O2 Atmosphere Research Articles

A {Ru(C6H6)}-Containing Isopolymolybdate with Good Photocatalytic Activity for Oxidative Coupling of Amines, and Proton Conduction Properties.

We present a nonclassical {Ru(C6H6)}-containing isopolymolybdate Cs8K2Na2H4{[(C6H6)Ru]6Mo24O86}·35H2O (1) via one-pot reaction. The crystallographic characterization of compound 1 revealed that it contains an unusual {Mo24O86} cluster together with six {Ru(C6H6)} groups, having the largest number of {Ru(C6H6)} groups within the field of {Ru(C6H6)}-containing polyoxometalates. Results showed that compound 1 displayed excellent proton conductivity (9.8 × 10-3 S cm-1) at 90 °C and 95% relative humidity. Based on the calculation result of activation energy, which was more than 0.4 eV (1.47 eV), it was determined that the proton conduction process for compound 1 was in accordance with the Vehicle mechanism. More interestingly, compound 1 was exploited as a catalyst to achieve the heterogeneous oxidative coupling of amines and realized a high yield (98.9%) toward N-benzylidenebenzylamine under ambient temperature and visible light irradiation (>400 nm) and O2 atmosphere.

The impact of calcination atmosphere on Cr(Ⅵ) conversion in correction raw materials for high iron red mud

ABSTRACT The aim of this study was to investigate a new approach for reducing the production of harmful Cr(VI) heavy metals in the collaborative disposal of Red mud by cement enterprises. The study examined the effects of different ratios on the conversion rate of Cr(VI) in clinker under various calcination temperatures and atmospheres, and analyzed the raw material composition, clinker composition, and Cr(VI) content using XRD and XPS. The results indicate that the conversion rate of Cr(VI) is positively correlated with the concentration of oxygen, with the highest conversion rate of 93.4% achieved at 15% oxygen concentration. XPS analysis revealed that the peak intensity of Cr(VI) in clinker calcined under 4% O2 atmosphere was significantly higher than that of the sample calcined under 4000 mg/kg CO atmosphere. The study also found that the concentration of CO can reduce the conversion rate of Cr(VI) at high calcination temperatures, while at low calcination temperatures, the change in CO concentration has little effect on the conversion rate of Cr(VI). The specific objectives include examining the effects of different ratios, calcination temperatures, and atmospheres on the conversion rate of Cr(VI) in clinker. Additionally, when the ratio is the same as the calcination atmosphere, increasing the calcination temperature leads to an increase in the conversion rate of Cr(VI). The obtained results suggest a new approach for reducing the production of Cr(VI) in the collaborative disposal of Red mud by cement enterprises, which could have practical applications in engineering environmental protection.

Ba3Ti0.4W1.6O8.6: An Oxygen- and B-Site-Deficient 9R Hexagonal Perovskite Exhibiting Triple Conduction.

The hexagonal perovskite derivatives Ba3M'M″O8.5 featuring a hybrid structure composed of 9R hexagonal perovskite and palmierite structure motifs exhibit significant oxide ionic conductivity due to the highly disordered oxide-ion and M-cation sublattices. Herein, we report the structure and electrical properties of the perovskite Ba3Ti0.4W1.6O8.6. Three-dimensional (3D) electron diffraction (ED), neutron powder diffraction (NPD), and neutron pair distribution functions (nPDF) revealed a 9R hexagonal perovskite structure for Ba3Ti0.4W1.6O8.6 with fully occupied central M2 sites, partially occupied outer M1 sites, and oxygen-deficient cubic c-BaO2.6 sublayers. These cation and oxygen arrangements differ significantly from those in Ba3M'M″O8.5 and enable Ba3Ti0.4W1.6O8.6 to capture atmospheric water and O2, resulting in triple conduction (oxide ion, proton, and hole) under wet air conditions. Proton and oxide ion conductions predominate at temperatures <400 and >650 °C in wet Ar and dry air, respectively. Bond-valence site energy calculations, together with structure analysis, deciphered that the two-dimensional oxide-ion diffusion pathways along the c-BaO2.6 layers are disrupted by the M1 vacancies, thereby resulting in relatively low oxide ionic conductivity. Our findings open up a new strategy of utilizing the cation's propensity of coordination geometry to design new oxygen- and B-site-deficient perovskites and thus achieve desired conductivity.

Sustainable photocatalytic hydrogen peroxide production over octonary high-entropy oxide

The direct utilization of solar energy for the artificial photosynthesis of hydrogen peroxide (H2O2) provides a reliable approach for producing this high-value green oxidant. Here we report on the utility of high-entropy oxide (HEO) semiconductor as an all-in-one photocatalyst for visible light-driven H2O2 production directly from H2O and atmospheric O2 without the need of any additional cocatalysts or sacrificial agents. This high-entropy photocatalyst contains eight earth-abundant metal elements (Ti/V/Cr/Nb/Mo/W/Al/Cu) homogeneously arranged within a single rutile phase, and the intrinsic chemical complexity along with the presence of a high density of oxygen vacancies endow high-entropy photocatalyst with distinct broadband light harvesting capability. An efficient H2O2 production rate with an apparent quantum yield of 38.8% at 550 nm can be achieved. The high-entropy photocatalyst can be readily assembled into floating artificial leaves for sustained on-site production of H2O2 from open water resources under natural sunlight irradiation.

Exploring the mechanism of alkali metal K-catalyzed biomass char gasification using in-situ DRIFTS and molecular simulation

Although alkali metal potassium (K)-catalyzed char gasification has been widely studied, the detailed mechanism of this process is still not fully understood. To study this catalytic mechanism in more detail, high-temperature in-situ DRIFTS experiments were carried out for the gasification of cellulose char with K and cellulose char without K under H2O and O2 atmospheres, transient gasification experiment of char with K under H2O atmosphere, and char with K gasification under isotope water atmospheres. Peaks at 1945 cm−1 and 2020 cm−1 were observed. Combined with the theoretical spectra obtained by quantum chemical simulations and the prediction of catalytic gasification intermediates by molecular dynamics simulations, these two peaks were confirmed to represent char-polyynes species. Based on this result, a new mechanism is proposed: K interacts with carboxyl groups and aromatic ketones to promote desorption, thereby exposing active sites. Then, K reacts with the edge of the activated char to form numerous highly active char-polyynes species. The polyynes edge of this char-polyynes phase provides ideal adsorption–desorption sites, enabling further reaction with the gasifier. Thus, gas desorption is promoted. The adsorption and desorption peaks of catalytic gasification under the H2O atmosphere were located at 1400 cm−1 and 1300 cm−1, and these peaks represented stable adsorption states and unstable desorption precursors, respectively. Based on this, adsorption–desorption theory was analyzed more comprehensively, and the adsorption–desorption process was divided into three stages: initial adsorption, intermediate conversion, and desorption. The comprehensive new mechanism proposed in this paper provides a better understanding of the nature of char catalytic gasification at a deeper level.

Catalytic performances of Ag/SiC catalysts for styrene epoxidation in O2 atmosphere

SiC supported Ag catalysts were prepared by an impregnation-reduction method for styrene epoxidation in O2 atmosphere. Under the condition of 100 °C, 0.5 MPa O2 and 4 h, 5 wt% Ag/SiC catalyst achieved styrene conversion of 98.5 % and styrene oxide selectivity of 69.7 %. Further studies show that O2 was activated on the Ag surface and then formed reactive oxygen species, 1O2 and •O2-. Based on the O2 adsorption results, the atomic ratio of O/Ag larger than 0.5 indicated that more oxygen species had spilled over to the SiC surface. In-situ diffuse reflectance Fourier transform infrared spectroscopy and Density Functional Theory calculation results showed that styrene was adsorbed on the SiC surface. The active oxygen species generated on the Ag surface could spill over to the SiC surface, reacting with the adsorbed styrene to produce styrene oxide or benzaldehyde. In addition, the catalyst exhibits good stability.

Synthesis of Double Benzimidazole‐Fused Quinazolines and Pyrimidines Catalyzed by Recyclable Magnetic Cu‐MOF‐74

Abstract2‐(2‐Bromoaryl)‐ and 2‐(2‐bromovinyl)benzimidazoles are combined and cyclized with benzimidazoles using a catalytic amount of magnetic Cu‐MOF‐74 (Fe3O4@SiO2@Cu‐MOF‐74) and a base under O2 atmosphere, yielding the corresponding double benzimidazole‐fused quinazolines and pyrimidines. The catalyst can be recovered using a magnetic bar and reused multiple times without significant loss of catalytic activity. The reaction mechanism likely involves the initial formation of a C−N coupled intermediate through nucleophilic aromatic substitution, followed by oxidative cyclization.

Efficacy of active modified atmosphere packaging containing thymol on fortification of antioxidant capacity and reducing the microbial contamination of pomegranate arils

Pomegranate arils pose a significant challenge when it comes to preserving their nutritional value and preventing microbial contamination. This study aimed to explore the impact of thymol fumigation and active modified atmosphere packaging (MAP) on enzymatic activity and microbial contamination prevention in pomegranate arils. The results indicated that arils stored in a high O2 atmosphere (HO2A) with thymol had notably different catalase (CAT) and peroxidase (POD) activity levels compared to other treatments. These arils exhibited the highest CAT activity and the lowest POD activity. The highest phenylalanine ammonia-lyase (PAL) activity was observed in arils stored in HO2A with thymol, although it was not significantly different from those stored in a high CO2 atmosphere (HCO2A) with thymol (P&lt;0.05). Arils stored in a low oxygen atmosphere (LO2A) and HCO2A with thymol showed the highest polyphenol oxidase (PPO) activity levels, while arils in HO2A with thymol had the lowest. The HO2A with thymol treatment resulted in the lowest presence of psychrophilic bacteria, although it was not significantly different from arils stored in LO2A with thymol (P&lt;0.01). Based on cluster analysis results, HO2A with thymol, LO2A with thymol, and HCO2A with thymol could be considered the most effective treatments for extending the storage life of packaged pomegranate arils.

Origin of sulfate in post-snowball-Earth oceans: river inputs vs. shelf-derived H2S

A synthesis of global barite sulfate isotope data from approximately 635 million years ago, at the end of a global glaciation, undermines the hypothesis that river sulfate was the primary carrier of the distinctive 17O-depleted atmospheric O2 signature of the time. Instead, an aqueous H2S oxidation model on the shelf emerges as a compelling alternative, though it demands extensive validation across multiple fronts by the scientific community.

The Azobis(isobutyronitrile)-Promoted Oxidative Radical α-Cyanation of Imine under Atmospheric O2.

Herein, we report an azobis(isobutyronitrile) (AIBN)-promoted radical α-cyanation of in situ formed imine under atmospheric O2. This oxidative radical addition (ORA) procedure proceeds with the sequential homocleavage of AIBN, extrusion of N2, and capture of O2 toward an O-centered radical, which is converted to a cyano radical by β-scission. Then, the insertion of the cyano radical into the imine C═N bond forms an aminyl radical, leading to α-cyano imine after 1,2-hydrogen atom transfer (HAT) and H abstraction. Such a transition-metal-free procedure features mild reaction conditions and a broad substrate scope, employing molecular O2 as a clean terminal oxidant.

Enhancing Stability of Surface Au under Oxidizing Conditions through Reduced Bulk Au Content.

Contrary to the common assumption that a higher bulk content of precious metals facilitates the preservation of more surface noble metal by serving as a reservoir for surface enrichment, we demonstrate that a lower bulk content of Au results in a more stable arrangement of Au atoms at the surface of Cu-Au nanoparticles when exposed to an O2 atmosphere. Using ambient pressure X-ray photoelectron spectroscopy, we investigate the surface segregation and oxidation behavior of Cu-Au nanoparticles across various compositions. Our results reveal that in Au-rich nanoparticles exposed to an H2 atmosphere, surface segregation prompts the formation of a continuous Au-enriched shell, which subsequently oxidizes into a complete CuOx shell upon transitioning to an O2 atmosphere. Conversely, in Au-poor nanoparticles during H2 treatment, segregation results in the emergence of Au clusters embedded within the surface layer, persisting upon exposure to O2. This unexpected phenomenon shows that reducing the bulk content of precious metals can enhance the surface stability of noble atoms under oxidizing conditions, as further demonstrated by comparing the catalytic performance of Cu-Au nanoparticles with varying Au bulk contents in CO oxidation.

Extending Raspberry Shelf Life and Maintaining Postharvest Quality with CO2 Atmospheres

Raspberry (Rubus idaeus L.) fruit are known for their extremely short shelf life. Decay, leakiness, and loss of firmness are the most common limiting factors contributing to their short storage life. However, storage in elevated CO2 and reduced O2 atmospheres can delay senescence in fruit by reducing softening, respiration and ethylene production rates, and pathogen growth. In this study, raspberries were exposed to four different CO2 atmospheres—15 kPa CO2 and 6 kPa O2 (15 kPa); 8 kPa CO2 and 13 kPa O2 (8 kPa); 5 kPa CO2 and 16 kPa O2 (5 kPa); or 0.03 kPa CO2 and 21 kPa O2 (0.03 kPa)—and were evaluated for their postharvest quality periodically during two weeks of storage in 2020 and 2021. Raspberry fruits kept in a 15 kPa CO2 atmosphere followed by 8 kPa CO2 had higher firmness, brighter red color, and the least fungal decay or leakiness. In all atmospheres, the total anthocyanin content increased over time, although the rate of increase was slowed by high CO2. The raspberries’ visual attributes deteriorated over time in all atmospheres, but high CO2 atmospheres slowed the rate of deterioration. After five days, the quality of air-stored raspberries was significantly degraded, while the raspberries stored in elevated CO2 maintained good quality for up to ten days.

Online in-situ modification of biochar for the efficient removal of elemental mercury and co-benefit of SO2/NO removal

In this study, non-thermal plasma discharge was proposed for online in-situ modification of biochar injected into coal-biomass co-combustion flue gas, aiming to achieve the combined removal of elemental mercury (Hg0), NO, and SO2 from flue gas. After plasma discharge, the pore structure of biochar was slightly improved whereas the surface morphology of biochar was almost unchanged. After plasma discharge under O2, SO2, and HCl atmospheres, the oxygen, sulfur, and chlorine contents of biochar were obviously increased. More exactly, additional functional groups were formed on the modified biochar surface, such as CO, C(O)OC, CS, and CCl. Compared with raw biochar, the biochar modified under HCl, SO2, O2, H2O and CO2 atmospheres exhibited higher Hg0 removal efficiency, and longer modification time resulted in better Hg0 removal performance. The optimal modification atmosphere and reaction temperature were the simulated flue gas (SO2 + HCl + CO2 + O2 + H2O + NO + N2) and 20 ℃-100 ℃, respectively. The modified biochar exhibited excellent resistance to SO2 and H2O. The addition of HCl, CO2, NO, and O2 contributed to Hg0 removal. The removal efficiency of NO and SO2 attained a maximum of 100 %. The Hg0 removal mechanism was further revealed, where CO, C(O)OC, CS, and CCl served as active components.

High-Temperature Chlorination of Rhodium Using Alkali-Metal and Alkaline-Earth-Metal Chlorides

AbstractThis study was aimed at investigating an effective chlorination method for Rh and its oxide to develop an efficient Rh extraction process. The feasibility of using alkali-metal and alkaline-earth-metal chlorides (NaCl, KCl, MgCl2, and CaCl2) as chlorinating agents was evaluated from the perspective of thermodynamics; the prediction results revealed MgCl2 as a suitable agent for chlorinating metallic Rh and Rh2O3 in an oxygen-containing atmosphere. The thermodynamic analysis results were then experimentally validated. Metallic Rh converted to RhCl3 when mixed with MgCl2 and heated at 973 K (700 °C) in an O2 atmosphere. The Rh2O3 powder was efficiently chlorinated when reacted with liquid MgCl2 at 1073 K (800 °C) in an Ar–1 pct O2 atmosphere. Therefore, the chlorination of Rh using MgCl2 is feasible; its use has potential to make the extraction and recovery of Rh from various raw materials more efficient. Graphical Abstract

Apneic uptake of atmospheric O2 by deeply hypothermic nestlings of the white-footed mouse (Peromyscus leucopus): circulation and lungs.

Nestling white-footed mice (Peromyscus leucopus) are born in the earliest days of spring in cold climates. If the nestlings are by accident exposed to ambient temperatures near freezing (0-7°C) at early ages (2-10 days old), they may experience body temperatures (Tbs) equally low. During such hypothermia, although their heart keeps beating, they become apneic (cease inhaling and exhaling). However, they have an exceptional ability (e.g., compared to Mus musculus) to tolerate these conditions for at least several hours, after which they revive if rewarmed by parents. This paper addresses the physiology of the apneic period. We show that apneic, hypothermic nestlings undergo physiologically important exchanges of gases with the atmosphere. These gas exchanges do not occur across the skin. Instead they occur via the trachea and lungs even though the animals are apneic. Most significantly, when hypothermic neonates are in apnea in ordinary air, they take up O2 steadily from the atmosphere throughout the apneic period, and the evidence available indicates that this O2 uptake is essential for the nestlings' survival. At Tbs of 2-7°C, the nestlings' rate of O2 consumption varies quasi-exponentially with Tb and averages 0.04 mL O2 g- 1 h- 1, closely similar to the rate expressed by adult mammalian hibernators in hibernation at similar Tbs. Morphometric analysis indicates that, at all focal ages, O2 transport along the full length of the trachea can take place by diffusion at rates adequate to meet the measured rates of metabolic O2 consumption.

How Landmass Distribution Influences the Atmospheric Dynamics of Tidally Locked Terrestrial Exoplanets

Interpretation of the ongoing efforts to simulate the atmospheres of potentially habitable terrestrial exoplanets requires that we understand the underlying dynamics and chemistry of such objects to a much greater degree than 1D or even simple 3D models enable. Here, for the tidally locked habitable-zone planet TRAPPIST-1e, we explore one effect which can shape the dynamics and chemistry of terrestrial planets: the inclusion of an Earth-like land–ocean distribution with orography. To do this we use the Earth-system model WACCM6/CESM2 to run a pair of TRAPPIST-1e models with N2–O2 atmospheres and with the substellar point fixed over either land or ocean. The presence of orography shapes atmospheric transport, and in the case of Earth-like orography, breaks the symmetry between the Northern and Southern Hemispheres which was previously found in slab ocean models. For example, peak zonal jet speeds in the Southern Hemisphere are 50%–100% faster than similar jets in the Northern Hemisphere. This also affects the meridional circulation, transporting equatorial material toward the south pole. As a result we also find significant changes in the atmospheric chemistry, including the accumulation of potentially lethal quantities of ozone at both the south pole and the surface. Future studies which investigate the effects of landmass distribution on the dynamics of exoplanetary atmospheres should pay close attention to both the dayside land fraction as well as the orography of the land. Simply modeling a flat landmass will not give a complete picture of its dynamical impact.

Exploring the influence of atmospheric CO2 and O2 levels on the utility of nitrogen isotopes as proxy for biological N2 fixation.

Biological N2 fixation (BNF) is traced to the Archean. The nitrogen isotopic fractionation composition (δ15N) of sedimentary rocks is commonly used to reconstruct the presence of ancient diazotrophic ecosystems. While δ15N has been validated mostly using organisms grown under present-day conditions; it has not under the pre-Cambrian conditions, when atmospheric pO2 was lower and pCO2 was higher. Here, we explore δ15N signatures under three atmospheres with (i) elevated CO2 and no O2 (Archean), (ii) present-day CO2, and O2 and (iii) future elevated CO2, in marine and freshwater, heterocytous cyanobacteria. Additionally, we augment our data set from literature for more generalized dependencies of δ15N and the associated fractionation factor epsilon (ε = δ15Nbiomass - δ15NN2) during BNF in Archaea and Bacteria, including cyanobacteria, and habitats. The ε ranges between 3.70‰ and -4.96‰ with a mean ε value of -1.38 ± 0.95‰, for all bacteria, including cyanobacteria, across all tested conditions. The expanded data set revealed correlations of isotopic fractionation of BNF with CO2 concentrations, toxin production, and light, although within 1‰. Moreover, correlation showed significant dependency of ε to species type, C/N ratios and toxin production in cyanobacteria, albeit it within a small range (-1.44 ± 0.89‰). We therefore conclude that δ15N is likely robust when applied to the pre-Cambrian-like atmosphere, stressing the strong cyanobacterial bias. Interestingly, the increased fractionation (lower ε) observed in the toxin-producing Nodularia and Nostoc spp. suggests a heretofore unknown role of toxins in modulating nitrogen isotopic signals that warrants further investigation.IMPORTANCENitrogen is an essential element of life on Earth; however, despite its abundance, it is not biologically accessible. Biological nitrogen fixation is an essential process whereby microbes fix N2 into biologically usable NH3. During this process, the enzyme nitrogenase preferentially uses light 14N, resulting in 15N depleted biomass. This signature can be traced back in time in sediments on Earth, and possibly other planets. In this paper, we explore the influence of pO2 and pCO2 on this fractionation signal. We find the signal is stable, especially for the primary producers, cyanobacteria, with correlations to CO2, light, and toxin-producing status, within a small range. Unexpectedly, we identified higher fractionation signals in toxin-producing Nodularia and Nostoc species that offer insight into why some organisms produce these N-rich toxic secondary metabolites.

Influence of temperature, oxygen partial pressure, and microstructure on the high-temperature oxidation behavior of the SiC Layer of TRISO particles

Tristructural isotropic (TRISO)-coated fuel particles are designed for use in high-temperature gas-cooled nuclear reactors, featuring a structural SiC layer that may be exposed to oxygen-rich environments over 1000 °C. Surrogate TRISO particles were tested in 0.2–20 kPa O2 atmospheres to observe the differences in oxidation behavior. Oxide growth mechanisms remained consistent from 1200–1600 °C for each PO2, with activation energies of 228 ± 7 kJ/mol for 20 kPa O2 and 188 ± 8 kJ/mol for 0.2 kPa O2. At 1600 °C, kinetic analysis revealed a change in oxide growth mechanisms between 0.2 and 6 kPa O2. In 0.2 kPa O2, oxidation produced raised oxide nodules on pockets with nanocrystalline SiC. Oxidation mechanisms were determined using Atom probe tomography. Active SiC oxidation occurred in C-rich grain boundaries with low PO2, leading to SiO2 buildup in porous nodules. This phenomenon was not observed at any temperature in 20 kPa O2 environments.

Exploring Corymbia torelliana hydrochar combustion kinetics through thermogravimetric analysis, peak deconvolution and reaction profile modelling.

This study aims to conduct an applied and innovative investigation to enhance the energy quality of wood residues through hydrothermal carbonization pretreatment. For this purpose, the treatment was carried out at three different temperatures: 180, 220, and 240°C under autogenous pressure. The in natura material and the hydrochars were characterized, and thermogravimetric analyses were performed in an O2 atmosphere with heating rates of 2.5, 5, 10, and 20°Cmin-1. The global activation energy for natura biomass combustion was determined to be 112.49kJ.mol-1. On the other hand, the hydrothermal carbonization process promoted a reduction in this value for the 94.85kJ.mol-1. The conversion function for the in natura biomass was characterized as , order 1, while the hydrochars was 2(1-α) [-ln(1-α)] (1⁄2), Avrami-Erofe'ev I. Triple kinetic parameters were ascertained, and the conversion curves along with their respective derivatives were modeled, exhibiting minimal deviations between theoretical and experimental data. This facilitated the mathematical representation of the reaction processes and allowed for a comprehensive comparison of the results.

Unraveling the Effect of Oxygen Vacancy on WO3 Surface for Efficient NO2 Detection at Low Temperature.

Oxygen vacancies (VO) in metal oxide semiconductors play an important role in improving gas-sensing performance of chemiresistive gas sensors. Nonetheless, there is still a lack of clear understanding of the inherent mechanism of the influence of oxygen vacancies on gas sensing due to generally focusing on the concentration of VO. Herein, oxygen vacancies were rationally modulated in WO3 nanoflower structures via an annealing process, resulting in a transformation of VO from neutral (VO0) to a doubly ionized (VO2+) state. Density functional theory (DFT) calculations indicate that VO2+ is significantly more efficient than VO0 for NO2 detection in competition with atmospheric O2. Benefiting from a high concentration of VO2+, the WO3-450 (WO3 annealed at 450 °C) sensor exhibits excellent sensing performance with an ultrahigh sensitivity (3674.1 to 5 ppm NO2), superior selectivity, and long-term stability (one month). Furthermore, the sensor with the wide range of concentration detection not only can detect NO2 gas with parts per million (ppm) but also can detect NO2 with parts per billion (ppb) level concentration, with a high sensibility reaching 2.8 to 25 ppb NO2 and over 100 to 100 ppb NO2. This study elucidates the oxygen vacancy mediated sensing mechanism toward NO2 and provides an effective strategy for the rational design of gas sensors with high sensing performance.