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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 91 records · Page 5
All sourcesNASA NTRSDOE OSTI
NASA NTRS1988

Electrocatalytic reduction of oxygen on modified oxide surfaces

A first step which frequently occurs in the reduction of dioxygen, e.g., at the cathode of the alkaline fuel cell, is the two-electron reduction to the peroxyl ion, HO bar 2. For the efficiency of the fuel cell, this ion must be further reduced, or decomposed, to OH(-). Rate constants for HO bar 2 decomposition have been determined in 31 percent KOH at 25 C for the following catalysts in the form of suspended powders and Teflon-bonded electrodes: Pt, Au, cobalt tetrametoxyl phenyl porphyrin (CoTMPP), and La sub 0.5Pb sub 0.5MnO3. Rates were normalized to unit surface area measured by several methods as suitable. Where possible, four methods were used to measure rate constants: gasometric, oxygen probe, rotating disk electrode, and open-circuit potential decay. Steady-state polarization was also tried but was not as satisfactory. Comparisons are given for the methods in regard to reliability, applicability to the material, and convenience.

Chaffins, Scott A.↗
DOE OSTI2025

Bifunctionality of supported metal hydrodeoxygenation catalysts

The transition to sustainable energy relies on innovative methods to convert biomass-derived compounds into viable biofuels. In this study, the hydrodeoxygenation (HDO) of 6-undecanone is used as a model reaction to screen bifunctional catalysts, where metal sites facilitate hydrogenation and the support promotes deoxygenation, enabling high conversion and selectivity toward desirable alkanes for biofuel production. This reaction is particularly relevant as it represents a critical step in upgrading volatile fatty acids, derived from biomass, into long-chain hydrocarbons suitable for fuel applications. By examining a range of metals (nickel, cobalt, and tin) on different supports, it is revealed that the choice of metal–support combination is critical to catalyst performance. Zeolite beta's 3D microporous structure and adjustable acidity provide an ideal environment for fine-tuning metal–support interactions (MSIs), which are essential for balancing deoxygenation with alkane isomerization, a desirable trait for biofuels.

09 BIOMASS FUELS↗
NASA NTRS1981

Cathode catalysts for primary phosphoric acid fuel cells

Alkylation or carbon Vulcan XC-72, the support carbon, was shown to provide the most stable bond type for linking cobalt dehydrodibenzo tetraazannulene (CoTAA) to the surface of the carbon; this result is based on data obtained by cyclic voltammetry, pulse voltammetry and by release of 14C from bonded CoTAA. Half-cell tests at 100 C in 85% phosphoric acid showed that CoTAA bonded to the surface of carbon (Vulcan XC-72) via an alkylation procedure is a more active catalyst than is platinum based on a factor of two improvement in Tafel slope; dimeric CoTAA had catalytic activity equal to platinum. Half-cell tests also showed that bonded CoTAA catalysts do not suffer a loss in potential when air is used as a fuel rather than oxygen. Commercially available polytetrafluroethylene (PTFE) was shown to be unstable in the fuel cell environment with degradation occurring in 2000 hours or less. The PTFE was stressed at 200 C in concentrated phosphoric acid as well as electrochemically stressed in 150 C concentrated phosphoric acid; the surface chemistry of PTFE was observed to change significantly. Radiolabeled PTFE was prepared and used to verify that such chemical changes also occur in the primary fuel cell environment.

Source record↗
NASA NTRS1986

Biosynthetic Porphyrins and the Origin of Photosynthesis

Since the prebiotic atmosphere was anaerobic, if not reducing, a useful function of primordial photosynthesis would have been to photooxidize reduced substrates such as Fe(+2), S(-2) or reduced organic molecules and to emit hydrogen. Experiments have shown that the early biogenic pigments uroporphyrin and coproporphyrin do photooxidize organic compounds and emit hydrogen in the presence of a platinum catalyst. These experiments were carried out in dilute aqueous solution near neutral pH under anaerobic atmosphere, and quantum yields near 10-2 were obtained. Thus relevant prebiotic conditions were maintained. Rather then to further optimize conditions, attempts were made to replace the platinum catalyst by a more prebiotically suitable catalyst. Trials with an Fe4S4(SR)4 cluster, in analogy to the present hydrogenase and nitrogenase, were not successful. However, experiments using cobalt complexes to catalyze the formation of hydrogen are promising. In analogy with biological photosynthetic systems which group pigments, electron transfer molecules and enzymes in clusters for efficiency, it was found that binding the biogenic porphyrins to the polyvinyl alcohol used to support the platinum catalyst did increase the quantum yield of the reaction. It was also found that ultraviolet light can serve to photo-oxidize porphyrinogens to porphyrins under anaerobic conditions. Thus the formation of the colorless porphyriogens by the extraordinarily simple biosynthetic pathway would not be a problem because of the prevalence of UV light in the prebiotic, anoxic atmosphere.

David Mauzerall↗
DOE OSTI2026

Engineering CoO x ‑Based Self-Supported Anodes for Pure-Water-Fed Anion-Exchange-Membrane Electrolysis

Commercial membrane electrolyzers rely on acidic fluorocarbon membranes and ionomers, requiring the use of expensive IrO x -based oxygen-evolution catalysts. Anion-exchange-membrane water electrolyzers (AEMWEs) operate in an alkaline environment, enabling the use of non-precious-metal catalysts. Here, we study and engineer CoO x -based catalyst-coated anodes deposited via hydrothermal synthesis directly onto porous transport layers both with and without thermal annealing. The self-supported, nanoneedle-structured Co3O4 anode, formed by annealing the as-synthesized cobalt carbonate hydroxide, Co­(CO3) x (OH) y , outperforms the baseline Co3O4 nanoparticle ink-based anode in pure-water-fed AEMWE due to the improved catalyst-layer continuity and thus number of electroactive Co species. The as-synthesized and unannealed Co­(CO3) x (OH) y , however, appears to undergo substantial conversion to a more-active CoO x (OH) y phase predominantly at the surface, with nominal Co3+ present and higher electrical conductivity, lowering the cell voltage to ∼200 mV at 1.0 A·cm–2 in pure-water-fed AEMWE compared to the conventional Co3O4 nanoparticle anodes. We analyze the differences in electrode electrochemical response between pure-water and KOH feed modes, finding distinct activation and degradation modes. The Co­(CO3) x (OH) y anode shows significant activation and slower degradation linked to the conversion to oxyhydroxide. We propose catalyst layer designs that promote both hydroxide and electron transport, alongside interfacial engineering strategies to obtain high performance while mitigating anode degradation.

anion-exchange-membrane water electrolysis↗
DOE OSTI2026

Thermally Stable Co@C3N4 Single-Atom Catalysts for CO Oxidation: Atomic-Level Insights into Structure and Activity

Single Co atoms supported on C3N4 (Co@C3N4) have demonstrated high activity and selectivity in photocatalysis. However, the investigation of structure–function relationships and reaction mechanisms under photocatalytic conditions is very challenging due to the complex conditions of light absorption, charge transfer, and catalysis. In this study, we employed thermal CO oxidation as a prototypical probe reaction to benchmark the intrinsic catalytic performance and track the active-site evolution of Co@C3N4. Single Co atoms were identified and shown to be the catalytically active sites for CO oxidation based on control experiments and isotope-labeling experiments. The Co sites remained atomically dispersed before, during, and after the reaction with temperatures up to 400 °C, as established by in situ X-ray absorption fine structure (XAFS) combined with density functional theory (DFT), FDMNES simulations, and dynamic-time-warping (DTW)-assisted X-ray absorption near edge structure (XANES) matching. Together with theoretical calculations, the integrated analysis reveals a stable coordination environment under reaction conditions, which correlates with sustained activity, establishing Co@C3N4 single-atom catalysts as thermally stable CO oxidation catalysts. Beyond these findings, the current study provides a workflow for unambiguously assigning active sites in Co@C3N4 for thermal CO oxidation. This workflow will aid the understanding of their behavior in photocatalysis in the future, where light-driven dynamics obscure direct structure–function links. Notably, this study provides fundamental insights for the rational design of robust single-atom catalysts and a foundation for the broader application of Co@C3N4 catalysts in oxidation reactions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Photocatalytic Semi‐Hydrogenation of Acetylene to Polymer‐Grade Ethylene with Molecular and Metal–Organic Framework Cobaloximes

Abstract The semi‐hydrogenation of acetylene in ethylene‐rich gas streams is a high‐priority industrial chemical reaction for producing polymer‐grade ethylene. Traditional thermocatalytic routes for acetylene reduction to ethylene, despite progress, still require high temperatures and high H 2 consumption, possess relatively low selectivity, and use a noble metal catalyst. Light‐powered strategies are starting to emerge, given that they have the potential to use directly the abundant and sustainable solar irradiation, but are ineffective. Here an efficient, >99.9% selective, visible‐light powered, catalytic conversion of acetylene to ethylene is reported. The catalyst is a homogeneous molecular cobaloxime that operates in tandem with a photosensitizer at room temperature and bypasses the use of non‐environmentally friendly and flammable H 2 gas feed. The reaction proceeds through a cobalt‐hydride intermediate with ≈100% conversion of acetylene under competitive (ethylene co‐feed) conditions after only 50 min, and with no evolution of H 2 or over‐hydrogenation to ethane. The cobaloxime is further incorporated as a linker in a metal–organic framework; the result is a heterogeneous catalyst for the conversion of acetylene under competitive (ethylene co‐feed) conditions that can be recycled up to six times and remains catalytically active for 48 h, before significant loss of performance is observed.

Stone, Aaron E. B. S.↗
DOE OSTI2026

Tuneable electronic coupling in linked bis(cubane) cobalt-oxo clusters

A family of cobalt-oxo bis(cubane) complexes wherein each subunit is derived from the Co 4 O 4 cubane, a known water oxidation catalyst, was synthesized. Both 4,4′-bipyrdine and pyrazine were demonstrated to serve as viable bridging ligands. Through an analysis of their half-wave splitting potentials, it was determined that pyrazine-bridged bis(cubane)s exhibit inter-cubane electronic coupling, and that this coupling may be tuned through ligand substitution. Electrostatic contributions to the half-wave splitting potentials were evaluated and found to result in “non-conformist” behavior related to the ion-pairing ability of the electrolytes.

Maddi, Vincent J. P. [University of California, Be↗
DOE OSTI2025

X-ray Transient Absorption Spectroscopy Reveals Light Responses of Cobalt Centers in Co-Pi OER Catalytical Devices under Electrochemical Biases

Here, operando X-ray transient absorption measurements were successfully performed for the first time on the Co-Pi catalyst, confirming a photoreduction in Co-Pi under 400 nm blue light excitation. This provides key insights into spectroelectrochemical mechanistic studies of relevant oxygen evolution catalysts and guidance for photocatalysis using these metal oxides. Limiting blue-light exposure of these films should allow for better self-healing and higher turnover in photon-driven water oxidation. These results also demonstrate the importance of performing XTA measurements under operating conditions. Further development of this technique will allow for analysis of complex materials such as tethered molecules on surfaces and in complex device architectures to yield beneficial data for applied materials.

electrochemical cells↗
NASA NTRS2004

Spatial Distributions of Metal Atoms During Carbon SWNTs Formation: Measurements and Modelling

Experiments and modelling have been undertaken to clarify the role of metal catalysts during single-wall carbon nanotube formation. For instance, we wonder whether the metal catalyst is active as an atom, a cluster, a liquid or solid nanoparticle [1]. A reactor has been developed for synthesis by continuous CO2-laser vaporisation of a carbon-nickel-cobalt target in laminar helium flow. The laser induced fluorescence technique [2] is applied for local probing of gaseous Ni, Co and CZ species throughout the hot carbon flow of the target heated up to 3500 K. A rapid depletion of C2 in contrast to the spatial extent of metal atoms is observed in the plume (Fig. 1). This asserts that C2 condenses earlier than Ni and Co atoms.[3, 4]. The depletion is even faster when catalysts are present. It may indicate that an interaction between metal atoms and carbon dimers takes place in the gas as soon as they are expelled from the target surface. Two methods of modelling are used: a spatially I-D calculation developed originally for the arc process [5], and a zero-D time dependent calculation, solving the chemical kinetics along the streamlines [6]. The latter includes Ni cluster formation. The peak of C2 density is calculated close to the target surface where the temperature is the highest. In the hot region, C; is dominant. As the carbon products move away from the target and mix with the ambient helium, they recombine into larger clusters, as demonstrated by the peak of C5 density around 1 mm. The profile of Ni-atom density compares fairly well with the measured one (Fig. 2). The early increase is due to the drop of temperature, and the final decrease beyond 6 mm results from Ni cluster formation at the eutectic temperature (approx.1600 K).

Cau, M.↗
DOE OSTI2024

Circumventing Kinetic Barriers to Metal Hydride Formation with Metal–Ligand Cooperativity

We report the two-electron, one-proton mechanism of cobalt hydride formation for the conversion of [Co III Cp(P Ph 2 N Bn 2 )(CH 3 CN)] 2+ to [HCo III Cp(P Ph 2 NBn 2 )] + . This complex catalytically converts CO 2 to formate under CO 2 reduction conditions, with hydride formation as a key elementary step. Through a combination of electrochemical measurements, digital simulations, theoretical calculations, and additional mechanistic and thermochemical studies, we outline the explicit role of the P Ph 2 N Bn 2 ligand in the proton-coupled electron transfer (PCET) reactivity that leads to hydride formation. We reveal three unique PCET mechanisms, and we show that the amine on the P Ph 2 N Bn 2 ligand serves as a kinetically accessible protonation site en route to the thermodynamically favored cobalt hydride. Cyclic voltammograms recorded with proton sources that span a wide range of pK a values show four distinct regimes where the mechanism changes as a function of acid strength, acid concentration, and timescale between electrochemical steps. Peak shift analysis was used to determine proton transfer rate constants where applicable. Furthermore, this work highlights the astute choices that must be made when designing catalytic systems, including the basicity and kinetic accessibility of protonation sites, acid strength, acid concentration, and timescale between electron transfer steps, to maximize catalyst stability and efficiency.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Interplay between element-specific distortions and electrocatalytic oxygen evolution for cobalt–iron hydroxides

A microscopic understanding of how Fe-doping of Co(OH) 2 improves electrocatalytic oxygen evolution remains elusive. We study two Co 1–x Fex(OH) 2 series that differ in fabrication protocol and find composition alone poorly correlates to catalyst performance. Structural descriptors extracted using X-ray diffraction, X-ray absorption spectroscopy, and Raman spectroscopy reveal element-specific distortions in Co 1–x Fe x (OH) 2 . These structural descriptors are composition-dependent within individual sample series but inconsistent across fabrication protocols, revealing fabrication-dependence in catalyst microstructure. Correlations between structural parameters from different techniques show that Fe–O resists bond length changes, forcing distortion of Co environments. We find the difference in O–M–O bond angles between Co and Fe sites to correlate with electrocatalytic behavior across both sample series, which we attribute to asymmetric distortion of potential energy surfaces for the Co(III) to Co(IV) oxidation. A Tafel slope consistent with a rate-limiting step without electron transfer emerges as the O–Co–O angle decreases, implying a distortion-induced transition in the rate-limiting step. The fabrication dependence of electronic and bonding structure in the catalysts should be considered in theoretical and high-throughput analyses of electrocatalyst materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1991

The effects of platinum on nickel electrodes in the nickel hydrogen cell

Under conditions of nickel precharge in nickel-hydrogen cells, it is possible for platinum complex ions to form at the platinum catalyst electrode when no hydrogen is present. Platinum complex ions have been shown to interact with the active material in the nickel electrode to catalyze the formation of a nickel-cobalt compound within the active material lattice. This compound is readily identified by its characteristic voltage signature. A mechanism for the formation of this compound is proposed, and the effects that this compound has on the performance of the nickel electrode in the nickel-hydrogen cell are described.

Albert H Zimmerman↗
DOE OSTI2025

Supported-Single Nickel Atom Catalysts for the Methanation of Carbon Dioxide

Synthesis of twenty-seven bimetallic catalysts consisting of nickel and one of nine different dopants (B, Co, Cu, Fe, Mg, Mn, Sn, V, and Zn) supported on three different metal oxides (Al 2 O 3 , CeO 2 , and SiO 2 ) is carried out via organometallic grafting. The catalysts are evaluated for their activity and selectivity for the CO 2 methanation reaction at a feed ratio of H 2 /CO 2 of 4 at 300 °C in a high-throughput flow reactor system. After in situ pre-activation (500 °C in H 2 ), Ni/Co/CeO 2 exhibited high conversion (84.3%) and selectivity for methane (99.6%). Ni/Co/CeO 2 was characterized by high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction, H 2 -temperature-programmed reduction (H 2 -TPR), and CO 2 -temperature-programmed desorption (CO 2 -TPD). HRTEM showed the presence of single Ni and Co atoms on ceria after pre-reduction at 500 °C and after the methanation reaction at 300 °C for 15 h. XPS determined that the strong interaction between Ni, Co, and ceria increased after the reduction, leading to a charge transfer between Ni and Ce that created oxygen vacancies in ceria. Nickel was found to be Ni 2+ in the as-prepared material and was partially reduced in the presence of cobalt and after the activation in H 2 at 500 °C. The DFT results show that both nickel and cerium exhibit lower Bader charges in the Ni/Co/CeO 2 system, confirming that the presence of cobalt enhances the reduction of both Ni and Ce through electronic interactions. This indicates that single cationic Ni atoms are highly effective for the methanation reaction. In conclusion, the organometallic grafting technique is found to be efficient for synthesizing catalysts with highly homogeneous dispersed species at low metal loadings (0.16 wt % Ni–0.15 wt % Co), which leads to high turnover frequency (up to 248.7 h –1 ) and durability for methanation.

CO2 conversion↗
DOE OSTI2024

Solvent-free synthesis of Co single atom and nanocluster decorated N-doped carbon for efficient oxygen reduction

The advancement of efficient, cheap, and durable catalysts for oxygen reduction reaction (ORR) to substitute Pt/C in metal-air batteries is of paramount importance. However, traditional solvent-based methods fall short in terms of environmental benign and scalability. Herein, a solvent-free organic-inorganic self-assembly approach is explored to construct cobalt single atom and cobalt nanocluster decorated nitrogen-doped porous carbon spheres (Co-SA/NC@NCS). The solvent-free synthesis demonstrates an impressively high yield (282 g/L) and the resultant Co-SA/NC@NCS possesses a high N content (6.9 wt%). Density functional theory calculations disclose that the Co-SAs and Co-NCs are able to optimize the surface oxygen adsorption capability and enhance the conductivity of the NCS, thereby facilitating the ORR performance. Here, the solvent-free synthesis is also feasible for the synthesis of other non-noble metal element (Fe, Ni, and Zn) decorated nitrogen-doped porous carbon spheres.

Nitrogen-doped carbon↗
DOE OSTI2025

Data-Driven Discovery of Bimetallic Nanoparticles Catalysts for the Hydrogenolysis of Polyethylene

Supported platinum nanoparticles are known to convert polyolefins to high-quality liquid hydrocarbons with hydrogen under relatively mild conditions. However, no systematic study has been undertaken using bimetallic catalysts for polyethylene upcycling. Specifically, a total of 98 monometallic and bimetallic combinations (Ag, Cr, Co, Cu, Fe, Ga, In, Mn, Ni, Pd, Pt, Rh, Ru, Zr) on alumina were synthesized utilizing surface organometallic chemistry (SOMC) technique via robotic platform. These were investigated at a small scale (10 mg of catalyst and 50 mg of polyethylene) for their activity for the hydrogenolysis of polyethylene in a high-throughput batch reactor. Combinations of Ni and Co were selected as candidates with high activity toward conversion into paraffin oils. Reaction conditions were optimized with Ni/Co/Al 2 O 3 catalyst at a larger scale (300 mg catalyst and 3 g polyethylene) to obtain a high yield (93.1%) of paraffin wax with desired properties (M n = 380 Da) and low polydispersity (Đ = 1.2). Ni/Co/Al 2 O 3 was compared against Co/Ni/Al 2 O 3 to understand the role of the deposition sequence. When Co is deposited before Ni, a layer of cobalt aluminate is formed upon reduction, stabilizing the deposition of 5 nm metallic Ni particles. When nickel is deposited before Co, particles are larger (average >20 nm) and more oxidized (Ni δ+ in NiAl 2 O 4 ), decreasing the availability of the catalytically active metallic Ni. In conclusion, the difference in electronic environments was also described by DFT calculations, which revealed that smaller 3D clusters of Ni are preferred on CoAl2O4 over the 3D clusters on NiAl 2 O 4 and that these smaller clusters are more reducible, as confirmed experimentally.

Polymer↗
DOE OSTI2026

Modulating coordinate site occupancy in high-entropy spinel electrocatalysts

High entropy spinel oxides provide a versatile platform for electrocatalysis because multiple metal cations can be incorporated into a single crystalline lattice, enabling tunable electronic structures. However, controlling how these cations distribute between tetrahedral and octahedral coordination sites remains a major challenge, limiting rational catalyst design. Here, we modulate cation coordination site occupancy between tetrahedral and octahedral sites in a Co–Fe–Cr–Mn–Ni framework by introducing a sixth cation (Zn, Ga, Mg, or Al) with distinct site preference energies. Using density functional theory, synchrotron X-ray absorption spectroscopy, and magnetic circular dichroism, we demonstrate that Zn preferentially occupies tetrahedral sites, driving increased octahedral occupancy of cobalt. This redistribution increases the population of octahedrally coordinated cobalt in mixed oxidation states, enhances electrical conductivity, and improves oxygen evolution reaction activity. Our findings establish coordination site occupancy as a critical design parameter, providing a strategic pathway for tailoring multicomponent spinel electrocatalysts with optimized performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

Basal Plane Doping to Activate Colloidal MoS 2 Nanosheets for Catalytic Hydrodeoxygenation of para- Cresol

The valorization of biomass into biofuels is a critical process for producing renewable fuels. Hydrodeoxygenation (HDO), particularly over doped molybdenum disulfide (MoS 2 ), a transition metal dichalcogenide (TMD) material, is a common representative catalytic reaction system for converting biomass-derived materials into useful hydrocarbons. However, the location and role of dopants, such as Co, in HDO is not fully understood. The effects of dopant location and oxidation state are often precluded by inhomogeneity in the ensemble properties of nanosheet size and dopant dispersion, as well as difficulty in observing the behavior of atomic site behavior directly. Using a colloidal approach to synthesize cobalt-doped MoS 2 nanosheets with controlled dopant concentration, combined with X-ray absorption spectroscopy (XAS) and density functional theory (DFT) calculations, we determine that basal plane doped Co (25% Co:Mo mole ratio) shows peak catalytic activity in HDO of para-cresol, a model biomass-derived compound, and that basal Co sites are demonstrably more active than edge sites. By observing these doping effects in MoS 2 catalysts for HDO, we can further optimize not only the production of carbon-neutral fuels but also direct the tailoring of doped TMD catalysts toward their intended applications.

36 MATERIALS SCIENCE↗