUELED POWER PLANTS↗

Contactless measurement of equilibrium electron concentrations in n -type InAs/InAs1−xSbx type-II superlattices

Measurements of the equilibrium majority carrier electron concentration (n0) in narrow-bandgap n-type InAs/InAs1−xSbx type-II superlattices are made using contactless time-resolved microwave reflectance (TMR). By calibrating TMR decays to the number of optically injected electron-hole pairs, direct conversion to carrier lifetimes as a function of excited carrier density is made and allowing for accurate measurement of n0. The temperature dependence of both n0 and the intrinsic carrier density (ni) are measured using this method, where n0 = 1 × 1015 cm−3 and ni = 1.74 × 1011 cm−3 at 100 K. These results provide non-destructive insight into critical parameters that directly determine infrared photodetector dark diffusion current.

Olson, B. V. (ORCID:0000000314212541)↗

Performance Criteria for Capture and/or Immobilization Technologies (Revision 1)

The capture and subsequent immobilization of regulated volatile radionuclides from the off-gas streams of a used nuclear fuel (UNF) reprocessing facility has been a topic of substantial research interest for the US Department of Energy and its international counterparts. Removal of specific radionuclides from the plant effluent streams before discharge to the environment is required to meet regulations set forth by the US Environmental Protection Agency. Upon removal, the radionuclides, as well as associated sorbents that cannot be regenerated in a cost-effective manner, are destined for conversion to a waste form. Research in separation and capture methodologies has included a wide range of technology types, and studies of waste forms are correspondingly diverse. In considering the future development and implementation of both sorbents and waste forms, it is necessary to identify benchmark measures of performance to objectively evaluate each sorbent system or waste form. Sets of performance criteria and associated metrics have been developed for sorbent and waste form evaluation. These criteria address physical, radiological, and chemical characteristics, technical practicality, technical maturity, cost, and, for sorbents, system performance. The criteria and metrics appear to be robust and should be applicable despite the eventual waste classification (as either high- or low-level waste). They are flexible enough to address both aqueous reprocessing and electrochemical reprocessing of UNF. These criteria sets can serve as tools to evaluate performance at multiple stages within the development process, and in this revision (Revision 1) they have been used to assess technologies relating to krypton/xenon separations and iodine capture from off-gas streams arising from UNF reprocessing. Assessment of krypton/xenon separations using engineered forms of two zeolite minerals (silver mordenite and hydrogen mordenite in a polyacrylonitrile-based binder [AgZ-PAN/HZ-PAN]) found that the zeolite-based separation is relatively advanced in its development, but several key issues require resolution. First, desorption processes for both krypton and xenon require refinement to provide an understanding of the product purity that can be achieved. Second, adsorption rate data is needed in order to calculate the bed depth required for effective separation. Finally, it is strongly recommended that a technical review of krypton/xenon separation by AgZ-PAN/HZ-PAN be performed to synergize available data and assess the cost savings and operational benefits that may be realized from implementation of this technology. Assessment of metal organic frameworks (MOFs) for their use in the separation of krypton/xenon found that the ideal separation would be performed using a single-column system with a MOF selective for krypton over xenon. A robust research effort should work to identify a krypton-selective MOF designed to operate at temperatures of approximately 0°C or higher, which could be preferred over cryogenic krypton/xenon capture for used fuel reprocessing off-gas streams. In the case of the CaSDB-MOF (the most well-understood xenon sorbent to date), two issues are judged of high importance. First, xenon breakthrough capacity for the CaSDB-MOF in prototypical conditions should be determined. Preliminary research indicates that breakthrough may be near immediate, presenting a substantial obstacle in separative system design. Second, development of desorption methodology should be performed to determine regeneration time, energy requirements, and the product stream composition. Silver-based sorbents (AgZ and AgAero) for use in iodine capture from the dissolver off-gas were evaluated against the established criteria. These sorbents are significantly better understood for this application as a result of research efforts over the past decade. The potential implementation of AgAero at a large scale is hindered by its physical degradation by components of the dissolver off-gas stream. Less is known about the adsorption of iodine by these sorbents from other off-gas streams in the plant. Initial experimental efforts have been closely coordinated in an effort to understand organic iodine (such as would be found in the vessel off-gas) adsorption by AgZ and AgAero. Future work should expand this experimental program, and analysis of other reprocessing facility off-gas streams such as the vitrification off-gas stream should be conducted to better understand other potential applications for iodine sorbents. A review of iodine waste form development shows that this area is diverse and that multiple promising waste forms have been identified for the immobilization of radioactive iodine. Efforts related to the direct conversion of iodine sorbents (including AgZ and AgAero) should be continued because of the advantages of direct conversion in a waste management strategy and other sorbents should continue to be advanced as merited.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗