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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 487 records · Page 27
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

Flux Synthesis of Lattice‐Engineered Rutile Solid Solutions for Acidic Oxygen Evolution

Developing efficient and stable electrocatalysts for the acidic oxygen evolution reaction (OER) is vital for advancing proton exchange membrane water electrolysis (PEMWE) technologies. Here, in this study, we report a flux synthesis of nitrogen-doped Ti–Ru rutile-type solid-solution oxides (M-TiRu 4 ) using molten NaNO 3 as the flux medium. The flux medium promotes the low-temperature conversion of TiN to rutile TiO 2 , while in situ-formed RuO 2 nanoparticles facilitate lattice templating and couple with interfacial ion migration, enabling the formation of homogeneous solid solutions with abundant lattice heterogeneity. Simultaneously, nitrogen atoms are stably incorporated into the lattice of solid solutions, inducing bandgap narrowing, which enhances electronic conductivity. The developed M-TiRu 4 catalyst exhibits exceptional acidic OER performance, delivering a low overpotential of 194 mV at 10 mA cm −2 , superior durability over 600 h, and a Ru mass activity 7.8 times that of commercial RuO 2 . At the device level, M-TiRu 4 enables PEMWE operation at 1.64 V @ 2 A cm −2 and maintains stable performance at 500 mA cm −2 for 200 h with a minimal degradation rate of 20 µV h −1 . This work demonstrates a robust approach for designing high-performance, durable acidic OER catalysts via synergistic lattice and electronic structure engineering, paving the way for next-generation water-splitting technologies.

Wang, Fan [Univ. of Tennessee, Knoxville, TN (Unit↗
DOE OSTI2026

Electronegativity-Guided Site Differentiation in High-Entropy Alloy for pH-universal Hydrogen Evolution Reactions

Enhancing the intrinsic activity of transition metal catalysts for the hydrogen evolution reaction (HER) remains a critical challenge in sustainable energy conversion. Herein, we report an electronegativity-guided site differentiation strategy in a single-phase CoNiCuMoW high-entropy alloy (HEA) via electrodeposition by incorporating high-electronegativity 4d/5d orbital transition metals (Mo, W) into the face-centered cubic (fcc) matrix (CoNiCu). The as-synthesized HEA demonstrates exceptional HER performance in all pH conditions, delivering an outstanding overpotential of 65 mV (alkaline), 28 mV (acidic), and 155 mV (neutral) at a current density of 100 mA cm−2, showing performance comparable to commercial Pt/C and has excellent long-term stability at high current density (1 A cm−2, 1000 h). X-Ray absorption spectroscopy (XAS) and density functional theory (DFT) calculations reveal that the incorporation of Mo/W simultaneously alters the local coordination environment and induces element-dependent charge redistribution, accompanied by a system-level d-band center downshift, thereby optimizing the hydrogen binding strength across multimetallic sites. Meanwhile, oxophilic Mo/W sites lower the water dissociation energy barrier. These synergistic effects collectively enable efficient and durable pH-universal HER performance.

Wu, Yutong↗
DOE OSTI2023

In Situ Reconstructed Mo–doped Amorphous FeOOH Boosts the Oxygen Evolution Reaction

Developing a fast and highly active oxygen evolution reaction (OER) catalyst to change energy kinetics technology is essential for making clean energy. Herein, we prepare three-dimensional (3D) hollow Mo-doped amorphous FeOOH (Mo-FeOOH) based on the precatalyst MoS 2 /FeC 2 O 4 via in situ reconstruction strategy. Mo-FeOOH exhibits promising OER performance. Specifically, it has an overpotential of 285 mV and a durability of 15 h at 10 mA cm –2 . Characterizations indicate that Mo was included inside the FeOOH lattice, and it not only modifies the electronic energy levels of FeOOH but also effectively raises the inherent activity of FeOOH for OER. Additionally, in situ Raman analysis indicates that FeC 2 O 4 gradually transforms into the FeOOH active site throughout the OER process. Finally, this study provides ideas for designing in situ reconstruction strategies to prepare heteroatom doping catalysts for high electrochemical activity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Excess Surface Area in Bioelectrochemical Systems Causes ion Transport Limitations

We investigated ion transport limitations on 3D graphite felt electrodes by growing Geobacter sulfurreducens biofilms with advection to eliminate external mass transfer limitations. We characterized ion transport limitations by: (i) showing that serially increasing NaCl concentration up to 200mM increased current linearly up to a total of þ273% vs. 0mM NaCl under advective conditions; (ii) growing the biofilm with a starting concentration of 200mM NaCl, which led to a maximum current increase of 400% vs. current generation without NaCl, and (iii) showing that un-colonized surface area remained even after steadystate current was reached. After accounting for iR effects, we confirmed that the excess surface area existed despite a non-zero overpotential. The fact that the biofilm was constrained from colonizing and producing further current under these conditions confirmed the biofilms under study here were ion transport-limited. Our work demonstrates that the use of high surface area electrodes may not increase current density when the system design allows ion transport limitations to become dominant.

Environmental Molecular Sciences Laboratory↗
DOE OSTI2018

Co-Mo-P Based Electrocatalyst for Superior Reactivity in the Alkaline Hydrogen Evolution Reaction

Energy efficient hydrogen production via electrochemical and/or photoelectrochemical water splitting holds significant potential for clean and sustainable energy. Toward this end, a significant amount of research has been focused on developing active earth abundant metal catalysts for the hydrogen evolution reaction (HER) for use in acidic and alkaline media. Here, we report an earth abundant metal-based catalyst for HER under alkaline conditions. The catalyst consisting of Co, Mo and P had a similar HER activity as the precious metal platinum under the conditions used in the study. The Co-Mo-P catalyst is amorphous and was prepared by room temperature electrodeposition. The best Co-Mo-P catalyst exhibited an overpotential of ~30–35 mV for HER at a geometrical current density of 10 mA cm -2 in an alkaline medium. An amorphous Co-Mo-P model was used to simulate the energetics of HER intermediates with density functional theory (DFT). The DFT study suggests that a Co-Mo center acts as the water-dissociation site enhancing the alkaline medium HER.

catalysis (heterogeneous)↗
DOE OSTI2018

Exploring the Effect of Gold Support on the Oxygen Reduction Reaction Activity of Metal Porphycenes

It has been a long-standing goal to find alternative, cost effective catalysts for oxygen reduction reaction (ORR) in fuel cells. Molecular complexes capable of efficiently catalyzing ORR, when supported on a conducting solid surface could provide interesting hybrid materials combining the best of homogeneous and heterogeneous catalysis. Here, we utilize density functional theory to study the ORR activity of molecular (unsupported) and gold supported 3d metal (II)-porphycenes (MPc). All the 3d metal-porphycenes adsorb strongly on the Au(111) support with negative free energy of formation ranging from 1.0–3.0 eV while solvation lowers the energy of molecular MPc by only 0.5 eV compared to the gas phase. These indicate that the 3d MPc are stable and anchored firmly to the gold surface under ORR conditions. Based on our analysis, the gold support enhances the ORR activity in some of the examined MPc systems. We find that the molecular MnPc and FePc are the best ORR electrocatalysts with theoretical overpotentials of 0.44 V and 0.36 V. Thus, this work highlights the important role of the support in preserving/increasing the activity of molecular catalyst.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Intercalating MnO 2 Nanosheets With Transition Metal Cations to Enhance Oxygen Evolution

The catalytic activity of MnO 2 nanosheets towards oxygen evolution depends highly on their interlayer environment. We present a systematic investigation on fine-tuning of the interlayer environment of MnO 2 nanosheets by intercalation through a facile cation exchange with inexpensive first-row transition metal cations, including Ni 2+ , Co 2+ , Cu 2+ , Zn 2+ , and Fe 3+ ions. Among them, the Ni-intercalated MnO 2 nanosheets show remarkably enhanced OER activity and long-term stability, compared to pristine MnO 2 nanosheets. The overpotential of 330 mV at a current density of 10 mA cm -2 is observed for the Ni-intercalated MnO 2 nanosheets. The ehancement mechanism of OER is studied by comparing physiochemical properties, such as the oxidation state of Mn, the interlayer distance, the increase in the disorder/twisting of MnO 6 octahedra, and the interlayer cooperative binding of water molecules. The Ni intercalation, different from other metal cations, strengthens the Mn-O bond perpendicularly to the layer chains to facilitate the interlayer catalysis possibly between two Mn sites, and thus promotes the efficiency of oxygen evolution.

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

Iridium Incorporation into MnO 2 for an Enhanced Electrocatalytic Oxygen Evolution Reaction

Here, we have investigated the structure and activity of electrocatalysts for the oxygen evolution reaction (OER) that had low loadings of Ir incorporated into the 2D layered MnO 2 , (birnessite, nominally δ-MnO 2 ) and the 3D MnO 2 (pyrolusite, β-MnO 2 ). The Ir-incorporated β-MnO 2 (Ir/β-MnO 2 ) electrocatalysts were prepared for the first time via a thermally induced phase transition of δ-MnO 2 containing 16-22 wt% Ir. This phase transition of δ-MnO 2 to β-MnO 2 was facilitated by the presence of Ir in the structure, as both Ir in IrO 2 and Mn in β-MnO 2 could adopt a thermodynamically favored rutile structure. Extended X-ray absorption fine structure (EXAFS) of Ir/β-MnO 2 showed that the catalyst consisted of Ir substituted into the crystalline β-MnO 2 lattice. 22 wt% Ir/β-MnO 2 (60 μg Ir cm $\ ^{-2}_{geo}$) exhibited an OER overpotential (η) of 337 mV, lower than the η for commercial IrO 2 . This η was constant for 6 h, at 10 mA cm $\ ^{-2}_{geo}$ in 0.5 M H 2 SO 4 . EXAFS, high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) and X-ray absorption near edge structure (XANES) showed that 22 wt% Ir/β-MnO 2 had a strained structure containing ~41% Mn 3+ , an OER active species, along with a modified Ir bond covalency consisting of both Ir-O-Ir and Ir-O-Mn.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2023

Computational Discovery of Active and Selective Metal‐Nitrogen‐Graphene Catalysts for Electrooxidation of Water to H 2 O 2

A direct electrosynthesis of H 2 O 2 from either O 2 or H 2 O is an attractive strategy to replace the energy-intensive industrial anthraquinone process. Two-electron water oxidation reaction (2e-WOR) offers several advantages over the oxygen reduction reaction such as better mass transfer due to the absence of gas-phase reactants. However, 2e-WOR is a more challenging and less studied process with only a handful of metal oxides exhibiting reasonable activity/selectivity properties. Herein, we employ density-functional-theory calculations to screen a variety of metal-nitrogen-graphene structures for 2e-WOR. As a consequence of scaling between the adsorption energies of reaction intermediates, we determine a linear relation between selectivities for the first and second reaction steps of 2e-WOR, viz. that if selectivity toward adsorbed OH is improved, then selectivity toward H 2 O 2 at the subsequent step is decreased. We also find that selectivity and activity are linearly scaled in such a way that a higher activity (i.e., a lower overpotential) leads to a lower selectivity for the H 2 O 2 formation step. Based on the obtained results several chemistries, e.g., containing NiN x -C moieties, are predicted to rival the best-performing metal oxides such as ZnO and CaSnO 3 in terms of combination of their activity/selectivity characteristics for 2e-WOR.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Experimental and Computational Evidence of Highly Active Fe Impurity Sites on the Surface of Oxidized Au for the Electrocatalytic Oxidation of Water in Basic Media

Addition of Fe to Ni- and Co-based (oxy)hydroxides has been shown to enhance the activity of these materials for electrochemical oxygen evolution. Here we show that Fe cations bound to the surface of oxidized Au exhibit enhanced oxygen evolution reaction (OER) activity. We find that the OER activity increases with increasing surface concentration of Fe. Density functional theory analysis of the OER energetics reveals that oxygen evolution over Fe cations bound to a hydroxyl-terminated oxidized Au (Fe-Au 2 O 3 ) occurs at an overpotential ~0.3V lower than over hydroxylated Au 2 O 3 (0.82V). This finding agrees well with experimental observations and is a consequence of the more optimal binding energetics of OER reaction intermediates at Fe cations bound to the surface of Au 2 O 3 . These findings suggest that the enhanced OER activity reported recently upon low-potential cycling of Au may be due to surface Fe impurities rather than to "superactive" Au(III) surfaquo species.

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

Nitrate Radical Facilitates Indirect Benzyl Alcohol Oxidation on Bismuth(III) Vanadate Photoelectrodes

Bismuth(III) vanadate (BiVO 4 ) films show activity for direct benzyl alcohol (PhCH 2 OH) oxidation to benzaldehyde (PhCHO) in acetonitrile solvent. Introducing tetrabutylammonium nitrate (Bu 4 NNO 3 ) drastically reduces the overpotential required to generate the PhCHO product while maintaining a high faradaic efficiency (FE) >90%. BiVO 4 corrosion accompanies PhCH 2 OH oxidation. However, the presence of nitrate ions (NO 3 - ) results in significantly less bismuth- and vanadium-ion leaching (determined by ICP-MS analysis), as well as reduced surface roughening (determined by SEM imaging). In this reaction, it is proposed that rate-determining NO 3 - oxidation generates a highly reactive nitrate radical (NO 3 ∙) that reacts with PhCH 2 OH by hydrogen-atom abstraction (HAT). NO 3 - is stoichiometrically consumed by the irreversible formation of electrochemically inert HNO 3 , characterized by an EC i mechanism, rather than a catalytic EC' mechanism. In the presence of PhCH 2 OH, NO 3 - oxidation on BiVO 4 becomes more facile; every order of magnitude increase in PhCH 2 OH concentration shifts the NO 3 - / NO 3 ∙ equilibrium potential negatively by 200 mV. The shift results from the introduction of a consumption pathway for the nitrate radical intermediate via a coupled chemical step with benzyl alcohol. This report is the first example of photoelectrochemical NO 3 ∙ generation to initiate indirect PhCH 2 OH oxidation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2017

Deactivation of a Cobalt Catalyst for Water Reduction through Valence Tautomerism

The activity of the water reduction catalyst [Co III (L 1 )(pyr) 2 ]PF 6 (1), where (L 1 ) 2- is a bis-amido pyridine ligand and pyr is pyrrolidine, is investigated. Catalyst 1 has an overpotential of 0.54 V and a high observed TOF of 23 min -1 , albeit for a relatively short time. Considering the significant activity of 1 and aiming to improve catalyst design, a detailed structural and electronic study is performed to understand the mechanisms of deactivation. Experimental and theoretical evidence support that the metal-reduced [Co I (L 1 )] - is in tautomeric equilibrium with the ligand-reduced [Co II (L 1 .)] - species. While [Co I (L 1 )] - favors formation of a Co III -H - relevant for catalysis, the [Co II (L 1 .)] - species leads to ligand protonation, structural distortions, and, ultimatley, catalyst deactivation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Tuning the Activity of Heterogeneous Cofacial Cobalt Porphyrins for Oxygen Reduction Electrocatalysis through Self‐Assembly

Abstract We report a suite of coordination‐driven self‐assembled prisms for heterogeneous electrocatalytic oxygen reduction (ORR) differing in the molecular clips linking two porphyrin faces in a cofacial arrangement. ORR activities and selectivities of monomeric CoTPyP along with cofacial prisms Ox‐Co , Oxa‐Co , and Benzo‐Co were probed using cyclic voltammetry and rotating ring‐disk techniques. All species were immobilized as heterogeneous catalysts on glassy carbon electrodes using a Nafion ink method. The selectivities of Ox‐Co , Oxa‐Co , and Benzo‐Co prisms towards H 2 O as determined by RRDE were 87, 97, and 75 %, respectively. The current density of the Oxa‐Co plateaus at five times that of Pt/C when normalized per Co/Pt. The high synthetic yield (79 %), competitive overpotential ( η ≈800 mV) and high selectivity (%H 2 O ≈97 %) of the Oxa‐Co highlights how self‐assembly can be used to address multi‐electron multi‐proton transformations using polynuclear catalysts.

Oldacre, Amanda N.↗
DOE OSTI2016

Nitrogen‐Doped Nanoporous Graphenic Carbon: An Efficient Conducting Support for O 2 Cathode

Abstract Herein, we synthesize a nanoporous N‐doped graphenic carbon with high surface area and a higher graphenization/graphitic degree by further developing the metallothermic reduction of gaseous CO 2 by adding N 2 into the gas flow. The N‐doped nanoporous carbon is composed of both a highly porous graphenic and non‐graphitic matrix and homogeneously dispersed ordered graphitic nanodomains, which constitute a very unique composite carbon structure. The resulting N‐doped graphenic carbon exhibits much more favorable reactivity as a carbon conducting support in the O 2 cathode of Li‐O 2 batteries, increasing the specific capacity of the GC electrode from 5300 to 9600 mAh g −1 . The N‐doped carbon also exhibits lower overpotentials during initial cycling for the charging process as well as an enhanced cycling performance compared to the undoped carbon. These results demonstrate that N‐doping has a strong correlation with the enhanced performance of O 2 cathode of Li‐O 2 batteries.

Xing, Zhenyu↗
DOE OSTI2020

Polymer Entrapment Flash Pyrolysis for the Preparation of Nanoscale Iridium-Free Oxygen Evolution Electrocatalysts

This paper describes the use of a new polymer entrapment flash pyrolysis (PEFP) method for making nanoscale yttrium ruthenate (Y 2 Ru 2 O 7-δ ) electrocatalysts. Here, this approach effectively reduced the synthesis temperature of phase-pure pyrochlore catalysts from 1000 °C to 550 °C, and greatly suppressed the sintering of catalyst particles. The supported nanocrystalline Y 2 Ru 2 O 7-δ catalysts showed enhanced activity towards oxygen evolution reaction (OER) in acidic electrolyte and were stable at 1.50 V for the comparative study (>20 h) under the current density of 10 mA/cm 2 geo in chronopotentiometry testing. This is equivalent to an overpotential value of 270 mV, about half of that of the reference IrO 2 catalyst. X-ray absorption spectroscopy (XAS) and transmission electron microscopy (TEM) analysis showed that the high-surface-area Y 2 Ru 2 O 7-δ catalyst had an oxygen-deficient structure. This study provides a route to the synthesis of fine ceramic (or oxide)-based electrocatalysts for making high-performing electrocatalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Implications of the unpaired spins in Li-O 2 battery chemistry and electrochemistry: A minireview

Recent experimental and theoretical reports suggest that the valence states of oxygen species residing in the Li–O 2 cell discharge products can be very complex. The Li–O 2 discharge products may consist of composite structures of Li/O 2 compounds, such as Li 2 O 2 , O-rich Li 2 O 2 , LiO 2 -like superoxide, and Li 2 O, which can be both crystalline and amorphous phase. Some impurities can also be present owing to undesired parasitic reactions associated with electrolyte decomposition. In particular, the observation of unpaired spins associated with Li–O 2 discharge products may be because of the oxygen-rich environment of the Li–O 2 cell, which results in reduced oxygen radical species (e.g., O 2 – , LiO 2 , etc.). The presence of unpaired spins in Li–O 2 cell products can have a significant impact on electrolyte stability and cell performance (e.g., overpotential, electrical conductivity). Furthermore, besides standard ex situ experimental characterization, accurate and robust in situ experimental characterizations (e.g., EPR, NMR, Raman, and FTIR spectroscopy) in combination with well-controlled materials synthesis techniques are further needed to probe the time-evolution reaction mechanism of these unpaired electron spins within the Li–O 2 cell environment for better materials understanding and future Li–O 2 battery design.

25 ENERGY STORAGE↗
DOE OSTI2016

Tunable Oxygen Functional Groups as Electrocatalysts on Graphite Felt Surfaces for All‐Vanadium Flow Batteries

Abstract A dual oxidative approach using O 2 plasma followed by treatment with H 2 O 2 to impart oxygen functional groups onto the surface of a graphite felt electrode. When used as electrodes for an all‐vanadium redox flow battery (VRB) system, the energy efficiency of the cell is enhanced by 8.2 % at a current density of 150 mA cm −2 compared with one oxidized by thermal treatment in air. More importantly, by varying the oxidative techniques, the amount and type of oxygen groups was tailored and their effects were elucidated. It was found that O−C=O groups improve the cells performance whereas the C−O and C=O groups degrade it. The reason for the increased performance was found to be a reduction in the cell overpotential after functionalization of the graphite felt electrode. This work reveals a route for functionalizing carbon electrodes to improve the performance of VRB cells. This approach can lower the cost of VRB cells and pave the way for more commercially viable stationary energy storage systems that can be used for intermittent renewable energy storage.

Estevez, Luis↗