SEARCH · Search NASA

Results for “Thermochemical process”

Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

SourceResearch connectionFrom yearThrough year

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 199 records · Page 11

All sources NASA NTRS DOE OSTI

NASA NTRS2001

Unsteady Spherical Diffusion Flames in Microgravity

The absence of buoyancy-induced flows in microgravity (mu-g) and the resulting increase in the reactant residence time significantly alters the fundamentals of many combustion processes. Substantial differences between normal gravity (ng) and (mu-g) flames have been reported in experiments on candle flames, flame spread over solids, droplet combustion, and others. These differences are more basic than just in the visible flame shape. Longer residence times and higher concentration of combustion products in the flame zone create a thermochemical environment that changes the flame chemistry and the heat and mass transfer processes. Processes such as flame radiation, that are often ignored in ng, become very important and sometimes even controlling. Furthermore, microgravity conditions considerably enhance flame radiation by: (i) the build-up of combustion products in the high-temperature reaction zone which increases the gas radiation, and (ii) longer residence times make conditions appropriate for substantial amounts of soot to form which is also responsible for radiative heat loss. Thus, it is anticipated that radiative heat loss may eventually extinguish the "weak" (low burning rate per unit flame area) mu-g diffusion flame. Yet, space shuttle experiments on candle flames show that in an infinite ambient atmosphere, the hemispherical candle flame in mu-g will burn indefinitely. This may be because of the coupling between the fuel production rate and the flame via the heat-feedback mechanism for candle flames, flames over solids and fuel droplet flames. Thus, to focus only on the gas-phase phenomena leading to radiative extinction, aerodynamically stabilized gaseous diffusion flames are examined. This enables independent control of the fuel flow rate to help identify conditions under which radiative extinction occurs. Also, spherical geometry is chosen for the mu-g experiments and modeling because: (i) It reduces the complexity by making the problem one-dimensional; (ii) The spherical diffusion flame completely encloses the soot which is formed on the fuel rich side of the reaction zone. This increases the importance of flame radiation because now both soot and gaseous combustion products co-exist inside the high temperature spherical diffusion flame. (iii) For small fuel injection velocities, as is usually the case for a pyrolyzing solid, the diffusion flame in mu-g around the solid naturally develops spherical symmetry. Thus, spherical diffusion flames are of interest to fires in mu-g and identifying conditions that lead to radiation-induced extinction is important for spacecraft fire safety.

Atreya, Arvind↗

NASA NTRS2003

Radiant Extinction Of Gaseous Diffusion Flames

The absence of buoyancy-induced flows in microgravity (mu:g) and the resulting increase in the reactant residence time significantly alters the fundamentals of many combustion processes. Substantial differences between normal gravity (ng) and :g flames have been reported in experiments on candle flames [1, 2], flame spread over solids [3, 4], droplet combustion [5,6], and others. These differences are more basic than just in the visible flame shape. Longer residence times and higher concentration of combustion products in the flame zone create a thermochemical environment that changes the flame chemistry and the heat and mass transfer processes. Processes such as flame radiation, that are often ignored in ng, become very important and sometimes even controlling. Furthermore, microgravity conditions considerably enhance flame radiation by: (i) the build-up of combustion products in the high-temperature reaction zone which increases the gas radiation, and (ii) longer residence times make conditions appropriate for substantial amounts of soot to form which is also responsible for radiative heat loss. Thus, it is anticipated that radiative heat loss may eventually extinguish the Aweak@ (low burning rate per unit flame area) :g diffusion flame. Yet, space shuttle experiments on candle flames show that in an infinite ambient atmosphere, the hemispherical candle flame in :g will burn indefinitely [1]. This may be because of the coupling between the fuel production rate and the flame via the heat-feedback mechanism for candle flames, flames over solids and fuel droplet flames. Thus, to focus only on the gas-phase phenomena leading to radiative extinction, aerodynamically stabilized gaseous diffusion flames are examined. This enables independent control of the fuel flow rate to help identify conditions under which radiative extinction occurs. Also, spherical geometry is chosen for the :g experiments and modeling because: (i) It reduces the complexity by making the problem one-dimensional. (ii) The spherical diffusion flame completely encloses the soot which is formed on the fuel rich side of the reaction zone. This increases the importance of flame radiation because now both soot and gaseous combustion products co-exist inside the high temperature spherical diffusion flame. (iii) For small fuel injection velocities, as is usually the case for a pyrolyzing solid, the diffusion flame in :g around the solid naturally develops spherical symmetry. Thus, spherical diffusion flames are of interest to fires in :g and identifying conditions that lead to radiation-induced extinction is important for spacecraft fire safety.

Berhan, S.↗

DOE OSTI2022

Facile synthesis and phase stability of Cu-based Na 2 Cu(SO 4 ) 2 · x H 2 O ( x = 0–2) sulfate minerals as conversion type battery electrodes

Mineral exploration forms a key approach for unveiling functional battery electrode materials. The synthetic preparation of naturally found minerals and their derivatives can aid in designing of new electrodes. Herein, saranchinaite Na 2 Cu(SO 4 ) 2 and its hydrated derivative kröhnkite Na 2 Cu(SO 4 ) 2 ·2H 2 O bisulfate minerals have been prepared using a facile spray drying route for the first time. The phase stability relation during the (de)hydration process was examined synergising in situ X-ray diffraction and thermochemical studies. Kröhnkite forms the thermodynamically stable phase as the hydration of saranchinaite to kröhnkite is highly exothermic (-51.51 ± 0.63 kJ mol -1 ). Structurally, kröhnkite offers a facile 2D pathway for Na+ ion migration resulting in 20 times higher total conductivity than saranchinaite at 60 °C. Both compounds exhibited a conversion redox mechanism for Li-ion storage with the first discharge capacity exceeding 650 mA h g -1 (at 2 mA g -1 vs. Li + /Li) upon discharge up to 0.05 V. Post-mortem analysis revealed that the presence of metallic Cu in the discharged state is responsible for high irreversibility during galvanostatic cycling. This study reaffirms the exploration of Cu-based polyanionic sulfates, which while having limited (de)insertion properties, can be harnessed for conversion-based electrode materials for batteries.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2026

Hydrogenolysis Versus Hydrocracking for Polyolefin Upcycling

Global plastic production has reached 413.8 million metric tons in 2024 and is forecasted to surpass 1.2 billion metric tons by 2050. Polyolefins, mainly polyethylene (PE) and polypropylene (PP), dominate single-use packaging and account for approximately 55% of global plastic waste. The chemical inertness that makes these materials desirable for commercial applications also renders them persistent in the environment. Current recycling technologies have proven to be insufficient to divert plastic waste from landfills or environmental loss due to technical limitations and poor economic incentives. Conventional mechanical recycling is a form of downcycling, in which the polymer remelting process results in products with inferior material properties and reduced market value. Pyrolysis, a thermochemical route used for the chemical recycling of plastic wastes into refinery feedstock, requires severe conditions, typically 400–600 °C in an oxygen-free environment. The high temperature drives up energy costs and produces a wide range of poorly defined products, including undesirable light gases and heavy tars that pose challenges for downstream processing. As an alternative, catalytic chemical recycling offers a promising route for converting waste polyolefins back into value-added hydrocarbons—such as fuels, lubricant base oils, and other chemical feedstocks—at temperatures typically below 300 °C. This opinion article focuses on two dominant pathways in heterogeneous catalysis that are used to cleave the C–C bonds of polyolefins: hydrogenolysis and hydrocracking. Both catalytic pathways have the potential to selectively convert polyolefin waste into valuable fuels and chemical feedstocks under mild conditions. Notably, while hydrocracking primarily yields branched hydrocarbon products, hydrogenolysis predominantly produces linear hydrocarbons. Here, we compare the mechanisms and catalyst designs for hydrocracking and hydrogenolysis, analyze critical technical challenges from catalyst stability to process engineering, and provide an outlook on how these complementary pathways can be used to repurpose plastic waste into valuable products.

Zhang, Ruoxi [Iowa State Univ., Ames, IA (United S↗

DOE OSTI2023

Accuracy of DFT computed oxygen-vacancy formation energies and high-throughput search of solar thermochemical water-splitting compounds

The enthalpy change involved in metal oxide reduction is a key quantity in various processes related to energy conversion and storage, and is of particular interest for computational prediction. Often this prediction involves the simulation of a high temperature reduction process with a 0K methodology like density functional theory (DFT), and it is not infrequent for the high temperature and 0K stable crystal structures to differ. This introduces a conundrum with regards to the choice of crystal structure to utilize in the computation, with approaches in the literature varying and experimental validation remaining scarce. In this work we address both the crystal structure conundrum and the experimental validation, and then apply the insights we gain to guide a high-throughput search for new materials for solar thermochemical water-splitting applications. By computing the DFT+U oxygen vacancy formation energy (ΔE vf ) of a selection of ABO 3 compounds and comparing different crystal structures for each composition, we highlight the issues that arise when the structure utilized in the computation is dynamically unstable at 0K, namely the presence of an artificial lowering of ΔE vf , and the lack of convergence of ΔE vf with cell size. We solve these limitations by identifying and employing a suitable surrogate dynamically stable structure. We then validate the predictive power of our calculations against appositely generated experimental measurements of reduction enthalpy for a series of Hubbard U values, finding an accuracy ranging between 0.2-0.6 eV/O. In light of such conclusions, we revise and expand a previous a high-throughput DFT study on ABO 3 perovskite oxides. As a result, we provide a list of candidate STCH materials, highlight trends with redox-active cation and structural distortion, and identify Mn 4+ , Mn 3+ and Co 3+ as the most promising redox-active cations.

08 HYDROGEN↗

DOE OSTI2023

A reduced-order modeling of a tubular solar reactor for long duration thermochemical energy storage

The storage of solar energy in a solid form, referred to as a “solar fuel”, can be achieved through a process known as endothermic solar thermochemistry. This process transforms the absorbed solar energy into a stable and retrievable form that can be stored for extended periods of time. This paper presents a low–order heat transfer model of a counter–current tubular falling bed reactor designed to produce thermally reduced magnesium manganese oxide pellets for long duration thermochemical energy storage. The energy required for the endothermic reduction was supplied by concentrated solar energy or renewable electricity via indirect heating of the gas and solid reactants flowing in a ceramic tube. The counter-current gas flow enhances the mixing of the solid particles with the heat recuperation zone, allowing the gas and particles to enter and exit the tubular reactor close to room temperature. Further, the reactor was vertically oriented and was heated circumferentially by an adjustable level heat flux along a finite segment of its length. The temperature distribution of the reactor in response to transient changes along the tube was modeled by considering conduction, convection, and radiation heat transfer. Governing equations for the heat transfer model were solved by discretizing the reactor tube into a finite number of control volumes and using an energy balance for the heat exchange between the reactor wall, gas, and particles within the control volume. The energy absorbed during this endothermic reaction was modeled numerically by fitting the data of the chemical conversion rate with the corresponding temperature of particles in the heating zone. The numerical model has been experimentally validated using a reactor prototype made of a 121.92 cm alumina tube heated by a 7kW electric tube–furnace. The alumina tube receives magnesium manganese oxide pellets of 3.66±0.516 mm in diameter from the top, and a counter–current gas flow from the bottom. The reactor wall temperature was monitored by six thermocouples installed along the reactor tube length. The experimental procedure was numerically simulated, and the temperature variation along the reactor tube was compared with a matrix of experimental runs for a range of particles mass flowrates (0.75–1.25g/s) and corresponding gas flowrates (36–65 SLPM). The reactor system was heated gradually from room temperature to a steady state temperature of 1673K, and then cooled down to room temperature. The heating and cooling processes were simulated, and the numerical and experimental results were compared throughout processes. The numerical model showed similar trends to the experimental results, with an error of 0.69 to 7.9% for the particle inlet and 0.7 to 7.9% for the gas inlet during steady-state operation. The proposed numerical model can be implemented as a simplified physical model to design a feedback control system to regulate reactor temperature.

14 SOLAR ENERGY↗

DOE OSTI2022

Investigation of Cutter–Woodchip Contact Pressure in a New Biomass Comminution System

A Crumbler ® rotary shear system was recently developed to process fuel-grade woodchips into feedstocks having more uniform particle sizes for improved flowability and higher thermochemical output yield than a traditional hammer mill. It represents a significant innovation in the state of the art of biomass comminution equipment. However, the milling unit has experienced significant abrasive wear of the feeding teeth and cutters when processing hard and dusty feedstocks, such as logging residue and corn stover. Here, we present initial simulation results from a finite-element stress analysis of the rotary shear, which is used to investigate the dynamics of interaction between the cutters and woodchips. This is the first step for optimizing the cutter design to improve the system lifetime and processing efficiency, thus reducing downtime and improving overall productivity.

42 ENGINEERING↗

DOE OSTI2023

Contact pressure analysis to allow improved design for the clearing plate in a biomass comminution system

For biomass processing systems, feedstocks with small but equal sizes can improve flowability and thermochemical outputs. The Crumbler rotary shear system was designed to achieve such ideal feedstocks to reduce costs and energy throughout the biomass supply chain. Improving the wear resistance of major components in this system is important to decrease the cost. Accelerating the feedstock flow through the rotary shear machine plays an equivalent role of improving its efficiency. An analytical analysis and a finite-element analysis of the stationary clearing plate are presented in this work. Here, these tools are used to investigate the effect of contact surface curvature on the impact pressure. The optimized new clearing plate design is expected to improve the component’s lifetime and wood chips flowability. The field tests confirm that the trend of the new clearing plate design guided by FEA. The optimization method, model verification, and validation experience applied in this work can also be applied to other static components with similar simple contact wear problems.

09 BIOMASS FUELS↗

DOE OSTI2023

Near-Critical CO 2 -Assisted Liquefaction-Extraction of Biomass and Wastes to Fuels and Value-Added Products

With the growing need for sustainable carbon-neutral liquid fuels, low-grade feedstocks, such as lignocellulosic biomass, and municipal solid wastes offer sufficient potential via thermochemical conversion. But the existing thermochemical means are limited in feed flexibility and scalability and require significant processing (energy and costs) of the intermediates. Bio-oil/biocrude intermediate from fast pyrolysis and hydrothermal techniques is impeded by issues of stability and oxygen content, along with hydrotreating viability. To address these issues, we investigated a novel pathway of near-critical CO 2 -assisted integrated liquefaction-extraction (NILE) technology in conceptual aspects for conversion of various biomass and municipal solid wastes into high-quality biocrude with high compatibility for co-hydrotreating with traditional fossil crude for liquid fuel needs in power and transportation sectors. Using supercritical CO 2 for dewatering wet feedstocks, for liquefaction, and extraction for lighter biocrude has produced biocrude with lower oxygen content by 50%, lowered metal content by 90%, stable viscosity, low acidity, and good aging stability compared to that produced from hydrothermal liquefaction along with higher hydrotreating and co-hydrotreating compatibility. Hydrotreating of the biocrude extract from supercritical CO 2 extraction also was feasible with no detected coke deposition, an oxygen content of 1%, and catalyst deactivation. Here, the validation and capabilities of the NILE concept urge for its further development to obtain sustainable liquid fuels with lower greenhouse gas emissions and costs.

09 BIOMASS FUELS↗

NASA NTRS1981

Production cost comparisons of hydrogen from fossil and nuclear fuel and water decomposition

The comparative costs entailed in producing hydrogen by major technologies that rely on petroleum, natural gas, coal, thermochemical cycles, and electrolysis are examined. Techniques were developed for comparing these processes by formulating the process data and economic assessments on a uniform and consistent basis. These data were normalized to permit a meaningful comparative analysis of product costs of these processes.

Ekman, K. R.↗

NASA NTRS1986

Thermoanalytical characterization of several Antarctic meteorites

Thermodynamic data for several meteorites from Antarctica (5 achondrites, 2 chondrites, and 1 iron) were derived. The thermochemical response to heating in air was examined. The effects of oxidation processes can often be better identified by comparing the differential thermal analysis (DTA)-curves for heating in air with those obtained for heating in an oxidation-suppressed argon atmosphere. The thermoanalytical method can be helpful in determining the degree of weathering of meteoritic material.

Lang, B.↗

NASA NTRS1994

The stability of hibonite, melilite and other aluminous phases in silicate melts: Implications for the origin of hibonite-bearing inclusions from carbonaceous chondrites

Phase fields in which hibonite and silicate melt coexist with spinel CaAl4O7, gehlenitic melilite, anorthite or corundum at 1 bar in the system CaO-MgO-Al2O3-SiO2-TiO2 were determined. The hibonites contain up to 1.7 wt% SiO2. For TiO2, the experimentally determined partition coefficients between hibonite and coexisting melt D(sub i)(sup Hib/L), vary from 0.8 to 2.1 and generally decrease with increasing TiO2 in the liquid. Based on Ti partitioning between hibonite and melt, bulk inclusion compositions and hibonite-saturated liquidus phase diagrams, the hibonite in hibonite-poor fluffy Type A inclusions from Allende and at least some hibonite from hibonite-rich inclusions is relict, although much of the hibonite from hibonite-glass spherules probably crystallized metasably from a melt. Bulk compositions for all of these CAIs are consistent with an origin as melite + hibonite + spinel + perovskite phase assembalges that were partially altered and in some cases partially or completely melted. The duration of the melting event was sufficient to remove any Na introduced by the alteration process but frequently insufficient to dissolve all of the original hibonite. Simple thermochemical models developed for meteoritic melilite and hibonite solid solutions were used to obtain equilibration temperatures of hibonite-bearing phase assemblages with vapor. Referenced to 10(exp -3) atm, hibonite + corundum + vapor equilibrated at approximately 1260 C and hibonite + spinel +/- melilite + vapor at 1215 +/- 10 C. If these temperatures reflect condensation in a cooling gas of solar composition, then hibonite +/- corundum condensed first, followed by spinel and then melilite. The position of perovskite within this sequence is uncertain, but it probably began to condense before spinel. This sequence of phase appearances and relative temperatures is generally consistent with observed textures but differs from expectations based on classical condensation calculations in that equilibration temperatures are generally lower than predicted and melilite initially condenses with or even after spinel. Simple thermochemical modes for the substitution of trace elements into the Ca site of meteoritic hibonites suggest that virtually all Eu is divalent in early condensate hibonites but that Eu(2+)/Eu(#+) decreases by a factor of 20 or more during the course of condensation primarily because the ratio is proportional to the partial pressure of Al, which decreases dramatically as aluminous phase condense. The relative sizes of Eu and Yb anomalies in meteoritic hibonites and inclusions may be partly due to this effect.

Beckett, J. R.↗

DOE OSTI2023

Solar Thermochemical Ammonia Production (STAP) (Final Report)

Ammonia (NH 3 ) is an energy-dense chemical and a vital component of fertilizer. In addition, it is a carbon-neutral liquid fuel and a potential candidate for thermochemical energy storage for high-temperature concentrating solar power (CSP). Currently, NH 3 synthesis occurs via the Haber-Bosch process, which requires high pressures (15-25 MPa) and medium to high temperatures (400-500 °C). N 2 and H 2 are essential feedstocks for this NH 3 production process. H 2 is generally derived from methane via steam reforming; N 2 is sourced from air, after oxygen removal via combustion of hydrocarbons. Both processes consume hydrocarbons, resulting in the release of CO 2 . In addition, hydrocarbon fuels are burned to produce the heat and mechanical energy required to perform the NH 3 reaction, further increasing CO 2 emissions. Overall, the production of ammonia via the Haber-Bosch (H-B) process is responsible for up to 1.4% of the world’s carbon emissions. The development of a renewable pathway to NH 3 synthesis, which utilizes concentrated solar irradiation as a process heat instead of fossil fuels and operates under low or ambient pressure, will result in a decrease (or elimination) of greenhouse gas emissions as well as avoid the cost, complexity, and safety issues inherent in high-pressure processes. Most current efforts to “green” ammonia production involve either electrolysis or simply replacing the energy source for H-B with renewable electricity, but otherwise leaving the process intact. The effort proposed here would create a new paradigm for the synthesis of NH 3 utilizing solar-thermal heat, water, and air as feedstocks, providing a truly green method of production. The overall objective of the STAP (Solar Thermal Ammonia Production) project was to develop a solar thermochemical looping technology to produce and store nitrogen (N 2 ) from air for the subsequent production of ammonia (NH 3 ) via an advanced two-stage process. The goal is a cost-effective and energy efficient technology for the renewable N 2 production and synthesis of NH 3 from H 2 (produced from H 2 O) and air using solar-thermal energy from concentrating sunlight, under pressures an order of magnitude lower than H-B NH 3 production. Our process involves two looping cycles, which do not require catalysts and can be recycled. Over the course of the STAP project, we (1) developed and deeply characterized oxide materials for N 2 separation; (2) developed a method for the synthesis of metal nitrides, producing a series of quaternary compounds that have been heretofore unreported; (3) modeled, designed, and fabricated bench-scale tube and on-sun reactors for the N 2 production step and demonstrated the ability to separate N 2 over multiple cycles in the tube reactor; (4) designed and fabricated a bench-scale Ammonia Synthesis Reactor (ASR) and demonstrated the proof of concept of NH 3 synthesis via a novel looping process using metal nitrides over multiple cycles; and (5) completed a systems- and technoeconomic analysis showing the feasibility of ammonia production on a larger scale via the STAP process. The development of renewable, low-cost NH 3 will be of great interest to the chemicals industry, particularly agricultural sectors. The CSP industry should be both an important customer and potential end-user of this technology, as it affords the capability of synthesizing a promising thermochemical storage material on-site. Since the NH 3 synthesis step also requires H 2 , there will exist a symbiotic relationship between this technology and solar-thermochemical water-splitting applications. Green ammonia synthesis will result in the decarbonization of a hydrocarbon-intensive industry, helping to meet the Administration goal of industrial decarbonization by 2050. The resulting decrease in CO 2 and related pollutants will improve health and well-being of society, particularly for those living in the vicinity of commercial production plants.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2023

Materials Design Directions for Solar Thermochemical Water Splitting

The sustainable, economical production of molecular hydrogen is a crucial component of a net zero-greenhouse-gas-emissions future. Solar thermochemical water splitting (STWS) offers a renewable route to hydrogen with the potential to help decarbonize several industries, including transportation, manufacturing, mining, metals processing, and electricity generation, as well as provide sustainable hydrogen as a chemical feedstock. STWS uses high temperatures generated from concentrated sunlight or other sustainable means for high-temperature heat to produce hydrogen and oxygen from steam. For example, in its simplest form of a two-step thermochemical cycle, a redox-active metal oxide is heated to ≈1700-2000 K, driving off molecular oxygen while producing oxygen vacancies in the material. The reduced metal oxide then cools (ideally with the extracted heat recuperated for re-use) and, in a separate step, comes into contact with steam, which reacts with oxygen vacancies to produce molecular hydrogen while recovering the original state of the metal oxide. Despite its promising use of the entire solar spectrum to split water thermochemically, the current estimated cost of hydrogen produced via STWS is ≈4-6× the U.S. Department of Energy (DOE) Hydrogen Shot target value of $1/kg. One contributing approach to bridging this cost gap is the design of new materials with improved thermodynamic properties to enable higher efficiencies. The state-of-the-art (SOA) redox-active metal oxide for STWS is ceria (CeO 2 ), due to its close to optimal, although too high, oxygen vacancy formation enthalpy and large configurational and electronic entropy of reduction. However, ceria requires high operating temperatures and its efficiency is insufficient. Therefore, efforts to increase the efficiency of STWS cycles have focused on further optimizing oxygen vacancy formation enthalpies and augmenting the reduction entropy via substitution or doping and materials discovery schemes. Examples of the latter include the perovskites BaCe 0.25 Mn 0.75 O 3 and (Ca,Ce)(Ti,Mn)O 3 . These efforts and others have revealed intuitive chemical principles for the efficient and systematic design of more effective materials, such as the strong correlation between the enthalpies of crystal bond dissociation and solid-state cation reduction with the enthalpy of oxygen vacancy formation, as well as configurational entropy augmentation via the coexistence of two or more redox-active cation sublattices. The purpose of this chapter is to prepare the reader with an up-to-date account of STWS redox-active materials, both the SOA and promising newcomers, as well as to provide chemically intuitive strategies for improving their cycle efficiencies through materials design – in conjunction with ongoing efforts in reactor engineering and gas separations – to reach the cost points for commercial viability. First, we will introduce the thermodynamics of STWS using a two-step, metal-oxide, thermochemical cycle with economics in mind. We also will compare the pros and cons of processes that do or do not involve phase changes. Second, we will describe the qualities that make ceria the SOA STWS redox-active material, as well as its limitations. Third, we will survey some of the most promising candidates to date in the search for materials to supplant ceria, emphasizing the post-ternary, metal-oxide-perovskite alloys. Lastly, we will enumerate and discuss the following materials design directions for STWS redox-active materials: crystal reduction potentials as a proxy for oxygen vacancy formation enthalpies, engineering the electronic and configurational entropy of reduction via f-shells and simultaneous redox, and vetting materials stability via temperature-dependent phase diagrams and melting-point prediction.

08 HYDROGEN↗

DOE OSTI2023

A Novel Molten Salt System for CO 2 Based Oxidative Dehydrogenation with Integrated Carbon Capture (Final Technical Report)

The objective of this project was to develop a comprehensive proof-of-concept for sustainable and cost-effective production of propionic acid and value-added olefins from carbon dioxide (CO 2 ) in power plant flue gas and domestic shale gas resources. This was realized via a molten-salt-mediated oxidative dehydrogenation (MM-ODH) process that performs CO 2 capture (from power plant flue gas) and CO 2- assisted alkane oxidative dehydrogenation in a two-step, thermochemical scheme. The resulting carbon monoxide (CO) and light olefin (e.g., ethylene from ethane ODH) can be subsequently converted into propionic acid via the industrially proven hydrocarboxylation process.

20 FOSSIL-FUELED POWER PLANTS↗

NASA NTRS1976

Chemistry and spectroscopy of the Jovian atmosphere

A comprehensive review is given of the chemistry and spectroscopic studies of the Jovian atmosphere. Thermochemical equilibrium models for determining atmospheric composition are considered along with possible disequilibrating processes, and studies of the photochemistry of H2, CH4, NH3, H2S, and PH3 using the modeling methods are summarized. It is shown that photodissociation and advection are the major disequilibrating processes in Jupiter's atmosphere, that lightning and charged-particle bombardment are relatively minor factors in the planet's bulk chemistry, and that the existence of living organisms on the planet is highly improbable. Spectroscopic investigations of Jupiter are discussed, emphasizing recent observations of absorption bands due to CH4, NH3, H2, He, and D. Spectroscopic abundance determinations are examined for H2, HD, CH4, CH3D, NH3, C2H6, C2H2, and PH3. Upper limits are given for the abundances of several unobserved gases in the visible atmosphere, including H2S, HCl, SiH4, benzene, purines, pyrimidines, and their derivatives.

Prinn, R. G.↗

DOE OSTI2020

Conceptual Basis and Techno-Economic Modeling for Integrated Algal Biorefinery Conversion of Microalgae to Fuels and Products (2019 NREL TEA Update: Highlighting Paths to Future Cost Goals via a New Pathway for Combined Algal Processing)

The report documents the conceptual basis for a new potential Combined Algal Processing design strategy which may allow more flexibility in accommodating different algal biomass feedstock compositions, by enabling upgrading of both protein and carbohydrates in a single step, without a strict requirement for either component to be in soluble or monomeric form, while maintaining effective wet lipid extraction techniques to enable high lipid recoveries. In light of previously-established constraints around algal biomass costs (which are significantly higher than lignocellulosic terrestrial biomass), the present CAP processing strategy reflects an integrated biorefinery concept producing both fuels and value-added chemical coproducts as a means to improve profitability and generate coproduct revenues to help drive down the minimum fuel selling price (MFSP) towards economically viable levels. Namely, this report highlights an integrated CAP biorefinery process and associated technical targets that would be required to achieve U.S. Department of Energy target MFSP goals of $2.5/gallon gasoline equivalent by 2030. This is accomplished by a process involving low-cost seasonal storage of algal biomass during high-growth seasons, rapid flash hydrolysis pretreatment of the biomass, solvent extraction of pretreated biomass, cleanup and fractionation of lipids into triglyceride and free fatty acid fractions, and a series of thermochemical conversion steps to upgrade carbohydrates and protein to hydrocarbon fuels. These steps include mild oxidative treatment (MOT), a process originally investigated at NREL for upgrading lignin, followed by catalytic ketonization and hydrotreating of MOT products to fuels. Isolated triglycerides are sent to a coproduct train, with the base case focused on upgrading to polyurethane foams as a high-value, high-market-volume coproduct.

09 BIOMASS FUELS↗

DOE OSTI2025

Photoelectrochemical Hydride Generation with Oxide-Coated Silicon

Photoelectrochemical generation of a potent organic hydride donor at silicon is demonstrated. Two different oxide-coated p-type silicon photoelectrodes reduced 1,2,3,5,6-pentamethyl-1H-benzo[d]imidazol-3-ium hexafluorophosphate, [PMBI][PF 6 ], to its corresponding imidazole hydride, PMBIH, in the presence of a proton source. Under 1 sun illumination, in acetonitrile with 1,5-diazabicyclo[4.3.0]non-5-ene (DBN) buffer, the p-Si photoelectrodes convert PMBI + to PMBIH with good Faradaic efficiencies (FEs): 78% FE at −2.3 V vs Fc +/0 for Si|TiO 2 and 83% FE at −2.6 V vs Fc +/0 for Si|SiO 2 (where Si|SiO 2 represents silicon coated with an oxide layer). Generally, the Si|TiO 2 catalyzed the reaction at milder potentials than Si|SiO 2 , but the Si|SiO 2 had better selectivity for PMBIH generation over H 2 evolution than Si|TiO 2 . In light of prior studies of these photoelectrodes, the differences in selectivity and onset potential suggest a difference in mechanism, likely an outer-sphere electron transfer (ET) mechanism at the SiO 2 surface and potentially a proton-coupled ET process at the TiO 2 surface. To help understand reaction efficiency and identify areas of improvement, a thermochemical model for understanding net hydride transfer from the semiconductor to an acceptor in solution was developed. We find that the reactions in the present system are quite downhill. The high overpotentials (even while maintaining selectivity over H 2 evolution) emphasize the need for improved catalysts. Furthermore, this approach to evaluate the thermodynamics of net hydride transfer should be broadly valuable for electrochemical and photoelectrochemical processes.

14 SOLAR ENERGY↗