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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.

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All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Structured illumination with thermal imaging (SI-TI): A dynamically reconfigurable metrology for parallelized thermal transport characterization

The recent push for the “materials by design” paradigm requires synergistic integration of scalable computation, synthesis, and characterization. Among these, techniques for efficient measurement of thermal transport can be a bottleneck limiting the experimental database size, especially for diverse materials with a range of roughness, porosity, and anisotropy. Traditional contact thermal measurements have challenges with throughput and the lack of spatially resolvable property mapping, while non-contact pump-probe laser methods generally need mirror smooth sample surfaces and also require serial raster scanning to achieve property mapping. Here, we present structured illumination with thermal imaging (SI-TI), a new thermal characterization tool based on parallelized all-optical heating and thermometry. Experiments on representative dense and porous bulk materials as well as a 3D printed thermoelectric thick film (~50 μm) demonstrate that SI-TI (1) enables paralleled measurement of multiple regions and samples without raster scanning; (2) can dynamically adjust the heating pattern purely in software, to optimize the measurement sensitivity in different directions for anisotropic materials; and (3) can tolerate rough (~3 μm) and scratched sample surfaces. Here, this work highlights a new avenue in adaptivity and throughput for thermal characterization of diverse materials.

42 ENGINEERING↗
DOE OSTI2023

Discovery of a Hybrid System for Photocatalytic CO 2 Reduction via Attachment of a Molecular Cobalt-Quaterpyridine Complex to a Crystalline Carbon Nitride

While recent reports have demonstrated the attachment of molecular catalysts to amorphous, graphitic carbon nitrides (g-CN) for light-driven CO 2 reduction, approaches to the utilization of crystalline carbon nitrides have remained undiscovered. Herein, a functional hybrid photocatalyst system has been found using a crystalline carbon nitride semiconductor, poly(triazine imide) lithium chloride (PTI-LiCl), with a surface-attached CoCl 2 (qpy-Ph-COOH) catalyst for CO 2 reduction. The molecular catalyst attaches to PTI-LiCl at concentrations from 0.10 to 4.30 wt % and exhibits ∼96% selectivity for CO production in a CO 2 -saturated, aqueous 0.5 M KHCO 3 solution. Optimal loadings were found to be within 0.42–1.04 wt % with rates between 1,400 and 1,550 μmol CO/g·h at an irradiance of 172 mW/cm 2 (λ = 390 nm) and apparent quantum yields of ∼2%. This optimized loading is postulated to represent a balance between maximal turnover frequency (TOF; 300+ h –1 ) and excess catalyst that can limit excited-electron lifetimes, as probed via transient absorption spectroscopy. An increase in the incident irradiance yields a concomitant increase in the TOFs and CO rates only for the higher catalyst loadings, reaching up to 2,149 μmol CO/g·h with a more efficient use of the catalyst surface capacity. The lower catalyst loadings, by comparison, already function at maximal TOFs. Higher surface loadings are also found to help mitigate deactivation of the molecular catalysts during extended catalytic testing (>24 h) owing to the greater net surface capacity for CO 2 reduction, thus representing an effective strategy to extend lifetime. The hybrid particles can be deposited onto an FTO substrate to yield ∼60% Faradaic efficiency for photoelectrochemical CO production at −1.2 V vs Ag/AgCl bias. In conclusion, these results demonstrate the synergistic combination of a crystalline carbon nitride with a molecular catalyst that achieves among the highest known rates in carbon-nitride systems for the light-driven CO 2 reduction to CO in aqueous solution with >95% selectivity.

CO2 reduction↗
DOE OSTI2020

Nickel/gallium modified HZSM-5 for ethane aromatization: Influence of metal function on reactivity and stability

Bimetallic catalysts often outperform their monometallic counterparts due to the synergistic effect. Here we reported that the Ni/Ga co-functionalized HZSM-5 catalyst, specifically with Ni 1 /Ga 1 stoichiometric ratio, shows significantly improved selectivity (above 80 %) and stability than the Ni/HZSM-5 catalyst and higher activity (with identical selectivity) than the Ga/HZSM-5 catalyst in ethane aromatization. According to the transient experiment, the Ga and Ni 1 Ga 1 /HZSM-5 catalysts show an induction period of a few minutes. However, for Ni/HZSM-5 and Ni 1 Ga 1/3 /HZSM-5, the induction period increased to >10 min and >30 min, respectively, where up to 100 % of ethane was converted into methane and coke through cracking/hydrogenolysis. Furthermore, based on the generalized power-law equation model, a modified model for deactivation kinetic was proposed. Consequently, the influence of the metal function on the kinetic parameters was discussed. We anticipate the formation of Ni 3 Ga intermetallic alloy and its synergy with the exchanged Ga δ+ to be responsible for optimal BTX formation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1997

Cryogenics and the Human Exploration of Mars

Current plans within NASA involve extending the human exploration of space from low earth orbit into the solar system, with the first human exploration of Mars presently planned in 2011. Integral to all hum Mars mission phases is cryogenic fluid management. Cryogenic fluids will be required both as propellant and for In-Situ Resource Utilization (ISRU). Without safe and efficient cryogen storage human Mars missions will not be possible. Effective control and handling of cryogenic fluids is the key to affordable Mars missions, and advancing active thermal control technology is synergistic with all of NASA's exploration initiatives and with existing and future instrument cooling programs, including MTPE and Origins. Present mission scenarios for human exploration require cryogenic propellant storage for up to 1700 days and for up to 60 metric tons. These requirements represent increases of an order of magnitude over previous storage masses and lifetimes. The key cryogenic terminology areas to be addressed in human Mars missions are long-term propellant storage, cryogenic refrigeration, cryogenic liquefaction, and zero gravity fluid management. Long-term storage for the thermal control of cryogenic propellants is best accomplished with a mix of passive and active technologies. Passive technologies such as advanced multilayer insulation (MLI) concepts will be combined with the development of active coolers (cryogenic refrigerators). Candidates for long-life active cooling applications include Reverse Turbo-Brayton, Stirling, and Pulse-Tube coolers. The integration of passive and active technologies will form a hybrid system optimized to minimize the launch mass while preserving the cryogenic propellants. Since cryogenic propellants are the largest mass that Mars missions must launch from earth, even a modest reduction in the percentage of propellant carried results in a significant weight saving. This paper will present a brief overview of cryogenic fluid management technology as it applies to the current human Mars mission scenarios.

Salerno, Louis J.↗
DOE OSTI2025

Polyethylene Glycol Surface Modification and Polythiophene Side-Chain Chemistry: A Combined Strategy toward High-Capacity Lithium-Ion Battery Anodes

In the development of high-capacity lithium-ion batteries (LIBs), the combined optimization of active material interfaces and polymer binder chemistry plays a critical role in improving electrode performance and longevity. This work explores a dual design strategy incorporating polyethylene glycol (PEG) surface modification and carboxylated polythiophene side-chain tailoring to enhance the electrochemical behavior of magnetite (Fe 3 O 4 )-based anodes. PEG is employed to improve interfacial stability, while carboxylated polythiophene binders with varying alkyl side-chain lengths─poly[3-(potassium-4-butanoate)thiophene-2,5-diyl] (P3KBT), poly[3-(potassium-5-pentanoate)thiophene-2,5-diyl] (P3KPT), and poly[3-(potassium-6-hexanoate)thiophene-2,5-diyl] (P3KHT)─are used to modulate molecular interactions and ion transport. Among these three analogs, the PEG–Fe 3 O 4 –P3KHT electrode exhibits superior ion-transfer kinetics, the highest capacity retention, and the lowest charge-transfer resistance after extended cycling. Compared to their non-PEG analogs, PEG-coated electrodes demonstrate enhanced structural integrity and electrochemical behavior, emphasizing the synergistic effects of surface modification and side-chain chemistry. These findings highlight the importance of interfacial interactions and molecular design in achieving robust and high-performance composite anodes for next-generation LIBs.

Fe3O4↗
DOE OSTI2022

Revealing nanomechanical deformation at the interface and degradation in all-thin-film inorganic electrochromic devices

Recently, progress in electrochromic (EC) devices has been made in optimizing electrode and device configurations and performance. However, the ion insertion/de-insertion induced charge transfer (CT) nanomechanical effect has remained unexplored, i.e., repetitive electrode size changes at the nanoscale and stress/strain generated during electrochemical cycling, which is the focus of this work due to its intimate correlation with the elastic and plastic deformation at the interface. Considering the intervalence electrons, excellent electrochemical kinetics, and dramatic color changes, tungsten oxide (WO 3 ) and nickel oxide (NiO) films are configured as the EC cathode and anode materials, respectively, within a full device. Upon extended cycles (>10 000), the void generation and delamination that occurred at the interface account for performance decay. Encouraged by the findings, nanoindentation mechanical tests and electrical kelvin probe force microscopy were employed to investigate the CT induced effects at the interface. There is a dramatic increase of up to 45% in the elastic Young's modulus in colored/charged WO 3 at ~40 mC cm -2 . Here, the correlation between CT and synergistic mechanical effect is interpreted by the Lippman equation. Interestingly, despite the charged state (colored; lithiated) with a relatively flat morphology bringing an ~3.4 times higher electrostatic surface potential, the electrical work function unexpectedly decreases, arising from the dominant effect of the dipole layer potential over the chemical potential. The interatomic cohesive energy and equilibrium distance increase bury the seeds for mechanical deformation in the long run. This work provides fundamental insights into electro-chemo mechanics and interdisciplinary concerted interfacial effects at the nano/atomic level. The dependence of surface potential, stress, work function, and cohesive energy on electrochemical kinetics has been interpreted.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Mobility Energy Productivity Evaluation of Prediction-Based Vehicle Powertrain Control Combined with Optimal Traffic Management

Transportation vehicle and network system efficiency can be defined in two ways: 1) reduction of travel times across all the vehicles in the system, and 2) reduction in total energy consumed by all the vehicles in the system. The mechanisms to realize these efficiencies are treated as independent (i.e., vehicle and network domains) and, when combined, they have not been adequately studied to date. This research aims to integrate previously developed and published research on Predictive Optimal Energy Management Strategies (POEMS) and Intelligent Traffic Systems (ITS), to address the need for quantifying improvement in system efficiency resulting from simultaneous vehicle and network optimization. POEMS and ITS are partially independent methods which do not require each other to function but whose individual effectiveness may be affected by the presence of the other. In order to evaluate the system level efficiency improvements, the Mobility Energy Productivity (MEP) metric is used. MEP specifically measures the connectedness of a system while accounting for time and energy externalities of modes that provide mobility in a given location. A SUMO model is developed to reflect real traffic patterns in Fort Collins, Colorado and data is collected by a probe SUMO vehicle which is validated against data collected on a real vehicle driving the same routes through the city. Individual vehicle and system level efficiencies are calculated using SUMO outputs for scenarios which integrate POEMS and ITS independently as well as jointly. Results from application of POEMS and ITS show improvement in energy consumption and travel times respectively when compared to the respective baseline scenarios. Our conclusion is that there are promising synergistic benefits to travel time and energy efficiency when POEMS and ITS are combined.

ADVANCED PROPULSION SYSTEMS↗
NASA NTRS2004

Sensor for Monitoring Nanodevice-Fabrication Plasmas

The term plasma process diagnostics (PPD) refers to a spectroscopic technique and sensing hardware that have been proposed for monitoring plasma processes used to fabricate electronic devices that feature sizes as small as several nanometers. Nanometer dimensions are characteristic of the quantum level of miniaturization, where single impurity atoms or molecules can drastically change the local properties of the nanostructures. Such changes may be purposely used in nanoscale design but may also be extremely damaging or cause improper operation of the fabricated devices. Determination of temperature and densities of reactants near the developing features is important, since the structural synthesis is affected by characteristics of the local microenvironment. Consequently, sensors capable of nonintrusive monitoring with high sensitivity and high resolution are essential for real-time atomistic control of reaction kinetics and minimizing trace contamination in plasma processes used to fabricate electronic nanodevices. Such process-monitoring sensors are required to be compact, multiparametric, and immune to the harsh environments of processing plasmas. PPD is intended to satisfy these requirements. The specific technique used to implement plasma diagnostics with a PPD sensor would be an advanced version of continuous-wave cavity-ringdown spectroscopy (CW-CRDS) capable of profiling spectral line broadenings in order to derive both Doppler and Stark components. CRDS is based on measurements of the rate of absorption of laser light in an optical resonator. The ultimate sensitivity results from a very long absorption path length within the cavity and immunity to variations in incident laser intensity. The proposed version of this technique would involve the use of multiplexing tunable laser diodes and an actively modulated high-reflectivity optical resonator, thus offering a synergistic combination of simplicity, compactness, high sensitivity, and high resolution. The multiplexing capabilities of diode lasers could be utilized to make the PPD sensor a single, simple, compact, and inexpensive tool for the acquisition of multiparametric data. A PPD sensor would be capable of continuous measurement of such physical parameters as gas temperature, gas velocity, electron number density, and absolute densities of reacting chemical species. A laser beam can be easily adjusted to analyze the immediate vicinity of the growing nanostructures (or features etched down) in real time. The absorption enhancement in an optical cavity would afford the sensitivity needed for measurement of the temperature and densities of species at concentrations significantly lower than measurable by other nonintrusive techniques. It is anticipated that fully developed PPD sensors would enable simultaneous measurement of local temperature and determination of plasma species responsible for the synthesis and functionalization of nanodevices. These sensors would also enable tracking the pathways and origins of damaging contaminants, thereby providing feedback for adjustment of processes to optimize them and reduce contamination. The PPD sensors should also be useful for optimization of conventional microelectronics manufacturing plasma processes. Going beyond plasma processes for fabrication of electronic devices, PPD sensors could be used for monitoring of atoms, molecules, ions, radicals, clusters, and particles in a variety of other settings, including outer space. Because of their high sensitivity, such sensors could also prove useful for detecting traces of illegal drugs and explosives.

Bolshakov, Alexander↗
DOE OSTI2022

Hydrogen generation via ammonia decomposition on highly efficient and stable Ru-free catalysts: approaching complete conversion at 450 °C

We report Hydrogen (H 2 ) is a prospective zero-carbon and high-energy-density fuel alternative to fossil fuels for generating power and clean energy. Ammonia (NH 3 ) is a promising H 2 (17.7%) carrier, which can easily overcome the challenges associated with H 2 storage and transportation. Thermocatalytic ammonia decomposition reaction (ADR) is an effective way to produce clean H 2 but it relies on the use of expensive and rare ruthenium (Ru)-based catalysts at elevated temperatures (>500 °C), hence is not sustainable and economically feasible. Herein, we report a synergistic strategy to design a heterostructured Ru-free catalyst, consisting of CoNi alloy nanoparticles well-dispersed on a MgO–CeO 2 –SrO mixed oxide support with potassium promotion. The resulting K–CoNi alloy –MgO–CeO 2 –SrO catalyst presents 97.7% and 87.5% NH 3 conversion efficiency at 450 °C at gas hourly space velocities (GHSVs) of 6000- and 12 000-mL h -1 g cat -1 , respectively. At 500 °C, the H 2 production rate (57.75 mmol g cat -1 min -1 ) becomes comparable to that of most of the reported Ru-based catalysts. The catalyst stability has been successfully demonstrated in both a fixed-bed reactor under high pressure (120 h at 5.0 bar) and a membrane reactor prototype (600 h at 1.5 bar) at 500 °C. High-temperature in situ XPS analysis, temperature-programmed desorption/reduction, and density functional theory calculations have been carried out to elucidate the possible active sites and performance enhancement mechanisms. This work highlights the importance of constructing optimal interfaces between active metal nanoparticles and oxide support for boosting the NH 3 to H 2 conversion efficiency and long-term stability.

25 ENERGY STORAGE↗
DOE OSTI2023

Simulating energy performance of buildings: a study using eQUEST and Energy Star ® portfolio manager

Commercial buildings consume significant energy in the United States and exhibit high potential for energy use reduction through retrofits. Benchmarking and energy simulation are well established tools in the industry to identify potential improvements and measure performance. Analysis to identify most sensitive retrofit parameters to energy performance can optimize investment and available energy savings. Presented study demonstrates methodology using a static model to determine sensitivity of building design and retrofit parameters with respect to energy performance. Calibrated simulation energy models (eQUEST) of two distribution centers (A, B) are presented. A fractional factorial analysis is conducted on retrofit parameters of efficiency measures targeting the highest energy consumers, and the results are benchmarked using Energy Star® Portfolio Manager. A custom Microsoft Excel® based simulation model is created to simulate occupancy levels, lighting, plug loads, and other equipment used in various spaces throughout the day. For Building A, efficient lighting was the most influential parameter for energy savings, carbon savings and benchmarking score; whereas, for Building B, HVAC efficiency was most influential for energy and demand controlled ventilation and economizers was most influential for benchmarking score. While retrofit projects can save energy and carbon emissions, variation in source-site ratios and state grid emissions, benchmarking scores may not always reflect equivalent improvement. State grid emissions factors, natural gas composition are difficult to model and hence not considered in this study. In conclusion, the synergistic analysis presented, emphasizes the importance of benchmarking and efficiency retrofits in promoting sustainable building practices to reduce energy consumption.

29 ENERGY PLANNING, POLICY, AND ECONOMY↗
DOE OSTI2022

Regulating Electronic Structure of Single-Atom Catalysts toward Efficient Bifunctional Oxygen Electrocatalysis

We report electronic structure of single-atom catalysts (SACs) is critical for bifunctional oxygen electrocatalysis by adjusting the binding energy in oxygen-containing intermediates. However, the regulation of electronic structure has always been a challenge to improve catalytic reactivity. Herein, by introducing a heterogenous metal, the electronic structure through a direct bonding interaction to the active center atom is effectively adjusted. Partial charge transfer between the two atoms optimizes the binding energy of intermediates and reducing the energy barrier of the catalytic reaction. Theoretical calculations confirm these effects and the uniform distribution of 3d orbitals, leading to the improvement of bifunctional oxygen electrocatalytic reactivity. Benefiting from these attributes, the as-constructed bifunctional catalyst enables outstanding electrocatalytic performances in both oxygen reduction and hydrogen oxidation in various energy storage systems. The generality and expandability of this strategy is demonstrated by further successful development of other dual-metal catalysts systems with various active metals.

36 MATERIALS SCIENCE↗
DOE OSTI2024

Molecular insights into the in situ early-stage assembly of metal–organic frameworks on cellulose nanofibrils

The integration of metal–organic frameworks (MOFs) into renewable matrices, including those derived from cellulose, to create cellulose/MOF hybrids has attracted significant interest due to the synergistic combination of cellulosic biopolymer properties and MOFs' multifunctional features. The interfacial interactions between cellulose and MOF not only ensure stable bonding, but ultimately also determine the bulk physical properties of the macroscopic composites. However, the mechanistic understanding of the in situ assembly between the two materials remains unclear. In this study, we employ a combination study of synthesis, experimental characterization, and molecular dynamics simulations to explore the early-stage assembly of a cellulose/MOF hybrid. Our results revealed that the growth of MOF clusters on the 2,2,6,6-tetramethyl-1-piperidinyloxy oxidized cellulose nanofibrils (TOCNF) follows an inhomogeneous sequential transformation pathway. The carboxylates of TOCNF form coordination-like bonds with the metal ions, while the hydroxyl groups of TOCNF form hydrogen bonds with MOF ligands. These interactions provide the initial nucleation sites that mediate the growth of MOF clusters and also guide the assembly of larger MOF clusters onto the TOCNF substrate. In conclusion, the fundamental insights into the in situ assembly of MOF nanoparticles on cellulosic substrates are essential for the rational design of high-performance materials with tailored morphology and optimized properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2002

Techniques Optimized for Reducing Instabilities in Advanced Nickel-Base Superalloys for Turbine Blades

The High-Speed Research (HSR) Airfoil Alloy program developed fourth-generation single-crystal superalloys with up to an 85 F increase in creep rupture capability over current production airfoil alloys. Recent results have been generated at the NASA Glenn Research Center on these fourth-generation alloys, but in coated form, for subsonic turbine blade applications under NASA's Ultra-Efficient Engine Technology (UEET) Program. One goal for UEET is to optimize the airfoil alloy/thermal barrier coating system for 3100 F turbine inlet temperatures. The state-of-the art turbine blade airfoil system consists of a superalloy single crystal that provides the basic mechanical performance of the airfoil. A thermal barrier coating is used to reduce the temperature of the base superalloy, and a bondcoat is deposited between the base material and the thermal barrier coating. The bondcoat improves the oxidation and corrosion resistance of the base superalloy and improves the spallation resistance of the thermal barrier coating. A commercial platinum aluminide bondcoat was applied to the HSR-developed alloys, and a diffusion zone developed as a result of interaction between the bondcoat and the superalloy. Optimized strength is obtained for superalloys when the refractory element content is high and the limits of microstructural stability are approached or exceeded slightly. For fourthgeneration alloys, instability leads to the formation of topologically close packed (TCP) phases, which form internally in the superalloy, and a secondary reaction zone (SRZ), which forms under the diffusion zone. There was a concern that excessive quantities of either TCP or SRZ might decrease the mechanical properties of the superalloy, with SRZ thought to be particularly detrimental and its formation unpredictable. Thus, an SRZreduction effort was initiated in the NASA UEET Program so that methods developed during the HSR project could be optimized further to reduce or eliminate the SRZ. An SRZ is a three-phase constituent composed of TCP and stringers of gamma phase in a matrix of gamma prime. An incoherent grain boundary separates the SRZ from the gammagamma prime microstructure of the superalloy. The SRZ is believed to form as a result of local chemistry changes in the superalloy due to the application of the diffusion aluminide bondcoat. Locally high surface stresses also appear to promote the formation of the SRZ. Thus, techniques that change the local alloy chemistry or reduce surface stresses have been examined for their effectiveness in reducing SRZ. These SRZ-reduction steps are performed on the test specimen or the turbine blade before the bondcoat is applied. Stressrelief heat treatments developed at NASA Glenn have been demonstrated to reduce significantly the amount of SRZ that develops during subsequent high-temperature exposures. Stress-relief heat treatments reduce surface stresses by recrystallizing a thin surface layer of the superalloy. However, in alloys with very high propensities to form SRZ, stress relief heat treatments alone do not eliminate SRZ entirely. Thus, techniques that modify the local chemistry under the bondcoat have been emphasized and optimized successfully at Glenn. One such technique is carburization, which changes the local chemistry by forming submicron carbides near the surface of the superalloy. Detailed characterizations have demonstrated that the depth and uniform distribution of these carbides are enhanced when a stress relief treatment and an appropriate surface preparation are employed in advance of the carburization treatment. Even in alloys that have the propensity to develop a continuous SRZ layer beneath the diffusion zone, the SRZ has been completely eliminated or reduced to low, manageable levels when this combination of techniques is utilized. Now that the techniques to mitigate SRZ have been established at Glenn, TCP phase formation is being emphasized in ongoing work under the UEET Program. The limitsf stability of the fourth-generation alloys with respect to TCP phase formation are currently being defined along with high-temperature creep rupture properties. In addition, a regression model is being developed at Glenn for the prediction of the presence of TCP phase in the microstructure and SRZ under the diffusion zone. The model is based on a design-of-experiments methodology with emphasis on the potential synergistic effects of alloying elements.

MacKay, Rebecca A.↗
DOE OSTI2020

Modeling Synergistic Fuel Cell Membrane Degradation with Mitigating Effects of Cerium

During operation, polymer-electrolyte-membrane (PEM) fuel cells undergo mechanical and chemical degradation mechanisms, which behave synergistically and lead to accelerated membrane degradation over time. This study builds upon previous modeling work on mechanical degradation as described by a pinhole in the membrane and the effects of cerium on chemical degradation.1 By combining these two models, analysis can be carried out on the coupled degradation methods and how the mitigation effects of cerium disrupt the degradation cycle. The mechanical model represents a pinhole in the membrane using an effective void fraction, which allows for increased gas crossover through the membrane and impacts the membrane transport and mechanical properties. A microkinetic model for the chemical degradation is included in the model, including attack of the membrane polymer by hydroxyl radicals as well as the mitigation reaction for quenching of hydroxyl radicals with cerium. A concentrated solution theory approach is used to model the transport of cerium ions throughout the cell.2 The model results show how the location of cerium in the cell can be used to prevent chemical degradation. In addition, the model shows how cerium slows down the rate of pinhole growth by reducing the gas crossover and membrane thinning rate. Finally, the model can be used to optimize the distribution of cerium in the membrane and catalyst layers by balancing trade-offs between lowering degradation rates and decreasing fuel cell performance.

25 ENERGY STORAGE↗
DOE OSTI2022

Precursor prioritization for p-cymene production through synergistic integration of biology and chemistry

Abstract The strategy of synergistic application of biological and chemical catalysis is an important approach for efficiently converting renewable biomass into chemicals and fuels. In particular, the method of determining the appropriate intermediate between the two catalytic methods is critical. In this work, we demonstrate p -cymene production through the integration of biosynthesis and heterogenous catalysis and show how a preferred biologically derived precursor could be determined. On the biological side, we performed the limonene and 1,8-cineole production through the mevalonate pathway. Titers of 0.605 g/L and a 1.052 g/L were achieved, respectively. This difference is in agreement with the toxicity of these compounds toward the producing microorganisms, which has implications for subsequent development of the microbial platform. On the heterogeneous catalysis side, we performed the reaction with both biological precursors to allow for direct comparison. Using hydrogenation/dehydrogenation metals on supports with acid sites, both limonene and 1,8-cineole were converted to p -cymene with similar yields under equivalent reaction conditions. Thus, we could determine that the most promising strategy would be to target 1,8-cineole, the higher titer and lower toxicity bio-derived precursor with subsequent catalytic conversion to p -cymene. We further optimized the biological production of 1,8-cineole via fed-batch fermentation and reached the titer of 4.37 g/L which is the highest known 1,8-cineole titer from microbial production. This work provides a valuable paradigm for early stage considerations to determine the best route for the high-efficiency production of a target biobased molecule using an integration of biology and chemistry.

09 BIOMASS FUELS↗
DOE OSTI2026

Hollow-structured Ni-N-C catalysts for highly selective CO 2 electroreduction

Atomically dispersed single-atom catalysts have emerged as promising non-precious catalyst alternatives to expensive Ag and Au catalysts for electrochemical CO 2 reduction reaction (CO 2 RR). In particular, nickel-nitrogen-carbon (Ni-N-C) catalysts have demonstrated a high faradaic efficiency (FE) toward CO formation at low overpotentials. Nonetheless, the exact nature of Ni active sites under CO 2 RR remains elusive and conventional Ni-N-C catalysts are limited by microporosity and low density of Ni single atoms, hindering performance in CO 2 electrolyzers. Here, we report the synthesis of hollow-structured Ni-N-C ( hs -Ni-N-C) catalysts via a post-synthesis modification (PSM) strategy using partial ligand exchange of 2-methylimidazole with 3-amino-1,2,4-triazole. This approach enables the formation of a hollow structure, resulting in more than a twofold increase in Ni atom density compared to regular Ni-N-C (r-Ni-N-C). In a zero-gap CO 2 electrolyzer, the optimized hs -Ni-N-C allows for achieving an FE CO of 97% at a current density of > 100 mA cm⁻ 2 , while maintaining high CO selectivity with stable performance over 100 h at 2.5 V. hs-Ni-N-C shows a more than sevenfold increase in the CO partial current density relative to r-Ni-N-C resulting from the combined effects of a higher density of Ni single-atom sites, improved kinetics, and lower transport resistance under the operating conditions, as indicated by electrochemical impedance spectra and distribution of relaxation times analysis. Operando high energy-resolution X-ray absorption spectroscopy (XAS) reveals that atop-bonded CO on Ni single sites induces dynamic transformations of the Ni–N coordination environment, leading to a symmetric coordination structure of hs -Ni-N-C. Under CO 2 RR, the catalysts undergo a more pronounced structural change and form a minor fraction of Ni nanoparticles. Density functional theory calculations are consistent with the XAS results and provide molecular insights showing that the interplay between protonation and CO adsorption leads to adsorbate-induced restructuring of the Ni single atom. This work demonstrates the synergistic role of hollow structure and high-density Ni atoms in governing CO 2 RR selectivity and provides mechanistic insights into the structural dynamics of single-atom catalysts under operating conditions.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Connecting agriculture and renewable energy: insights into microclimatic changes, physiological, biochemical, and yield responses under agrivoltaics: a review

Agrivoltaics, the synergistic integration of agriculture and solar energy production on the same piece of land, has emerged as a compelling dual-use solution that maximizes land productivity while simultaneously addressing the need for sustainable agricultural practices and renewable energy generation. Despite the growing global interest in this dual-use system, the microclimatic shifts created beneath solar panels and their consequences for crop performance remain insufficiently synthesized. This review highlights the intricate interactions between agrivoltaics systems and plant microclimates, discussing their impacts on various physiological processes, metabolic pathways, and overall yield responses in different crop species. Evidence indicates that moderated light intensity and altered microclimates can enhance water-use efficiency, stabilize photosynthetic function, and trigger beneficial metabolic adjustments; however, responses remain highly species-specific and strongly dependent on regional climate conditions and panel configuration. Yield outcomes vary widely among vegetables, cereals, pulses, and fruit crops, highlighting the necessity for tailored agronomic strategies and crop selection within agrivoltaic designs. A critical knowledge gap identified in this review concerns the limited understanding of molecular and omics-level responses underlying plant adaptation to agrivoltaic environments. We further provide a detailed and interdisciplinary overview of adaptive agronomic strategies, and optimal crop selection, tailored to agrivoltaic systems. Despite the benefits of land use efficiency and simultaneous food and energy production, challenges remain concerning initial investment, technological adaptation, social and legal barriers, and shade-induced yield penalties. Further research in this area will be critical to enhancing the agricultural, environmental, and economic sustainability of agrivoltaics while simultaneously augmenting their practical utility and appeal to farmers in the future.

14 SOLAR ENERGY↗
DOE OSTI2020

Sensitivity and Uncertainty Quantification of Transition Scenario Simulations

This report documents the first collective attempt at developing and applying capabilities to quantify uncertainties, assess parametric sensitivities, and optimize multiple parameters and metrics in fuel cycle simulations generated by the SA&I Campaign. To do this, external codes that were designed to perform sensitivity analysis and uncertainty quantification (SA&UQ) needed to be coupled to the SA&I Campaign’s nuclear fuel cycle simulators (NFCS). In FY20, two approaches were pursued: 1) coupling Cyclus to an ORNL-internal code called MOT (Metaheuristic Optimization Tool) and 2) coupling DYMOND to the opensource SA&UQ tool kit Dakota. The primary objective of having these NFCS/SA&UQ coupled capabilities is to better inform DOE-NE and other stakeholders on the results generated from the NFCS. For a given set of fuel cycle strategies, policies, and technology assumptions that make up a fuel cycle scenario, these NFCS have traditionally been used by the SA&I Campaign to provide quantitative answers in terms of year-by-year mass flows, infrastructure requirements, costs, etc. With these newly developed coupled capabilities, the SA&I Campaign can now efficiently simulate hundreds or thousands of these scenarios, sample large ranges of parameters and assumptions, and use the unique features of the SA&UQ tools to process the data. This enables providing answers with known and propagated uncertainties, determining the sensitivity of important metrics to different parameters and assumptions, quantifying how much fuel cycle and technology parameters impact each other, and producing optimized fuel cycle strategies for single and multiple variables. To demonstrate these new capabilities, the Cyclus/MOT was used to model several scenarios ranging from simple fleet retirements to transitions to advanced reactors. Specifically, for a transition scenario from LWRs to SFRs and advanced LWRs, uncertainty quantification, sensitivity analysis, and optimization studies were applied to cases involving single and multiple parameter (input) and single and multiple metric (output) variations. In addition, a similar transition scenario was modeled to demonstrate how to optimize the reprocessing capacity parameter to minimize two performance metrics while taking into account uncertainties from two other parameters. Lastly, a depletion module based on SCALE/ORIGEN was added in Cyclus to simulate the third scenario that was designed to quantify the impact of the modeling assumption that all LWR used nuclear fuel have the same burnup. The newly developed DYMOND/Dakota capability was also applied to a transition scenario from the existing fleet to small modular reactors and fast reactors. This particular scenario involves not only explicit isotopic depletion via ORIGEN-2, but also includes multirecycling and utilizing the criticality search feature to determine the fresh fuel composition of recycled fuel, a feature unique to the DYMOND NFCS. A large database of simulations were run with 4 main parameters that were sampled: start date of reprocessing, reprocessing capacity, energy demand growth rate, and advanced reactor share of the fleet. The 4 main metrics were uranium consumption, enrichment requirements, waste generation, and levelized cost of electricity using data from the Cost Basis Report. The demonstrated SA&UQ results include those that inform on how to choose parameters to avoid “failed” scenarios, Sobol’ indices that inform on the importance of various parameters individually and synergistically, and Analysis of Variance (ANOVA) studies that decompose parameter ranges into groups and informs on whether variations are statistically significant.

Feng, B.↗