O2 Reaction Research Articles

Experimental study of the influence of O2 content on electrical and optical characteristics of He/CF4 APPJ

CF4 is an important source of reactive F-containing species (RFS) so that it is used to mix with inert gas as the working gas of atmospheric pressure plasma jet (APPJ) for material surface fluoridation modification. The addition of a small amount of O2 can increase the density of RFS in He/CF4 APPJ. Therefore, the hydrodynamic, electrical and optical properties of He/CF4/O2 APPJ interacting with the dielectric are experimentally investigated in this paper. Meanwhile, the influence of the excitation source on plasma discharge is discussed in detail and the internal mechanism of the experimental phenomenon in this paper is analyzed using the simulation results based on the model established in the previous paper. It is found that the addition of a small amount of O2 can increase the intensity and accelerate the axial propagation speed of He/CF4 APPJ due to the low ionization energy of O2 and the increase of the Penning ionization between metastable He and O2. With the increase of O2 content, the stability of the discharge is gradually enhanced due to the electron attachment reaction of O2 and the position of the primary current pulse in each half voltage cycle gradually approaches the position of the peak voltage because the increase in O2 content raises the breakdown threshold in dielectric barrier discharge region. In the presence of downstream dielectric, the addition of 0.1%O2 does not significantly change the radial development radius of APPJ due to the higher electron attachment rate and electron collision excitation loss power. The discharge pulse intensity is generally reduced compared to the absence of dielectric and the glow discharge in the strict sense no longer exists. The continuous spectrum intensity of RFS increases with the addition of a small amount of O2 while decreases significantly when O2 content is too high.

Volatility and chemical composition of secondary organic aerosol derived from acenaphthylene and acenaphthene under various oxidant conditions

Acenaphthene (ACE) and acenaphthylene (ACY), distinguished by their unique structures, exhibit high reactivity among polycyclic aromatic hydrocarbons (PAHs). Particularly, the rapid ozonolysis of the carbon-carbon double bond in ACY and the swift oxidation of the fused cyclopenta ring in both ACE and ACY by NO3 underscore their distinct atmospheric fate. Through the utilization of a thermo denuder and high-resolution mass spectrometry, the chemical composition and volatility of four types of secondary organic aerosols (SOA) derived from ACE and ACY are investigated. The chemical composition of SOA formed by ACY ozonolysis is characterized by low O: C ratios and high unsaturation, suggesting the retention of aromatic structures. This leads to measured high SOA volatility and is consistent with the low reactivity of O3 with aromatic compounds. In contrast to ozonolysis, the reaction of NO3 with ACY could yield SOA with very low volatility, characterized by abundant dimers and highly oxidized products. Furthermore, the prevalence of compounds with 11 carbon atoms suggests the presence of complex mechanisms in the ACY oxidation process initiated by NO3, where dealkylation reactions and cleavage reactions may be pivotal. The diverse chemical composition and volatility of SOA from ACE and ACY reacting with NO3 radicals highlight the substantial impact of precursor structure on SOA chemical composition, particularly concerning the presence of active carbon-carbon double bonds. The higher O: C ratio of SOA from OH-initiated oxidation of ACE indicates the significant role of OH in the oxidation of PAHs. These findings offer valuable insights into the atmospheric fate of these PAHs, underscoring the necessity for a comprehensive understanding of their degradation processes and the formation of SOA.

Bioinspired binary-site catalysts for novel urea-assisted Zn-air battery: A transfer station between renewable energy and hydrogen

The slow reaction kinetics of oxygen electrode is the bottleneck restricting the development of rechargeable Zn-air batteries (ZABs). In order to further improve the energy conversion efficiency of ZABs, a novel urea-assisted ZAB system was proposed by replacing oxygen evolution reaction (OER) with urea oxidation reaction (UOR) with lower theoretical thermodynamic potential. Inspired by nature’s ingenious structure-function, a “leaf-branch” CoNi@NCNTs-LDH/CC binary-site electrocatalyst was designed for the above system, where spatially separated branches and leaves serve as the main active sites for ORR and UOR, respectively. A build-in electric field from CoNi-LDH to CoNi@NCNTs is formed at the interface of the composite, which plays a command effect, effectively triggering the accumulation of O2 and urea reactants around the CoNi and LDH sites, respectively, and thus improving the efficiency of both ORR and UOR reactions. Based on that, a conceptual urea-assisted rechargeable ZAB is demonstrated to have significantly decreased charging voltage, higher energy conversion efficiency (74.6 %) compared with the conventional ZAB, as well as high urea elimination rates. Considering the urea-assisted ZAB with high energy conversion efficiency and wastewater treatment versatility as an energy transfer station applied in a high value-added agricultural system, uninterrupted hydrogen production and wastewater treatment of agricultural wastewater can be simultaneously achieved using sustainable energy sources.

Quasi-Classical Trajectory Calculation of Rate Constants Using an Ab Initio Trained Machine Learning Model (aML-MD) with Multifidelity Data.

Machine learning (ML) provides a great opportunity for the construction of models with improved accuracy in classical molecular dynamics (MD). However, the accuracy of a ML trained model is limited by the quality and quantity of the training data. Generating large sets of accurate ab initio training data can require significant computational resources. Furthermore, inconsistent or incompatible data with different accuracies obtained using different methods may lead to biased or unreliable ML models that do not accurately represent the underlying physics. Recently, transfer learning showed its potential for avoiding these problems as well as for improving the accuracy, efficiency, and generalization of ML models using multifidelity data. In this work, ab initio trained ML-based MD (aML-MD) models are developed through transfer learning using DFT and multireference data from multiple sources with varying accuracy within the Deep Potential MD framework. The accuracy of the force field is demonstrated by calculating rate constants for the H + HO2 → H2 + 3O2 reaction using quasi-classical trajectories. We show that the aML-MD model with transfer learning can accurately predict the rate constants while reducing the computational cost by more than five times compared to the use of more expensive quantum chemistry training data sets. Hence, the aML-MD model with transfer learning shows great potential in using multifidelity data to reduce the computational cost involved in generating the training set for these potentials.

Elucidating the electron confinement effect on CeFeW/ZrO2 catalysts to enhance SO2 resistance in the low temperature NH3-SCR reaction

Currently, the inefficiency of the catalysts for NOx removal in the presence of SO2 in NH3-SCR reaction still prevalent. The problem of how to improve the SO2 tolerance at low temperature is still a common direction for researchers to work together. In this work, the CeFeW/ZrO2 catalyst prepared by a two-step hydrothermal method exhibited excellent SO2 resistance and SO2 had basically no impact on the CeFeW/ZrO2 catalyst activity. The superior catalytic performance and SO2 tolerance of CeFeW/ZrO2 catalyst mainly originated from that Ce acted as a functional site to form Ce-O-Fe, which altered the local electronic environment through electron confinement effect, increased the proportion of Fe3+/(Fe2+ + Fe3+) and surface chemisorption oxygen as well as the formation of oxygen vacancies on one hand. On the other hand, Fe sites exhibited excellent SO2 capacity and preferentially reacted with SO2, the metal sulfates Fe2(SO4)3 and FeSO4 restrained the formation and deposition of NH4HSO4 and (NH4)2SO4 on the catalyst surface. Simultaneously, the Ce-O-Fe-SO42− species ensured the electron transfer between Ce and Fe, and the redox properties of the catalyst were remained, thus the L-H mechanism on the CeFeW/ZrO2 catalyst could still be carried out smoothly under the conditions of the presence of SO2. Moreover, DFT calculation confirmed that the adsorption ability of NO, NH3 and O2 was enhanced over CeFeW/ZrO2 catalyst, which resulted in an excellent SO2 tolerance.

Effect of pH on the ozonolysis degradation of p-nitrophenol in aquatic environment and the synergistic effect of hydroxy radical.

Density functional theory (DFT) was employed to elucidate the mechanisms for ozonolysis reaction of p-nitrophenol (PNP) and its anion form aPNP. Thermodynamic data, coupled with Average Local Ionization Energies (ALIE) analysis, reveal that the ortho-positions of the OH/O- groups are the most favorable reaction sites. Moreover, rate constant calculations demonstrate that the O3 attack on the C2-C3 bond is the predominant process in the reaction between neutral PNP and O3. For the aPNP + O3 reaction, the most favorable pathways involve O3 attacking the C1-C2 and C6-C1 bonds. The rate constant for PNP ozonolysis positively correlates with pH, ranging from 5.47 × 108 to 2.86 × 109M-1s-1 in the natural aquatic environment. In addition, the formation of hydroxyl radicals in the ozonation process of PNP and the mechanisms of its synergistic reaction of PNP with ozone were investigated. Furthermore, the ozonation and hydroxylation processes involving the intermediate OH-derivatives were both thermodynamically and kinetic analyzed, which illustrate that OH radicals could promote the elimination of PNP. Finally, the toxic of PNP and the main products for fish, daphnia, green algae and rat were assessed. The findings reveal that certain intermediates possess greater toxicity than the original reactant. Consequently, the potential health risks these compounds pose to organisms warrant serious consideration.

Physiological and molecular mechanisms of ZnO quantum dots mitigating cadmium stress in Salvia miltiorrhiza

This study delved into the physiological and molecular mechanisms underlying the mitigation of cadmium (Cd) stress in the model medicinal plant Salvia miltiorrhiza through the application of ZnO quantum dots (ZnO QDs, 3.84 nm). A pot experiment was conducted, wherein S. miltiorrhiza was subjected to Cd stress for six weeks with foliar application of 100 mg/L ZnO QDs. Physiological analyses demonstrated that compared to Cd stress alone, ZnO QDs improved biomass, reduced Cd accumulation, increased the content of photosynthetic pigments (chlorophyll and carotenoids), and enhanced the levels of essential nutrient elements (Ca, Mn, and Cu) under Cd stress. Furthermore, ZnO QDs significantly lowered Cd-induced reactive oxygen species (ROS) content, including H2O2, O2−, and MDA, while enhancing the activity of antioxidant enzymes (SOD, POD, APX, and GSH-PX). Additionally, ZnO QDs promoted the biosynthesis of primary and secondary metabolites, such as total protein, soluble sugars, terpenoids, and phenols, thereby mitigating Cd stress in S. miltiorrhiza. At the molecular level, ZnO QDs were found to activate the expression of stress signal transduction-related genes, subsequently regulating the expression of downstream target genes associated with metal transport, cell wall synthesis, and secondary metabolite synthesis via transcription factors. This activation mechanism contributed to enhancing Cd tolerance in S. miltiorrhiza. In summary, these findings shed light on the mechanisms underlying the mitigation of Cd stress by ZnO QDs, offering a potential nanomaterial-based strategy for enhancing Cd tolerance in medicinal plants.

Reaction of SO3 with H2SO4 and its implications for aerosol particle formation in the gas phase and at the air–water interface

Abstract. The reactions between SO3 and atmospheric acids are indispensable in improving the formation of aerosol particles. However, relative to those of SO3 with organic acids, the reaction of SO3 with inorganic acids has not received much attention. Here, we explore the atmospheric reaction between SO3 and H2SO4, a typical inorganic acid, in the gas phase and at the air–water interface using quantum chemical (QC) calculations and Born–Oppenheimer molecular dynamics simulations. We also report the effect of H2S2O7, the product of the reaction between SO3 and H2SO4, on new particle formation (NPF) in various environments using the Atmospheric Cluster Dynamics Code (ACDC) kinetic model and QC calculations. The present findings show that the gas-phase reactions of SO3 + H2SO4 without and with water molecules are both low-energy-barrier processes. With the involvement of interfacial water molecules, H2O induced the formation of the S2O72-⋯H3O+ ion pair, HSO4- mediated the formation of the HSO4-⋯H3O+ ion pair, and the deprotonation of H2S2O7 was observed and proceeded on the picosecond timescale. The present findings suggest the potential contribution of the SO3–H2SO4 reaction to NPF and aerosol particle growth, showing that (i) although H2S2O7 is easily hydrolyzed with water to form H2SO4, it can directly participate in H2SO4–NH3-based cluster formation and can present a more obvious enhancement effect on SA–A-based cluster formation, and (ii) the formed interfacial S2O72- can attract candidate species from the gas phase to the water surface and, thus, accelerate particle growth.

Using Io's Sulfur Isotope Cycle to Understand the History of Tidal Heating

AbstractStable isotope fractionation of sulfur offers a window into Io's tidal heating history, which is difficult to constrain because Io's dynamic atmosphere and high resurfacing rates leave it with a young surface. We constructed a numerical model to describe the fluxes in Io's sulfur cycle using literature constraints on rates and isotopic fractionations of relevant processes. Combining our numerical model with measurements of the 34S/32S ratio in Io's atmosphere, we constrain the rates for the processes that move sulfur between reservoirs and model the evolution of sulfur isotopes over time. Gravitational stratification of SO2 in the upper atmosphere, leading to a decrease in 34S/32S with increasing altitude, is the main cause of sulfur isotopic fractionation associated with loss to space. Efficient recycling of the atmospheric escape residue into the interior is required to explain the 34S/32S enrichment magnitude measured in the modern atmosphere. We hypothesize this recycling occurs by SO2 surface frost burial and SO2 reaction with crustal rocks, which founder into the mantle and/or mix with mantle‐derived magmas as they ascend. Therefore, we predict that magmatic SO2 plumes vented from the mantle to the atmosphere will have lower 34S/32S than the ambient atmosphere, yet are still significantly enriched compared to solar‐system average sulfur. Observations of atmospheric variations in 34S/32S with time and/or location could reveal the average mantle melting rate and hence whether the current tidal heating rate is anomalous compared to Io's long‐term average. Our modeling suggests that tides have heated Io for >1.6 Gyr if Io today is representative of past Io.

Synthesis and photocatalytic activity of BiOI particles: An efficient visible-light-driven degradation of organic pollutants in aqueous environments

Bismuth oxyiodide (BiOI) particles were successfully fabricated through solvothermal activation using bismuth (III) nitrate pentahydrate and potassium iodide as precursors. The photocatalytic activities of BiOI were investigated under the influence of synthesis temperature (120–200 °C) with a fixed duration of 12 h. The physical-chemical properties of the samples were systematically investigated using X-ray diffraction, scanning electron microscopy, N2-sorption isotherm techniques, and pH of the point of zero charge (pHpzc). The prepared BiOI exhibited a single phase with a non-uniform 2D morphology with different sizes, an average crystallite size of 30 nm, and a BET surface area of 20.71 m²g−1. The zero-point charge was determined to be 7.7. The photocatalytic performance under simulated solar light irradiation was investigated by examining the effects of dye initial concentration, catalyst dose, and dye pH. Remarkably, BiOI synthesized at 160 °C demonstrated an impressive 85% removal efficiency of 10 ppm MO (methyl orange) at normal pH levels (pH 6.8) within 120 min under visible light irradiation, along with the highest rate constant of 0.01418 min−1. The quenching effects of different scavengers indicate the significant role of reactive O2•– and a minor role of hVB+ and •OHads in the photocatalytic process. These findings underscore the potential of BiOI particles as efficient photocatalysts for environmental applications, particularly in the degradation of organic pollutants in water using solar light irradiation.

Production of oxygenated volatile organic compounds from the ozonolysis of coastal seawater

Abstract. Dry deposition of ozone (O3) to the ocean surface and the ozonolysis of organics in the sea surface microlayer (SSML) are potential sources of volatile organic compounds (VOCs) to the marine atmosphere. We use a gas chromatography system coupled to a Vocus proton-transfer-reaction time-of-flight mass spectrometer to determine the chemical composition and product yield of select VOCs formed from ozonolysis of coastal seawater collected from Scripps Pier in La Jolla, California. Laboratory-derived results are interpreted in the context of direct VOC vertical flux measurements made at Scripps Pier. The dominant products of laboratory ozonolysis experiments and the largest non-sulfur emission fluxes measured in the field correspond to Vocus CxHy+ and CxHyOz+ ions. Gas chromatography (GC) analysis suggests that C5–C11 oxygenated VOCs, primarily aldehydes, are the largest contributors to these ion signals. In the laboratory, using a flow reactor experiment, we determine a VOC yield of 0.43–0.62. In the field at Scripps Pier, we determine a maximum VOC yield of 0.04–0.06. Scaling the field and lab VOC yields for an average O3 deposition flux and an average VOC structure results in an emission source of 10.7 to 167 Tg C yr−1, competitive with the DMS source of approximately 20.3 Tg C yr−1. This study reveals that O3 reactivity to dissolved organic carbon can be a significant carbon source to the marine atmosphere and warrants further investigation into the speciated VOC composition from different seawater samples and the reactivities and secondary organic aerosol (SOA) yields of these molecules in marine-relevant, low NOx conditions.

A new chapter in the never ending story of cycloadditions: The puzzling case of SO2 and acetylene.

A comprehensive study of the different classes of cycloaddition reactions ([3+2], [2+2], and [2+1]) of SO2 to acetylene and ethylene has been performed using density functional theory (DFT) and composite wavefunction methods. The [3+2] cycloaddition reaction, that was previously explored in the context of the cycloaddition of thioformaldehyde S-methylide (TSM) to ethylene and acetylene, proceeds in a concerted way to the formation of stable heterocycles. In this paper, we extend our study to the [2+2] and [2+1] cycloadditions of SO2 to acetylene, which would produce 1,1-oxathiete-2-oxide and thiirene-1,1-dioxide, respectively. One of the main conclusions is that cyclic 1,1-oxathiete-2-oxide can open through a relatively easy breaking of the SO single bond and rearrange toward sulfinyl acetaldehyde (SA). The SA molecule can easily undergo several internal rearrangements, which eventually lead to sulfenic acid and sulfoxide derivatives of ethenone, 1,2,3-dioxathiole, and CO plus sulfinylmethane. The most probable path, however, produces 2-thioxoacetic acid, whose derivatives (or those of the corresponding acetate) are usually obtained by Willgerodt-Kindler-type sulfuration of acetates. This product can in turn decompose, leading to the final products CO2 and H2CS. Comparison of this decomposition path with that of 2-amino-2-thioxoacetic acid shows that the process occurs through different H-transfer processes.

THE INFLUENCE OF QUERCETIN ON THE PRODUCTION OF REACTIVE OXYGEN-NITROGEN FORMS IN THE STRUCTURE OF THE INTERSTITIAL SPACE OF RAT TESTICLES WITH LONG-TERM EFFECT OF TRIPTORELIN

Quercetin is a flavonoid commonly found in fruits, vegetables, and seeds. Flavonoids can help prevent cardiovascular diseases, reduce the risk of degenerative brain processes and cancer. Studies have shown that blocking the synthesis of luteinising hormone can lead to oxidative stress in the liver, heart, and salivary glands of rats. The purpose of this study was to assess alterations in the interstitial space of rat testes, identify sources of nitric oxide production, and measure the intensity of oxidative stress in the testes during long-term experimental central blocking of luteinising hormone synthesis by tryptorelin. The study was conducted on 15 sexually mature male white rats. The animals were divided into two groups. The first group (control) received a subcutaneous injection of 0.9% sodium chloride solution. The second group (experimental) received a subcutaneous injection of tryptorelin at a dose of 0.3 mg/kg of active ingredient for 365 days, with simultaneous addition of quercetin to the diet, which was administered orally through a gastric tube three times a day. Total nitric oxide production was assessed by measuring the activity of total NO synthase (gNOS). The activity of gNOS was determined by the increase in nitrite (NO2-) after incubation in Tris-buffered saline. The nitrite concentration was determined using the Gris-Ilosvay reagent at a wavelength of 540 nm. The activity of the inducible (iNOS) and constitutive (cNOS) isoforms was also determined using a selective iNOS inhibitor, aminoguanidine hydrochloride. The production of superoxide anion radical (O2--) was measured by the increase in the formation of diformazan resulting from the reaction of O2-- with nitroblue tetrazolium after incubation in a buffered solution containing sodium hydroxide. The administration of quercetin mitigates the adverse effects of tryptorelin on the structural and functional components of the connective tissue in the rat testes. This effect is observed on day 365 and is characterised by fibrosis and impaired nitric oxide production by constitutive isoforms of NO synthase.

Multifunctional Gold Nanozyme-Engineered Amphotericin B for Enhanced Antifungal Infection Therapy.

Chronic wounds of significant severity and acute injuries are highly vulnerable to fungal infections, drastically impeding the expected wound healing trajectory. The clinical use of antifungal therapeutic drug is hampered by poor solubility, high toxicity and adverse reactions, thereby necessitating the urgent development of novel antifungal therapy strategy. Herein, this study proposes a new strategy to enhance the bioactivity of small-molecule antifungal drugs based on multifunctional metal nanozyme engineering, using amphotericin B (AmB) as an example. AmB-decorated gold nanoparticles (AmB@AuNPs) are synthesized by a facile one-pot reaction strategy, and the AmB@AuNPs exhibit superior peroxidase (POD)-like enzyme activity, with maximal reaction rates (Vmax) 3.4 times higher than that of AuNPs for the catalytic reaction of H2O2. Importantly, the enzyme-like activity of AuNPs significantly enhanced the antifungal properties of AmB, and the minimum inhibitory concentrations of AmB@AuNPs against Candida albicans (C. albicans) and Saccharomyces cerevisiae (S. cerevisiae) W303 are reduced by 1.6-fold and 50-fold, respectively, as compared with AmB alone. Concurrent in vivo studies conducted on fungal-infected wounds in mice underscored the fundamentally superior antifungal ability and biosafety of AmB@AuNPs. The proposed strategy of engineering antifungal drugs with nanozymes has great potential for enhanced therapy of fungal infections and related diseases.

Regioselectivity and confinement effects for catalytic conversion of carbohydrates within zeolite H-BEA

Zeolites have established the importance during biomass conversion, and H-form zeolites, although extensively used, produce hydroxymethylfurfural (HMF) with low yields. Herein, dispersion-corrected density functional calculations are employed with aim to comprehensively understand glucose conversion to HMF within zeolite H-BEA and unravel the role of confinement effects. The low HMF yields originate from regioselectivity: The preferentially activated O3 and O6 sites are significantly driven to humin precursors, while less reactive O1 and O2 sites lead favorably to HMF. Glucose-to-fructose isomerization occurs only at O5 site, while seems unnecessary for HMF production. Owing to the peculiar confinement effects, HMF precursors are prone to emerge within H-BEA, both upon dehydration and during catalysis, while may turn to be acyclic within aqueous solutions. Direct conversion to levulinic acid without HMF as intermediate thus becomes difficult within acidic zeolites. Results facilitate catalyst design for biomass conversion, and further understanding of regioselective catalysis and confinement effects.

Single-holed cobalt - nitrogen - carbon hollow structure with oxidase-mimicking activity for the chemiluminescence determination of β - galactosidase activity.

A single-holed cobalt - nitrogen - carbon (Co - N - C) hollow structure nanozyme has been fabricated by in situ growth of zeolitic imidazolate framework (ZIF - 67) on the polystyrene (PS) sphere and following treatment by high-temperature carbonization. The Co - N - C nanostructure mimics the activity of oxidase and can activate O2 into reactive oxygen species (ROS), giving a remarkable enhancement on the chemiluminescence (CL) signal of luminol - O2 reaction. The Co - N - C oxidase mimic has further been exploited in the biosensing field by the determination of the activity of β - galactosidase (β - gal). The CL method for β - gal activity has a linear range of 0.5mU·L-1 to 5.0 U·L-1, a detection limit of 0.167mU·L-1, and the precision of 3.1% (5.0 U·L-1, n = 11). This method has been employed to assess inhibitor screening of β - gal and determine activity of β - gal in spiked human serum samples.

Experimental and kinetic study of ammonia oxidation and NOx emissions at elevated pressures

To investigate the effects of pressure and equivalence ratio on ammonia oxidation and the emission of NOx, experiments were conducted in a flow reactor at atmospheric pressure and 5.0 MPa between 600 and 1250 K, with equivalence ratios ranging from 0.125 to 1.0. In addition, a kinetic model applicable to ammonia oxidation under high-pressure conditions was developed and validated against the performance of other recently published kinetic models with reference to several parameters associated with the ammonia oxidation and the emission of NOx under high-pressure conditions. The developed model was also validated against previously published experimental data collected under high-pressure conditions, and it can accurately capture the data obtained. The study found that the increase in pressure and oxygen content significantly enhanced the reactivity of NH3 and consequently resulted in increased NO and N2O concentrations at low temperatures. Based on a kinetic analysis using the developed model, the HO2 content was identified as the key factor influencing the difference in reactivity between atmospheric and high pressure. Sensitivity analysis revealed that H + O2 (+M) = HO2 (+M) inhibits NH3 consumption at atmospheric pressures but has a promoting effect at high pressures, because at high pressures the reaction generates a significant amount of HO2 radicals at low temperatures, increasing the reaction activity and reducing the onset temperature of ammonia oxidation. The H2NO system becomes even more critical under higher pressure, as more NH2 and O2 are converted to H2NO and NO. H2NO, NO, and N2O act as chain carriers in the reaction sequence, converting NH2 and O2 to OH and NO and accelerating the process of ammonia oxidation. At the same time, higher pressure enhances the NOx formation pathway due to the large amount of HO2 generated. However, as temperatures increase, O and OH radicals increase and DeNOx pathways dominate, resulting in lower NO and N2O contents. In the context of the equivalence ratios, the increase in the O2 content enhances the generation of HO2, leading to a greater tendency for NH2 to be converted in the NH2 + HO2 = HNO + H2O and NH2 + HO2 = H2NO + OH reaction pathways to HNO and H2NO, respectively. The HNO and H2NO produced are subsequently converted to NOx.

Chlorobenzene Oxidation over Phosphotungstic-Acid-Coated Cerium Oxide: Synergistic Effect of Phosphotungstic and Cerium Oxide and Inhibition Mechanism of Sulfur Dioxide

Ce–based catalysts exhibit a poor stability and activity in chlorinated volatile organic compound (Cl–VOC) oxidation due to their rapid Cl poisoning. Herein, phosphotungstic acid (HPW) was coated on CeO2 to improve its activity and stability for chlorobenzene (CB) oxidation. The HPW coating not only promoted CB adsorption onto CeO2, but also provided Brønsted acid sites to CeO2 for Cl species removal as HCl, thus avoiding Cl poisoning. Hence, a synergistic effect of CeO2 and HPW on HPW/CeO2 was observed, resulting in superior CB oxidation activity and stability. Additionally, to improve the sulfur resistance of the catalyst, the inhibition mechanism of SO2 on CB oxidation by HPW/CeO2 was explored. HPW/CeO2 was prone to sulfation due to the formation of Ce2(SO4)3 from the reaction of SO2 and CeO2. Thus, the oxidation ability of HPW/CeO2; the amount of adsorption sites for CB adsorption; and the amounts of Ce4+ bonded with O2−, lattice oxygen species, and adsorbed oxygen species were decreased by SO2. Meanwhile, SO2 competed with CB for the adsorption sites on HPW/CeO2. Therefore, CB oxidation by HPW/CeO2 was remarkably restrained by SO2. The present work promotes further work on Cl–VOC removal by Ce-based catalysts for anti-SO2 poisoning modification in the future.

Role of turbulence in ozone chemistry: Segregation effect implicated from multiscale modeling over Hong Kong

By influencing the mixing of reactive species in the atmosphere, turbulence affects the rates at which chemical species react, specifically in the planetary boundary layer. To analyze the turbulent segregation effect on the atmospheric ozone photochemistry, coupled meso-to micro-scale simulations are performed over Hong Kong, a polluted megacity. The comparison of the ozone production rates between the mesoscale model and the large-eddy simulations (LES) indicates that the resolved turbulent processes inhibit the mixing of the reactants, and thereby slow down the reaction rate between NO and O3, resulting in a smaller net O3 production when represented by a LES simulation. The calculated segregation intensities show clear correlations with the emission distribution, revealing that the segregation effect is significant in urban areas with inhomogeneous pollution sources, including traffic emissions. The evolution of the eddy structure plays a significant role in the diurnal variation of the segregation intensity. Applying the obtained segregation intensities to the mesoscale output, the NO–O3 reaction rate decreases with results closer to those provided by the LES model. This confirms the importance of the segregation effect on fast chemical reactions and provides insights into the parameterization of the segregation effect in mesoscale models, which do not resolve turbulent eddies.

Improving the Catalytic Performance of BaMn0.7Cu0.3O3 Perovskite for CO Oxidation in Simulated Cars Exhaust Conditions by Partial Substitution of Ba.

The sol-gel method, adapted to aqueous media, was used for the synthesis of BaMn0.7Cu0.3O3 (BMC) and Ba0.9A0.1Mn0.7Cu0.3O3 (BMC-A, A = Ce, La or Mg) perovskite-type mixed oxides. These samples were fully characterized by ICP-OES, XRD, XPS, H2-TPR, BET, and O2-TPD and, subsequently, they were evaluated as catalysts for CO oxidation under different conditions simulating that found in cars exhaust. The characterization results show that after the partial replacement of Ba by A metal in BMC perovskite: (i) a fraction of the polytype structure was converted to the hexagonal BaMnO3 perovskite structure, (ii) A metal used as dopant was incorporated into the lattice of the perovskite, (iii) oxygen vacancies existed on the surface of samples, and iv) Mn(IV) and Mn(III) coexisted on the surface and in the bulk, with Mn(IV) being the main oxidation state on the surface. In the three reactant atmospheres used, all samples catalysed the CO to CO2 oxidation reaction, showing better performances after the addition of A metal and for reactant mixtures with low CO/O2 ratios. BMC-Ce was the most active catalyst because it combined the highest reducibility and oxygen mobility, the presence of copper and of oxygen vacancies on the surface, the contribution of the Ce(IV)/Ce(III) redox pair, and a high proportion of surface and bulk Mn(IV). At 200 °C and in the 0.1% CO + 10% O2 reactant gas mixture, the CO conversion using BMC-Ce was very similar to the achieved with a 1% Pt/Al2O3 (Pt-Al) reference catalyst.