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Results for “water oxidation reaction”

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 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
NASA NTRS1986

Supercritical water oxidation of products of human metabolism

Although the efficient destruction of organic material was demonstrated in the supercritical water oxidation process, the reaction kinetics and mechanisms are unknown. The kinetics and mechanisms of carbon monoxide and ammonia oxidation in and reaction with supercritical water were studied experimentally. Experimental oxidation of urine and feces in a microprocessor controlled system was performed. A minaturized supercritical water oxidation process for space applications was design, including preliminary mass and energy balances, power, space and weight requirements.

Tester, Jefferson W.↗
DOE OSTI2024

CsO x Nanostructures on Au(111): Morphology- and Size-dependent Activity for the Water–Gas Shift Reaction

Alkali oxides are typically used as promoters of heterogeneous catalysts for the water–gas shift (WGS; H 2 O + CO → H 2 + CO 2 ) reaction. On Au(111), CsO x exhibits diverse nanostructures at varying coverages, as revealed by scanning tunneling microscopy. Clusters of cesium oxide (Cs 2 O 2 ) nucleate at elbow sites of the Au(111) herringbone when θ Cs is less than 0.1 ML. Subsequently, these clusters transform into two-dimensional (2D) islands (Cs 2 O, Cs 2 O 2 , CsO 2 ) as the cesium coverage increases (θ Cs > 0.1 ML). Both types of CsO x nanostructures enable the WGS process on Au(111). The highest activity was seen for the cesium oxide clusters which facilitated the partial dissociation of water and binding of CO. The CO ads and OH ads groups were not strongly bound and probably reacted to yield a short-lived HOCO intermediate that led to gaseous H 2 and CO 2 . The 2D islands of CsO x also enabled the WGS but their efficiency was reduced due to the formation of cesium hydroxide compounds (limiting mobility of OH groups) and the generation of CO 3 and C species (blocking of active centers). The fact that the performance of the CsO x /Au(111) catalysts changed dramatically with variations in the chemical properties of the CsO x nanostructures indicates that the alkali oxide was an integral part of the active phase, playing a central role in the activation and conversion of the reactants. To attach the label of “promoter” to CsO x is a simplification that does not help in the design and optimization of catalysts for C1 chemistry. In conclusion, to achieve a rational design, one must consider the structural and chemical properties of the alkali oxide.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Dynamic structure of active sites in ceria-supported Pt catalysts for the water gas shift reaction

Oxide-supported noble metal catalysts have been extensively studied for decades for the water gas shift (WGS) reaction, a catalytic transformation central to a host of large volume processes that variously utilize or produce hydrogen. There remains considerable uncertainty as to how the specific features of the active metal-support interfacial bonding—perhaps most importantly the temporal dynamic changes occurring therein—serve to enable high activity and selectivity. Here we report the dynamic characteristics of a Pt/CeO 2 system at the atomic level for the WGS reaction and specifically reveal the synergistic effects of metal-support bonding at the perimeter region. We find that the perimeter Pt 0 -O vacancy -Ce 3+ sites are formed in the active structure, transformed at working temperatures and their appearance regulates the adsorbate behaviors. We find that the dynamic nature of this site is a key mechanistic step for the WGS reaction.

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

Unravelling the water oxidation mechanism on NaTaO 3 -based photocatalysts

Understanding the detailed kinetics and mechanisms of water oxidation is crucial because water oxidation is the bottleneck reaction in overall water splitting. In this work, we investigated photocatalytic water oxidation on NaTaO 3 -based photocatalysts. With in situ FT-IR spectroscopy, two new water oxidation intermediates with IR absorption peaks centered at 1058 and 935 cm –1 were observed and assigned to Ta(VI)=O and Ta(O 2 ) peroxo species, respectively. With H 2 18 O as the reactant and NaTa 16 O 3 as the photocatalyst, both 16 O 18 O and 18 O 2 were evolved continuously from overall water splitting as analyzed by mass spectroscopy (MS), demonstrating that the lattice O atoms in NaTaO 3 -based photocatalysts participate in the formation of O 2 during the reaction. DFT results are consistent with the formation of Ta=O, 16 O 18 O and 18 O 18 O intermediates and products, while predicting that several water oxidation pathways are thermodynamically accessible for water oxidation on NaTaO 3 . Based on these observations, we propose a three-step two-site mechanism for photocatalytic water oxidation on NaTaO 3 -based photocatalysts in which lattice oxygen plays a key role. The elucidation of the present mechanism should help in broadly understanding water oxidation on semiconductor-based photocatalysts.

14 SOLAR ENERGY↗
DOE OSTI2023

Electrochemical phenyl oxidation: A limiting factor of oxygen evolution reaction in water electrolysis

This mini review explains the electrochemical phenyl oxidation of ionomers in the anode catalyst layers of the water electrolyzer that significantly impacts the performance and durability of the device. Although the relevant studies on phenyl oxidation on platinum group metal-free catalysts under high electrode potential are scarce, several studies with platinum group metal catalysts indicated that the impact of electrochemical phenyl oxidation can be profound. In the first part, this review summarizes ionomer-catalyst interactions that impact alkaline electrochemical devices, emphasizing the importance of minimizing interactions between the phenyl moiety of ionomers and oxygen evolution reaction catalysts. In the second part, we discuss the adsorption energies of phenyl groups found in ionomer fragments on different oxygen evolution catalysts. Finally, the mitigation strategies of electrochemical phenyl oxidation for advanced water electrolyzers are briefly discussed at the end of the review.

25 ENERGY STORAGE↗
NASA NTRS2003

Interactions of Water Vapor with Oxides at Elevated Temperatures

Many volatile metal hydroxides form by reaction of the corresponding metal oxide with water vapor. These reactions are important in a number of high temperature corrosion processes. Experimental methods for studying the thermodynamics of metal hydroxides include: gas leak Knudsen cell mass spectrometry, free jet sampling mass spectrometry, transpiration and hydrogen-oxygen flame studies. The available experimental information is reviewed and the most stable metal hydroxide species are correlated with position in the periodic table. Current studies in our laboratory on the Si-O-H system are discussed.

Jacobson, Nathan↗
DOE OSTI2022

Design and characterization of surface molecular assemblies for the preparation of solar fuels

A key issue in solar energy conversion is the utilization of solar energy for the preparation of solar fuels. In this area, artificial photosynthesis offers promising approaches for the conversion of H 2 O and CO 2 into usable solar fuels. This review highlights both the design and characterization of surface molecular assemblies for the preparation of solar fuels. It includes mechanistic summaries of the details of the underlying surface chemical reactions including water oxidation and proton/water reduction. The surface mechanisms are shown to integrate molecular reactivity with surface electron transfer in integrated assemblies that lead to impressive efficiencies for water oxidation and proton or CO 2 reduction.

catalysts and catalysis↗
NASA NTRS1973

Reactions of HO2 with carbon monoxide and nitric oxide and of O/1 D/ with water.

Investigation of the reactions of the hydroperoxyl radical with carbon monoxide and nitric oxide in a static system, and reexamination of the reaction of O(1 D) with water. The HO2 radicals were generated by the photolysis of N2O at 2139 A in the presence of excess H2O or H2 and smaller amounts of CO and O2. The O(1 D) atoms produced from the photolysis of N2O react with H2O or with H2 to give OH radicals in the case of H2O or OH radicals and H atoms in the case of H2. With H2O, two OH radicals are produced for each O(1 D) removed at low pressures, but the OH yield drops as the pressure is raised. This drop is attributed to an insertion reaction which removes from 10 to 30% of the O(1 D) atoms at about 650 torr of H2O at 200 F. The OH radicals generated can react with either CO or H2 to produce H atoms, which then add to O2 to produce HO2. In the absence of NO, the HO2 radicals could react by two routes, while with NO present NO2 is produced in a long chain process.

Simonaitis, R.↗
DOE OSTI2023

Infrared Spectroscopic Observation of Oxo- and Superoxo-Intermediates in the Water Oxidation Cycle of a Molecular Ir Catalyst

Molecular Ir catalysts have emerged as an important class of model catalysts for understanding structure–activity relationships in water oxidation, a reaction that is central to renewable fuel synthesis. Prior efforts have mostly focused on controlling and elucidating the emergence of active species from prepared precursors. However, the development of efficient and stable molecular Ir catalysts also necessitates probing of reaction intermediates. To date, relatively little is known about the key intermediates in the cycles of the molecular Ir catalysts. Herein, we probed the catalytic cycle of a homogeneous Ir catalyst (“blue dimer”) at a Au electrode/aqueous electrolyte interface by combining surface-enhanced infrared absorption spectroscopy (SEIRAS) with phase-sensitive detection (PSD). Cyclic voltammograms (CVs) from 1.4 to 1.7 VRHE (RHE = reversible hydrogen electrode) give rise to a band at ~818 cm –1 , whereas CVs from 1.4 to ≥1.85 VRHE generate an additional band at ~1146 cm –1 . Isotope labeling experiments indicate that the bands at ~818 and ~1146 cm –1 are attributable to oxo (Ir V =O) and superoxo (Ir IV –OO • ) moieties, respectively. Furthermore, this study establishes PSD-SEIRAS as a sensitive tool for probing water oxidation cycles at electrode/electrolyte interfaces and demonstrates that the relative abundance of two key intermediates can be tuned by the thermodynamic driving force of the reaction.

25 ENERGY STORAGE↗
NASA NTRS2000

Water Vapor Effects on Silica-Forming Ceramics

Silica-forming ceramics such as SiC and Si3N4 are proposed for applications in combustion environments. These environments contain water vapor as a product of combustion. Oxidation of silica-formers is more rapid in water vapor than in oxygen. Parabolic oxidation rates increase with the water vapor partial pressure with a power law exponent value close to one. Molecular water vapor is therefore the mobile species in silica. Rapid oxidation rates and large amounts of gases generated during the oxidation reaction in high water vapor pressures may result in bubble formation in the silica and nonprotective scale formation. It is also shown that silica reacts with water vapor to form Si(OH)4(g). Silica volatility has been modeled using a laminar flow boundary layer controlled reaction equation. Silica volatility depends on the partial pressure of water vapor, the total pressure, and the gas velocity. Simultaneous oxidation and volatilization reactions have been modeled with paralinear kinetics.

Opila, E. J.↗
DOE OSTI2020

The Fast-Track Water Oxidation Channel on BiVO 4 Opened by Nitrogen Treatment

BiVO 4 is one of the most promising photoanode materials for water-splitting systems. Nitrogen incorporation into a BiVO 4 surface overcomes the known bottleneck in its charge-transfer kinetics into the electrolyte. We explored the role of nitrogen in the surface charge recombination and charge-transfer kinetics by employing transient photocurrent spectroscopy at the time scale of surface recombination and water oxidation kinetics, transient absorption spectroscopy, and X-ray photoelectron spectroscopy. We attributed the activity enhancement mechanism to the accelerated V 5+ /V 4+ redox process, in which incorporated nitrogen suppresses a limiting surface recombination channel by increasing the oxygen vacancies.

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

Second Coordination Sphere Effects in an Evolved Ru Complex Based on Highly Adaptable Ligand Results in Rapid Water Oxidation Catalysis

A new Ru complex containing the deprotonated 2,2':6',2"-terpyridine-6,6"-diphosphonic acid (H 4 tPa) and pyridine (py) of general formula [Ru II (H 3 tPa-κ-N 3 O)(py) 2 ] + , 2 + , has been prepared and thoroughly characterized by means of spectroscopic and electrochemical techniques, X-ray diffraction analysis, and density functional theory (DFT) calculations. Complex 2 + presents a dynamic behavior in the solution that involves the synchronous coordination and the decoordination of the dangling phosphonic groups of the tPa 4– ligand. Yet, at oxidation state IV, complex 2 + becomes seven coordinated with the two phosphonic groups now bonded to the metal center. Further, at this oxidation state at neutral and basic pH, the Ru complex undergoes the coordination of an exogenous OH – group from the solvent that leads to an intramolecular aromatic O atom insertion into the CH bond of one of the pyridyl groups, forming the corresponding phenoxo-phosphonate Ru complex [Ru III (tPaO-κ-N 2 O P O C )(py) 2 ] 2– , 4 2– , where tPaO 5– is the 3-(hydroxo-[2,2':6',2"-terpyridine]-6,6"-diyl)bis(phosphonate) ligand. This new in situ generated Ru complex, 4 2– , has been isolated and spectroscopically and electrochemically characterized. In addition, a crystal structure has been also obtained using single-crystal X-ray diffraction techniques. Complex 4 2– turns out to be an exceptional water oxidation catalyst achieving record maximum turnover frequencies (TOF max ) on the order of 16 000 s –1 . A mechanistic analysis complemented with DFT calculations has further been carried out, showing the critical role of intramolecular second coordination sphere effects exerted by the phosphonate groups in lowering the activation energy at the rate-determining step.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Elucidating Hydrogen Reaction-Induced Water Desorption from Oxide-Passivated Metal Surfaces for Plasma Applications

Elucidating the mechanisms responsible for sub-microsecond desorption of water and other impurities from electrode surfaces at high heating rates is crucial for understanding pulsed power behavior. Ionization of desorbed impurities in the vacuum regions causes power or current loss; devising methods to limit such desorption during the short time scale of pulsed power is needed to improve corresponding applications. Previous molecular modeling studies have strongly suggested that, under high vacuum conditions, the amount of water impurity desorbing from oxide surfaces on metal electrodes is at a sub-monolayer level at room temperature, which appears insufficient to explain observed pulsed power energy losses at high current densities. In this work, we apply Density Functional Theory (DFT) techniques to show that hydrogen trapped inside iron metal can diffuse into hematite (α-Fe 2 O 3 ) on the metal surface, ultimately reacting with the oxide to form Fe(II) and H 2 O. The latter desorbs at elevated temperature and may explain the anomalous amount of desorbed impurity inferred from pulsed-power experiments. We also apply a suite of characterization techniques to demonstrate that when iron metal is heated to 650 °C, the dominant surface oxide component becomes α-Fe 2 O 3 . The oxide facets exposed are found to be a mixture of (0001), (10-10), and others, in agreement with the DFT models used.

74 ATOMIC AND MOLECULAR PHYSICS↗
NASA NTRS1992

MSATT Workshop on Chemical Weathering on Mars

The topics covered with respect to chemical weathering on Mars include the following: Mars soil, mineralogy, spectroscopic analysis, clays, silicates, oxidation, iron oxides, water, chemical reactions, geochemistry, minerals, Mars atmosphere, atmospheric chemistry, salts, planetary evolution, volcanology, Mars volcanoes, regolith, surface reactions, Mars soil analogs, carbonates, meteorites, and reactivity.

Burns, Roger↗
NASA NTRS1983

An investigation of sulfate production in clouds using a flow-through chemical reactor model approach

A flow-through chemical reactor model is developed to describe the mass transfer and chemical processes that atmospheric gases undergo in clouds. The model includes the simultaneous absorption of SO2, NH3, O3, NO(x), HNO3, CO2 and H2O2, the accompanying dissociation and oxidation reactions in cloud water, considers electrical neutrality, and includes qualitative parameterization of cloud microphysics. The model is used to assess the importance of the oxidation reactions H2O2-S(IV), O3-S(IV), and S(IV)-Mn(2+) catalysis, and the effects of cloud parameters such as drop size, rain intensity, liquid water content, and updraft velocity. Both precipitating and nonprecipitating clouds are studied. Model results predict sulfate production rates varying from 3 percent/hr to 230 percent/hr. The actual rate is highly dependent on the chemical composition of the uptake air and the physical conditions of the cloud. Model results also show that both the H2O2 and the O3 oxidation reactions can be significant.

Hong, M. S.↗