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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 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Stabilization of the Active Ruthenium Oxycarbonate Phase for Low-Temperature CO 2 Methanation

Interstitial carbon-doped RuO 2 catalyst with the newly reported ruthenium oxycarbonate phase is a key component for low-temperature CO 2 methanation. However, a crucial factor is the stability of interstitial carbon atoms, which can cause catalyst deactivation when removed during the reaction. In this work, the stabilization mechanism of the ruthenium oxycarbonate active phase under reaction conditions is studied by combining advanced operando spectroscopic tools with catalytic studies. Three sequential processes: carbon diffusion, metal oxide reduction, and decomposition of the oxycarbonate phase and their influence by the reaction conditions, are discussed. We present how the reaction variables and catalyst composition can promote carbon diffusion, stabilizing the oxycarbonate catalytically active phase under steady-state reaction conditions and maintaining catalyst activity and stability over long operation times. In addition, insights into the reaction mechanism and a detailed analysis of the catalyst composition that identifies an adequate balance between the two phases, i.e., ruthenium oxycarbonate and ruthenium metal, are provided to ensure an optimum catalytic behavior.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

New monoclinic ruthenium dioxide with highly selective hydrogenation activity

H x RuO 2 acts as a standalone catalyst exhibiting selective hydrogenation under mild conditions. Mobile protons embedded in the oxide lattice play an important role in stabilizing the distorted structure, and facile proton dynamics is key to improving catalytic properties.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS2012

Experimental Study of the Partitioning of Siderophile Elements in a Crystallizing Lunar Magma Ocean

The distributions of trace elements between the lunar interior and pristine crustal rocks were controlled by the composition of starting materials, lunar core formation, and crystallization of the lunar magma ocean (LMO) [1]. This study focuses on the partitioning of highly siderophile elements (HSE) including Re, Os, Ir, Ru, Pt, Rh, Pd and Au as well as the moderately siderophile elements Mo and W, and the lithophile elements of Hf and Sr. Our experiments also include Ga, which can be slightly siderophile, but is mostly considered to be chalcophile. Partitioning of these elements is not well known at the conditions of a crystallizing LMO. Previous studies of HSE partitioning in silicate systems have yielded highly variable results for differing oxygen fugacity (fO2) and pressure [2-4]. For example, under certain conditions Pt is compatible in clinopy-roxene [2] and Rh and Ru are compatible in olivine [3]. The silicate compositions used for these experiments were nominally basaltic. Ruthenium, Rh, and Pd are incompatible in plagioclase under these conditions[4]. However, this latter study was done at extremely oxidizing conditions and at atmospheric pressure, possibly limiting the applicability for consideration of conditions of a crystallizing LMO. In this study we address the effects of pressure and oxygen fugacity on the crystal/liquid partition coefficients of these trace elements. We are especially interested in the plagioclase/melt partition coefficients so that it may be possible to use reverse modeling to constrain the concentrations of these elements in the lunar mantle through their abundances in pristine crustal rocks.

Galenas, M.↗
DOE OSTI2025

Breaking the passivation barrier via d-p orbital optimization for stable hydrogen production and sulfion upgrading

The development of energy-efficient hydrogen production technologies represents a critical pathway toward achieving global carbon neutrality objectives. This work provides fundamental insights into overcoming catalyst passivation challenges in sulfide oxidation reaction (SOR)-coupled hydrogen evolution reaction (HER) systems through precise orbital hybridization engineering. Our theoretical simulations reveal that sulfur-passivated ruthenium surfaces can effectively modulate d-p orbital hybridization, significantly reduce d-electron activity while stabilizing long-chain S 8 species and decreasing intermediate adsorption energies. Furthermore, metal carbides/ruthenium heterostructure (MC/Ru, M = V, Mo, W) was designed to achieve simultaneous optimization of both HER (∆G H* = −0.11 eV) and SOR (∆G RDS = 1.51 eV) via work-function-mediated interfacial electron transfer, which effectively tailors surface electronic states. Guided by theoretical predictions, we successfully synthesized a series of metal carbides/ruthenium/nitrogen-doped carbon catalysts based on a solid-phase reaction and designated as MC/Ru@NC (M = V, Mo, W). The optimized VC/Ru@NC catalyst exhibits exceptional performance in a membrane-free two-electrode system, achieving an ultralow cell voltage of 0.76 V at 200 mA cm −2 with outstanding stability over 1600 h, while maintaining 97.5 % Faradaic efficiency for hydrogen production and 73.8 % sulfur recovery efficiency.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Rethinking 𝛼−RuCl 3 : Parameters, models, and phase diagram

RuCl 3 was likely the first ever deliberately synthesized ruthenium compound, following the discovery of the 44 Ru element in 1844. For a long time it was known as an oxidation catalyst, with its physical properties being discrepant and confusing, until a decade ago when its allotropic form 𝛼−RuCl 3 rose to exceptional prominence. This “rediscovery” of 𝛼−RuCl 3 has not only reshaped the hunt for a material manifestation of the Kitaev spin liquid, but it has opened the floodgates of theoretical and experimental research in the many unusual phases and excitations that the anisotropic-exchange magnets as a class of compounds have to offer. Given its importance for the field of Kitaev materials, it is astonishing that the low-energy spin model that describes this compound and its possible proximity to the much-desired spin-liquid state is still a subject of significant debate ten years later. In the present study, we argue that the existing key phenomenological observations put strong natural constraints on the effective microscopic spin model of 𝛼−RuCl 3 , and specifically on its spin-orbit-induced anisotropic-exchange parameters that are responsible for the nontrivial physical properties of this material. These constraints allow one to focus on the relevant region of the multidimensional phase diagram of the 𝛼−RuCl 3 model, suggest an intuitive description of it via a different parametrization of the exchange matrix, offer a unifying view on the earlier assessments of its parameters, and bring closer together several approaches to the derivation of anisotropic-exchange models. We explore extended phase diagrams relevant to the 𝛼−RuCl 3 parameter space using quasiclassical, Luttinger-Tisza, exact diagonalization, and density-matrix renormalization-group methods, demonstrating a remarkably close quantitative accord between them on the general structure and hierarchy of the phases, with the zigzag, ferromagnetic, and incommensurate phases that are proximate to each other. As a result, one of the highlights is the detailed agreement on the nature of the incommensurate phases that realize two distinct counterrotating helical states.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2022

A quantitative model of charge injection by ruthenium chromophores connecting femtosecond to continuous irradiance conditions

A kinetic framework for the ultrafast photophysics of tris(2,2-bipyridine)ruthenium(II) phosphonated and methyl-phosphonated derivatives is used as a basis for modeling charge injection by ruthenium dyes into a semiconductor substrate. By including the effects of light scattering, dye diffusion, and adsorption kinetics during sample preparation and the optical response of oxidized dyes, quantitative agreement with multiple transient absorption datasets is achieved on timescales spanning femtoseconds to nanoseconds. In particular, quantitative agreement with important spectroscopic handles—the decay of an excited state absorption signal component associated with charge injection in the UV region of the spectrum and the dynamical redshift of a ~500 nm isosbestic point—validates our kinetic model. Pseudo-first-order rate coefficients for charge injection are estimated in this work, with an order of magnitude ranging from 10 11 to 10 12 s –1 . The model makes the minimalist assumption that all excited states of a particular dye have the same charge injection coefficient, an assumption that would benefit from additional theoretical and experimental exploration. Here, we have adapted this kinetic model to predict charge injection under continuous solar irradiation and find that as many as 68 electron transfer events per dye per second take place, significantly more than prior estimates in the literature.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Activity and selectivity for CO 2 methanation of clusters and nanoplates of ruthenium dispersed on ceria: In-situ studies with XAFS and DRIFTS

The performance of Ru/CeO 2 catalysts under CO 2 hydrogenation conditions was studied using in situ X-ray absorption fine structure (XAFS) and diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) to understand the structural evolution and chemical nature of each component under reaction conditions. The catalysts were prepared using a reverse microemulsion method that maximized the dispersion of RuOx particles on ceria. A RuO x → Ru transformation was observed upon exposure of the RuO x /CeO 2 systems to H 2 at 250 °C. For a sample with 5% molar Ru, two-dimensional clusters (2-4 atoms) of Ru formed on top of the ceria support. An increase in the loading of ruthenium to 20% molar led to the formation of nanoplates of the metal 2-3 atomic layers thick. Both Ru structures were highly dispersed on ceria. They were oxidized after exposure to CO 2 at 250 °C. However, under CO 2 /H 2 mixture, they remained in a metallic state as two-dimensional clusters and nanoplates. In situ DRIFTS studies, the 5% and 20% Ru/CeO 2 catalysts showed distinct reaction intermediates when exposed to CO 2 or CO 2 /H 2 (1/4) reaction mixtures. Normalized to the Ru molar percentage, the 5% Ru/CeO 2 system was the most active catalyst exhibiting a selectivity of ~ 60% CH 4 and 40% CO at 250 °C. On the other hand, under the same reaction conditions, the 20% Ru/CeO 2 system was less active but had a CH 4 selectivity close to 80%. In conclusion, these results highlight the importance of the structure of the metallic Ru particles as a factor that determines the catalytic performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1978

Solar photolysis of water

A cyclic process is described for the solar photolysis of water, including a first stage in which water is reduced in the presence of a Eu(+2) photooxidizable reagent producing hydrogen and spent oxidized Eu(+3) reagent. The spent reagent Eu(+3) is reduced by means of a transition metal ligand complex reductant, RuL(+3) in a photoexcited state, such as a ruthenium pyridyl complex. Due to competing reactions between the photolysis and regeneration products, the photooxidation reaction must be separated from the regeneration in space and time by supporting the reagent and/or the reductant on solid supports and utilizing pH, wavelength and flow control to maximize hydrogen and oxygen production.

Ryason, P. R.↗
NASA NTRS2010

Process for Making a Noble Metal on Tin Oxide Catalyst

To produce a noble metal-on-metal oxide catalyst on an inert, high-surface-area support material (that functions as a catalyst at approximately room temperature using chloride-free reagents), for use in a carbon dioxide laser, requires two steps: First, a commercially available, inert, high-surface-area support material (silica spheres) is coated with a thin layer of metal oxide, a monolayer equivalent. Very beneficial results have been obtained using nitric acid as an oxidizing agent because it leaves no residue. It is also helpful if the spheres are first deaerated by boiling in water to allow the entire surface to be coated. A metal, such as tin, is then dissolved in the oxidizing agent/support material mixture to yield, in the case of tin, metastannic acid. Although tin has proven especially beneficial for use in a closed-cycle CO2 laser, in general any metal with two valence states, such as most transition metals and antimony, may be used. The metastannic acid will be adsorbed onto the high-surface-area spheres, coating them. Any excess oxidizing agent is then evaporated, and the resulting metastannic acid-coated spheres are dried and calcined, whereby the metastannic acid becomes tin(IV) oxide. The second step is accomplished by preparing an aqueous mixture of the tin(IV) oxide-coated spheres, and a soluble, chloride-free salt of at least one catalyst metal. The catalyst metal may be selected from the group consisting of platinum, palladium, ruthenium, gold, and rhodium, or other platinum group metals. Extremely beneficial results have been obtained using chloride-free salts of platinum, palladium, or a combination thereof, such as tetraammineplatinum (II) hydroxide ([Pt(NH3)4] (OH)2), or tetraammine palladium nitrate ([Pd(NH3)4](NO3)2).

Davis, Patricia↗
DOE OSTI2024

Reductive Dynamic and Static Excited State Quenching of a Homoleptic Ruthenium Complex Bearing Aldehyde Groups

A new homoleptic Ru polypyridyl complex bearing two aldehyde groups on each bipyridine ligand, [Ru(dab) 3 ](PF 6 ) 2 , where dab is 4,4′-dicarbaldehyde-2,2′-bipyridine, was synthesized, characterized, and utilized for iodide photo-oxidation studies. In acetonitrile (CH 3 CN) solution, the complex displayed an intense metal-to-ligand charge transfer (MLCT) absorbance maximum at 475 nm (ε = 22,000 M –1 cm –1 ) and an infrared (IR) band at 1712 cm –1 assigned to the pendent aldehyde groups. Visible light excitation in air-saturated solution resulted in room temperature photoluminescence (PL) with a maximum at 675 nm, a quantum yield, ϕ PL = 0.048, and an excited state lifetime, τ ο = 440 ns, from which radiative and nonradiative relaxation rate constants were extracted, k r = 9.1 × 10 4 s –1 and knr = 1.8 × 10 6 s –1 . Pulsed visible light excitation yielded transient UV–vis and IR absorption spectra consistent with an MLCT excited state; relaxation occurred with the maintenance of two isosbestic points in the visible region, and a lifetime that agreed with that measured by time-resolved PL. Cyclic voltammetry studies in a CH 3 CN solution with 0.1 M TBAPF 6 electrolyte revealed a quasi-reversible oxidation, E°(Ru III/II ) = +1.25 V vs. Fc +/0 , and three sequential one-electron reductions at −1.10, −1.25, and −1.54 V vs. Fc +/0 . Here, an excited state reduction potential of E°(Ru *2+/+ ) = +0.89 V vs. Fc +/0 was estimated with the Rehm–Weller expression. Titration of tetrabutylammonium iodide, TBAI, into a CD 3 CN solution of [Ru(dab) 3 ](PF 6 ) 2 resulted in significant shifts in the aldehyde H atom and 3,3′-biypridyl resonances that were analyzed with a 1:1 equilibrium model, from which K eq = 460 M –1 was extracted, increasing to 5800 M –1 when the solvent was changed to acetone-d 6 . Iodide titrations resulted in a significant quenching of the [Ru(dab) 3 ] *2+ lifetime and quantum yield in both CH 3 CN and acetone solvents. In CH 3 CN, the quenching was mainly dynamic and well described by the Stern–Volmer model, from which a quenching rate constant, k q , of 4.5 × 10 10 M –1 s –1 and an equilibrium constant, K eq , of 8.3 × 10 3 M –1 were obtained. In acetone, the static quenching pathway by iodide was greatly enhanced, with a K eq of 1.2 × 10 4 M –1 and a higher k q of 9.2 × 10 10 M –1 s –1 .

Aldehydes↗
DOE OSTI2025

Backbone editing and deconstruction of polyethylene by Beckmann rearrangement and hydrogenolysis

Polyethylene is the most widely produced commodity plastic and is used in many applications, including packaging, insulation, and medical devices. However, the inertness of polyethylene makes chemical recycling inefficient and challenging. We report the conversion of oxidized high-density and low-density polyethylene, formed by direct, catalytic oxidation, to polyamides by Beckmann rearrangement of the corresponding oximes. These polyamides have enhanced surface properties over those of unmodified polyethylene, while maintaining the same, favorable mechanical profiles. The amide sites were reductively cleaved by hydrogenolysis with ruthenium-based catalysts to furnish alcohol- and amine-terminated fragments, which were used for the synthesis of polyurea-urethanes with poly(tetrahydrofuran) and methylene diphenyl diisocyanate. These experiments show how to install cleavable moieties into the backbone of polyethylene to facilitate deconstruction and the generation of new materials to affect greater sustainability in polyolefins.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Powerful Organic Molecular Oxidants and Reductants Enable Ambipolar Injection in a Large-Gap Organic Homojunction Diode

Doping has proven to be a critical tool for enhancing the performance of organic semiconductors in devices like organic light-emitting diodes. However, the challenge in working with high-ionization-energy (IE) organic semiconductors is to find p-dopants with correspondingly high electron affinity (EA) that will improve the conductivity and charge carrier transport in a film. Here, we use an oxidant that has been recently recognized to be a very strong p-type dopant, hexacyano-1,2,3-trimethylene-cyclopropane (CN6-CP). The EA of CN6-CP has been previously estimated via cyclic voltammetry to be 5.87 eV, almost 300 meV higher than other known high-EA organic molecular oxidants. We measure the frontier orbitals of CN6-CP using ultraviolet and inverse photoemission spectroscopy techniques and confirm a high EA value of 5.88 eV in the condensed phase. The introduction of CN6-CP in a film of large-band-gap, large-IE phenyldi(pyren-1-yl)phosphine oxide (POPy 2 ) leads to a significant shift of the Fermi level toward the highest occupied molecular orbital and a 2 orders of magnitude increase in conductivity. Using CN6-CP and n-dopant (pentamethylcyclopentadienyl)(1,3,5-trimethylbenzene)ruthenium (RuCp*Mes)2, we fabricate a POPy 2 -based rectifying p–i–n homojunction diode with a 2.9 V built-in potential. Blue light emission is achieved under forward bias. Furthermore, this effect demonstrates the dopant-enabled hole injection from the CN6-CP-doped layer and electron injection from the (RuCp*Mes) 2 -doped layer in the diode.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Preparation, characterization, and structural studies of new ruthenium(II) and ruthenium(III) complexes incorporating pyrazole ligands

Multimetallic complexes containing disparate metals have been established to have practical utilities. We previously reported a strategy for preparing such species by using combinations of neutral pyrazole (Hpyz, C 3 N 2 H 4 ) and anionic pyrazolyl ligands (pyz, C 3 N 2 H 3 – ), and herein are reported several new complexes that should be capable of incorporating a second metal center. Two of the complexes, [Ru(1,5-cod)(Hpyz) 3 Cl][BPh 4 ] and Ru(1,5-cod)(Hpyz) 2 (pyz) 2 (cod = cyclooctadiene), were prepared from [Ru(cod)Cl 2 ] 2 , while [Ru(tmeda)(Hpyz) 2 Cl 2 ][BF 4 ] (tmeda = tetramethylethylenediamine) was prepared from the neutral Ru(II) complex Ru(tmeda)(Hpyz) 2 Cl 2 via one electron oxidation by the ferricinium ion. The first two complexes, one cationic and the other uncharged, involve Ru(II), while the tmeda complex involves Ru(III). Finally, all three species have been structurally characterized.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
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 OSTI2025

Regeneration of Benzimidazole-Based Organohydrides Mediated by Ru Catalysts

Benzimidazole-based organohydrides (BIHs) are versatile hydride, electron, and proton donors in a variety of artificial photosynthetic systems for the generation of solar fuels. Currently, BIHs are often used in stoichiometric rather than catalytic processes. The catalytic regeneration of BIHs from their oxidized form (BI + ) is an urgent necessity in order to allow the development of recyclable systems and devices, but viable examples are scarce and require large overpotentials. Here, in this study, we report the electrocatalytic regeneration of a series of BIHs with varying hydricities, promoted by a ruthenium half-sandwich complex, [(HMB)Ru(bpy)(H)]+ (HMB = η 6 -C 6 Me 6 , bpy = 2,2′-bipyridine), in the presence of tributylammonium (HNBu 3 + ) as a proton source. This metal hydride was generated in situ from the 2e - reduction/protonation of the corresponding solvento-complex. In comparison to the direct cathodic reduction of BI + in the presence of HNBu 3 + , the use of this ruthenium catalyst allowed efficient regeneration of BIHs at less negative potentials, with Faradaic efficiencies up to 80% and significantly higher conversion yields due to the circumvention of the dimerization pathway and the stepwise reduction and protonation reactions. Finally, the thermodynamic challenges involved in the regeneration of very hydridic BIHs mediated by Ru hydride catalysts were examined.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

A two-stage strategy for upcycling chlorine-contaminated plastic waste

Abstract Chemical upcycling of polyolefin plastic waste to lubricant, wax and fuel-range hydrocarbons over metal-based catalysts is a crucial technological solution to the enormous environmental threat posed by plastic waste. However, currently available methods are incompatible with chlorine-contaminated feedstocks. Here we report a two-stage strategy for upcycling chlorine-contaminated polypropylene. First, magnesia–alumina mixed oxide at 30 bar H 2 and 250 °C serves as a chlorine trap by rapidly forming solid chloride, resulting in nearly complete chlorine extraction from the polyolefin melt. This enables the upcycling of plastic waste with up to 10% polyvinyl chloride content to lubricants over ruthenium-based catalysts, in the second stage. The strategy is also applicable to chlorinated aromatics and alkanes. The proposed strategy renders hydrocracking and hydrogenolysis catalysts less sensitive to the chlorine impurities in feedstocks while eliminating HCl emissions and chlorine contamination in products. It could incentivize further progress in plastics upcycling.

Environmental Sciences & Ecology↗