O2 Reaction Research Articles

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.

Heterogeneous photochemical uptake of SO2 on typical brown carbon species: A significant sulfate source

The heterogeneous reactions of SO2 on organic aerosols (OA) have been proposed as a significant source of sulfates. The photochemical conversion of SO2 to sulfates on the surface of light-absorbing OA, i.e., brown carbon (BrC), remained slight understanding. Herein, the photochemical uptake of SO2 on typical BrC species, including aromatic carbonyl compounds (ACs), polycyclic aromatic hydrocarbons (PAHs) and phenols (PHs), was systematically investigated by a flow tube reactor. Light can significantly promote the uptake of SO2 on all BrC species used here, especially for ACs. The initial and steady-state uptake coefficients (γi and γss) of SO2 exhibited positive relationships with the light intensity, whereas they negatively correlated with the initial SO2 concentration. Significant sulfate formation was clearly observed with in situ attenuated total internal reflection infrared (ATR-IR) spectrometer, and H2O and O2 had obvious enhancement effects on the sulfate production. Photoinduced •OH, which primarily originated from •O2− that was generated through an electron transfer process on BrC under irradiation, was determined to be a key driver for the oxidation of SO2 to sulfates. Finally, SO2 lifetime and sulfate formation rate were evaluated on the basis of experimental results, highlighting potential contributions of BrC photochemistry to atmospheric SO2 loss and sulfate sources.

Influence of Wind Flows on Surface O3 Variation over a Coastal Province in Southeast China

Surface ozone (O3) is influenced not only by anthropogenic emissions but also by meteorological factors, with wind direction being one of the most overlooked factors. Here, we combine the observational data of both O3 and wind flow to compare the variation in surface O3 with wind direction between coastal and inland regions of Fujian, a province in the southeast coast of China with complicated topography. We further conduct a numerical simulation using a global chemical transport model, GEOS-Chem, to interpret the observational results, explore the linkages between these O3 variations and wind flows, and identify the dominant processes for the occurrence of high O3 that varies with wind flows. The results from the observations over 2015–2021 suggest that, over coastal regions, surface O3 concentrations show a strong dependence on wind flow changes. On average, during the daytime, when southeasterly winds prevail, the mean of O3 concentrations reaches 83.5 μg/m3, which is 5.0 μg/m3 higher than its baseline values (the mean O3 concentrations), while the northwesterly winds tend to reduce surface O3 by 6.4 μg/m3. The positive O3 anomalies with southeasterly wind are higher in the autumn and summer than in the spring and winter. During the nighttime, the onshore northeasterly winds are associated with enhanced O3 levels, likely due to the airmass containing less NO2, alleviating the titration effects. Over inland regions, however, surface O3 variations are less sensitive to wind flow changes. The GEOS-Chem simulations show that the prevailing southeasterly and southwesterly winds lead to the positive anomaly of chemical reactions of O3 over coastal regions, suggesting enhanced photochemical production rates. Furthermore, southeasterly winds also aid in transporting more O3 from the outer regions into the coastal regions of Fujian, which jointly results in elevated surface O3 when southeasterly winds dominates. When affected by wind flows in different directions, the chemical reaction and transport in the inland regions do not exhibit significant differences regarding their impact on O3. This could be one of the reasons for the difference in O3 distribution between coastal and inland regions. This study could help to deepen our understanding of O3 pollution and aid in providing an effective warning of high-O3 episodes.

Study on the Vertical Distribution and Transport of Aerosols in the Joint Observation of Satellite and Ground-Based LiDAR

The mechanism of aerosol pollution transport remains highly elusive owing to the myriad of influential factors. In this study, ground station data, satellite data, ground-based LiDAR remote sensing data, sounding data, ERA5 reanalysis and a backward trajectory model were combined to investigate the formation process and optical properties of winter aerosol pollution in Beijing and surrounding areas. The analysis of ground station data shows that compared to 2019 and 2021, the pandemic lockdown policy resulted in a decrease in the total number of pollution days and a decrease in the average concentration of particulate matter in the Beijing area in 2020. The terrain characteristics of the Beijing-Tianjin-Hebei (BTH) made it prone to northeast and southwest winds. The highest incidence of aerosol pollution in Beijing occurs in February and March during the spring and winter seasons. Analysis of a typical heavy aerosol pollution process in the Beijing area from 28 February to 5 March 2019 shows that dust and fine particulate matter contributed to the primary pollution; surface air temperature inversion and an average wind speed of less than 3 m/s were conducive to the continuous accumulation of pollutants, which was accompanied by the oxidation reaction of NO2 and O3, forming photochemical pollution. The heavy aerosol pollution was transmitted and diffused towards the southeast, gradually eliminating the pollution. Our results provide relevant research support for the prevention and control of aerosol pollution.

Distinct Site Motifs Activate O2 and H2 on Supported Au Nanoparticles in Liquid Water.

Au nanoparticles catalyze the activation and conversion of small molecules with rates and kinetic barriers that depend on the dimensions of the nanoparticle, composition of the support, and presence of catalytically culpable water molecules that solvate these interfaces. Here, molecular interpretations of steady-state rate measurements, kinetic isotope effects, and structural characterizations reveal how the interface of Au nanoparticles, liquid water, and metal oxide supports mediate the kinetically relevant activation of H2 and sequential reduction of O2-derived intermediates during the formation of H2O2 and H2O. Rates of H2 consumption are 10-100 fold greater on Au nanoparticles supported on metal oxides (e.g., titania) compared to more inert and hydrophobic materials (carbon, boron nitride). Similarly, Au nanoparticles on reducible and Lewis acidic supports (e.g., lanthana) bind dioxygen intermediates more strongly and present lower barriers (<22 kJ mol-1) for O-O bond dissociation than inert interfaces formed with silica (>70 kJ mol-1). Selectivities for H2O2 formation increase significantly as the diameters of the Au nanoparticles increase because differences in nanoparticle size change the relative fractions of exposed sites that exist at Au-support interfaces. In contrast, site-normalized rates and barriers for H2 activation depend weakly on the size of Au nanoparticles and the associated differences in active site motifs. These findings suggest that H2O aids the activation of H2 at sites present across all surface Au atoms when nanoparticles are solvated by water. However, molecular O2 preferentially binds and dissociates at Au-support interfaces, leading to greater structure sensitivity for barriers of O-O dissociation across different support identities and sizes of Au nanoparticles. These insights differ from prior knowledge from studies of gas-phase reactions of H2 and O2 upon Au nanoparticle catalysts within dilute vapor pressures of water (10-4 to 0.1 kPa H2O), in which catalysis occurs at the perimeter of the Au-support interface. In contrast, contacting Au catalysts with liquid water (55.5 M H2O) expands catalysis to all surface Au atoms and enables appreciable H2O2 formation.