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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 OSTI2021

Zinc–hydrogen and zinc–iridium pairs in β-Ga 2 O 3

Zinc-doped monoclinic gallium oxide (β-Ga 2 O 3 :Zn) has semi-insulating properties that could make it a preferred material as a substrate for power devices. In this work, infrared and UV/Visible spectroscopy were used to investigate the defect properties of bulk β-Ga 2 O 3 :Zn crystals. As-grown crystals contain a single O-H stretching mode at 3486.7 cm -1 due to a neutral ZnH complex. A deuterium-annealed sample displays the corresponding O-D stretching mode at 2582.9 cm -1 , confirming the O-H assignment. A strong Ir 4+ electronic transition at 5147.6 cm -1 is also observed, along with sidebands attributed to ZnIr pairs. These sidebands show distinct differences compared with Mg-doped samples; most importantly, several peaks are attributed to Ir 4+ paired with a Zn on the tetrahedral Ga(I) site. Annealing under an oxygen atmosphere produced insulating material with a resistance above 1 TΩ.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Iridium pair sites anchored to Zr 6 O 8 nodes of the metal–organic framework UiO-66 catalyze ethylene hydrogenation

Isolated metal pair sites on metal oxide and zeolite supports are drawing attention as catalysts, because—in contrast to single atomically dispersed metals—they provide neighboring metal centers that can act cooperatively. We now report pairs of iridium atoms anchored to the Zr 6 O 8 nodes of the metal–organic framework (MOF) UiO-66, synthesized by chemisorption of Ir 2 (μ-OCH 3 ) 2 (COD) 2 (COD is cyclooctadienyl) followed by removal of the COD ligands. The supported species were characterized with infrared spectra of adsorbed CO combined with iridium LIII-edge extended X-ray absorption fine structure and high-energy-resolution fluorescence detection X-ray absorption near edge (HERFD XANES) spectra. The HERFD XANES spectra were recorded with the sample in a variety of atmospheres in which the iridium pair sites were stable, including CO, H 2 , and C 2 H 4 + H 2 at temperatures in the range of 35–80 °C. The data provide sensitive measures of the electronic structure of the iridium in the pair sites. The samples were evaluated as catalysts for ethylene hydrogenation, with the pair-sites being more selective for hydrogenation than analogous isolated atomically dispersed iridium, which catalyzes both hydrogenation and isomerization. Metal pair sites on MOFs offer uncharted opportunities for catalysts having reactivities associated with neighboring metal centers.

36 MATERIALS SCIENCE↗
DOE OSTI2021

The Effect of Material Properties on Oxygen Evolution Activity and Assessing Half-Cell Screening as a Predictive Tool in Electrolysis

Iridium-based oxygen evolution catalysts are screened in this study for activity and stability with rotating disk electrode (RDE) half-cells. This study focuses on the electrochemical and materials approaches needed to characterize oxygen evolution catalysts, and include testing for activity, stability, composition, oxide content, and structure. Findings also discuss recommendations for data interpretation and detail the difficulties of comparing catalysts across materials sets with different elemental and oxide compositions, and linking RDE activity to device-level performance. The materials evaluated are a mixture of oxides and metals, and several methods are used to quantify metal content, qualitatively assess oxide content, and determine total surface area. Oxygen evolution activities and stabilities are compared, where a wide range of results are reported. In general, higher RDE performances are found for catalysts that contained larger amounts of ruthenium and metals. Higher durability, however, is found for catalysts that only contained iridium and a higher proportion of oxides. Additionally, catalysts are evaluated for performance in membrane electrode assemblies to assess RDE as a predictive tool in electrolysis. While activity trends within individual material sets generally held between ex- and in-situ testing, RDE tends to overestimate the activity of more metallic catalysts when compared to device-level performance. These results stress the need for multiple metal/oxide baselines for mixed catalysts, to better project in-situ kinetics.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Organometallic complexes as preferred precursors to form molecular Ir(pyalk) coordination complexes for catalysis of oxygen evolution

Our previously reported ‘blue solution’ oxygen-evolution catalyst consists of an isomeric mixture of coordination complexes containing the (pyalk)Ir IV –O–Ir IV (pyalk) core unit and is thus entirely molecular but only when formed from organometallic precursors such as Cp*Ir(pyalk)Cl or Ir(pyalk)(CO) 2 (pyalk = (2-pyridyl)-2-propanolate). We now show that attempts to form it from such obvious coordination precursors as Na[Ir(pyalk)Cl 4 ] or Na[IrCl 2 (pyalk)(O 2 CPh) 2 ], under a variety of conditions, always fail in our hands, leading to a mixture of molecular ‘blue solution’ species and IrO x nanoparticles, rather than the purely homogeneous catalyst formed from organometallic precursors. The loss of the pyalk ligand during the oxidative activation is associated with the nanoparticle generation. External chelating ligands also failed to stop the nanoparticle formation. This work implies the paradoxical conclusion that organometallic complexes are effective as catalyst precursors, even when coordination complexes are the catalytically active species, since the inner-sphere organometallic ligands, although ultimately lost or degraded, may nevertheless have a stabilizing effect sufficient to suppress undesirable nanoparticle production pathways in the activation of the catalyst precursor. Finally, a key aspect of the present study is that organometallic complexes in general may be useful catalyst precursors even if the organometallic ligands are lost in the activation process.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Electrochemical cells for direct oxide reduction, and related methods

A method of direct oxide reduction includes forming a molten salt electrolyte in an electrochemical cell, disposing at least one metal oxide in the electrochemical cell, disposing a counter electrode comprising a material selected from the group consisting of osmium, ruthenium, rhodium, iridium, palladium, platinum, silver, gold, lithium iridate, lithium ruthenate, a lithium rhodate, a lithium tin oxygen compound, a lithium manganese compound, strontium ruthenium ternary compounds, calcium iridate, strontium iridate, calcium platinate, strontium platinate, magnesium ruthenate, magnesium iridate, sodium ruthenate, sodium iridate, potassium iridate, and potassium ruthenate in the electrochemical cell, and applying a current between the counter electrode and the at least one metal oxide to reduce the at least one metal oxide. Related methods of direct oxide reduction and related electrochemical cells are also disclosed.

Tripathy, Prabhat K.↗
DOE OSTI2020

Poison or Promoter? Investigating the Dual-Role of Carbon Monoxide in Pincer-Iridium-Based Alkane Dehydrogenation Systems via Operando Diffuse Reflectance Infrared Fourier Transform Spectroscopy

Pincer-ligated iridium complexes of the form [( R 4 PCP)IrL] ( R 4 PCP = κ 3 -C 6 H 3 -2,6-(XPR 2 ) 2 ; X = CH 2 , O; R = tBu, iPr) have previously been shown competent for acceptorless alkane dehydrogenation when supported on silica. It was observed by postcatalysis solid-state NMR that silica-tethered [(≡SiO- tBu 4 POCOP)Ir(C 2 H 4 )] (3-C 2 H 4 ) was converted fully to [(≡SiO- tBu 4 POCOP)Ir(CO)] (3-CO) at 300 °C. In this work, the characterization of species under dehydrogenation reaction conditions far from equilibrium between butane and butenes (approach to equilibrium Q/K eq = 0.3 at 300 °C) is performed with operando Diffuse Reflectance Infrared Fourier–Transform Spectroscopy (DRIFTS) to show the kinetics of species conversion from 3-C 2 H 4 to 3-CO. It is further found that [(≡SiO- tBu 4 POCOP)IrHCl] (3-HCl), a species considered to be a precatalyst for alkane dehydrogenation, is also fully converted to 3-CO. Here, a mechanism of decomposition is proposed that implicates surface silanol groups, while carbon monoxide acts as a “stabilizer” for the catalyst by promoting their reductive elimination and maintaining the complex in the I oxidation state.

02 PETROLEUM↗
DOE OSTI2023

Computational analysis of metal–metal bonded dimetal tetrabenzoate redox potentials in the context of ammonia oxidation electrocatalysis

Metal–metal bonded complexes are promising candidates for catalyzing redox transformations. Of particular interest is the oxidation of ammonia to dinitrogen, an important half reaction for the potential utilization of ammonia as a fuel or hydrogen carrier. This work computationally explores 30 different metal–metal bonded dimers (5 different metal centers and 6 different benzoate ligand derivatives) to explore the tunability of the redox potential when ammonia is bound to the complexes as an axial ligand, modeling the first step in ammonia oxidation electrocatalysis. We calculate the redox potentials of these compounds, making reference to experimental data when appropriate, identifying two degrees of tunability: a coarse adjustment, changing the metal center, allows for a wide range of redox potentials to be accessed (from +1.0 to –2.0 V vs. ferrocene/ferrocenium in acetonitrile solution) and a fine adjustment, the para-substituent of the benzoate derivative, which affects the redox potential in a smaller range based on the electron donating/withdrawing effects of the substituent. Ruthenium and osmium tetrabenzoate catalysts are prime candidates for next generation ammonia oxidation catalysts because their redox potentials fall within the direct ammonia fuel cell “viability zone” bracketed by the thermodynamic potentials of oxygen reduction (ORR) and nitrogen reduction (NRR). Rhodium tetrabenzoate species fall above the ORR potential, suggesting ammonia oxidation promoted by Rh 2 catalysts could instead be used to facilitate hydrogen production through coupling to hydrogen evolution at a cathode. The redox potentials of rhenium and iridium tetrabenzoate catalysts fall below the NRR potential suggesting that these compounds could be further investigated in the context of electrochemical ammonia synthesis. Each redox event studied involves electron transfer from the M–M δ* orbital regardless of choice of metal or benzoate ligand derivative; this leads us to believe that the chemical reactivity of the various studied compounds will be similar in the context of ammonia oxidation.

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

Charge ordering in Ir dimers in the ground state of Ba 5 AlIr 2 O 11

It has been well established experimentally that the interplay of electronic correlations and spin-orbit interactions in Ir 4+ and Ir 5+ oxides results in insulating J eff = 1/2 and J eff = 0 ground states, respectively. However, in compounds where the structural dimerization of iridium ions is favorable, the direct Ir d-d hybridization can be significant and takes a key role. Here, in this study, we investigate the effects of direct Ir d-d hybridization in comparison with electronic correlations and spin-orbit coupling in Ba 5 AlIr 2 O 11 , a compound with Ir dimers. Using a combination of ab initio many-body wave-function quantum chemistry calculations and resonant inelastic x-ray scattering experiments, we elucidate the electronic structure of Ba 5 AlIr 2 O 11 . We find excellent agreement between the calculated and the measured spin-orbit excitations. Contrary to expectations, the analysis of the many-body wave function shows that the two Ir (Ir 4+ and Ir 5+ ) ions in the Ir 2 O 9 dimer unit in this compound preserve their local J eff character close to 1/2 and 0, respectively. The local point group symmetry at each of the Ir ions plays an important role, significantly limiting the direct d-d hybridization. Our results emphasize that minute details in the local crystal field environment can lead to dramatic differences in the electronic states in iridates and 5d oxides in general.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2024

Revealing the role of redox reaction selectivity and mass transfer in current–voltage predictions for ensembles of photocatalysts

Photocatalysts are conceptually simple reaction units where nanoscale semiconductors integrated with catalysts drive a pair of redox reactions on illumination. However, the proximity of reaction sites performing cathodic and anodic reactions poses dire challenges to realize large light-to-fuel conversion efficiencies. In this study, a powerful, yet straightforward, equivalent-circuit detail-balance modeling framework is developed and applied to evaluate the performance of photocatalytic systems featuring multiple light absorbers. Specifically, low bandgap iridium-doped strontium titanate is modeled as a Z-scheme photocatalyst to achieve desirable hydrogen evolution and iron-based redox shuttle oxidation reactions. Our model has unique capabilities to simulate competing redox reactions and address mass-transfer limitations. In a significant departure from state-of-the-art circuit models, our study develops tools to perform load-line analyses by incorporating a net electrochemical load curve that includes both desired and competing redox reactions. Consequently, reaction selectivity is predicted from equivalent circuit models for photocatalytic and photoelectrochemical systems. Our investigation into ensembles comprised of multiple, semi-transparent light absorbers reveals their potential to outperform a single, optically thick light absorber, particularly when operated under mass-transfer-limited conditions. However, this outcome hinges on minimizing mass-transfer rates of select redox species to prevent undesired reactions of hydrogen oxidation and/or redox shuttle reduction. Our findings demonstrate that reaction selectivity can be achieved by tuning asymmetry in redox species mass-transfer even with perfectly symmetric electrocatalytic charge-transfer coefficients. The influences of various kinetic, mass-transfer, and thermodynamic parameters are explored to offer crucial insights for synthesis of the next-generation of photocatalysts and selective coatings, and reactor designs.

25 ENERGY STORAGE↗
DOE OSTI2021

A highly efficient atomically thin curved PdIr bimetallene electrocatalyst

Abstract The multi-metallene with an ultrahigh surface area has great potential in precise tuning of surface heterogeneous d-electronic correlation by surface strain effect for the distinctive surface electronic structure, which is a brand new class of promising 2D electrocatalyst for sustainable energy device application. However, achieving such an atomically thin multi-metallene still presents a great challenge. Herein, we present a new synthetic method for an atomic-level palladium-iridium (PdIr) bimetallene with an average thickness of only ∼1.0 nm for achieving superior catalysis in the hydrogen evolution reaction (HER) and the formic acid oxidation reaction (FAOR). The curved PdIr bimetallene presents a top-ranked high electrochemical active area of 127.5 ± 10.8 m2 gPd+Ir−1 in the reported noble alloy materials, and exhibits a very low overpotential, ultrahigh activity and improved stability for HER and FAOR. DFT calculation reveals that the PdIr bimetallene herein has a unique lattice tangential strain, which can induce surface distortion while concurrently creating a variety of concave-convex featured micro-active regions formed by variously coordinated Pd sites agglomeration. Such a strong strain effect correlates the abnormal on-site active 4d10-t2g-orbital Coulomb correlation potential and directly elevates orbital-electronegativity exposure within these active regions, resulting in a preeminent barrier-free energetic path for significant enhancement of FAOR and HER catalytic performance.

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

Electrolyzer Performance Loss from Accelerated Stress Tests and Corresponding Changes to Catalyst Layers and Interfaces

Stress tests are developed for proton exchange membrane electrolyzers that utilize low catalyst loading, elevated potential, and frequent cycling with square- and triangle-waves to accelerate anode catalyst layer degradation during intermittent operation. Kinetics drive performance losses (ohmic/transport secondary) and are accompanied by decreasing exchange current density, decreasing cyclic voltammetric capacitance, and increasing polarization resistance. Decreased kinetics are likely due to a combination of iridium (Ir) migration into electrochemically inaccessible locations in the anode or membrane, Ir particle growth (supported by X-ray scattering), changes in the extent of the Ir oxidation state (supported by X-ray absorption spectroscopy), and anode catalyst layer reordering. Decreasing catalyst/transport layer contact and catalyst/membrane interfacial tearing may add contact resistances and account for increasing ohmic losses. Performance losses for low and moderate catalyst loading, as well as from accelerated and model wind/solar cycling protocols, were likewise dominated by kinetics but vary in severity. Additionally, accelerated cycling (1 cycle per minute) appears to reasonably accelerate relevant loss mechanisms and can be used to project electrolyzer lifetime from anode deterioration. Ongoing accelerated stress test development and studies into performance loss mechanisms will continue to be critical as electrolysis shifts to intermittent power and low-cost applications.

30 DIRECT ENERGY CONVERSION↗
DOE OSTI2020

IHS-60 Stored Energy Analysis

The IHS-60 consists of a General Purpose Heat Source (GPHS) Fueled Clad (FC) that has been hot isostatically pressed to eliminate the gap between the iridium clad and the fuel pellet, thus preventing differential motion between the pellet and the clad in shock and vibration environments. The vented FC is enclosed within a Molybdenum barrier comprising the liner body and the lower support member. The slip- t Molybdenum liner members serve as a mechanical barrier to plutonia contact of the tantalum alloy (T-111) strength member in the event the iridium clad should fail. The slip- t liner is not a barrier to gaseous transport, so a tantalum getter is installed near the vent region of the FC to preclude potential oxygen transport to the T-111 interior surface. The T-111 strength member encloses the Molybdenum liner assembly and provides for both helium gas retention and isotope fuel containment under impact and external pressure environments. It is surrounded by an outer clad of Hastelloy-S which protects the strength member from external oxidation and corrosive sources during nominal operation and in the event of off-nominal operation or accidents. Both the strength member and outer clad parts are closed with seal welds. The strength member and outer clad are the primary containment members of the 60-Watt IHS. The iridium clad contains the fuel pellet during nominal operation and mild accident environments, but it is not considered to be a primary containment member.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2024

Ruthenium-lead oxide for acidic oxygen evolution reaction in proton exchange membrane water electrolysis

Developing an active and stable anode catalyst for the proton exchange membrane water electrolyzer (PEM-WE) is a critical objective to enhance the economic viability of green hydrogen technology. However, the expensive iridium-based electrocatalyst remains the sole practical material with industrial-level stability for the acidic oxygen evolution reaction (OER) at the anode. Ruthenium-based catalysts have been proposed as more cost-effective alternatives with improved activity, though their stability requires enhancement. The current urgent goal is to reduce costs and noble metal loading of the OER catalyst while maintaining robust activity and stability. Here, in this study, we design a Ru-based OER catalyst incorporating Pb as a supporting element. This electrocatalyst exhibits an OER overpotential of 201 mV at 10 mA.cm -2 , simultaneously reducing Ru noble metal loading by similar to 40%. Normalization of the electrochemically active surface area unveils improved intrinsic activity compared to the pristine RuO 2 catalyst. During a practical stability test in a PEM-WE setup, our developed catalyst sustains stable performance over 300 h without notable degradation, underscoring its potential for future applications as a reliable anodic catalyst.

Electrocatalysis↗
DOE OSTI2020

A pair of metal organic framework (MOF)-derived oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) catalysts for zinc-air batteries

Metal organic frameworks (MOFs) are amazing precursors for the development of functional catalysts due to their ability of being modified both structurally and in terms of composition. Here this work presents a pair of MOF - derived oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) catalysts for the advancement of zinc-air batteries. Zeolitic imidazolate frameworks (ZIF) are known as ideal materials to create doped carbons. Combining with a sacrificial tellurium template, we have developed a “pseudo-carbon nanotube” with a ZIF-8 that is doped with a mixture of zinc, cobalt, and iron. The resulting mixed-metal doped porous carbon nanotubes (CoFeZn@pCNT) show excellent catalytic activity for ORR with a half-way ORR potential (E 1/2 ) of 0.87 V vs. RHE (reverse hydrogen electrode). Iridium-based catalysts are known as the best option for OER so far, but it is not viable for practical applications due to cost restrictions. Previous research into alternative catalysts has focused on metal oxides with first-row transition metals. Metal sulfides provide superior conductivity compared to metal oxides and are a new frontier in the search for affordable, active, and stable OER catalysts. By combining cobalt, iron, and nickel into a MOF structure (ZIF-67), followed by a sulfurization process, a MOF-derived mixed-metal sulfide catalyst (FeCoNi–S@ZIF) has been developed in this study. The resulting catalysts show an onset OER potential of 1.65 V vs. RHE at 10 mA cm -2 and exhibit remarkable stability for the operation of zinc-air batteries.

25 ENERGY STORAGE↗
DOE OSTI2020

Voltammetry measurements in lithium chloride-lithium oxide (LiCl–Li 2 O) salt: An evaluation of working electrode materials

Instrumentation to provide process monitoring (PM) and safeguards for the oxide reduction (OR) step in the electrochemical processing of used oxide nuclear fuel is necessary to ensure equipment is operated as declared. Cyclic voltammetry (CV) has been proposed for real-time monitoring of the operation of an OR process for safeguards purposes. In this study, different materials including 316 stainless steel (SS), tantalum (Ta), molybdenum (Mo), tungsten (W), platinum (Pt), and iridium (Ir) were evaluated as potential working electrode (WE) materials based on their chemical inertness, corrosion resistance, and sensitivity in detecting Li 2 O and other chloride salts in the OR electrolyte. Of the electrodes evaluated, 316 SS, Ir, and Pt all performed reasonably well in the LiCl-Li 2 O electrolyte. Here, stainless steel was operated in the cathodic potential and had reasonable corrosion resistance and is relatively inexpensive. Iridium could be operated in both the cathodic and anodic potentials and was the most corrosion resistant of those evaluated. Platinum is limited to the anodic potential range, had reasonable corrosion resistance, and was the most sensitive to Li 2 O concentrations in the salt. In the development of a stand-alone safeguards instrumentation, our recommendation is a CV sensor fitted with both Ir and Pt WEs. The results in this study may also be helpful for anode material selection in other electrometallurgy industries, such as molten salt electrolysis.

98 NUCLEAR DISARMAMENT, SAFEGUARDS, AND PHYSICAL P↗
DOE OSTI2021

Iridium valence variation and carrier sign tuning in ( Ca , Ba ) x La 2 – x CuIrO 6 double perovskites

Here, we report the structure and properties of ( Ca , Ba ) x La 2 – x CuIrO 6 . The rock-salt double perovskite structure goes through a P 1 ¯ to P 2 1 / n phase transition with increasing Ba content but not with Ca content. In both cases, the Ir ion is oxidized from 4 + to 5 + with increasing substitution. Transport and magnetic properties measurements reveal that all compositions are insulating with hysteretic spin-freezing magnetic behavior. Seebeck coefficient measurements reveal a large thermopower change from + 176 μ V /K in La 2 CuIrO 6 to – 223 μ V /K with increasing Ba content in Ba x La 2 – x CuIrO 6 . This behavior is modeled well by the Heikes formula for correlated hopping conduction. ( Ca , Ba ) x La 2 – x CuIrO 6 provides a model system for investigations of other systems with similar carrier sign tuning, with applications toward semiconductors and thermoelectric materials.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Degradation Effects at the Porous Transport Layer/Catalyst Layer Interface in Polymer Electrolyte Membrane Water Electrolyzer

The porous transport layer (PTL)/catalyst layer (CL) interface plays a crucial role in the achievement of high performance and efficiency in polymer electrolyte membrane water electrolyzers (PEMWEs). This study investigated the effects of the PTL/CL interface on the degradation of membrane electrode assemblies (MEAs) during a 4000 h test, comparing the MEAs assembled with uncoated and Ir-coated Ti PTLs. Our results show that compared to an uncoated PTL/CL interface, an optimized interface formed when using a platinum group metal (PGM) coating, i.e., an iridium layer at the PTL/CL interface, and reduced the degradation of the MEA. The agglomeration and formation of voids and cracks could be found for both MEAs after the long-term test, but the incorporation of an Ir coating on the PTL did not affect the morphology change or oxidation of IrO x in the catalyst layer. In addition, our studies suggest that the ionomer loss and restructuring of the anodic MEA can also be reduced by Ir coating of the PTL/CL interface. Optimization of the PTL/CL interface improves the performance and durability of a PEMWE.

30 DIRECT ENERGY CONVERSION↗