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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 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2020

A Review on Challenges and Successes in Atomic-Scale Design of Catalysts for Electrochemical Synthesis of Hydrogen Peroxide

Hydrogen peroxide is a valuable chemical oxidant with a wide range of applications in a variety of industrial processes, especially in water sanitization. Electrochemical synthesis of hydrogen peroxide (H 2 O 2 ) through a two-electron oxygen reduction reaction (2e-ORR) or a two-electron water oxidation reaction (2e-WOR) has emerged as an appealing process for onsite production of this chemically valuable oxidant. On-site produced H 2 O 2 can be applied for wastewater treatment in remote locations or any applications where H 2 O 2 is needed as an oxidizing agent. Overall, this Review studies the theoretical efforts in understanding the challenges in catalysis for electrochemical synthesis of H 2 O 2 as well as providing design principles for more efficient catalyst materials.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Defective Carbon-Based Materials for the Electrochemical Synthesis of Hydrogen Peroxide

Hydrogen peroxide (H 2 O 2 ), an important industrial chemical, is currently produced through an energy-intensive anthraquinone process that is limited to large-scale facilities. Small-scale decentralized electrochemical production of H 2 O 2 via a two-electron oxygen reduction reaction (ORR) offers unique opportunities for sanitization applications and the purification of drinking water. The development of inexpensive, efficient, and selective catalysts for this reaction remains a challenge. Here in this paper, we examine two different porous carbon-based electrocatalysts and show that they exhibit high selectivity for H 2 O 2 under alkaline conditions. By rationally varying synthetic methods, we explore the effect of pore size on electrocatalytic performance. Furthermore, by means of density functional calculations, we point out the critical role of carbon defects. Our theory results show that the majority of defects in graphene are naturally selective for the two-electron reduction of O 2 to H 2 O 2 , and we identify the types of defects with high activity.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Revelation of the dynamic progression of hypoxia-reoxygenation injury by visualization of the lysosomal hydrogen peroxide

Hydrogen peroxide (H{sub 2}O{sub 2}) plays an important role in pathological conditions, such as cerebral ischemia-reperfusion (I-R) injury. Fluorescent probes may serve as valuable tools to detect the amount, temporal and spatial distribution of H{sub 2}O{sub 2} in living cells. To investigate the role of lysosomal H{sub 2}O{sub 2} involved in cerebral I-R injury, we designed and synthesized a lysosome-targetable two-photon fluorescent probe ztl-4, through expansion and substitution of the original pyridazinone scaffold, conjugation of electronic-donating aromatic ring and precise terminal modification of the alkyl linker. The probe ztl-4 exhibited fast, sensitive and highly selective response toward H{sub 2}O{sub 2}. ztl-4 could image exogenous H{sub 2}O{sub 2} in SH-SY5Y cells and brain slices. In addition, ztl-4 was located in lysosomes with high colocalization coefficient compared with LysoTracker. ztl-4 was further applied for detecting the endogenous generation of H{sub 2}O{sub 2} in SH-SY5Y cells subjected to oxygen and glucose deprivation (OGD) or OGD/reoxygenation (OGD/R) injury. Both OGD- and OGD/R-induced cell injury caused a time-dependent increase of H{sub 2}O{sub 2} production within lysosomes. Moreover, OGD/R-treated cells showed much more amount of H{sub 2}O{sub 2} than OGD-treated cells, indicating that reoxygenation will promote H{sub 2}O{sub 2} accumulation in lysosomes of post-hypoxia cells. Therefore, the probe is suitable for monitoring the dynamic changes of lysosomal H{sub 2}O{sub 2} in cells. - Highlights: • New fluorescent probe displays high selectivity for H{sub 2}O{sub 2}. • The probe is lysosome-targetable. • The probe can real-time monitor hypoxia/reoxygenation injury-induced generation of H{sub 2}O{sub 2} in lysosomes of cells.

60 APPLIED LIFE SCIENCES↗
DOE OSTI2016

Homolytic cleavage of both heme-bound hydrogen peroxide and hydrogen sulfide leads to the formation of sulfheme

Many heme-containing proteins with a histidine in the distal E7 (HisE7) position can form sulfheme in the presence of hydrogen sulfide (H 2 S) and a reactive oxygen species such as hydrogen peroxide. For reasons unknown, sulfheme derivatives are formed specifically on solvent-excluded heme pyrrole B. Sulfhemes severely decrease the oxygen-binding affinity in hemoglobin (Hb) and myoglobin (Mb). Here, use of hybrid quantum mechanical/molecular mechanical methods has permitted characterization of the entire process of sulfheme formation in the HisE7 mutant of hemoglobin I (HbI) from Lucina pectinata. This process includes a mechanism for H 2 S to enter the solvent-excluded active site through a hydrophobic channel to ultimately form a hydrogen bond with H 2 O 2 bound to Fe(III). Proton transfer from H 2 O 2 to His64 to form compound (Cpd) 0, followed by hydrogen transfer from H 2 S to the Fe(III) H 2 O 2 complex, results in homolytic cleavage of the O–O and S–H bonds to form a reactive thiyl radical (HS*), ferryl heme Cpd II, and a water molecule. Subsequently, the addition of HS to Cpd II, followed by three proton transfer reactions, results in the formation of a three-membered ring ferric sulfheme that avoids migration of the radical to the protein matrix, in contrast to that in other peroxidative reactions. The transformation of this three-membered episulfide ring structure to the five-membered thiochlorin ring structure occurs through a significant potential energy barrier, although both structures are nearly isoenergetic. Both three- and five-membered ring structures reveal longer N B –Fe(III) bonds compared with other pyrrole nitrogen–Fe(III) bonds, which would lead to decreased oxygen binding. Altogether, these results are in agreement with a wide range of experimental data and provide fertile ground for further investigations of sulfheme formation in other heme proteins and additional effects of H 2 S on cell signaling and reactivity.

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

Modulation of sensory perception by hydrogen peroxide enables Caenorhabditis elegans to find a niche that provides both food and protection from hydrogen peroxide

Hydrogen peroxide (H 2 O 2 ) is the most common chemical threat that organisms face. Here, we show that H 2 O 2 alters the bacterial food preference of Caenorhabditis elegans , enabling the nematodes to find a safe environment with food. H 2 O 2 induces the nematodes to leave food patches of laboratory and microbiome bacteria when those bacterial communities have insufficient H 2 O 2 -degrading capacity. The nematode’s behavior is directed by H 2 O 2 -sensing neurons that promote escape from H 2 O 2 and by bacteria-sensing neurons that promote attraction to bacteria. However, the input for H 2 O 2 -sensing neurons is removed by bacterial H 2 O 2 -degrading enzymes and the bacteria-sensing neurons’ perception of bacteria is prevented by H 2 O 2 . The resulting cross-attenuation provides a general mechanism that ensures the nematode’s behavior is faithful to the lethal threat of hydrogen peroxide, increasing the nematode’s chances of finding a niche that provides both food and protection from hydrogen peroxide.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2022

Modular Plasma Microreactor for Intensified Hydrogen Peroxide Production

Sustainable and decentralized manufacturing of hydrogen peroxide (H 2 O 2 ) has been extensively sought to replace the energy- and waste-intensive anthraquinone process. We introduce a helical biphasic microreactor in a coaxial dielectric barrier discharge (DBD) configuration as a modular, adaptable, and scalable intensified unit for H 2 O 2 production. Geometric and operating parameters such as electrode length, applied voltage, and gas and liquid flow rates can be tuned to regulate the residence time, delivered power, and gas–liquid interfacial area. In turn, these affect the key output parameters, i.e., H 2 O 2 concentration, production rate, and energy yield. We found a direct correlation between the H 2 O 2 production rate and the product of the interfacial area and residence time in the plasma region. We investigated the H 2 O 2 formation pathways using DMSO as an ·OH radical scavenger and found that H 2 O 2 forms by the dissolution of gaseous H 2 O 2 at low interfacial areas and is enhanced probably due to the interfacial recombination of ·OH radicals at a large gas–liquid interfacial area. The reactor temperature can also be externally controlled to intensify the production rate and energy yield of H 2 O 2 . Concentrations of up to 33 mM can be attained with a small footprint reactor that features a maximum energy yield of 4 g kWh –1 . Here, the plasma microreactor could epitomize a powerful process intensification tool for sustainable and distributed chemical manufacturing.

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

Origin of Selective Production of Hydrogen Peroxide by Electrochemical Oxygen Reduction

Oxygen reduction reaction (ORR) is one of the most important electrochemical reactions. Starting from a common reaction intermediate *–O–OH, the ORR splits into two pathways, either producing hydrogen peroxide (H 2 O 2 ) by breaking the *–O bond or leading to water formation by breaking the O–OH bond. However, it is puzzling why many catalysts, despite the strong thermodynamic preference for the O–OH breaking, exhibit high selectivity for hydrogen peroxide. Moreover, the selectivity is dependent on the potential and pH, which remain not understood. Here, for this work, we develop an advanced first-principles model for effective calculation of the electrochemical reaction kinetics at the solid–water interface, which were not accessible by conventional models. Using this model to study representative catalysts for H 2 O 2 production, we find that breaking the O–OH bond can have a higher energy barrier than breaking *–O, due to the rigidity of the O–OH bond. Importantly, we reveal that the selectivity dependence on potential and pH is rooted into the proton affinity to the former/later O in *–O–OH. For single cobalt atom catalyst, decreasing potential promotes proton adsorption to the former O, thereby increasing the H 2 O 2 selectivity. In contrast, for the carbon catalyst, the proton prefers the latter O, resulting in a lower H 2 O 2 selectivity in acid condition. These findings explain the experiments and highlight the kinetic origins of the selectivity. Our work improves the understanding of ORR by uncovering the proton affinity as a new factor and provides a new model to effectively simulate the atomic-level kinetics of heterogeneous electrochemistry.

08 HYDROGEN↗
DOE OSTI2022

Plasma‐driven biocatalysis: In situ hydrogen peroxide production with an atmospheric pressure plasma jet increases the performance of OleT JE when compared to adding the same molar amount of hydrogen peroxide in bolus

Abstract Enzymes like fatty acid peroxygenase OleT JE are desirable enzymes for the industry. While they require inexpensive hydrogen peroxide for activity, the same hydrogen peroxide also causes overoxidation of their reactive heme center. Here, we generate hydrogen peroxide slowly in situ using the Cooperation in Science and Technology (COST)‐Jet, an atmospheric pressure plasma jet, to avoid overoxidizing OleT JE . The COST‐Jet was operated in helium with a water admixture to provide hydrogen peroxide for OleT JE activity. This helium/water admixture produced the highest enzyme turnover numbers after 2 min of treatment. These turnover numbers were even superior to using an equimolar amount of hydrogen peroxide to treat the enzymes exogenously, showing that this plasma source can provide a reliable amount of reaction mediator to support OleT JE activity.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2018

ToF-SIMS characterization of glyoxal surface oxidation products by hydrogen peroxide: A comparison between dry and liquid samples

As one of the simplest volatile organic compounds (VOCs), glyoxal and its oxidation products were considered to be important precursors to aqueous secondary organic aerosol (aqSOA) formation. Herein, we analyzed products from glyoxal oxidation by hydrogen peroxide in dry and liquid samples using time-of-flight secondary ion mass spectrometry (ToF-SIMS). ToF-SIMS spectra and spectral principal component analysis (PCA) were used to investigate surface oxidation products. Dry samples were prepared on clean silicon wafers. Liquid samples consisting of glyoxal and hydrogen peroxide (H2O2) were introduced to a vacuum compatible microfluidic reactor prior to UV illumination or dark aging followed by in situ liquid SIMS analysis. A number of reaction products were observed in both dry and liquid samples; different oligomers and carboxylic acids could be formed depending on reaction conditions. In addition, hydrolyzed products were observed in the liquid samples, but not in the dry samples. Although dry samples reveal some products of the aqueous process, they are not fully representative as results from those of the aqueous samples. Our findings suggest that the ability to characterize the liquid surface reaction products provides more realistic information of the reaction products associated with aqSOA formation in the atmosphere. Meanwhile, the high mass resolution spectra from the dry sample SIMS measurement are helpful to identify oxidation products in the liquid samples.

, Aqueous Secondary Organic Aerosol, Sample Prepar↗
DOE OSTI2026

Oxidative Deboronation of Boronic Acids by Hydrogen Peroxide in Planta Generates Borate for Cross-Linking of Rhamnogalacturonan II

Vascular plants require boron to cross-link the rhamnogalacturonan-II (RG-II) domain of pectin to form functional cell walls. Boronic acids, which form reversible esters with cis-diols like borate, have been proposed to influence RG-II cross-linking, though the mechanism remains unclear. We used suspension-cultured rose cells adapted to grow without boron to investigate the effect of boronic acids on RG-II dimerization. When grown with phenylboronic acid (PBA) as the sole boron source, nearly all RG-II was crosslinked, whereas methylboronic acid (MBA) only partially restored cross-linking. In contrast, in vitro assays showed that homogeneous RG-II monomers did not dimerize with alkyl or aryl boronic acids unless supplemented with hydrogen peroxide (H2O2), which oxidatively converts boronic acids to boric acid. Real-time NMR spectroscopy and density functional theory calculations provided insight into the reaction mechanism and energetics of oxidation respectively. Together, our data show that exogenous boronic acids are a source of boric acid for plants, and that the deboronation reaction generates aryl or alkyl alcohol byproducts that can undergo further chemical modification in planta. The fate and potential roles of these byproducts in planta remain to be determined.

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

Integrated Two-Stage Alkaline–Oxidative Pretreatment of Hybrid Poplar. Part 2: Impact of Cu-Catalyzed Alkaline Hydrogen Peroxide Pretreatment Conditions on Process Performance and Economics

Two-stage alkaline/copper 2,2'-bipyridine-catalyzed alkaline hydrogen peroxide (Cu-AHP) pretreatment is an effective strategy for improving the enzymatic digestibility of hybrid poplar. To reduce the chemical inputs and processing costs associated with this process, we investigated the effect of increasing the temperature for both the alkaline pre-extraction and the Cu-AHP pretreatment stages. The results indicate that increasing the alkaline pre-extraction and the Cu-AHP pretreatment temperatures from 30 to 120 and 80 °C, respectively, allowed us to reduce both the pretreatment time of the Cu-AHP stage and the chemical loadings. Incubating alkaline pre-extracted hybrid poplar for 12 h with 10% NaOH (w/w biomass), 8% hydrogen peroxide (w/w biomass), and a Cu 2+ and 2,2'-bipyridine (bpy) concentration of 1 mM yielded monomeric sugar yields of approximately 77% glucose and 66% xylose (based on the initial sugar composition) following enzymatic hydrolysis. Technoeconomic analysis (TEA) indicates that these changes to the two-stage alkaline/Cu-AHP pretreatment process could potentially reduce the minimum fuel selling price (MFSP) by more than $\$1.00$ per gallon of biofuel compared to the reference case where both stages were conducted at 30 °C with higher chemical inputs.

09 BIOMASS FUELS↗
DOE OSTI2018

A Dynamically Stabilized Single‐Nickel Electrocatalyst for Selective Reduction of Oxygen to Hydrogen Peroxide

Abstract On‐location electrochemical generation of H 2 O 2 is of great current interest. Herein, selective two‐electron reduction of O 2 to H 2 O 2 by a single [Ni II (H 2 O) 6 ] 2+ cation that is dynamically associated with a negatively charged metal–organic layer (MOL) by hydrogen bonding and coulombic interactions is reported. In contrast, Ni II centers covalently immobilized on the MOL reduce O 2 to H 2 O in a four‐ electron process. Oxygen adsorption by [Ni II (H 2 O) 6 ] 2+ followed by two‐electron reduction generates neutral [Ni II (H 2 O) 4 (OH)(OOH)] 0 , which momentarily disconnects from the negatively charged MOL to avoid the injection of additional electrons. Release of H 2 O 2 from [Ni II (H 2 O) 4 (OH)(OOH)] 0 regenerates [Ni II (H 2 O) 6 ] 2+ , which regains affinity to the MOL. Such dynamically associated Ni II single‐metal electrocatalysts ensure high selectivity and represent a new strategy for generating selective catalysts for electrochemical production of important chemicals.

Wang, Tingting↗
DOE OSTI2013

Inactivation of possible micromycete food contaminants using the low-temperature plasma and hydrogen peroxide

The inhibition effect of hydrogen peroxide aerosol, low-temperature plasma and their combinations has been studied on several micromycetes spores. The low-temperature plasma was generated in corona discharges in the open air apparatus with hydrogen peroxide aerosol. Micromycete spores were inoculated on the surface of agar plates, exposed solely to the hydrogen peroxide aerosol, corona discharge or their combination. After incubation the diameter of inhibition zone was measured. The solely positive corona discharge exhibits no inactivation effect, the solely negative corona discharge and solely hydrogen peroxide aerosol exhibit the inactivation effect, however their combinations exhibit to be much more effective. Low-temperature plasma and hydrogen peroxide aerosol present a possible alternative method of microbial decontamination of food, food packages or other thermolabile materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗