SEARCH · Search NASA

Results for “CATALYTIC ACTIVITY”

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 91 records · Page 5

All sources NASA NTRS DOE OSTI

DOE OSTI2024

Preparation of ultrathin sputtered gold films on palladium as efficient oxygen reduction electro-catalysts

Herein, we present the preparation of ultrathin gold (Au) films on different M (M = Pd, Pt, Rh, Ir, and Ru) electrodes (Au/M) using magnetron sputtering deposition for oxygen reduction reaction (ORR). The ORR electro-catalytic activities of prepared Au/M catalysts increase as follows: Au/Ru < Au/Ir < Au/Rh < Au/Pt < Au/Pd. Accordingly, the oxygen reduction catalytic behaviors of the Au-modified palladium (Au/Pd) thin films with various Au thicknesses (0.16, 0.24, 0.5, and 1 nm) are investigated in acidic environments. It is found that Au modifications can promote oxygen reduction performances due to the development of more catalytic active sites on the Pd catalyst through the existence of Au atoms. Noticeably, Au/Pd samples exhibit a connection in oxygen reduction ability as a function of Au thickness, with the ultrathin 0.16 nm Au/Pd being the most active ORR catalyst. Significantly, the 0.16 nm Au/Pd material demonstrates superior stability after 1000 potential cycles compared with the 0.16 nm Pt/Pd owing to the influence of Au coating and structurally stable surfaces. Therefore, surface modification with the deposition of Au films on Pd represents a favorable technique to boost both the ORR capability and stability of the electro-catalysts.

Magnetron sputtering↗

DOE OSTI2025

Enabling Ethanol Dehydrogenation Catalysis by Postsynthetic Anion Exchange of Triazolate-Based Metal–Organic Frameworks

Materials containing soft, polarizable elements are expanding the boundaries of catalytic properties, offering unique electronic communication and stability characteristics compared with their harder counterparts due to the enhanced covalent nature of metal–ligand interactions. However, integrating soft components like sulfur into metal–organic frameworks (MOFs) for catalytic applications remains a largely underexplored challenge. Here, we report the synthesis of a family of triazole-based MOFs and expand upon established postsynthetic anion exchange methods to incorporate sterically encumbered polarizable elements, such as alkyl thiolates. Single-crystal X-ray diffraction, coupled with elemental analysis, confirms the successful anion exchange within M 2 X 2 BBTA (M = Co, Ni; X = μ-Cl, μ-OH, μ-SH, μ-SMe, μ-SEt; H 2 BBTA = 1H,5H-benzo(1,2-d:4,5-d′)bistriazole). We found that the anion identity significantly impacts the catalytic activity and selectivity of the MOFs, especially in nonoxidative ethanol dehydrogenation. Temperature-programmed experiments indicated that the metal single sites act as catalytically active sites below 250 °C. This work not only expands the synthetic toolbox for incorporating polarizable components into MOFs but also provides critical insights into their catalytic potential.

Anions↗

NASA NTRS1985

Vapor deposited emittance/catalysis coatings for superalloys in heatshield applications

Statically oxidized Inconel 617 and MA 956 superalloys were prepared with vapor deposited aluminosilicate layers and exposed to temperatures which simulated reentry conditions. The aluminosilicate layers were 1-2 microns thick. The trials consisted of exposures to 1500-2300 F heat while surface temperatures were monitored with pyrometers. Analyses were then performed of the catalytic activity, oxidation phenomena, and radiative properties after thermal cycling the specimens for 8 hr. Both alloys were found to be catalytic to the recombination processes of dissociated species in the reentry environment. The coatings reduced the catalytic activity by 40 percent for both alloys but did not change the emittance. An enhanced Cr depletion zone was detected in the Inconel samples, implying that the coating did not prevent diffusion loss of Cr. The coated MA 956, on the other hand, gained weight over the course of the trials.

Clark, R. K.↗

DOE OSTI2025

Volcano‐like Activity Trends in Au@Pd Catalysts: The Role of Pd Loading and Nanoparticle Size

The addition of palladium (Pd) to preformed gold nanoparticles (Au NPs) enables the formation of core‐shell structures with enhanced catalytic performance in oxidation reactions. However, predicting the precise palladium content required to achieve maximum catalytic activity remains difficult based on current understanding. Herein, Pd was systematically introduced onto titania‐supported Au NPs (2, 6, and 10 nm) to evaluate their performance in benzyl alcohol oxidation. A volcano‐like trend in catalytic activity was observed, where activity increased with Pd addition, peaked, and then declined. The Pd loading required for maximum activity depended on Au NP size: ≈40 at% Pd/Au for 2.6 nm, ≈20 at% Pd/Au for 6.4 nm, and ≈12.5 at% Pd/Au for 10.6 nm. For Au NPs > 6 nm, peak activity aligned with monolayer Pd coverage, while for smaller NPs (2–3 nm), optimal Pd content was below monolayer predictions. X‐ray absorption spectroscopy revealed a core‐shell structure at low Pd content, but higher Pd loadings led to Pd diffusion into the Au core. This structural transformation likely caused activity decline, indicating that AuPd alloying negatively impacts catalysis. These results highlight that core‐shell Au@Pd catalysts outperform AuPd alloys and provide crucial insights for designing highly active bimetallic catalysts.

X-ray absorption spectroscopy↗

DOE OSTI2026

Thermal analysis of combustion synthesis of FeAlxOy catalysts for dehydrogenation of fossil fuels

The growing demand for hydrogen as a clean energy carrier highlights the need for its alternative production method with reduced CO₂ emissions. Microwave-assisted thermocatalytic dehydrogenation of fossil fuels offers a promising solution for clean hydrogen production, with FeAlxOy nanocomposites acting as efficient catalysts due to their thermal stability, catalytic activity, and microwave-absorption properties. FeAlxOy nanocomposites, fabricated by solution combustion synthesis (SCS), have shown good microwave-absorption and catalytic properties. However, the effects of synthesis parameters such as fuel type and Fe:Al molar ratio on the SCS process and properties of the final material are not well understood. The SCS process involves vaporization of water, thermal decomposition of the mixture components, and oxidation – reduction reactions. In the present work, thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) were utilized to study the SCS mechanism, with a focus on understanding decomposition processes. TGA provided insights into the thermal stability and mass loss profiles of the mixtures, while DSC quantified the heat release and identified reaction onset temperatures. Results demonstrated that the choice of fuel significantly influenced the thermal behavior and properties of FeAlxOy nanocomposites. Glycine-based mixtures exhibited superior thermal stability and complete decomposition in a single step with high heat release compared to citric acid-based mixtures, which required higher synthesis temperatures and experienced slower, two-step decomposition processes. These findings emphasize the effectiveness of glycine-fueled SCS in producing thermally stable and catalytically active FeAlxOy nanocomposites.

Martinez Espinoza, Laura Alejandra↗

DOE OSTI2024

Enhanced Activity from Coordinatively Unsaturated and Dynamic Zeolite-Bound Organoscandium Species

Scandium borohydride grafted into the micropores of the faujasite zeolite HY30 catalyzes the C–H borylation of benzene, whereas silica-grafted species are inactive. This catalytic activity may originate from grafting at a Brønsted acid site leading to a more electron-deficient rare earth center. Herein, we apply multinuclear double-resonance nuclear magnetic resonance (NMR) experiments to probe the structure and dynamics of zeolite- and silica-bound scandium borohydride complexes. The experiments reveal that scandium centers located within the zeolite micropores, in proximity to Al-created Brønsted sites, are more dynamic than rigid scandium sites grafted on silanols. Through a combination of NMR and molecular dynamics simulations, we show that the coordination of the scandium in the zeolite is labile, with the metal exchanging between two binding sites. As a result, the weak electron donation from the support that enables the movement of the Sc center leads to the formation of an undercoordinated metal center that cannot exist on silica, ultimately leading to the new catalytic activity of the species.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

DOE OSTI2025

Exsolution of NiCo alloys over Ruddlesden-Popper perovskite for mild electrochemical synthesis of ammonia on protonic ceramic electrochemical cells

Ammonia synthesis from renewable energies on protonic ceramic electrochemical cells (PCECs) shows great potential. The primary challenges in ammonia synthesis on PCECs include sluggish catalytic activity, competition from the hydrogen evolution reaction, and unsatisfactory durability of the cathode, which is the active site of ammonia generation. Here, in this study, we report an elaborate design of the cathode with an intended formula of Pr 4 Ni 1.79 Co 1.2R u 0.01 O 10-δ , where NiCo alloy nanoparticles are exsolved from Ruddlesden-Popper perovskite substrates after the reduction in 5 % H 2 /Ar at 400 °C for 1 h, for electrocatalysis of the nitrogen reduction reaction to ammonia. The host material Pr 4 Ni 1.8 Co 1.2 O 10-δ with embeddable layered structure and stability was deliberately chosen to fix the Ru cation and maximize the catalytic activity of NiCo. Also, density functional theory calculations suggest that Ru doping provides an optimal balance between structural stability and redox activity, facilitating the controlled exsolution of NiCo nanoparticles and enhancing catalytic performance. As a result, the composite electrode with exsolved NiCo alloy and abundant oxygen vacancies on fuel-electrode-supported PCECs achieves a superior electrochemical activity towards ammonia synthesis: a peak ammonia formation rate of 27.84 μg h −1 cm −2 and excellent Faradaic efficiencies of 62.6 % at 350 °C.

30 DIRECT ENERGY CONVERSION↗

NASA NTRS1981

A model for protocellular coordination of nucleic acid and protein syntheses

The proteinoid model for the coordination of protein synthesis with nucleic acid coding within the evolving protocell is discussed. Evidence for the self-ordering of amino acid chains, which would enhance the catalytic activity of a lysine-rich proteinoid, is presented, along with that for the preferential formation of microparticles, particularly proteinoid microparticles, in various solutions. Demonstrations of the catalytic activity of lysine-rich proteinoids in the synthesis of peptide and internucleotide bonds are pointed out. The view of evolution as a two stage sequence in which the geological synthesis of peptides evolved to the protocellular synthesis of peptides and oligonucleotides is discussed, and contrasted with the alternative view, in accord with the central dogma, that nucleic acids arose first then governed the production of proteins and protocells.

Fox, S. W.↗

NASA NTRS1990

Mechanistic studies of the CO-oxidation reaction on catalysts for use in long-life CO2 lasers

The catalytic recombination of carbon monoxide and oxygen was studied under conditions expected to be present in a sealed E-beam CO2 laser system. These conditions are typically a gas inlet temperature of 60 C, a substoichiometric CO/O2 ratio of ca. 2.5/1 with an oxygen feed rate of ca. 5 micromoles/s, a carrier gas comprising He, N2 and CO2 in the ratio of 3:2:1, near atmospheric pressure and a gas velocity of 4 m/s. Heterogeneous catalysts, based on precious metal supported on tin oxide, have been coated onto ceramic monoliths and tested for catalytic activity and stability after a reduction/passivation step. Two catalyst systems have been chosen. These are Pt/Pd/SnO2 and Pt/Ru/SnO2. Under the conditions described above, a characteristic decline in catalytic activity is apparent for both systems, and exit gas temperature has been recognized as a sensitive parameter by which to monitor the activity changes. A semilogarithmic plot of exit temperature as a function of time has revealed two distinct processes connected with the decline in activity: one process is associated with reduction of the oxidized precious metal (at Site A), whilst the other is related to the formation and approach to steady-state of an active site at the metal/support interface (Site B).

Dawood, Talat↗

DOE OSTI2025

Spin State Modulation via Magnetic Fields in Fe Single Atom Catalysts for High-Performance Aqueous Zinc–Sulfur Batteries

Aqueous zinc–sulfur battery has garnered significant attention as a high-energy, low-cost, and safe energy storage system. However, the multielectron transfer kinetics of sulfur cathodes are relatively slow, presenting challenges such as limited sulfur utilization and lower discharge voltage, which significantly hinder their practical applications. Here, in this study, we explored a comprehensive design approach for high-performance, long-cycle aqueous zinc–sulfur batteries. The simultaneous introduction of ZnI 2 and Fe single atoms (Fe-SAs) as catalytically active agents decouples the redox reactions, effectively facilitating ZnS oxidation and S reduction separately. The application of an external magnetic field regulates the spin state of Fe-SAs, further enhancing their catalytic activity and electron transfer capability. Electrochemical tests demonstrate that the S@Fe-NC HS/ZnI 2 cathode assembled under a magnetic field exhibits excellent rate performance, achieving an impressive specific capacity of 1399 mAh g –1 at a high current density of 5 A g –1 and good cycling stability over 300 cycles, representing the highest reported high-current discharge capacity to date. This study provides a comprehensive design framework for optimizing zinc–sulfur (Zn–S) battery performance and elucidates the influence of magnetic field-induced spin state modulation on catalytic behavior.

36 MATERIALS SCIENCE↗

DOE OSTI2024

Active species in chloroaluminate ionic liquids catalyzing low-temperature polyolefin deconstruction

Abstract Chloroaluminate ionic liquids selectively transform (waste) polyolefins into gasoline-range alkanes through tandem cracking-alkylation at temperatures below 100 °C. Further improvement of this process necessitates a deep understanding of the nature of the catalytically active species and the correlated performance in the catalyzing critical reactions for the tandem polyolefin deconstruction with isoalkanes at low temperatures. Here, we address this requirement by determining the nuclearity of the chloroaluminate ions and their interactions with reaction intermediates, combining in situ 27 Al magic-angle spinning nuclear magnetic resonance spectroscopy, in situ Raman spectroscopy, Al K-edge X-ray absorption near edge structure spectroscopy, and catalytic activity measurement. Cracking and alkylation are facilitated by carbenium ions initiated by AlCl 3 - tert -butyl chloride (TBC) adducts, which are formed by the dissociation of Al 2 Cl 7 − in the presence of TBC. The carbenium ions activate the alkane polymer strands and advance the alkylation cycle through multiple hydride transfer reactions. In situ 1 H NMR and operando infrared spectroscopy demonstrate that the cracking and alkylation processes occur synchronously; alkenes formed during cracking are rapidly incorporated into the carbenium ion-mediated alkylation cycle. The conclusions are further supported by ab initio molecular dynamics simulations coupled with an enhanced sampling method, and model experiments using n-hexadecane as a feed.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

NASA NTRS1996

Chance and necessity in the selection of nucleic acid catalysts

In Tom Stoppard's famous play [Rosencrantz and Guildenstern are Dead], the ill-fated heroes toss a coin 101 times. The first 100 times they do so the coin lands heads up. The chance of this happening is approximately 1 in 10(30), a sequence of events so rare that one might argue that it could only happen in such a delightful fiction. Similarly rare events, however, may underlie the origins of biological catalysis. What is the probability that an RNA, DNA, or protein molecule of a given random sequence will display a particular catalytic activity? The answer to this question determines whether a collection of such sequences, such as might result from prebiotic chemistry on the early earth, is extremely likely or unlikely to contain catalytically active molecules, and hence whether the origin of life itself is a virtually inevitable consequence of chemical laws or merely a bizarre fluke. The fact that a priori estimates of this probability, given by otherwise informed chemists and biologists, ranged from 10(-5) to 10(-50), inspired us to begin to address the question experimentally. As it turns out, the chance that a given random sequence RNA molecule will be able to catalyze an RNA polymerase-like phosphoryl transfer reaction is close to 1 in 10(13), rare enough, to be sure, but nevertheless in a range that is comfortably accessible by experiment. It is the purpose of this Account to describe the recent advances in combinatorial biochemistry that have made it possible for us to explore the abundance and diversity of catalysts existing in nucleic acid sequence space.

Review, Tutorial↗

DOE OSTI2024

Impact of Iron Species Dispersion on Fe/ZSM–5 Catalyst Performance for Methane Dehydroaromatization (MDA)

Methane dehydroaromatization (MDA) is one of the most promising technologies for directly transforming methane into aromatics. Unlike the extensively investigated Mo/ZSM-5 catalysts, the structure and, consequently, the catalytic activity of Fe/ZSM-5 are markedly influenced by the method of preparation, as shown here. In this study, we prepared 2 % and 4 % Fe/ZSM-5 catalysts via wet impregnation (WI) and incipient wetness impregnation (IWI). Characterizations (XRD, STEM, UV-Vis, NH 3 -TPD and H 2 -TPR) reveal that 2 %Fe-WI mainly possesses isolated or low-polymerized Fe species within zeolite channels, leading to a rapid activation and a higher benzene yield due to the faster reduction to iron suboxides under MDA conditions. In contrast, 2 %Fe-IWI contains bulk iron oxide aggregates, resulting in a slower activation as these aggregates transform into iron carbide through successive reduction and carbonization. Here, a deactivation kinetic study applied to the 2 % catalysts further demonstrates the quantitative relation between Fe site isolation and catalytic activity. Although both 4 % catalysts inevitably form sizable iron oxide clusters and particles due to the high Fe/Al ratio, similar trends are noted, with the WI catalysts exhibiting a shorter induction/activation period and a higher yield of benzene, paralleling observations made with 2 % catalysts.

03 NATURAL GAS↗

DOE OSTI2025

Cu-induced robust Ni 2+ /Ni 3+ transition on amorphous Ni hydroxide-based electrocatalysts for advancing electrochemical ammonia oxidation and hydrogen evolution

The electrochemical ammonia oxidation reaction (AOR) is a promising anodic reaction for hydrogen production, offering a lower theoretical potential compared to oxygen evolution reaction. Despite this thermodynamic advantage, AOR suffers from sluggish multi-electron transfer reaction kinetics and the regeneration of catalytically active Ni 3+ species, which limits both activity and durability. In this study, amorphous NiCu bimetallic catalysts were prepared via facile precipitating metal nitrate deposition (PMND) method. The addition of Cu induces a robust Ni 2+ /Ni 3+ transition, stabilizing catalytically active Ni 3+ species and modulating the electronic structure of Ni. It alters the oxidation and desorption behavior of nitrogen-containing intermediates and facilitating their conversions to NO x species, resulting in fast active site regeneration. Furthermore, amorphous structure provides abundant dangling bonds, which enhances the intrinsic reactivity and accessibility of active sites rather than increasing the number of active sites. As a result, these effects accelerate the overall reaction kinetics. The optimized NiCu 5:1 catalyst achieved an ammonia removal efficiency of ∼100 % and a hydrogen production rate of 2.45 mmol/(h∙cm 2 ) at 1.6 V RHE .

Amorphous electrocatalyst↗

NASA NTRS2023

Peptide conjugates with polyaromatic hydrocarbons can benefit the activity of catalytic RNAs

Early stages of life likely employed catalytic RNAs (ribozymes) in many functions that are today filled by proteins. However, the earliest life forms must have emerged from heterogenous chemical mixtures, which included amino acids, short peptides, and many other compounds. Here we explored whether the presence of short peptides can help the emergence of catalytic RNAs. To do this, we conducted an in vitro selection for catalytic RNAs from randomized sequence in the presence of ten different peptides with a prebiotically plausible length of eight amino acids. This in vitro selection generated dozens of ribozymes, one of them with ∼900-fold higher activity in the presence of one specific peptide. Unexpectedly, the beneficial peptide had retained its N-terminal Fmoc protection group, and this group was required to benefit ribozyme activity. The same, or higher benefit resulted from peptide conjugates with prebiotically plausible polyaromatic hydrocarbons (PAHs) such as fluorene and naphthalene. This shows that PAH-peptide conjugates can act as potent cofactors to enhance ribozyme activity. The results are discussed in the context of the origin of life.

Kevin J. Sweeney↗

DOE OSTI2024

Restructuring of the Lewis Acid Sites in Y-Modified Dealuminated Beta-Zeolite by Hydrothermal Treatment

Yttrium-modified dealuminated Betazeolite (Y-BEA) represents a type of Lewis acid zeolite that has gained attention for its potential to efficiently catalyze the conversion of biomass-derived oxygenates. The structure of the Y active sites and their dynamics during biomass conversion reactions, which normally involve substantial amounts of water, necessitate thorough investigation for the rational design of more active and stable catalysts. Here, we conducted a study where a series of Y-BEA catalysts with different yttrium loadings (1–7 wt.%) were subjected to hydrothermal treatment (450 °C, 20% water) and investigated for their structural and catalytic activity changes through a combination of multiple characterizations and kinetic measurements. The number of acid sites of Y-BEA decreased without a change in acid strength following the hydrothermal treatment, which was confirmed by the results of acid site titration, infrared spectroscopy of probe molecules, and kinetic measurements for probe reactions (acetone aldol condensation). Structural analysis using X-ray diffraction (XRD), specific surface area measurement, X-ray absorption spectroscopy (XAS), and X-ray photoelectron spectroscopy (XPS) demonstrated that both the zeolite structure and the isolation status of the Y site remain intact after hydrothermal treatment. Further, the Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) spectra, thermogravimetric analysis (TGA), and operando 1 H and 29 Si magic-angle spinning (MAS) nuclear magnetic resonance (NMR) revealed the dehydroxylation of Y-BEA induced by hydration-rearrangement-condensation restructuring during the high-temperature steam treatment. Dehydroxylation affects the structure of Y sites by reducing their vicinal silanol sites. In conclusion, this conversion of Lewis acidic Y sites into nonacidic sites is the primary factor behind the change in acid site quantity and catalytic activity on Y-BEA.

36 MATERIALS SCIENCE↗

DOE OSTI2026

Deciphering competing elementary steps to correlate electrocatalyst chemical state with activity

The overpotential in multielectron transfer heterogeneous electrocatalysis fundamentally arises from thermodynamic and kinetic disparities among elementary steps; however, deciphering coupled and competing steps has long remained a challenge. Here, we establish an electrochemical deconvolution paradigm based on key processes in electrocatalytic reactions, such as charge accumulation, electron/proton transfer, and intermediate evolution, to resolve competing elementary steps. Taking the oxygen evolution reaction as a prototypical reaction, we design a model catalyst featuring a precise isolated cation-anion vacancy pair and track the previously elusive electrochemical behavior of lattice oxygen by disentangling interference from adsorbed oxygen intermediates. Mechanistically, the lattice oxygen oxidation pathway originates from the spontaneous, nonelectrochemical deprotonation of replenished water molecules coordinated to unsaturated cation sites. Alternating current techniques further reveal that although lattice oxygen oxidation requires a higher potential than metal oxidation, it exhibits faster kinetics, providing insight into its superior catalytic activity. These findings establish a direct experimental correlation between the initial chemical state and the catalytic activity and prove surface-confined lattice oxygen cycling. Furthermore, expanding conventional potential-current analysis into a multidimensional framework enables disentanglement of thermodynamic and kinetic contributions of key elementary steps, thereby guiding the rational optimization of various complex multielectron transfer reactions.

OER↗

DOE OSTI2025

Rigid Supramolecular Aramid Nanotubes as Catalyst Supports

Solution‐phase heterogeneous catalysts benefit from nanoscale dimensions, which maximize specific surface area and enhance catalytic activity. However, the ease of recovering such nanocatalysts depends on the design of the support materials, which are often particle‐like. Rigid 1D nanomaterials are proposed as supports that can enhance separability while offering high volumetric specific surface area for greater catalyst loading and activity. Here, aramid amphiphiles (AAs) are designed to spontaneously self‐assemble in water into high‐aspect‐ratio supramolecular nanotubes with tunable surface chemistry. These AA nanotubes exhibit high persistence lengths (P = 750 ± 340 µm) and mechanical stiffnesses (3 N/m). Incorporating surface thiol groups enables immobilization of catalytic gold nanoparticles. The resulting AA nanotube‐gold nanoparticle complexes exhibit high catalytic activity, efficient recoverability via simple microfiltration, and sustained reusability over ten reaction cycles. This study demonstrates the utility of molecular self‐assembled 1D nanomaterials as versatile scaffolds for the reuse and recovery of nanoscale catalysts.

1D nanomaterials↗