Search NASA⌕ Search

SEARCH · Search NASA

Results for “hydrogen peroxide”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 361 records · Page 20
All sourcesNASA NTRSDOE OSTI
DOE OSTI2025

The Role of Interfaces and Charge for Chemical Reactivity in Microdroplets

A wide variety of reactions are reported to be dramatically accelerated in aqueous microdroplets, making them a promising platform for environmentally clean chemical synthesis. However, to fully utilize the microdroplets for accelerating chemical reactions requires a fundamental understanding of how microdroplet chemistry differs from that of a homogeneous phase. Here, in this work, we provide our perspective on recent progress to this end, both experimentally and theoretically. We begin by reviewing the many ways in which microdroplets can be prepared, creating water/hydrophobic interfaces that have been frequently implicated in microdroplet reactivity due to preferential surface adsorption of solutes, persistent electric fields, and their acidity or basicity. These features of the interface interplay with specific mechanisms proposed for microdroplet reactivity, including partial solvation, possible gas phase channels, and the presence of highly reactive intermediates. We especially highlight the role of droplet charge and associated electric fields, which appears to be key to understanding how certain reactions, like the formation of hydrogen peroxide and reduced transition metal complexes, are thermodynamically possible in microdroplets. Lastly, we emphasize opportunities for theoretical advances and suggest experiments that would greatly enhance our understanding of this fascinating subject.

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

Selectivity-Determining Steps in O 2 Reduction Catalyzed by Iron(tetramesitylporphyrin)

The oxygen reduction reaction (ORR) is the cathode reaction in fuel cells and its selectivity for water over hydrogen peroxide production is important for these technologies. Iron porphyrin catalysts have long been studied for the ORR, but the origins of their selectivity are not well understood because the selectivity-determining step(s) usually occur after the rate-determining step. We report here the effects of acid concentration, as well as other solution conditions such as acid pK a , on the H 2 O 2 /H 2 O selectivity in electrocatalytic ORR by iron(tetramesitylporphyrin) (Fe(TMP)) in DMF. The results show that selectivity reflects a kinetic competition in which the dependence on [HX] is one order greater for the production of H 2 O than H 2 O 2 . Based on such experimental results and computational studies, we propose that the selectivity is governed by competition between protonation of the hydroperoxo intermediate, Fe III (TMP)(OOH), to produce water versus dissociation of the HOO – ligand to yield H 2 O 2 . The data rule out a bifurcation based on the regioselectivity of protonation of the hydroperoxide, as suggested in the enzymatic systems. Furthermore, the analysis developed in this paper should be generally valuable to the study of selectivity in other multi-proton/multi-electron electrocatalytic reactions.

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

Ice Nucleating Particle Connections to Regional Argentinian Land Surface Emissions and Weather During the Cloud, Aerosol, and Complex Terrain Interactions Experiment

Abstract Here, we present a multi‐season study of ice‐nucleating particles (INPs) active via the immersion freezing mechanism, which took place in north‐central Argentina, a worldwide hotspot for mesoscale convective storms. INPs were measured untreated, after heating to 95°C, and after hydrogen peroxide digestion. No seasonal cycle of INP concentrations was observed. Heat labile INPs, which we define as “biological” herein, dominated the population active at −5 to −20°C, while non‐heat‐labile organic INPs (decomposed by peroxide) dominated at lower temperatures, from −20 to −28°C. Inorganic INPs (remaining after peroxide digestion), were minor contributors to the overall INP activity. Biological INP concentration active around −12°C peaked during rain events and under high relative humidity, reflecting emission mechanisms independent of the background aerosol concentration. The ratio of non‐heat‐labile organic and inorganic INPs was generally constant, suggesting they originated from the same source, presumably from regional arable topsoil based on air mass histories. Single particle mass spectrometry showed that soil particles aerosolized from a regionally common agricultural topsoil contained known mineral INP sources (K‐feldspar and illite) as well as a significant organic component. The INP activity observed in this study correlates well with agricultural soil INP activities from this and other regions of the world, suggesting that the observed INP spectra might be typical of many arable landscapes. These results demonstrate the strong influence of regional continental landscapes, emitting INPs of types that are not yet well represented in global models.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2022

Oxo dicopper anchored on carbon nitride for selective oxidation of methane

Abstract Selective conversion of methane (CH 4 ) into value-added chemicals represents a grand challenge for the efficient utilization of rising hydrocarbon sources. We report here dimeric copper centers supported on graphitic carbon nitride (denoted as Cu 2 @C 3 N 4 ) as advanced catalysts for CH 4 partial oxidation. The copper-dimer catalysts demonstrate high selectivity for partial oxidation of methane under both thermo- and photocatalytic reaction conditions, with hydrogen peroxide (H 2 O 2 ) and oxygen (O 2 ) being used as the oxidizer, respectively. In particular, the photocatalytic oxidation of CH 4 with O 2 achieves >10% conversion, and >98% selectivity toward methyl oxygenates and a mass-specific activity of 1399.3 mmol g Cu −1 h −1 . Mechanistic studies reveal that the high reactivity of Cu 2 @C 3 N 4 can be ascribed to symphonic mechanisms among the bridging oxygen, the two copper sites and the semiconducting C 3 N 4 substrate, which do not only facilitate the heterolytic scission of C-H bond, but also promotes H 2 O 2 and O 2 activation in thermo- and photocatalysis, respectively.

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

Emergent microrobotic oscillators via asymmetry-induced order

Abstract Spontaneous oscillations on the order of several hertz are the drivers of many crucial processes in nature. From bacterial swimming to mammal gaits, converting static energy inputs into slowly oscillating power is key to the autonomy of organisms across scales. However, the fabrication of slow micrometre-scale oscillators remains a major roadblock towards fully-autonomous microrobots. Here, we study a low-frequency oscillator that emerges from a collective of active microparticles at the air-liquid interface of a hydrogen peroxide drop. Their interactions transduce ambient chemical energy into periodic mechanical motion and on-board electrical currents. Surprisingly, these oscillations persist at larger ensemble sizes only when a particle with modified reactivity is added to intentionally break permutation symmetry. We explain such emergent order through the discovery of a thermodynamic mechanism for asymmetry-induced order. The on-board power harvested from the stabilised oscillations enables the use of electronic components, which we demonstrate by cyclically and synchronously driving a microrobotic arm. This work highlights a new strategy for achieving low-frequency oscillations at the microscale, paving the way for future microrobotic autonomy.

42 ENGINEERING↗
DOE OSTI2023

Redox-enabled electronic interrogation and feedback control of hierarchical and networked biological systems

Abstract Microelectronic devices can directly communicate with biology, as electronic information can be transmitted via redox reactions within biological systems. By engineering biology’s native redox networks, we enable electronic interrogation and control of biological systems at several hierarchical levels: proteins, cells, and cell consortia. First, electro-biofabrication facilitates on-device biological component assembly. Then, electrode-actuated redox data transmission and redox-linked synthetic biology allows programming of enzyme activity and closed-loop electrogenetic control of cellular function. Specifically, horseradish peroxidase is assembled onto interdigitated electrodes where electrode-generated hydrogen peroxide controls its activity. E. coli ’s stress response regulon, oxyRS , is rewired to enable algorithm-based feedback control of gene expression, including an eCRISPR module that switches cell-cell quorum sensing communication from one autoinducer to another—creating an electronically controlled ‘bilingual’ cell. Then, these disparate redox-guided devices are wirelessly connected, enabling real-time communication and user-based control. We suggest these methodologies will help us to better understand and develop sophisticated control for biology.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2024

Asgard archaea modulate potential methanogenesis substrates in wetland soil

The roles of Asgard archaea in eukaryogenesis and marine biogeochemical cycles are well studied, yet their contributions in soil ecosystems remain unknown. Of particular interest are Asgard archaeal contributions to methane cycling in wetland soils. To investigate this, we reconstructed two complete genomes for soil-associated Atabeyarchaeia, a new Asgard lineage, and a complete genome of Freyarchaeia, and predicted their metabolism in situ. Metatranscriptomics reveals expression of genes for [NiFe]-hydrogenases, pyruvate oxidation and carbon fixation via the Wood-Ljungdahl pathway. Also expressed are genes encoding enzymes for amino acid metabolism, anaerobic aldehyde oxidation, hydrogen peroxide detoxification and carbohydrate breakdown to acetate and formate. Overall, soil-associated Asgard archaea are predicted to include non-methanogenic acetogens, highlighting their potential role in carbon cycling in terrestrial environments.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2025

The role of Tyr34 in proton coupled electron transfer and product inhibition of manganese superoxide dismutase

Human manganese superoxide dismutase (MnSOD) plays a crucial role in controlling levels of reactive oxygen species (ROS) by converting superoxide (O$^{•–}_{2}$) to molecular oxygen (O 2 ) and hydrogen peroxide (H 2 O 2 ) with proton-coupled electron transfers (PCETs). A key catalytic residue, Tyr34, determines the activity of human MnSOD and also becomes post-translationally inactivated by nitration in various diseases associated with mitochondrial dysfunction. Tyr34 has an unusual pK a due to its proximity to the Mn metal and undergoes cyclic deprotonation and protonation events to promote the electron transfers of MnSOD. Neutron diffraction, X-ray spectroscopy, and quantum chemistry calculations in oxidized, reduced and product inhibited enzymatic states shed light on the role of Tyr34 in MnSOD catalysis. The data identify the contributions of Tyr34 in MnSOD activity that support mitochondrial function and give a thorough characterization of how a single tyrosine modulates PCET catalysis. Product inhibition occurs by an associative displacement mechanism.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2022

Dispersion and stability mechanism of Pt nanoparticles on transition-metal oxides

The heterogeneous catalysts of Pt/transition-metal oxides are typically synthesized through calcination at 500 °C, and Pt nanoparticles are uniformly and highly dispersed when hydrogen peroxide (H 2 O 2 ) is applied before calcination. The influence of H 2 O 2 on the dispersion and the stability of Pt nanoparticles on titania-incorporated fumed silica (Pt/Ti–FS) supports was examined using X-ray absorption fine structure (XAFS) measurements at the Pt L 3 and Ti K edges as well as density functional theory (DFT) calculations. The local structural and chemical properties around Pt and Ti atoms of Pt/Ti–FS with and without H 2 O 2 treatment were monitored using in-situ XAFS during heating from room temperature to 500 °C. XAFS revealed that the Pt nanoparticles of H 2 O 2 -Pt/Ti–FS are highly stable and that the Ti atoms of H 2 O 2 -Pt/Ti–FS support form into a distorted-anatase TiO 2 . DFT calculations showed that Pt atoms bond more stably to oxidized–TiO 2 surfaces than they do to bare- and reduced–TiO 2 surfaces. XAFS measurements and DFT calculations clarified that the presence of extra oxygen atoms due to the H 2 O 2 treatment plays a critical role in the strong bonding of Pt atoms to TiO 2 surfaces.

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

Redox active plant phenolic, acetosyringone, for electrogenetic signaling

Abstract Redox is a unique, programmable modality capable of bridging communication between biology and electronics. Previous studies have shown that the E. coli redox-responsive OxyRS regulon can be re-wired to accept electrochemically generated hydrogen peroxide (H 2 O 2 ) as an inducer of gene expression. Here we report that the redox-active phenolic plant signaling molecule acetosyringone (AS) can also induce gene expression from the OxyRS regulon. AS must be oxidized, however, as the reduced state present under normal conditions cannot induce gene expression. Thus, AS serves as a “pro-signaling molecule” that can be activated by its oxidation—in our case by application of oxidizing potential to an electrode. We show that the OxyRS regulon is not induced electrochemically if the imposed electrode potential is in the mid-physiological range. Electronically sliding the applied potential to either oxidative or reductive extremes induces this regulon but through different mechanisms: reduction of O 2 to form H 2 O 2 or oxidation of AS. Fundamentally, this work reinforces the emerging concept that redox signaling depends more on molecular activities than molecular structure. From an applications perspective, the creation of an electronically programmed “pro-signal” dramatically expands the toolbox for electronic control of biological responses in microbes, including in complex environments, cell-based materials, and biomanufacturing.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2020

The effect of chemically preintercalated alkali ions on the structure of layered titanates and their electrochemistry in aqueous energy storage systems

We introduce a novel chemical preintercalation synthesis technique based on a hydrogen peroxide induced sol–gel process to obtain alkali ion containing ternary layered titanates (MTO, where M = Li, Na, K). Synthesis parameters leading to the formation of single-phase materials with homogeneous elemental distribution are reported for each of the preintercalated ions. Our analyses indicate that the interlayer spacing in the structure of the layered titanates increases with the increase of the radius of the hydrated preintercalated ion. Scanning and transmission electron microscopy imaging revealed morphological diversity: the LTO phase crystallized as nanoplates assembled in “peony-like” spherical agglomerates while NTO and KTO particles exhibited a one-dimensional nanobelt or wire-like morphology, with the KTO nanobelts being shorter and more aggregated than the NTO nanobelts. Structural refinement corroborated by electron diffraction and high-resolution transmission electron microscopy revealed that the structure of the LTO phase is built by stacking Ti–O layers containing a single straight layer of connected TiO 6 octahedra. The layers in NTO and KTO structures form differently and consist of double Ti–O layers with two titanium rows and ragged arrangement of units built by TiO6 octahedra. The NTO electrodes exhibited the highest electrochemical performance in cells with aqueous 1 M Na 2 SO 4 electrolyte, followed by the KTO electrodes and then LTO electrodes, and this trend is maintained at various scan rates. The established relationships between the structure and electrochemical performance reveal that, in addition to interlayer distance and chemistry of the interlayer region, the structure of the layers can play an important role in charge storage properties of layered oxide electrodes. The double Ti–O layers in the structure of NTO and KTO phases provide a larger number of redox centers which could contribute to the superior electrochemical performance as compared to the LTO electrodes. Our findings indicate that layered materials containing double transition metal oxide layers are promising candidates for exfoliation and assembly with electronically conductive layers with the aim to create 2D heterostructures with high electrochemical performance.

25 ENERGY STORAGE↗
DOE OSTI2022

Catalyst and reactor design considerations for selective production of acids by oxidative cleavage of alkenes and unsaturated fatty acids with H 2 O 2

Oxidative cleavage of alkenes and unsaturated fatty acids with hydrogen peroxide gives an efficient and sustainable process to obtain mono- and di-acids for polymers and lubricants with fewer safety risks and less environmental impact than processes that utilize ozone or other inorganic oxidizers (e.g., permanganate, dichromate, etc.). Guided by insight into the mechanisms for competing reaction pathways (i.e., epoxidation of alkene on W–(η 2 -O 2 ) complexes vs. H 2 O 2 decomposition) and the apparent kinetics derived from kinetic experiments, here, we postulate that W-based heterogeneous catalysts can provide high performance and stable operations at low H 2 O 2 concentrations. Semi-batch reactors with continuous introduction of H 2 O 2 solutions offer the means to maintain low H 2 O 2 concentrations while providing sufficient quantities of H 2 O 2 to satisfy the reaction stoichiometry. We derived simple kinetic model equations for the epoxidation, ring-opening, oxidative cleavage, and oxidation steps and fit theses equations to batch experimental data to obtain kinetic parameters. Furthermore, this kinetic model describes the concentration profiles of reactant, oxidant, and products well as shown by agreement with experimental data. Further predictions of the optimal H 2 O 2 feed rate for semi-batch operation utilized by the proposed rate expressions and the reactor design equations suggest that low H 2 O 2 feed rate increases selectivity towards oxidative cleavage products and selective use of H 2 O 2 for oxidative cleavage pathway. Comparisons of oxidative cleavage of 4-octene in batch and semi-batch reactors show that semibatch reactors with optimized molar feed rates of H 2 O 2 increased oxidative cleavage product selectivities (76% to 99%; with an increase in butyric acid selectivity from 1% to 55%) and H 2 O 2 selectivity (3% to 30%). In addition, semibatch reaction conditions used avoid H 2 O 2 -mediated dissolution of W-atoms from the catalyst. Analysis of these findings suggest that solid oxide catalysts will be effective for continuous oxidative cleavage reactions if deployed within fixed-bed reactors that allow for distributed introduction of reactants and therefore low in situ concentrations of H 2 O 2 .

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

Tracking the reaction networks of acetaldehyde oxide and glyoxal oxide Criegee intermediates in the ozone-assisted oxidation reaction of crotonaldehyde

The reaction of unsaturated compounds with ozone (O 3 ) is recognized to lead to the formation of Criegee intermediates (CIs), which play a key role in controlling the atmospheric budget of hydroxyl radicals and secondary organic aerosols. The reaction network of two CIs with different functionality, i.e. acetaldehyde oxide (CH 3 CHOO) and glyoxal oxide (CHOCHOO) formed in the ozone-assisted oxidation reaction of crotanaldehyde (CA), is investigated over a temperature range between 390 K and 840 K in an atmospheric pressure jet-stirred reactor (JSR) at a residence time of 1.3 s, stoichiometry of 0.5 with a mixture of 1% crotonaldehyde, 10% O 2 , at an fixed ozone concentration of 1000 ppm and 89% Ar dilution. Molecular-beam mass spectrometry in conjunction with single photon tunable synchrotron vacuum-ultraviolet (VUV) radiation is used to identify elusive intermediates by means of experimental photoionization energy scans and ab initio threshold energy calculations for isomer identification. Addition of ozone (1000 ppm) is observed to trigger the oxidation of CA already at 390 K, which is below the temperature where the oxidation reaction of CA was observed in the absence of ozone. The observed CA + O 3 product, C 4 H 6 O 4 , is found to be linked to a ketohydroperoxide (2-hydroperoxy-3-oxobutanal) resulting from the isomerization of the primary ozonide. Products corresponding to the CIs uni- and bi-molecular reactions were observed and identified. A network of CI reactions is identified in the temperature region below 600 K, characterized by CIs bimolecular reactions with species like aldehydes, i.e., formaldehyde, acetaldehyde, and crotonaldehyde and alkenes, i.e., ethene and propene. The region below 600 K is also characterized by the formation of important amounts of typical low-temperature oxidation products, such as hydrogen peroxide (H 2 O 2 ), methyl hydroperoxide (CH 3 OOH), and ethyl hydroperoxide (C 2 H 5 OOH). Detection of additional oxygenated species such as alcohols, ketene, and aldehydes are indicative of multiple active oxidation routes. This study provides important information about the initial step involved in the CIs assisted oligomerization reactions in complex reactive environments where CIs with different functionalities are reacting simultaneously. It provides new mechanistic insights into ozone-assisted oxidation reactions of unsaturated aldehydes, which is critical for the development of improved atmospheric and combustion kinetics models.

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

Recycling organoiridium waste to [(1,5-cyclooctadiene)IrCl] 2

We report the first process for iridium element recovery from organoiridium waste that is quantitative, pyrolysis-free, and generates no iridium metal. Here, the key step is oxidative degradation of the waste by bleach to crude iridium(IV) hydroxide. Its treatment with hydrazine and then hydrogen peroxide gives synthetically important hexachloroiridic acid, which is converted to [(1,5-cyclooctadiene)IrCl] 2 in 87% yield.

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

Influence of crossover on capacity fade of symmetric redox flow cells

Volumetrically unbalanced compositionally symmetric cell cycling with potentiostatic (CV) or galvanostatic-with-potential-hold (CCCV) protocols is a rigorous technique for evaluating the calendar lifetime of reactants for redox flow batteries. Here, we evaluate the influence of reactant crossover through the membrane on symmetric cell cycling behavior. We tested symmetric cells of anthraquinone disulfonic acid (AQDS) with Nafion membranes of varied thickness and manufacture (NR211, NR212, N115, and N117, ranging 25–183 μm). Membranes were tested both as-received and pretreated with a common procedure of soaking in water at elevated temperature and then in dilute hydrogen peroxide. We found no significant difference in capacity fade rates of symmetric cells with any of the membranes as-received, indicating a negligible influence of crossover. However, we observed increased capacity fade with increased permeability through pretreated membranes. Supported by zero-dimensional modeling and operando UV-vis spectrophotometry, we propose a mechanism for net crossover in AQDS symmetric cells based on a higher time-averaged concentration of quinhydrone dimers in the non-capacity limiting side (NCLS) compared to the capacity limiting side (CLS), driving net crossover of AQDS reactants out of the CLS. Further, we illustrate other hypothetical scenarios of net crossover using the zero-dimensional model. Overall, many membrane–electrolyte systems used in symmetric cell studies have sufficiently low crossover flux as to avoid the influence of crossover on capacity fade, but under conditions of higher crossover flux, complex interactions of crossover and chemical reactions may result in diverse capacity fade trajectories, the mechanisms of which may be untangled with operando characterization and modeling.

25 ENERGY STORAGE↗
DOE OSTI2025

Electrochemical production of H 2 O 2 on palladium-based clusters driven by metal–support interaction

Utilizing palladium (Pd) clusters as active sites offers a promising route to minimize noble metal consumption in electrochemical hydrogen peroxide (H 2 O 2 ) production. In this work, we present a synthesis approach for anchoring Pd-based clusters onto carbon-supported CeO 2 nanosubstrates to enable efficient H 2 O 2 generation via the two-electron oxygen reduction reaction (ORR) pathway. By systematically adjusting Pd loading, we evaluated its impact on H 2 O 2 yield and production rate. The catalyst with the lowest Pd content (0.027 wt%) exhibited outstanding performance, achieving 97% H 2 O 2 selectivity, 94.2 faradaic efficiency at 0.7 V vs. RHE, and a peak production rate of 195.8 mol g Pd −1 h −1 . A formulation containing 0.35 wt% Pd delivered a peak ORR mass activity nearly three times as high as that of commercial 10 wt% Pd/C, while retaining comparable electrochemical stability. These enhancements are attributed to synergistic effects among isolated PdO clusters, CeO 2 nanocrystals, and the conductive carbon support, which together facilitate oxygen adsorption and promote the two-electron ORR pathway. Analysis after accelerated durability testing further revealed a tendency toward cluster agglomeration and mass transfer from smaller to larger nanocrystals, indicative of a coarsening mechanism. Overall, this study underscores the promise of low-Pd PdO–CeO 2 –carbon hybrid catalysts for scalable and efficient H 2 O 2 electrosynthesis, while highlighting stability as a critical area for future improvement.

36 MATERIALS SCIENCE↗