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At least 649 records · Page 36

Understanding and controlling the fundamental photochemistry of protonic solar energy conversion (Final Scientific/Technical Report)

The selectivity and activity of most fuel-forming reactions are tunable by the concentration of electrons, holes, protons, and/or hydroxides. That is one reason why traditional solar energy conversion processes are used to drive these reactions, where light directly increases the concentration of electrons and holes. We, instead, took a different approach, using light to increase the concentration of protons and/or hydroxides. For this, we leveraged photophysical and solid-state physics theories, techniques, and design strategies previously developed for the study of traditional solar energy conversion processes. We designed and fabricated several materials platforms based on molecular photoacid and photobase dyes coupled with ion-exchange polymer membranes and assessed their fundamental photoelectrochemistry. We demonstrated control over built-in electric potentials, photovoltages, proton-transfer kinetics, and efficiency limits to our approach. Understanding the basic science of these dye-sensitized protonic membranes and their photochemical mechanisms is of use to the DOE-relevant processes of solar photochemical fuel formation, solar photodialytic desalination, and solar cells. Moreover, functional materials that we developed from this project may be of use to several broad-reaching fields and may provide the foundation for a completely new, inexpensive, and robust solar energy conversion technology.

14 SOLAR ENERGY↗

Enhancing the Value of Wasted and Stranded Natural Gas Resources Through Conversion Into Aromatics Using Microwaves

Natural gas flaring results in the waste of significant amounts of valuable domestic energy resources while also producing undesirable environmental impacts. Transforming natural gas into value-added chemicals via direct nonoxidative reactions presents a compelling alternative to flaring. However, traditional thermal reactor systems face challenges due to thermodynamic limitations and poor catalyst stability. Microwave-assisted reactions offer a sustainable, on-demand approach for chemical production from natural gas, suitable for compact, flexible reactor systems at the well-site that can be powered by renewable energy. This method offers a novel, non-traditional approach in catalyst activation and product selectivity compared to a conventional thermal method, potentially leading to faster rates, higher selectivities, and higher conversion efficiencies. Despite these advantages, challenges exist, such as the low microwave-sensitivity of the state-of-the-art zeolite catalyst that is highly active for the methane dehydroaromatization reaction. This presentation will discuss recent research from the National Energy Technology Laboratory concerning microwave-assisted natural gas conversion directly into aromatics. It will address the difficulties with microwave heating of traditional thermochemical catalysts, and the application of Multiphysics modeling to understand temperature and field strength in the reactor, to enhance chemical conversion. The presentation will also cover how heating aids can mitigate heating challenges and transform microwave catalysis into a quasi-thermal kinetic problem. Additionally, catalyst activation and deactivation under microwave conditions will be examined, along with the future outlook and needs for microwave enhanced catalysis applications.

catalysis↗

Direct Air Reactive Capture and Conversion for Utility-Scale Energy Storage (Final Report)

This final report for FEW0277 summarizes the work performed over the project performance period of October 2021 – March 2025. This project was funded under the “Reactive Capture and Conversion R&D” lab call released in FY2021. The goal of the project was to develop dual-function materials and process for capturing CO 2 from the atmosphere and converting it into CH 4 . The work was organized into four parallel tracks in 1) direct air capture materials synthesis and characterization, 2) catalysts for CO 2 conversion, 3) mechanistic investigations via ab initio simulations, and 4) process modeling, technoeconomic analysis, and lifecycle assessment. The project was split into two budget periods. The first budget period focused on development of amine-based materials, due to their known performance for CO 2 direct air capture and their potential to act synergistically with metal catalysts to enable a low-temperature methanation pathway. The second budget period focused on development of alkali-based materials and a simulated-moving-bed process for high conversion catalytic reduction of captured CO 2 to CH 4 . All project milestones were completed during the project performance period and are summarized in this report. Our work resulted in publication of eight peer-reviewed manuscripts, one patent application, and numerous presentations given at domestic and international conferences and invited academic department seminars.

03 NATURAL GAS↗

Understanding_the_deactivation_mechanisms_of_ethanol_conversion_over_Cu-Y_Beta_catalyst

Direct conversion of bioethanol to C₃⁺olefins is a promising pathway for sustainable aviation fuel (SAF) production, but catalyst deactivation limits long-term operation. The stability and deactivation mechanisms of multifunctional Cu–Y/Beta zeolite catalysts were investigated for ethanol-to-olefins conversion over 300 h time-on-stream in the presence of H2. Catalytic testing reveals progressive losses in ethanol conversion and C₃⁺ olefin selectivity accompanied by increased acetaldehyde formation. The catalyst testing studies correlate with a suite of characterizations of fresh, spent, and regenerated catalysts to identify the deactivation factors. The loss of Y Lewis acid sites is the primary deactivation element. Reversible acid site deactivation is caused by coke deposition, which blocks Y-derived Lewis acid sites responsible for aldol condensation, MPV reduction, and alcohol dehydration. Minor irreversible deactivation is observed and possibly results from hydrothermal dehydroxylation of Y–silanol interactions, resulting in permanent loss of Lewis acidity without zeolite framework degradation or Y aggregation. Cu sites undergo limited agglomeration into small nanoparticles but contribute insignificantly to catalyst deactivation, under the investigated time frame. Oxidative regeneration removes coke and redistributes Cu sites, leading to full recovery of the initial catalytic performance though the Y Lewis acid sites are unable to fully recover. These findings establish Lewis acid site degradation as the primary deactivation mechanism impacting long-term catalyst stability

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Understanding the Impact of Hydrogen Activation by SrCe 0.8 Zr 0.2 O 3-δ Perovskite Membrane Material on Direct Non-Oxidative Methane Conversion

Direct non-oxidative methane conversion (DNMC) converts methane (CH 4 ) in one step to olefin and aromatic hydrocarbons and hydrogen (H 2 ) co-product. Membrane reactors comprising methane activation catalysts and H 2 -permeable membranes can enhance methane conversion by in situ H 2 removal via Le Chatelier's principle. Rigorous description of H 2 kinetic effects on both membrane and catalyst materials in the membrane reactor, however, has been rarely studied. In this work, we report the impact of hydrogen activation by hydrogen-permeable SrCe 0.8 Zr 0.2 O 3-δ (SCZO) perovskite oxide material on DNMC over an iron/silica catalyst. The SCZO oxide has mixed ionic and electronic conductivity and is capable of H 2 activation into protons and electrons for H 2 permeation. In the fixed-bed reactor packed with a mixture of SCZO oxide and iron/silica catalyst, stable and high methane conversion and low coke selectivity in DNMC was achieved by co-feeding of H 2 in methane stream. The characterizations show that SCZO activates H 2 to favor “soft coke” formation on the catalyst. The SCZO could absorb H 2 in situ to lower its local concentration to mitigate the reverse reaction of DNMC in the tested conditions. The co-existence of H 2 co-feed, SCZO oxide, and DNMC catalyst in the present study mimics the conditions of DNMC in the H 2 -permeable SCZO membrane reactor. The findings in this work offer the mechanistic understanding of and guidance for the design of H 2 -permeable membrane reactors for DNMC and other alkane dehydrogenation reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

N2-to-NH3 conversion by excess electrons trapped in point vacancies on 5f-element dioxide surfaces

Ammonia (NH 3 ) is one of the basic chemicals in artificial fertilizers and a promising carbon-free energy storage carrier. Its industrial synthesis is typically realized via the Haber−Bosch process using traditional iron-based catalysts. Developing advanced catalysts that can reduce the N 2 activation barrier and make NH 3 synthesis more efficient is a long-term goal in the field. Most heterogeneous catalysts for N 2 -to-NH 3 conversion are multicomponent systems with singly dispersed metal clusters on supporting materials to activate N 2 and H 2 molecules. Herein, we report single-component heterogeneous catalysts based on 5 f actinide dioxide surfaces (ThO 2 and UO 2 ) with oxygen vacancies for N 2 -to-NH 3 conversion. The reaction cycle we propose is enabled by a dual-site mechanism, where N 2 and H 2 can be activated at different vacancy sites on the same surface; NH 3 is subsequently formed by H − migration on the surface via associative pathways. Oxygen vacancies recover to their initial states after the release of two molecules of NH 3 , making it possible for the catalytic cycle to continue. Our work demonstrates the catalytic activities of oxygen vacancies on 5 f actinide dioxide surfaces for N 2 activation, which may inspire the search for highly efficient, single-component catalysts that are easy to synthesize and control for NH 3 conversion.

36 MATERIALS SCIENCE↗

Exponential Strong Converse for Successive Refinement with Causal Decoder Side Information

We consider the k-user successive refinement problem with causal decoder side information and derive an exponential strong converse theorem. The rate-distortion region for the problem can be derived as a straightforward extension of the two-user case by Maor and Merhav (2008). We show that for any rate-distortion tuple outside the rate-distortion region of the k-user successive refinement problem with causal decoder side information, the joint excess-distortion probability approaches one exponentially fast. Our proof follows by judiciously adapting the recently proposed strong converse technique by Oohama using the information spectrum method, the variational form of the rate-distortion region and Hölder’s inequality. The lossy source coding problem with causal decoder side information considered by El Gamal and Weissman is a special case (k = 1) of the current problem. Therefore, the exponential strong converse theorem for the El Gamal and Weissman problem follows as a corollary of our result.

42 ENGINEERING↗

An Assessment of the Conversion of Biomass and Industrial Waste Products to Activated Carbon

The production of biochar from biomass and industrial wastes provides both environmental and economic sustainability. An effective way to ensure the sustainability of biochar is to produce high value-added activated carbon. The desirable characteristic of activated carbon is its high surface area for efficient adsorption of contaminants. Feedstocks can include a number of locally available materials with little or negative value, such as orchard slash and crop residue. In this context, it is necessary to determine and know the conversion effects of the feedstocks to be used in the production of activated carbon. In the study conducted for this purpose; several samples (piñon wood, pecan wood, hardwood, dried grass, Wyoming coal dust, Illinois coal dust, Missouri coal dust, and tire residue) of biomass and industrial waste products were investigated for their conversion into activated carbon. Small samples (approximately 0.02 g) of the feedstocks were pyrolyzed under inert or mildly oxidizing conditions in a thermal analyzer to determine their mass loss as a function of temperature and atmosphere. Once suitable conditions were established, larger quantities (up to 0.6 g) were pyrolyzed in a tube furnace and harvested for characterization of their surface area and porosity via gas sorption analysis. Among the samples used, piñon wood gave the best results, and pyrolysis temperatures between 600 and 650 °C gave the highest yield. Slow pyrolysis or hydrothermal carbonization have come to the fore as recommended production methods for the conversion of biochar, which can be produced from biomass and industrial wastes, into activated carbon.

09 BIOMASS FUELS↗

Real Time Observation of Lithium Insertion into Pre-Cycled Conversion-Type Materials

Conversion-type electrode materials for lithium-ion batteries experience significant structural changes during the first discharge–charge cycle, where a single particle is taken apart into a number of nanoparticles. This structural evolution may affect the following lithium insertion reactions; however, how lithiation occurs in pre-cycled electrode materials is elusive. In this work, in situ transmission electron microscopy was employed to see the lithium-induced structural and chemical evolutions in pre-cycled nickel oxide as a model system. The introduction of lithium ions induced the evolution of metallic nickel, with volume expansion as a result of a conversion reaction. After pre-cycling, the phase evolutions occurred in two separate areas almost at the same time. This is different from the first lithiation, where the phase change takes place successively, with a boundary dividing the reacted and unreacted areas. Structural changes were restricted at the areas having large amount of fluorine, implying the residuals from the decomposition of electrolytes may have hindered the electrochemical reactions. This work provides insights into phase and chemical evolutions in pre-cycled conversion-type materials, which govern electrochemical properties during operation.

25 ENERGY STORAGE↗

Gene conversion is strongly induced in human cells by double-strand breaks and is modulated by the expression of BCL-x(L)

Homology-directed repair (HDR) of DNA double-strand breaks (DSBs) contributes to the maintenance of genomic stability in rodent cells, and it has been assumed that HDR is of similar importance in DSB repair in human cells. However, some outcomes of homologous recombination can be deleterious, suggesting that factors exist to regulate HDR. We demonstrated previously that overexpression of BCL-2 or BCL-x(L) enhanced the frequency of X-ray-induced TK1 mutations, including loss of heterozygosity events presumed to arise by mitotic recombination. The present study was designed to test whether HDR is a prominent DSB repair pathway in human cells and to determine whether ectopic expression of BCL-x(L) affects HDR. Using TK6-neo cells, we find that a single DSB in an integrated HDR reporter stimulates gene conversion 40-50-fold, demonstrating efficient DSB repair by gene conversion in human cells. Significantly, DSB-induced gene conversion events are 3-4-fold more frequent in TK6 cells that stably overexpress the antiapoptotic protein BCL-X(L). Thus, HDR plays an important role in maintaining genomic integrity in human cells, and ectopic expression of BCL-x(L) enhances HDR of DSBs. This is the first study to highlight a function for BCL-x(L) in modulating DSB repair in human cells.

NASA Discipline Radiation Health↗

Energy Conversion and Storage Requirements for Hybrid Electric Aircraft

Among various options for reducing greenhouse gases in future large commercial aircraft, hybrid electric option holds significant promise. In the hybrid electric aircraft concept, gas turbine engine is used in combination with an energy storage system to drive the fan that propels the aircraft, with gas turbine engine being used for certain segments of the flight cycle and energy storage system being used for other segments. The paper will provide an overview of various energy conversion and storage options for hybrid electric aircraft. Such options may include fuel cells, batteries, super capacitors, multifunctional structures with energy storage capability, thermoelectric, thermionic or a combination of any of these options. The energy conversion and storage requirements for hybrid electric aircraft will be presented. The role of materials in energy conversion and storage systems for hybrid electric aircraft will be discussed.

Energy Conversion↗

Insertion Loss of a Multi-Plane Light Conversion Device with Few Mode Fiber Outputs Under Atmospheric Conditions

A key challenge of photon counting optical communication is delivering light with atmospherically distorted wavefronts from the telescope to detectors efficiently. When using fiber coupled single photon detectors, the efficiency of the transmittance is constrained by the modes supported by the fiber. The number of modes supported by a fiber depends on the size of the core. The larger the core, the more modes supported. However, commercial off the shelf superconducting nanowire single photon detectors (SNSPDs) are currently limited in area, which limits the core size of the fibers that can efficiently couple to the detectors. To increase the amount of light that can be delivered to the detectors, NASA Glenn Research Center is considering many different fiber/detector architectures. This paper compares insertion loss of the fiber device for two different architectures: • a multi-plane light conversion device to split the light from a 30 µm core diameter fiber into 7 separate, 15 µm core diameter few-mode fibers butt-coupled to 7 single-element SNSPDs, • and a 30 µm core diameter multimode fiber butt-coupled to a 16 multi-element, SNSPD array. The measured insertion loss for each fiber device under emulated atmospheric conditions with D/r0 between 2 and 30 is presented. The multi-plane light conversion device shows a consistent ~1 dB loss more than the multimode fiber. Also presented is the measured uneven power splitting of the multiplane light conversion device, especially at lower D/r0. How this uneven power splitting contributes to system loss called blocking loss is discussed.

Multi-plane light conversion device↗

MINING NUCLEAR TRANSIENT DATA THROUGH SYMBOLIC CONVERSION

Dynamic Probabilistic Risk Assessment (DPRA) methodologies generate enormous amounts of data for a very large number of simulations. The data contain temporal information of both the state variables of the simulator and the temporal status of specific systems/components. In order to measure system performances, limitations and resilience, such data need to be carefully analyzed with the objective of discovering the correlations between sequence/timing of events and system dynamics. A first approach toward discovering these correlations from data generated by DPRA methodologies has been performed by organizing scenarios into groups using classification or clustering based algorithms. The identification of the correlations between system dynamics and timing/sequencing of events is performed by observing the temporal distribution of these events in each group of scenarios. Instead of performing “a posteriori” analysis of these correlations, this paper shows how it is possible to identify the correlations implicitly by performing a symbolic conversion of both continuous (temporal profiles of simulator state variables) and discrete (status of systems and components) data. Symbolic conversion is performed for each simulation by properly quantizing both continuous and discrete data and then converting them as a series of symbols. After merging both series together, a temporal phrase is obtained. This phrase preserves duration, coincidence and sequence of both continuous and discrete data in a uniform and consistent manner. In this paper it is also shown that by using specific distance measures, it is still possible to post-process such symbolic data using clustering and classification techniques but in considerably less time since the memory needed to store the data is greatly reduced by the symbolic conversion.

97 MATHEMATICS AND COMPUTING↗

The critical role of conversion cost and comparative advantage in modeling agricultural land use change

The theoretical difference in land use modeling approaches is an important uncertain factor in evaluating future climate scenarios in global economic and integrated assessment models. In this study, we compared several widely used land use modeling approaches including constrained optimization, constant elasticity of transformation (CET), the additive form of constant elasticity of transformation (ACET), logit, and Ricardian. We demonstrated that the approaches differ not only by the extent of parameter uses but also by the definition of conversion cost and the consideration of comparative advantage implied by land heterogeneity. We developed a generalized hybrid approach by incorporating ACET/logit and Ricardian to consider both conversion cost and comparative advantage. The hybrid approach was used to estimate future climate impacts on agriculture. The results indicated a welfare loss of 20 – 24 percent of crop value. It also demonstrated that ignoring land heterogeneity or land conversion cost would underestimate climate impacts on agriculture.

land use modeling, land heterogeneity, conversion ↗

Thermal conversion of municipal solid waste via hydrothermal carbonization: Comparison of carbonization products to products from current waste management techniques

Highlights: Black-Right-Pointing-Pointer Hydrothermal carbonization (HTC) is a novel thermal conversion process. Black-Right-Pointing-Pointer HTC converts wastes into value-added resources. Black-Right-Pointing-Pointer Carbonization integrates majority of carbon into solid-phase. Black-Right-Pointing-Pointer Carbonization results in a hydrochar with high energy density. Black-Right-Pointing-Pointer Using hydrochar as an energy source may be beneficial. - Abstract: Hydrothermal carbonization (HTC) is a novel thermal conversion process that may be a viable means for managing solid waste streams while minimizing greenhouse gas production and producing residual material with intrinsic value. HTC is a wet, relatively low temperature (180-350 Degree-Sign C) thermal conversion process that has been shown to convert biomass to a carbonaceous residue referred to as hydrochar. Results from batch experiments indicate HTC of representative waste materials is feasible, and results in the majority of carbon (45-75% of the initially present carbon) remaining within the hydrochar. Gas production during the batch experiments suggests that longer reaction periods may be desirable to maximize the production of energy-favorable products. If using the hydrochar for applications in which the carbon will remain stored, results suggest that the gaseous products from HTC result in fewer g CO{sub 2}-equivalent emissions than the gases associated with landfilling, composting, and incineration. When considering the use of hydrochar as a solid fuel, more energy can be derived from the hydrochar than from the gases resulting from waste degradation during landfilling and anaerobic digestion, and from incineration of food waste. Carbon emissions resulting from the use of the hydrochar as a fuel source are smaller than those associated with incineration, suggesting HTC may serve as an environmentally beneficial alternative to incineration. The type and extent of environmental benefits derived from HTC will be dependent on hydrochar use/the purpose for HTC (e.g., energy generation or carbon storage).

09 BIOMASS FUELS↗

High conversion Th-U{sup 233} fuel assembly for current generation of PWRs

This paper presents a preliminary design of a high conversion Th-U{sup 233} fuel assembly applicable for current generation of Pressurized Water Reactor (PWRs). The considered fuel assembly has a typical 17 x 17 PWR lattice. However in order to increase the conversion of Th{sup 232} to U{sup 233}, the assembly was subdivided into the two regions called seed and blanket. The central seed region has a higher than blanket U{sup 233} content and acts as a neutron source for the peripheral blanket region. The latest acts as a U{sup 233} breeder. While the seed fuel pins have a standard dimensions the blanket fuel radius was increased in order to reduce the moderation and to facilitate the resonance neutron absorption in blanket Th{sup 232}. The U{sup 233} content in the seed and blanket regions was optimized to achieve maximal initial to discharged fissile inventory ratio (FIR) taking into account the target fuel cycle length of 12 months with 3-batch reloading scheme. In this study the neutronic calculations were performed on the fuel assembly level using Helios deterministic lattice transport code. The fuel cycle length and the core k{sub eff} were estimated by applying the Non Linear Reactivity Model. The applicability of the HELIOS code for the analysis of the Th-based high conversion designs was confirmed with the help of continuous-energy Monte-Carlo code SERPENT. The results of optimization studies show that for the heterogeneous seed and blanket (SB) fuel assembly the FIR of about 0.95 can be achieved. (authors)

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Qualification of JEFF3.1.1 library for high conversion reactor calculations using the ERASME/R experiment

With its low CO{sub 2} production, Nuclear Energy appears to be an efficient solution to the global warming due to green-house effect. However, current LWR reactors are poor uranium users and, pending the development of Fast Neutron Reactors, alternative concepts of PWR with higher conversion ratio (HCPWR) are being studied again at CEA, first studies dating from the middle 80's. In these French designs, low moderation ratio has been performed by tightening the lattice pitch, achieving a conversion ratio of 0.8-0.9 with a MOX fuel coming from PWR UOX recycling. Theses HCPWRs are characterized by a harder neutron spectrum and the calculation uncertainties on the fundamental neutronics parameters are increased by a factor 3 regarding a standard PWR lattice, due to the major contribution of the Plutonium isotopes and of the epithermal energy range to the reaction rates. In order to reduce these uncertainties, a 3-year experimental validation program called ERASME has been performed by CEA from 1984 to 1986 in the EOLE reactor. Monte Carlo analysis of the ERASME/R experiments with the Monte Carlo code TRIPOLI4 allowed the qualification of the recommended JEFF.3.1.1 library for major neutronics parameters. K{sub eff} of the MOX under-moderated lattice is over-predicted by 440 {+-} 830 pcm (2{sigma}); the conversion ratio, indicator of the good use of uranium, is also slightly over-predicted: 2 % {+-} 4 % (2{sigma}) and the same for B4C absorber rods worth and soluble boron worth, over-predicted by 2 %, both in the 2 standard deviations range. The radial fission maps of heterogeneities (water-holes, B4C and fertile rods) are well reproduced: maximal (C-E)/E dispersion is 1.3 %, maximal power peak error is 2.7 %. The void reactivity worth is the only parameter poorly calculated with an overprediction of +12.4% {+-} 1.5%. ERASME/R analysis of MOX reactivity, void effect and spectral indexes will contribute to the reevaluation of {sup 241}Am and Plutonium isotopes nuclear data for the next library JEFF3.2. (authors)

21 SPECIFIC NUCLEAR REACTORS AND ASSOCIATED PLANTS↗

Preliminary neutronic study of D{sub 2}O-Cooled high conversion PWRs

This paper presents a preliminary neutronics analysis of tight-pitch D{sub 2}O-cooled high-conversion pressurised water reactors (HPWR) loaded with MOX fuel aiming at high Pu conversion and negative void coefficient. SCALE6.1 code has been exclusively utilized for this study. The analyses are performed in two separate parts. The first part of this paper investigates the performance of axial and internal blankets and seeks break-even or near-breeder core even without the presence of radial blankets. The analyses showed that the relative Pu mass balance was effectively increased by the addition of the axial blanket. The addition of only 4 cm of blanket resulted in the 4000 pcm increase in the void coefficient. Thus, the presence of the axial blanket made the void coefficient hardly negative. The second part of this paper performs sensitivity and uncertainty analyses of integral parameters (k{sub eff} and void coefficient) for selected systems in order to analyze the characters of this high-conversion PWR from different aspects. The uncertainty analysis of k{sub eff} showed that its breakup contributions for D{sub 2}O-HPWR were very similar to other fast systems (SFR and H{sub 2}O-HPWR) such that the key contributors were {sup 238}U inelastic and {sup 239}Pu ν-bar. However, breakup uncertainties of void coefficients showed that while those of D{sub 2}O-HPWR resembled to H{sub 2}O-HPWR, Na elastic became the significant contributor of the void coefficient uncertainty of SFR. Also sensitivity profiles of {sup 238}U inelastic and {sup 239}Pu ν-bar to the void coefficient revealed that those of SFR were quite dissimilar to both HPWRs. The study also found that while the absolute values of void coefficient uncertainty for D{sub 2}O-HPWR were invariant through the burnup, its percentage uncertainty was significantly increased.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗