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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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At least 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

Developing Scaling Relationships for Molecular Electrocatalysis through Studies of Fe-Porphyrin-Catalyzed O 2 Reduction

The oxygen reduction reaction (ORR) is a multiproton/multielectron transformation in which dioxygen (O 2 ) is reduced to water or hydrogen peroxide and serves as the cathode reaction in most fuel cells. The ORR (O 2 + 4e – + 4H + → 2H 2 O) involves up to nine substrates and thus requires navigating a complicated reaction landscape, typically with several high-energy intermediates. Many catalysts can perform this reaction, though few operate with fast rates and at low overpotentials (close to the thermodynamic potential). Attempts to optimize these parameters, both in homogeneous and heterogeneous electrocatalytic systems, have focused on modifying catalyst design and understanding kinetic/thermodynamic relationships between catalytic intermediates. One such method for analyzing and predicting catalyst reactivity and efficiency has been the development of “molecular scaling relationships”. In this work, we share our experience deriving and utilizing molecular scaling relationships for soluble, iron-porphyrin-catalyzed O 2 reduction in organic solvents. These relationships correlate turnover frequencies (TOF max ) and effective overpotentials (η eff ), properties uniquely defined for homogeneous catalysts. Following a general introduction of scaling relationships for both homogeneous and heterogeneous electrocatalysis, we describe the components of such scaling relationships: (i) the overall thermochemistry of the reaction and (ii) the rate and rate law of the catalyzed reaction. We then show how connecting these thermodynamic and kinetic parameters reveals multiple molecular scaling relationships for iron-porphyrin-catalyzed O 2 reduction. For example, the log(TOF max ) responds steeply to changes in ηeff that result from different catalyst reduction potentials (18.5 decades in TOF max /V in η eff ) but much less dramatically to changes in η eff that arise from varying the pKa of the acid buffer (5.1 decades in TOF max /V in η eff ). Thus, a single scaling relationship is not always sufficient for describing molecular electrocatalysis. This is particularly evident when the catalyst identity and reaction conditions are coupled. Using these multiple scaling relationships, we demonstrate that the metrics of turnover frequency and effective overpotential can be predictably tuned to achieve faster rates at lowered overpotentials. This Account uses a collection of related stories describing our research on soluble iron-porphyrin-catalyzed ORR to show how molecular scaling relationships can be derived and used for any electrocatalytic reaction. Such scaling relationships are powerful tools that connect the thermochemistry, mechanism, and rate law for a catalytic system. We hope that this collection shows the utility and simplicity of the molecular scaling approach for understanding catalysis, for enabling direct comparisons between catalyst systems, and for optimizing catalytic processes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Characterizing the Influence of Organic Polymers on the Specific Reactivity of Particulate Remedial Amendments

Commercially available particulate amendments demonstrate high reactivity for effective treatment of water soluble organic and inorganic contaminants in laboratory studies; however, transport of these particles is constrained in the subsurface. In many field applications, particulate amendments are mixed with organic polymers to enhance mobility for direct push applications or stabilize suspensions for high mass loadings. As such, the interactions between particulate amendments, organic polymers and contaminant species need to be systematically investigated to properly understand mechanistic processes that facilitate predictive performance metrics for specific applications in situ . In this study, batch experiments were conducted to quantify the effects of organic polymers (xanthan gum, guar gum, and sodium alginate), polymer concentration (800 and 4,000 mg/L), and aging (up to 28 days) on chromate treatment rate and capacity by two classes of amendments: reductants [granular zero-valent iron (gZVI), micron-ZVI (mZVI), sulfur modified iron (SMI)], and an adsorbent (bismuth sub-nitrate). When particulate amendments were suspended in polymer solutions, reductants retained between 84–100% of the amendment treatment capacity. Conversely, the adsorbent maintained 63–97% relative treatment capacity of the no-polymer control. Polymer solutions had a more pronounced impact on the rate of chromate removal; first order rates of chemical reduction decreased by as much as 70% and adsorption by up to 81% relative to the no-polymer controls. Polymer–amendment aging experiments also showed decreased Cr(VI) treatment capacity; reductants decreased by as much as 24% and adsorption decreased by as much as 44% after 28 days of incubation. While polymer suspensions are needed to aid the injection of particulate amendments into the subsurface, the results from this study indicate potential losses of treatment capacity and a decrease in the rate of remedial performance due to the physical and chemical interactions between polymer suspensions and reactive particulate amendments. Simple batch systems provide baseline characterization of tripartite interactions for the removal of Cr(VI). Additional work is needed to quantify the full impact of polymers on remedial outcomes under site relevant conditions at field scale.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2020

In situ reductive dissolution to remove Iodine-129 from aquifer sediments

The use of an aqueous reductant (Na-dithionite) with pH buffer (K-carbonate, pH 12) was evaluated in this laboratory study as a potential remedial approach for removing Fe oxide associated iodine and enhancing pump-and-treat extraction from iodine-contaminated sediments in the unconfined aquifer in the 200 West Area of the Hanford site. X-ray fluorescence data of untreated sediment indicated that iodine was largely associated with Fe (i.e., incorporated into Fe oxides), however, XANES data was inconclusive as to valence state. During groundwater leaching, aqueous and adsorbed iodine was quickly released, then additional iodine was slowly released potentially from dissolution of one or more surface phases. The Na-dithionite treatment removed greater iodine mass (2.9x) at a faster rate (1 to 4 orders of magnitude) compared to leaching with groundwater alone. Iron extractions for untreated and treated sediments showed a decrease in Fe(III)-oxides, which likely released iodine to aqueous solution. Solid phase inorganic carbon and aqueous Ca and Mg analysis further confirmed that significant calcite dissolution did not occur in these experiments meaning these phases did not release significant iodine. Although it was expected that, after treatment, 127 I concentrations would eventually be lower than untreated sediments, leaching experiments showed continued, elevated iodine concentrations for treated samples over 750 hours. Stop flow events during 1-D column leaching suggested that some iodide precipitated within the first few pore volumes. In the survey of metals during leaching, some silver was detected which could have been solubilized by the elevated pH of initial Na-dithionite injection. Then, silver (or other metals) could have subsequently precipitated with iodide during the initial stop flow event forming a slowly dissolving source. Although significantly greater iodine is removed with treatment, the long-term leaching needs to be investigated further as it may limit dithionite treatment at the field scale.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

Expanded Diversity of Microbial Groups Capable of Anaerobic Pyrite Reduction and Assimilation of Dissolution Products

Pyrite, the most abundant iron sulfide mineral in the Earth's crust, has traditionally been considered as a sink for iron and sulfur in the absence of oxygen. Recent research, however, has shown that anaerobic methanogenic archaea can reductively dissolve pyrite and assimilate its products as sources of iron and sulfur. This study explores whether other anaerobic bacteria, including fermentative, nitrate-, iron oxide-, fumarate-, and sulfate-respiring bacteria, can also reduce pyrite and use its dissolution products as sources of iron and sulfur. Results indicate that heterotrophic bacteria respiring fumarate or sulfate, or fermenting organic carbon, can reduce pyrite and assimilate released iron and sulfur. In contrast, nitrate- or iron oxide-respiring cells did not reduce pyrite, suggesting that microbial pyrite reduction is metabolism-specific. All strains capable of reducing pyrite could also use mackinawite as an iron and sulfur source. With the exception of fermentative Bacteroides, strains did not require direct contact with pyrite to reduce the mineral, indicating extracellular electron transfer via electron shuttles. These findings expand the known diversity of microbial groups capable of pyrite reduction and highlight the mineral's lability in various anaerobic environments, with potential implications for the biogeochemical cycles of iron, sulfur, carbon, and oxygen.

58 GEOSCIENCES↗
DOE OSTI2021

Iron-based sulfur and nitrogen dual doped porous carbon as durable electrocatalysts for oxygen reduction reaction

The widespread use of fuel cell technology is hampered by the use of expensive and scarce platinum metal in electrodes which is required to facilitate the sluggish oxygen reduction reaction (ORR). In this work, a viable synthetic approach was developed to prepare iron-based sulfur and nitrogen dual doped porous carbon (Fe@SNDC) for use in ORR. Benzimidazole, a commercially available monomer, was used as a precursor for N doped carbon and calcined with potassium thiocyanate at different temperatures to tune the pore size, nitrogen content and different types of nitrogen functionality such as pyridinic, pyrrolic and graphitic. The Fe@SNDC–950 with high surface area, optimum N content of about 5 at% and high amount of pyridinic and graphitic N displayed an onset potential and half-wave potential of 0.98 and 0.83 V vs RHE, respectively, in 0.1 M KOH solution. The catalyst also exhibits similar oxygen reduction reaction performance compared to Pt/C (20 wt%) in acidic media. Furthermore, when compared to commercially available Pt/C (20 wt%), Fe@SNDC–950 showed enhanced durability over 6 h and poison tolerance in case of methanol crossover with the concentration up to 3.0 M in oxygen saturated alkaline electrolyte. Finally, our study demonstrates that the presence of N and S along with Fe-N moieties synergistically served as ORR active sites while the high surface area with accessible pores allowed for efficient mass transfer and interaction of oxygen molecules to the active sites contributing to the ORR activity of the catalyst.

08 HYDROGEN↗
DOE OSTI2024

Effect of pretreatment conditions on Fe-ZSM-5 properties and performance for Fischer–Tropsch synthesis

Iron supported on ZSM-5 is a widely studied catalyst for Fischer–Tropsch synthesis (FTS). Iron is activated with H 2 , CO, or a mixture of CO and H 2 prior to FTS, resulting in phase transformations that make it challenging to understand structure–property relationships. Furthermore, in this work, we demonstrate that increasing the pretreatment temperature of Fe–Na-ZSM-5 reduces CO conversion irrespective of the reductant, but the product selectivity, iron particle size, composition, CO adsorption properties, and zeolite structure is dependent on both the pretreatment temperature and reductant. Pretreatment of Fe–Na-ZSM-5 in H 2 induces sintering of iron particles, increasing C 2 –C 4 olefins and C 5+ hydrocarbons selectivity from 19.0% and 14.0% at 350 °C to 28.2% and 25.4% at 770 °C, respectively. Conversely, CO pretreatment facilitates carbide formation, coke deposition, and CH 4 formation.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Atomically Revealing Bulk Point Defect Dynamics in Hydrogen‐Driven γ‐Fe 2 O 3 → Fe 3 O 4 → FeO Transformation

Understanding how point defects in the bulk govern redox transformations is essential for advancing hydrogen-based metal production and designing high-performance oxide materials. This study reveals the atomic-scale mechanisms driving hydrogen-induced reduction of γ-Fe 2 O 3 to Fe 3 O 4 , focusing on how bulk vacancy dynamics dictate structural evolution and reaction kinetics. A key finding is the pronounced contrast in defect behavior between the two oxides: in γ-Fe 2 O 3 , intrinsic Fe vacancies promote oxygen vacancy clustering, destabilizing the local lattice and driving nanopore formation. In contrast, Fe 3 O 4 exhibits a higher oxygen vacancy formation energy and lacks intrinsic Fe vacancies, suppressing vacancy aggregation and maintaining a dense, pore-free structure. This divergence governs distinct reduction pathways—γ-Fe 2 O 3 undergoes an interface-reaction-limited transformation confined to the γ-Fe 2 O 3 /Fe 3 O 4 boundary, while Fe 3 O 4 supports a uniform increase in oxygen vacancy concentration, enabling bulk-phase reduction to lower-oxide FeO. Integrated in situ electron microscopy and density functional theory modeling uncover a vacancy-mediated mechanism, where synergistic cation-anion vacancy dynamics steer microstructure evolution and phase progression. These insights highlight the critical role of vacancy dynamics in controlling oxide reactivity and offer a pathway toward vacancy engineering to enhance reduction kinetics in hydrogen metallurgy and to tailor porosity, reactivity, and structural resilience in oxide-based catalysts and energy materials.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Laser, vacuum and gas reaction chamber for operando measurements at NSLS-II's 28-ID-2

We present a laser reaction chamber that we have developed for in situ/operando X-ray diffraction measurements at the NSLS-II 28-ID-2 X-ray powder diffraction beamline. This chamber allows for rapid and dynamic sample heating under specialized gas environments, spanning ambient conditions down to vacuum pressures. We demonstrate the capabilities of this setup through two applications: laser-driven heating in polycrystalline iron oxide and in single-crystal WTe 2 . Our measurements reveal the ability to resolve chemical reaction kinetics over minutes with 1 s time resolution. This setup advances opportunities for in situ/operando X-ray diffraction studies of both bulk and single-crystal materials.

36 MATERIALS SCIENCE↗
NASA NTRS1987

Analysis of flow decay potential on Galileo

The risks posed to the NASA's Galileo spacecraft by the oxidizer flow decay during its extended mission to Jupiter is discussed. The Galileo spacecraft will use nitrogen tetroxide (NTO)/monomethyl hydrazine bipropellant system with one large engine thrust-rated at a nominal 400 N, and 12 smaller engines each thrust-rated at a nominal 10 N. These smaller thrusters, because of their small valve inlet filters and small injector ports, are especially vulnerable to clogging by iron nitrate precipitates formed by NTO-wetted stainless steel components. To quantify the corrosion rates and solubility levels which will be seen during the Galileo mission, corrosion and solubility testing experiments were performed with simulated Galileo materials, propellants, and environments. The results show the potential benefits of propellant sieving in terms of iron and water impurity reduction.

Cole, T. W.↗
NASA NTRS1991

Coproduction of volatiles and metals from extraterrestrial materials

Two main efforts in support of the general goals of SERC/culpr are presented. Investigations of processes for the coproduction of metals from extra-terrestrial materials in conjunction with plausible schemes for oxygen extraction continue. The principal emphasis was on the extraction and purification of iron from the ilmenite reduction process for oxygen, from the cathode metal deposits made in the magma electrolysis process for oxygen, and from native ferrous metal alloys on the moon and asteroids. All work on the separation and purification of ferrous metals was focussed upon the gaseous carbonyl process, a scheme that involves only temperatures attainable by passive thermal control. The exploration of a variety of schemes was initiated, involving the use of several different propulsion options and both propulsive and aerobraking capture at earth, for return of extraterrestrial resources to earth orbits. In addition, the search for new opportunities in space resource utilization continues. Examples include the continuation of work underway on: (1) the feasibility of locating solar power satellites in highly eccentric earth orbit; (2) the energetics of extracting the potential clean fusion fuel He-3 from the atmosphere for return to earth; and (3) the utility of a nuclear steam rocket (using non-terrestrial water as the working fluid) for transportation in the inner solar system.

Lewis, John S.↗
NASA NTRS1985

Sulfur diagenesis in marine sediments

Bacterial sulfate reduction occurs in all marine sediments that contain organic matter. Aqueous sulfide (HS-, H2S), one of the initial products of bacterial sulfide reduction, is extremely reactive with iron bearing minerals: sulfur is fixed into sediments as iron sulfide (first FeS and then Fe2S2). A working definition is given of sulfur diagenesis in marine sediments. Controls and consequences of sulfate reduction rates in marine sediments are examined.

Goldhaber, M.↗
NASA NTRS1976

Friction of iron lubricated with aliphatic and aromatic hydrocarbons and halogenated analogs

The influence of oxygen and various organic molecules on the reduction of the friction of an iron (011) single crystal surface was investigated. A comparison was made between aliphatic and aromatic structures, all of which contained six carbon atoms, and among various halogen atoms. Results of the investigation indicate that hexane and benzene give similar friction coefficients over a range of loads except at very light loads. At light loads, the friction decreased with an increase in the load where the halogens fluorine and chlorine are incorporated into the benzene molecular structure; however, over the same load range when bromine and iodine were present, the friction was relatively unchanged. The aliphatic compound chlorohexane exhibited lower friction coefficients than the aromatic structure chlorobenzene at very light loads. With the brominated benzene structures, however, friction was essentially the same. Oxygen was more effective in reducing friction than were the simple hydrocarbons.

Buckley, D. H.↗
NASA NTRS1989

Reactive iron in marine sediments

The influence of reactive iron oxides on sediment pore-water chemistry is considered in detail. A carefully calibrated extraction scheme is used to determine the depth distributions of reactive iron phases at two very different localities: the relatively iron-rich Mississippi Delta and the relatively iron-poor FOAM site in Long Island Sound. Closed system incubations are used to characterize the rates of reaction between sulfide and both naturally occurring and pure iron mineral phases. Rates of iron liberation to pore solution are measured in the presence and absence of sulfate reduction, and the origin of dissolved iron in organic-rich sediments is speculated upon.

Canfield, Donald E.↗
DOE OSTI2023

Adaptive learning-driven high-throughput synthesis of oxygen reduction reaction Fe–N–C electrocatalysts

Reducing human reliance on inefficient energy systems and fossil fuels has become more urgent due to the consequences of global climate change. However, traditional trial-and-error approaches have hampered our ability to accelerate the discovery and implementation of functional materials for efficient energy conversion devices, such as polymer electrolyte fuel cells (PEFCs). To address this, we develop an adaptive learning framework that integrates machine learning and state-of-the-art capabilities in high-throughput synthesis to achieve expedited optimization of iron-nitrogen-carbon PEFC oxygen reduction reaction (ORR) electrocatalysts. We use statistical inference, uncertainty quantification, and global optimization to build a computational design-of-experiment tool that identifies the optimum compositions to be investigated next to reduce the demands placed on experimental materials discovery. We benchmark the ability of the proposed strategy to discover optimum catalyst synthesis conditions in a six-dimensional search space when starting with a thirty-six-sample database. By following the adaptive learning strategy, we synthesize fourteen new catalysts from approximately ten billion unique compositions and discover four catalysts that outperform all original samples. The best machine learning-optimized catalyst is 33% more active than the highest-performing one in the initial database, showing an ORR activity seven times larger than those typically reported for the same class of materials.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Electrocatalysis of Oxygen Reduction Reaction in a Polymer Electrolyte Fuel Cell with a Covalent Framework of Iron Phthalocyanine Aerogel

Carbon aerogels have been studied in the context of fuel cell electrodes mainly as catalyst support materials due to their high surface area, porosity, and electrical conductivity. Recently, aerogels composed solely of inorganic molecular complexes have shown to be promising materials for the electrocatalysis of oxygen reduction reaction (ORR). These aerogels consist of atomically dispersed catalytic sites. Herein, we report on the synthesis and characterization of an aerogel-based catalyst: iron phthalocyanine aerogel. It was synthesized by coupling of ethynyl-terminated phthalocyanine monomers and then heat-treated at 800 °C to increase its electrical conductivity and catalytic activity. Further, the aerogels reported here were tested as catalysts for ORR in acidic conditions for the first time and found to have a ultra-high number of atomically dispersed catalytic sites (7.11 × 10 20 sites g –1 ) and very good catalytic activity (E onset = 0.9 V vs RHE and TOF = 9.2 × 10 –3 e – s –1 site –1 at 0.8 V vs RHE). The iron phthalocyanine aerogel was also studied in a proton exchange membrane fuel cell, reaching a peak power density of 292 mW cm –2 and an open circuit voltage of 0.83 V.

25 ENERGY STORAGE↗