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At least 37 records · Page 2

Electrochemical production of ozone and hydrogen peroxide

Methods of using ozone have been developed which sterilize instruments and medical wastes, oxidize organics found in wastewater, clean laundry, break down contaminants in soil into a form more readily digested by microbes, kill microorganisms present in food products, and destroy toxins present in food products. The preferred methods for killing microorganisms and destroying toxins use pressurized, humidified, and concentrated ozone produced by an electrochemical cell.

Murphy, Oliver J.↗

Scalable neutral H 2 O 2 electrosynthesis by platinum diphosphide nanocrystals by regulating oxygen reduction reaction pathways

Despite progress in small scale electrocatalytic production of hydrogen peroxide (H 2 O 2 ) using a rotating ring-disk electrode, further work is needed to develop a non-toxic, selective, and stable O 2 -to-H 2 O 2 electrocatalyst for realizing continuous on-site production of neutral hydrogen peroxide. We report ultrasmall and monodisperse colloidal PtP 2 nanocrystals that achieve H 2 O 2 production at near zero-overpotential with near unity H 2 O 2 selectivity at 0.27 V vs. RHE. Density functional theory calculations indicate that P promotes hydrogenation of OOH* to H 2 O 2 by weakening the Pt-OOH* bond and suppressing the dissociative OOH* to O* pathway. Atomic layer deposition of Al 2 O 3 prevents NC aggregation and enables application in a polymer electrolyte membrane fuel cell (PEMFC) with a maximum r(H 2 O 2 ) of 2.26 mmol h -1 cm -2 and a current efficiency of 78.8% even at a high current density of 150 mA cm -2 . Catalyst stability enables an accumulated neutral H 2 O 2 concentration in 600 mL of 3.0 wt% (pH = 6.6).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Discovery of LaAlO 3 as an efficient catalyst for two-electron water electrolysis towards hydrogen peroxide

Electrochemical two-electron water oxidation reaction (2e-WOR) has drawn significant attention as a promising process to achieve the continuous on-site production of hydrogen peroxide (H 2 O 2 ). However, compared to the cathodic H 2 O 2 generation, the anodic 2e-WOR is more challenging to establish catalysts due to the severe oxidizing environment. In this study, we combine density functional theory (DFT) calculations with experiments to discover a stable and efficient perovskite catalyst for the anodic 2e-WOR. Our theoretical screening efforts identify LaAlO 3 perovskite as a stable, active, and selective candidate for catalyzing 2e-WOR. Our experimental results verify that LaAlO 3 achieves an overpotential of 510 mV at 10 mA cm -2 in 4 M K 2 CO 3 /KHCO 3 , lower than those of many reported metal oxide catalysts. In addition, LaAlO 3 maintains a stable H 2 O 2 Faradaic efficiency with only a 3% decrease after 3 h at 2.7 V vs. RHE. This computation-experiment synergistic approach introduces another effective direction to discover promising catalysts for the harsh anodic 2e-WOR towards H 2 O 2 .

08 HYDROGEN↗

Hydrogen peroxide on the surface of Europa

Spatially resolved infrared and ultraviolet wavelength spectra of Europa's leading, anti-jovian quadrant observed from the Galileo spacecraft show absorption features resulting from hydrogen peroxide. Comparisons with laboratory measurements indicate surface hydrogen peroxide concentrations of about 0.13 percent, by number, relative to water ice. The inferred abundance is consistent with radiolytic production of hydrogen peroxide by intense energetic particle bombardment and demonstrates that Europa's surface chemistry is dominated by radiolysis.

Non-programmatic↗

Efficient electrosynthesis of hydrogen peroxide in neutral media using boron and nitrogen doped carbon catalysts

The two-electron electrocatalytic oxygen reduction reaction (2e - ORR) is a promising, sustainable, and efficient route for on-site and small-scale production of hydrogen peroxide (H 2 O 2 ) compared to the conventional anthraquinone oxidation process. Although heteroatom doped carbon materials are widely studied for the 2e - ORR, few studies have been conducted on the synergistic relationship between multiple doping elements on H 2 O 2 performance. Moreover, there is a lack of efficient and stable catalysts for H 2 O 2 electrosynthesis in neutral media. In this work, a series of boron and nitrogen co-doped carbon (BNC) catalysts are synthesized and assessed for the 2e - ORR in neutral pH electrolyte. Through X-ray photoelectron and absorption spectroscopy analyses, we characterize B–N–C moieties and correlate them with H 2 O 2 production performance. In rotating ring disk electrode measurements, BNC catalysts pyrolyzed at 900 °C exhibit H 2 O 2 Faradaic efficiency of ~70% and demonstrate excellent long-term stability over 10 hours of continuous operation. In a three-electrode flow cell, this catalyst achieves ~78% H 2 O 2 Faradaic efficiency and 0.9 mmol cm -2 h -1 productivity at 0.20 V vs. RHE, surpassing most previously reported carbon-based catalysts in neutral media. This work contributes fundamental insights into the role of boron and nitrogen heteroatom dopants toward 2e - ORR and highlights the practical viability of these catalysts for real world applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Organometallic catalysts for primary phosphoric acid fuel cells

A continuing effort by the U.S. Department of Energy to improve the competitiveness of the phosphoric acid fuel cell by improving cell performance and/or reducing cell cost is discussed. Cathode improvement, both in performance and cost, available through the use of a class of organometallic cathode catalysts, the tetraazaannulenes (TAAs), was investigated. A new mixed catalyst was identified which provides improved cathode performance without the need for the use of a noble metal. This mixed catalyst was tested under load for 1000 hr. in full cell at 160 to 200 C in phosphoric acid H3PO4, and was shown to provide stable performance. The mixed catalyst contains an organometallic to catalyze electroreduction of oxygen to hydrogen peroxide and a metal to catalyze further electroreduction of the hydrogen peroxide to water. Cathodes containing an exemplar mixed catalyst (e.g., Co bisphenyl TAA/Mn) operate at approximately 650 mV vs DHE in 160 C, 85% H3PO4 with oxygen as reactant. In developing this mixed catalyst, a broad spectrum of TAAs were prepared, tested in half-cell and in a rotating ring-disk electrode system. TAAs found to facilitate the production of hydrogen peroxide in electroreduction were shown to be preferred TAAs for use in the mixed catalyst. Manganese (Mn) was identified as a preferred metal because it is capable of catalyzing hydrogen peroxide electroreduction, is lower in cost and is of less strategic importance than platinum, the cathode catalyst normally used in the fuel cell.

Walsh, Fraser↗

Computational Study of Indium Oxide Photoelectrodes

Using a combination of first-principles molecular dynamics simulations and electronic structure calculations, we characterize the atomistic structure and vibrational properties of a photocatalytic surface of In 2 O 3 , a promising photoelectrode for the production of hydrogen peroxide. We then investigate the surface in contact with water and show that the electronic states of In 2 O 3 are appropriately positioned in energy to facilitate the two-electron water oxidation reaction (WOR) over the competing four-electron oxygen evolution reaction. In conclusion, we further propose that the use of strained thin films interfaced with water is beneficial in decreasing the optical gap of In 2 O 3 and thus in utilizing a wider portion of the solar spectrum for the WOR.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Exogenous Hemin alleviated cadmium stress in maize (Zea mays L.) by enhancing leaf photosynthesis, AsA-GSH cycle and polyamine metabolism

Cadmium (Cd) stress is one of the principal abiotic stresses that inhibit maize growth. The research was to explore (hemin chloride) Hemin (100 μmol L −1 ) on photosynthesis, ascorbic acid (AsA)-glutathione (GSH) cycle system, and polyamine metabolism of maize under Cd stress (85 mg L −1 ) using nutrient solution hydroponics, with Tiannong 9 (Cd tolerant) and Fenghe 6 (Cd sensitive) as experimental materials. The results showed that Hemin can increase leaf photosynthetic pigment content and ameliorate the ratio of Chlorophyll a/chlorophyll b ( Chla / Chlb ) under Cd stress. The values of ribose 1, 5-diphosphate carboxylase/oxygenase (RuBPcase) and phosphoenolpyruvate carboxylase (PEPCase), and total xanthophyll cycle pool [(violoxanthin (V), antiflavin (A) and zeaxanthin (Z)] increased, which enhancing xanthophyll cycle (DEPS) de-epoxidation, and alleviating stomatal and non-stomatal limitation of leaf photosynthesis. Hemin significantly increased net photosynthetic rate ( P n ), stomatal conductance ( g s ), transpiration rate ( T r ), photochemical quenching coefficient ( qP ), PSII maximum photochemical efficiency ( F v /F m ), and electron transfer rate ( ETR ), which contributed to the improvement of the PSII photosynthetic system. Compared with Cd stress, Hemin can reduce thiobartolic acid reactant (TBARS) content, superoxide anion radical (O 2 − ) production rate, hydrogen peroxide (H 2 O 2 ) accumulation, and the extent of electrolyte leakage (EL); decreased the level of malondialdehyde (MDA) content and increased the activities of superoxide dismutase (SOD), peroxidase (POD) and catalase (CAT); slowed the decrease in dehydroascorbic acid reductase (DHAR) and monodehydroascorbate reductase (MDHAR) activity and the increase in glutathione reductase (GR) and ascorbate peroxidase (APX) activity in leaves; promoted the increase in AsA and GSH content, decreased dehydroascorbic acid (DHA) and oxidized glutathione (GSSG), and increased AsA/DHA and GSH/GSSG ratios under Cd stress. Hemin promoted the increase of conjugated and bound polyamine content, and the conversion process speed of free putrescine (Put) to free spermine (Spm) and spermidine (Spd) in maize; decreased polyamine oxidase (PAO) activity and increased diamine oxidase (DAO), arginine decarboxylase (ADC), ornithine decarboxylase (ODC) and S-adenosylmethionine decarboxylase (SAMDC) enzyme activities in leaves under Cd stress.

Piao, Lin↗

Investigation of effect of propulsion system installation and operation on aerodynamics of an airbreathing hypersonic airplane at Mach 0.3 to 1.2

Results from an investigation of the effects of the operation of a combined turbojet/scramjet propulsion system on the longitudinal aerodynamic characteristics of a 1/60-scale hypersonic airbreathing launch vehicle configuration are presented. Decomposition products of hydrogen peroxide were used for simulation of the propulsion system exhaust.

Cubbage, J. M.↗

Jet Interference Effects on a Model of a Single-Engine Four Jet V/STOL Airplane at Mach Numbers from 0.60 to 1.00

An investigation was conducted in the Langley 16-foot transonic tunnel to determine the interference from four exhaust jets on the aerodynamic characteristics of a model of a V/STOL airplane. The single- engine four-jet turbofan power plant of the airplane was simulated by inducing tunnel airflow through two large side inlets and injecting the decomposition products of hydrogen peroxide into the internal flow. The heated gas mixture was exhausted through four nozzles located on the sides of the fuselage under the wing, two near the wing leading edge and two forward of the trailing edge; the nozzles were deflected downward 1.5 deg and outward 5.0 deg to simulate cruise conditions. The wing of the model was a clipped delta with leading-edge sweep of 40 deg, aspect ratio of 3.06, taper ratio of 0.218, thickness-chord ratio of 0.09 at the root and 0.07 at the tip, and 10 deg negative dihedral. Aerodynamic and longitudinal stability coefficients were obtained for the model with the tail removed, and for horizontal-tail incidences of 0 deg and -5 deg. Data were obtained at Mach numbers from 0.60 to 1.00, angles of attack from 0 deg to 12 deg, and with jet total-pressure ratios up to 3.1. Jet operation generally caused a decrease in lift, an increase in pitching-moment coefficient, and a decrease in longitudinal stability at subsonic speeds. The jet interference effects on drag were detrimental at a Mach number of 0.60 and favorable at higher speeds for cruising-flight attitudes.

Schmeer, James W.↗

Microcalorimetric Measurements of Hydrogen Peroxide Stability

Recent interest in propellants with nontoxic reaction products has led to a resurgence of interest in hydrogen peroxide for various propellant applications. Because hydrogen peroxide is sensitive to contaminants and materials interactions, stability and shelf life are issues. A relatively new, ultrasensitive heat measurement technique, isothermal microcalorimetry, is being used at the White Sands Test Facility to monitor the decomposition of hydrogen peroxide at near ambient temperatures. Isothermal microcalorimetry measures the beat flow from a reaction vessel into a surrounding heat sink. In these applications, microcalorimetry is approximately 1,000 times more sensitive than accelerating rate calorimetry or differential scanning calorimetry for measuring thermal events. Experimental procedures have been developed for the microcalorimetric measurement of the ultra-small beat effects caused by incompatible interactions of hydrogen peroxide. The decomposition rates of hydrogen peroxide at the picomole/sec/gram level have been measured showing the effects of stabilizers and peroxide concentration. Typical measurements are carried out at 40 C over a 24-hour period, This paper describes a method for the conversion of the heat flow measurements to chemical reaction rates based on thermochemical considerations. The reaction rates are used in a study of the effects of stabilizer levels on the decomposition of propellant grade hydrogen peroxide.

Davis, Dennis D.↗

Production of chemical products using electrochemical flow systems and slug flow and associated methods

Systems and methods for electrochemically producing chemical products are provided. In certain cases, the systems and methods described herein are capable of producing chemical products such as hydrogen peroxide in solutions with relatively low concentrations of electrolyte or other dissolved species at high efficiencies and/or low energetic cost. In some cases, redox mediators are used to temporally decouple direct electrochemical processes from the production of the chemical product.

Voskian, Sahag↗

Production of chemical products using electrochemical flow systems and mediators and associated methods

Systems and methods for electrochemically producing chemical products are provided. In certain cases, the systems and methods described herein are capable of producing chemical products such as hydrogen peroxide in solutions with relatively low concentrations of electrolyte or other dissolved species at high efficiencies and/or low energetic cost. In some cases, redox mediators are used to spatially decouple direct electrochemical processes from the production of the chemical product.

Murray, Alexander↗

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↗

Comparison of ozone formation attribution techniques in the northeastern United States

The Integrated Source Apportionment Method (ISAM) has been revised in the Community Multiscale Air Quality (CMAQ) model. This work updates ISAM to maximize its flexibility, particularly for ozone (O 3 ) modeling, by providing multiple attribution options, including products inheriting attribution fully from nitrogen oxide reactants, fully from volatile organic compound (VOC) reactants, equally from all reactants, or dynamically from NO x or VOC reactants based on the indicator gross production ratio of hydrogen peroxide (H 2 O 2 ) to nitric acid (HNO 3 ). The updated ISAM has been incorporated into the most recent publicly accessible versions of CMAQ (v5.3.2 and beyond). This study's primary objective is to document these ISAM updates and demonstrate their impacts on source apportionment results for O 3 and its precursors. Additionally, the ISAM results are compared with the Ozone Source Apportionment Technology (OSAT) in the Comprehensive Air-quality Model with Extensions (CAMx) and the brute-force method (BF). All comparisons are performed for a 4 km horizontal grid resolution application over the northeastern US for a selected 2 d summer case study (9 and 10 August 2018). General similarities among ISAM, OSAT, and BF results add credibility to the new ISAM algorithms. However, some discrepancies in magnitude or relative proportions among tracked sources illustrate the distinct features of each approach, while others may be related to differences in model formulation of chemical and physical processes. Despite these differences, OSAT and ISAM still provide useful apportionment data by identifying the geographical and temporal contributions of O 3 and its precursors. Both OSAT and ISAM attribute the majority of O 3 and NO x contributions to boundary, mobile, and biogenic sources, whereas the top three contributors to VOCs are found to be biogenic, boundary, and area sources.

54 ENVIRONMENTAL SCIENCES↗

Spectral Properties of Hydrated Salts at Low Temperature: Implications for Europa Mission Spectrometer Design

Knowledge of the surface composition of Europa is critical for modeling of surface and interior processes and especially for evaluation of astrobiological potential. While much information has been derived from the Galileo Near-Infrared Mapping Spectrometer (NIMS) investigation, some breakthroughs have created more questions than answers. Any future Europa mission will attempt to capitalize on lessons learned from NIMS and try to answer these questions. At present, the surface composition appears to be a mixture of water ice, hydrated salts, sulfur compounds, radiolysis products (such as hydrogen peroxide and possibly simple organics like formaldehyde) and some as yet unidentified component. The small spatial scale of heterogeneity in Europa's surface geology poses additional challenges for orbiting spectrometers due to spectral mixing effects.

Dalton, J. Brad↗

Oxygen Mass Flow Rate Generated for Monitoring Hydrogen Peroxide Stability

Recent interest in propellants with non-toxic reaction products has led to a resurgence of interest in hydrogen peroxide for various propellant applications. Because peroxide is sensitive to contaminants, material interactions, stability and storage issues, monitoring decomposition rates is important. Stennis Space Center (SSC) uses thermocouples to monitor bulk fluid temperature (heat evolution) to determine reaction rates. Unfortunately, large temperature rises are required to offset the heat lost into the surrounding fluid. Also, tank penetration to accomodate a thermocouple can entail modification of a tank or line and act as a source of contamination. The paper evaluates a method for monitoring oxygen evolution as a means to determine peroxide stability. Oxygen generation is not only directly related to peroxide decomposition, but occurs immediately. Measuring peroxide temperature to monitor peroxide stability has significant limitations. The bulk decomposition of 1% / week in a large volume tank can produce in excess of 30 cc / min. This oxygen flow rate corresponds to an equivalent temperature rise of approximately 14 millidegrees C, which is difficult to measure reliably. Thus, if heat transfer were included, there would be no temperature rise. Temperature changes from the surrounding environment and heat lost to the peroxide will also mask potential problems. The use of oxygen flow measurements provides an ultra sensitive technique for monitoring reaction events and will provide an earlier indication of an abnormal decomposition when compared to measuring temperature rise.

Ross, H. Richard↗

Carbon flowers as electrocatalysts for the reduction of oxygen to hydrogen peroxide

Small-scale and decentralized production of H 2 O 2 via electrochemical reduction of oxygen is of great benefit, especially for sanitization, air and water purification, as well as for a variety of chemical processes. The development of low-cost and high-performance catalysts for this reaction remains a key challenge. Carbon-based materials have drawn substantial research efforts in recent years due to their advantageous properties, such as high chemical stability and high tunability in active sites and morphology. Deeper understanding of structure–activity relationships can guide the design of improved catalysts. We hypothesize that mass transport to active sites is of great importance, and herein we use carbon materials with unique flower-like superstructures to achieve high activity and selectivity for O 2 reduction to H 2 O 2 . The abundance of nitrogen active sites controlled by pyrolysis temperature resulted in high catalytic activity and selectivity for oxygen reduction reaction (ORR). The flower superstructure showed higher performance than the spherical nanoparticles due to greater accessibility to the active sites. Chemical activation improves the catalysts’ performances further, driving the production of H 2 O 2 to a record-setting rate of 816 mmol·g cat -1 ·h -1 using a bulk electrolysis setup. In conclusion, this work demonstrates the development of a highly active catalyst for the sustainable production of H 2 O 2 through rational design and synthetic control. The understanding from this work provides further insight into the design of future carbon-based electrocatalysts.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗