Oxidation Of SO2 Research Articles

Enhanced visible-light-driven photocatalytic degradation via in-situ AIS/ZIS high-low junctions

The I-III-VI QDs Ag-In-S (AIS) exhibits excellent properties in photocatalysis because of the adjustable band gap, wide light absorption range, and multiple active sites. Introducing homologous or heterogeneous ions not only derives the composition into quaternary/ quinary quantum dots but also generates new sulfide QDs to form composites, which is an effective strategy to promote photoactivity. In this work, we in-situ synthesized the AIS/ZIS (AgIn5S8/Zn4In2S7) composite photocatalyst by introducing Zn2+ and changing the reaction temperature. We found that the composite photocatalyst could efficiently photodegrade larger concentrations of RhB than that of the previous reports. The superior photocatalytic activity was due to the formation of the type I high-low junction, which could effectively separate carriers. The photoelectrons on the CB of AIS reacted with dissolved oxygen to produce strongly oxidative O2–, which degraded RhB into intermediates and eventually into CO2 and H2O. This work not only reports an excellent photocatalyst but also offers new ideas on the design and manufacture of highly efficient high-low junction photocatalysts.

Influence of Germicidal UV (222 nm) Lamps on Ozone, Ultrafine Particles, and Volatile Organic Compounds in Indoor Office Spaces.

Germicidal ultraviolet lamps with a peak emission at 222 nm (GUV222) are gaining prominence as a safe and effective solution to reduce disease transmission in occupied indoor environments. While previous studies have reported O3 production from GUV222, less is known about their impact on other indoor constituents affecting indoor air quality, especially in real occupied environments. In this study, the effects of GUV222 on the levels of ozone (O3), ultrafine particles (UFPs), and volatile organic compounds (VOCs) were investigated across multiple offices with varying occupancies. O3 from the GUV222 operation was observed to increase linearly (∼300 μg h-1 m-1) with a UV light path length from 0 to 3 m beyond which it stabilized. When applied in offices, the O3 production models based on continuous measurements revealed O3 production rates of 1040 ± 87 μg h-1. The resulting increases in steady-state concentrations of 5-21 μg m-3 were highly dependent on the number of office occupants. UFP production occurred during both unoccupied and occupied conditions but predominantly in newly renovated offices. Time-resolved measurements with a proton-transfer-reaction time-of-flight mass spectrometer (PTR-TOF-MS) revealed clear alterations in office VOC concentrations. Unsurprisingly, O3 oxidation chemistry was observed, including monoterpene deprivation and 4-oxopentanal (4-OPA) production. But additionally, significant alterations from unidentified mechanisms occurred, causing increased levels of various PTR-TOF-MS signals including C2H5O2+ and C4H9+ hypothesized to arise from photoinduced formation or off-gassing during the GUV222 lamp operation.

On‐Purpose Production of Light Olefins Through Oxidative Dehydrogenation: An Overview of Recent Developments

AbstractProducts made from light olefins play an important role in our daily lives. Traditional light olefins production based on steam cracking and fluid catalytic cracking suffer from high energy consumption and CO2 emissions. Thereby, the continually increasing demand for light olefins needs to be met through more environmentally sustainable procedures. On‐purpose production routes are preferred choice among petrochemicals manufacturers, being energy efficient and having lower carbon footprint. Among them, oxidative dehydrogenation (ODH) of light paraffins is a thermodynamically favourable exothermic process as compared to non‐oxidative routes. They can be operated at lower temperatures and have propensity of low coke deposition on catalyst, thereby resisting rapid catalyst deactivation. Herein, we have analysed various catalytic systems utilised in the oxidative dehydrogenation process. We have reviewed role of support, chemical composition of catalyst, presence of dopant, oxidation state of active metal, controlled surface modification by oxidative and reductive pretreatments, and reaction factors for each system. The performance of various catalytic systems for ODH of ethane, propane and butane in the presence of O2, CO2, N2O and special oxidants have been reviewed. A short critical overview on emerging on‐purpose routes for the production of renewable 1,3 butadiene has also been discussed.

Sol-gel synthesis, structure and adsorption properties of LiMgxMn(2-x)O4 (0 ≤ x ≤ 0.7) Oxides

Lithium manganese оxides with a spinel structure LiMgxMn(2–x)O4, doped with Mg2+ ions in the range 0 ≤ x ≤ 0.7, were obtained by sol-gel synthesis. Phase composition and morphology of obtained оxides were studied by using X-ray phase analysis and scanning electron microscopy. It is shown, that in the studied range 0 ≤ x ≤ 0.7 Mg-doped lithium manganese оxides saved the structure of the original cubic spinel LiMn2O4, while an increase in parameter a was observed from 8.175 to 8.309 Å and average crystallite size practically unchanged (30–36 nm). Samples of the initial LiMn2O4 and Mg-doped spinels were represented by prismatic particles of submicron (0.1–0.2 µm) and micron (1.0–3.0 µm) sizes, respectively. The effect of the adsorbent dose (0.05–0.3 g/l) and pH (3.0–13.0) of the solution on the adsorption efficiency was studied. The adsorption isotherms of the LiMg0.3Mn1.7O4 samples were described by the Langmuir monomolecular adsorption equation. An increase in the temperature of the model solution from 25 to 45°C was accompanied by an increase in the maximum adsorption of the LiMg0.3Mn1.7O4 samples from 10.50 to 10.98 mmol/g, which indicates the endothermic nature of the adsorption process. The kinetics of adsorption was well described by a pseudo-second order equation, which indicates the occurrence of chemical interaction during the adsorption process.

The Feasibility of Using Electrostatic Interactions for Immobilizing Ru-bda Catalysts in Covalent Organic Framework: A Proof-of-concept.

Heterogenetization of molecular catalysts effectively resolves the separation issues of homogeneous catalysts and expands their application scenarios. In recent years, more and more studies have been using non-covalent interactions to achieve the heterogenization of molecular catalysts. Herein, electrostatic attraction was used to immobilize molecular catalysts, Ru-bda small molecular catalysts in COF materials, where the charged Ru-bda catalysts were immobilized in the oppositely charged COF with a high [Ru] loading content of ~0.2 mmol [Ru] g-1 COF. The leakage experiment verified that the immobilization of Ru-bda catalysts in COF by electrostatic interactions is stable in 0.1 M HClO4 and less than 5% of molecular Ru-bda catalysts were leached into the solution in 2 hours. The chemical water oxidation experiment was conducted as a model catalysis reaction to verify the feasibility of using electrostatic interactions for immobilizing Ru-bda catalysts in COFs. The prepared Ru(bda)@COFs demonstrate a high catalytic activity of 268 μmol L-1 s-1 O2 for chemical water oxidation, illustrating the electrostatic attractions between COF and small molecules that can be used to immobilize homogeneous catalysts in heterogeneous materials. However, the robustness of COF material itself under catalytic conditions should be considered in practical applications.

Stark seasonal contrast of fine aerosol levels, composition, formation mechanism, and characteristics in a polluted megacity.

In this study, we investigated the temporal variation of organic and inorganic aerosol with its optical properties in Mumbai (India), an urban coastal region. Mean PM2.5concentrations during the sampling period were 175μg/m3 (winter) and 90μg/m3 (summer). During winter, the average concentrations of organic (OC), elemental (EC), and water-soluble organic carbon (WSOC) were three times higher than in summer. Secondary organic carbon (SOC) contribution in OC was higher in summer (78%) than in winter (53%), and strong solar radiation in summer likely caused this outcome. Aerosols were slightly acidic in both seasons, with an average pH of 5.7 (winter) and 6.0 (summer). A correlation was observed between SOC and the acidity of particles in summer (R2 = 0.6), indicating some amount of acid-catalysed SOC formation. In both seasons, the sulphate oxidation ratio (SOR) was higher than the nitrate oxidation ratio (NOR), which may reflect a preference for SO2 oxidation over NO2 or the difference in partitioning ammonium nitrate into ammonium sulphate under high RH. The dominant mechanism of SOC formation (gas vs aqueous phase oxidation) also showed seasonal variation. In winter, a relatively steep reduced major axis (RMA) slope of O3/CO suggests gas phase oxidation was the dominant mechanism of SOC production. Winter has more BrC fraction than summer, indicating higher absorbing aerosols, though the efficiency of absorbing the light was higher in summer. To assess the radiative forcing of PM2.5 on a local scale, an effective carbon ratio (ECR) was computed. The findings pointed to a local radiative heating impact caused by PM2.5. The spectral slope ratio and MAE at 250 to 300nm ratio (E2/E3) revealed a higher abundance of high molecular weight species in WSOC during summer than in winter.

Weak magnetic field for enhanced degradation of sulfamethoxazole by the CoFe2O4/PAA system: Insights into performance and mechanism

In this work, a novel approach coupling a heterogeneous weak magnetic field (WMF) with the CoFe2O4/peroxyacetic acid (PAA) system was employed to enhance the degradation of sulfamethoxazole (SMX). Under the optimized conditions of 50 mT WMF, 0.1 g/L CoFe2O4, 0.2 mM PAA, and initial pH 6.0, a complete degradation of 10 μM SMX was achieved in 25 min, exhibiting a high synergistic coefficient of 1.61. This result indicates a significant synergistic effect among WMF, CoFe2O4, and PAA in effectively degrading SMX. The introduction of WMF did not alter the pH application range of the CoFe2O4/PAA system. Furthermore, the degradation efficiency of SMX by the CoFe2O4/PAA/WMF system was significantly reduced in the presence of humic acid (HA) and bicarbonate ions (HCO3−), while chloride ions (Cl−) exhibited a minor inhibitory effect. Quenching experiments and electron paramagnetic resonance (EPR) analysis reveal that WMF did not alter the types of reactive oxygen species (ROS) generated in the CoFe2O4/PAA system. The degradation of SMX in the CoFe2O4/PAA/WMF system involved both radical (CH3C(O)O∙ and CH3C(O)OO∙) and non-radical (1O2) oxidation pathways, driven by the redox cycling between ≡Co2+/≡Co3+ and PAA, as well as the rapid adsorption and transformation of oxygen (O2) at oxygen vacancies (OV), respectively. The presence of WMF enhanced the utilization of PAA by CoFe2O4 by improving the convection and mass transport in the solution, facilitating the formation of superoxide anion (O2∙−) and supplemented lattice oxygen (O2−) through the directional migration of paramagnetic O2 towards the CoFe2O4 surface, thus significantly promoting ROS formation. Additionally, the degradation pathways of SMX in the CoFe2O4/PAA/WMF system were proposed based on density functional theory (DFT) calculations and the detected transformation products (TPs). The toxicity of SMX was effectively reduced, as verified by predictions from the Ecological Structure-Activity Relationship Model (ECOSAR) procedure. The excellent catalytic performance, reusability, and effective degradation of various organic pollutants demonstrated by the CoFe2O4/PAA/WMF system suggest its potential as a promising strategy for water treatment.

Antibacterial mechanism of atmospheric cold plasma against Pseudomonas fluorescens and Pseudomonas putida and its preservation application on in-packaged red shrimp paste

This study aimed to investigate the antibacterial mechanism of atmospheric cold plasma (ACP) against Pseudomonas fluorescens and Pseudomonas putida and its preservation effect on red shrimp paste. A reactive species (RS) assay showed that O3, H2O2, and total nitric oxide were generated after ACP treatment, which possessed great potential for antibacterial and food preservation. In vitro antibacterial results showed that excess RS inhibited bacterial activity through cell membrane damage. Molecular docking predictions and enzyme activity assays indicated that ACP-induced RS might deactivate dehydrogenases (such as malic dehydrogenase) by oxidatively modifying the active sites. Fluorescence quantification experiments validated the damage of RS to dsDNA. Further preservation tests on shrimp paste demonstrated that ACP treatment significantly delayed the increase in total viable count, Pseudomonas count, and total volatile basic‑nitrogen during refrigeration. This study deepened the understanding of the antibacterial mechanism of ACP and highlighted its potential application as a new preservation method.

Surface Optimization of Noble-Metal-Free Conductive [Mn1/4Co1/2Ni1/4]O2 Nanosheets for Boosting Their Efficacy as Hybridization Matrices.

Conductive 2D nanosheets have evoked tremendous scientific efforts because of their high efficiency as hybridization matrices for improving diverse functionalities of nanostructured materials. To address the problems posed by previously reported conductive nanosheets like poorly-interacting graphene and cost-ineffective RuO2 nanosheets, economically feasible noble-metal-free conductive [MnxCo1-2xNix]O2 oxide nanosheets are synthesized with outstanding interfacial interaction capability. The surface-optimized [Mn1/4Co1/2Ni1/4]O2 nanosheets outperformed RuO2/graphene nanosheets as hybridization matrices in exploring high-performance visible-light-active (λ>420nm) photocatalysts. The most efficient g-C3N4-[Mn1/4Co1/2Ni1/4]O2 nanohybrid exhibited unusually high photocatalytic activity (NH4 + formation rate: 1.2mmol g-1 h-1), i.e., one of the highest N2 reduction efficiencies. The outstanding hybridization effect of the defective [Mn1/4Co1/2Ni1/4]O2 nanosheets is attributed to the optimization of surface bonding character and electronic structure, allowing for improved interfacial coordination bonding with g-C3N4 at the defect sites. Results from spectroscopic measurements and theoretical calculations reveal that hybridization helps optimize the bandgap energy, and improves charge separation, N2 adsorptivity, and surface reactivity. The universality of the [Mn1/4Co1/2Ni1/4]O2 nanosheet as versatile hybridization matrices is corroborated by the improvement in the electrocatalytic activity of hybridized Co-Fe-LDH as well as the photocatalytic hydrogen production ability of hybridized CdS.

Sulfur-resistant mechanism of MnOx@CeO2@MgO core-shell catalyst in simultaneous removal of NOx and chlorobenzene

Herein, Mn-Ce based catalysts with different structures were rationally designed to explore their sulfur-resistant mechanism for simultaneous removal of NOx and chlorobenzene (CB) from waste incineration at low temperature. In the presence of SO2, MnOx@CeO2@MgO exhibits the highest sulfur resistance among prepared catalysts. Both NOx and CB conversion over MnOx@CeO2@MgO can reach up to 80% at 300 °C. However, the significant deactivation is observed for MnCeMgOx within all temperature ranges. For the selectivity of products, MnOx@CeO2@MgO displays the excellent N2 selectivity (93%) and good CO2 selectivity (80%) at 300 °C. Compared with NO reduction, SO2 has a greater impact on CB destruction due to the consumption of reactive oxygen species during SO2 oxidation. The reduction of active oxygen is proposed to be the reason for the significant inhibition of CB oxidation. The addition of MgO shell increases the proportion of lattice oxygen, which is beneficial to improving the sulfur resistance of MnOx@CeO2@MgO catalyst. In addition, SO2 can react with MgO preferentially to protect the active sites and improve the sulfur resistance. This work indicates that MnOx@CeO2@MgO core-shell catalyst with good sulfur tolerance and stability is expected to be applied in the potential application.

Robust palladium oxide nano-cluster catalysts using atomic ions and strong interactions for high-performance methane oxidation

Optimizing metal catalyst structures to achieve desired states is vital for efficient surface reactions, yet remains challenging due to the lack of well-defined precursor materials and weak metal-support interaction. Palladium-based catalysts, when not properly tailored for complete methane oxidation exhibit insufficient performance. Herein, we fabricate Pd oxide nano-clusters supported on SSZ-13 using atomic ions with strong metal-support interaction (SMSI). Steam treatment of Pd/SSZ-13 transforms Pd particles into ions and induces SMSI. Subsequently, CO reduction and O2 oxidation yield mildly sintered Pd oxide nano-clusters firmly anchored on extra-framework Alpenta sites of SSZ-13, facilitating superior activity. The robustness from SMSI prevents irreversible deactivation, and water-resistance by complete dehydration suppresses reversible degradation in wet conditions. This catalyst exhibits high performance in bench-scale reactions using monolith catalysts, ensuring applicability for industrial methane abatement. The results demonstrate that sequential treatment to Pd/SSZ-13 offers a promising approach for tailoring metal structures to enable high-performance methane oxidation.

Assessing the effectiveness of SO2, NOx, and NH3 emission reductions in mitigating winter PM2.5 in Taiwan using CMAQ

Abstract. Taiwan experiences higher air pollution in winter when fine particulate matter (PM2.5) levels frequently surpass national standards. This study employs the Community Multiscale Air Quality model to assess the effectiveness of reducing SO2, NOx, and NH3 emissions on PM2.5 secondary inorganic species (i.e., SO42-, NO3-, and NH4+). For sulfate, ∼ 43.7 % is derived from the chemical reactions of local SO2 emission, emphasizing the substantial contribution of regionally transported sulfate. In contrast, nitrate and ammonium are predominantly influenced by local NOx and NH3 emissions. Reducing SO2 emissions decreases sulfate levels, which in turn leads to more NH3 remaining in the gas phase, resulting in lower ammonium concentrations. Similarly, reducing NOx emissions lowers HNO3 formation, impacting nitrate and ammonium concentrations by decreasing the available HNO3 and leaving more NH3 in the gas phase. A significant finding is that reducing NH3 emissions decreases not only ammonium and nitrate but also sulfate by altering cloud droplet pH and SO2 oxidation processes. While the impact of SO2 reduction on PM2.5 is less than that of NOx and NH3, it emphasizes the complexity of regional sensitivities. Most of western Taiwan is NOx-sensitive, so reducing NOx emissions has a more substantial impact on lowering PM2.5 levels. However, given the higher mass emissions of NOx than NH3 in Taiwan, NH3 has a more significant consequence in mitigating PM2.5 per unit mass emission reduction (i.e., 2.43 × 10−5 and 0.85 × 10−5 µg m−3 (t yr−1)−1​​​​​​​ for NH3 and NOx, respectively, under current emission reduction). The cost-effectiveness analysis suggests that NH3 reduction outperforms SO2 and NOx reduction (i.e., USD 0.06 billion yr−1 µg−1 m3, USD 0.1 billion yr−1 µg−1 m3, and USD 1 billion yr−1 µg−1 m3 for NH3, SO2, and NOx, respectively, under the current emission reduction). Nevertheless, the costs of emission reduction vary due to differences in methodology and regional emission sources. Overall, this study considers both the efficiency and costs, highlighting NH3 emissions reduction as a promising strategy for PM2.5 mitigation in the studied environment in Taiwan.

Spontaneous Molecular Bromine Production in Sea-Salt Aerosols.

Bromine chemistry is responsible for the catalytic ozone destruction in the atmosphere. The heterogeneous reactions of sea-salt aerosols are the main abiotic sources of reactive bromine in the atmosphere. Here, we present a novel mechanism for the activation of bromide ions (Br-) by O2 and H2O in the absence of additional oxidants. The laboratory and theoretical calculation results demonstrated that under dark conditions, Br-, O2 and H3O+ could spontaneously generate Br and HO2 radicals through a proton-electron transfer process at the air-water interface and in the liquid phase. Our results also showed that light and acidity could significantly promote the activation of Br- and the production of Br2. The estimated gaseous Br2 production rate was up to 1.55×1010 molecules cm-2 ⋅ s-1 under light and acidic conditions; these results showed a significant contribution to the atmospheric reactive bromine budget. The reactive oxygen species (ROS) generated during Br- activation could promote the multiphase oxidation of SO2 to produce sulfuric acid, while the increase in acidity had a positive feedback effect on Br- activation. Our findings highlight the crucial role of the proton-electron transfer process in Br2 production; here, H3O+ facilitates the activation of Br- by O2, serves as a significant source of atmospheric reactive bromine and exerts a profound impact on the atmospheric oxidation capacity.

Lifetime of nitric oxide produced by surface dielectric barrier discharge in controlled atmospheres: Role of O2 content

Nitric oxide (NO) is an invaluable multifunctional chemical in agri-food applications; for example, it plays a role in plant growth, development, and stress tolerance. One of the interesting implications of NO is the suppression of fruit ripening and the resulting increase in shelf life. Since a high concentration of NO is producible in atmospheric plasmas, increasing attempts in plasma agriculture have been made to study several types of plasma reactors operated in air. However, as NO is rapidly oxidized by oxygen (O2) and/or ozone (O3), the use of NO produced in atmospheric plasmas is naturally nontrivial, and the lifetime of NO is highly sensitive to the reactor environments. Here, we investigated the time development of O3 and nitrogen oxides (NOx=1–3) in a surface dielectric barrier discharge (sDBD) reactor with respect to the O2 content of the controlled atmosphere (N2+O2). In situ optical absorption spectroscopy enabled the observation of the dynamics of O3 and NOx under gas-tight conditions. In these plasma reactors, NO became a dominant species after the chemical mode transition from O3 to NO occurred. We found that a lower O2 content correlated to a faster appearance of NO in the plasma reactor. The NO lifetime significantly increased as the O2 content decreased from 20 to 5 % in the plasma reactor, while the maximum concentration of NO decreased. Our findings indicated that the appropriate control of the O2 content is essential in atmospheric plasma reactors dependent on O3 and/or NOx applications.

Crucial role of nitrogen vacancies in carbon activated persulfate toward nonradical abatement of micropollutants from secondary effluent

Biomass-derived carbonaceous materials exhibit fascinating potentials in nonradical oxidation of micropollutants (MPs) by activating persulfate and their performances mainly rest on graphitic N. However, the simultaneously derived N vacancy received little attention. Herein, a graphene-like material rich in N vacancy was synthesized from coffee residues. It showed excellent removal efficiency (95 %) and degradation kinetics (0.21 min−1) in abating tetracycline antibiotics from secondary effluent and significant biotoxicity was diminished. Solid nonradical oxidation consisting of electron transfer (89 %) and singlet oxygen (1O2) oxidation (11 %) was determined. By tracking 1O2 source and electron flow, ketone group appeared at N vacancy was found as the critical site to grab electrons from peroxydisulfate (PDS) with production of 1O2. Then the electrons were transferred to graphitic N driven by the microelectric field between them. This work notices the function of vacancies in biomass resources for high-efficient removal of MPs from real water matrix.

Studies on a novel oxo-vanadium(V) complex of a tridentate ONO Schiff base ligand: Synthesis, characterization, X-ray crystal structure, Hirshfeld surface analysis, biological and catalytic activity

This study reports the successful synthesis and characterization of a novel oxovanadium(V) complex, [VO(L)(MeOH)(MeO)], prepared from 2-hydroxy-3-methoxybenzaldehyde and 2-methyl-3-aminoquinazoline. To elucidate the structure of the complex, we employed comprehensive characterization techniques such as CHN analysis, molar conductivity measurements, FT-IR, 1H NMR, UV-Vis spectroscopy, and single-crystal X-ray diffraction. The X-ray analysis confirmed an octahedral geometry around the V(V) center, coordinated with donor atoms from the deprotonated Schiff base ligand, an oxido group, a methanol molecule, and a methoxy group. Hirshfeld surface analysis was employed to evaluate intermolecular interactions.Furthermore, the complex exhibited impressively efficient catalytic activity in glucose oxidation under mild conditions (aqueous solution, room temperature, O2 oxidant), achieving a conversion rate of 98 %. Additionally, the antibacterial activity of the ligand and complex against various bacterial strains, including Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, and Bacillus cereus, was evaluated. The results demonstrated promising antibacterial potential of the [VO(L)(MeOH)(MeO)] complex, particularly against E. coli, P. aeruginosa, and B. cereus. These findings suggest potential applications of this new oxovanadium(V) complex in both catalysis and antibacterial treatments.

Oxidation Behavior of Lightweight Al0.2CrNbTiV High Entropy Alloy Coating Deposited by High-Speed Laser Cladding

High-temperature oxidation resistance is the major influence on the high-temperature service stability of refractory high entropy alloys. The oxidation behavior of lightweight Al0.2CrNbTiV refractory high entropy alloy coatings with different dilution ratios at 650 °C and 800 °C deposited by high-speed laser cladding was analyzed in this paper. The oxidation kinetic was analyzed, the oxidation resistance mechanism of the Al0.2CrNbTiV coating was clarified with the analysis of the formation and evolution of the oxidation layer, and the effect of the dilution rate on high-temperature performances was revealed. The results showed that the oxide layer was mainly composed of rutile oxides (Ti, Cr, Nb)O2 after isothermal oxidation at 650 °C and 800 °C for 50 h. The Al0.2CrNbTiV coating in low dilution exhibited better oxidation performance at 650 °C, due to the dense oxide layer formed with the synergistic growth of fine AlVO3 particles and (Ti, Cr, Nb)O2, and higher percentage of Cr, Nb in (Ti, Cr, Nb)O2 strengthened the lattice distortion effect to inhibit the penetration of oxygen. The oxide layer formed at 800 °C for the Al0.2CrNbTiV coating was relatively loose, but the oxidation performance of the coating in high dilution improved due to the precipitation of Cr2Nb-type Laves phases along grain boundaries, which inhibits the diffusion of oxygen.

Study of photocatalytic activity in two light ranges of Sr2Mn0.4Ti0.6O4 oxide with the K2NiF4-type structure

Study of photocatalytic activity in two light ranges of Sr2Mn0.4Ti0.6O4 oxide with the K2NiF4-type structure

Spontaneous Molecular Bromine Production in Sea‐Salt Aerosols

AbstractBromine chemistry is responsible for the catalytic ozone destruction in the atmosphere. The heterogeneous reactions of sea‐salt aerosols are the main abiotic sources of reactive bromine in the atmosphere. Here, we present a novel mechanism for the activation of bromide ions (Br−) by O2 and H2O in the absence of additional oxidants. The laboratory and theoretical calculation results demonstrated that under dark conditions, Br−, O2 and H3O+ could spontaneously generate Br and HO2 radicals through a proton–electron transfer process at the air–water interface and in the liquid phase. Our results also showed that light and acidity could significantly promote the activation of Br− and the production of Br2. The estimated gaseous Br2 production rate was up to 1.55×1010 molecules cm−2 ⋅ s−1 under light and acidic conditions; these results showed a significant contribution to the atmospheric reactive bromine budget. The reactive oxygen species (ROS) generated during Br− activation could promote the multiphase oxidation of SO2 to produce sulfuric acid, while the increase in acidity had a positive feedback effect on Br− activation. Our findings highlight the crucial role of the proton‐electron transfer process in Br2 production; here, H3O+ facilitates the activation of Br− by O2, serves as a significant source of atmospheric reactive bromine and exerts a profound impact on the atmospheric oxidation capacity.

Structurally optimized rosette-like microspheres carbon with Fe-Ni single atom sites for bifunctional oxygen electrocatalysis in Zinc-Air batteries

Developing a secure and effective bifunctional oxygen catalyst for the ORR and OER is still a significant obstacle in the design of rechargeable zinc-air batteries. Here, a hollow rose-shaped bifunctional electrocatalyst is synthesized with an sacrificial template strategy (FeNi-NC). X-ray absorption fine structure analysis reveals the FeNi-NC catalyst contains FeN4 and NiN4 active sites as well as FeNi3 alloy. This hollow, flower-like structure performs low density, large specific surface area, and high permeability. Its inner cavities not only provide additional triple-phase interfaces to accelerate the reduction and oxidation of O2, but also enhance the diffusion of reactants on the catalyst. By controlling the input of Fe and nickel metal salts, the dispersion of active sites can be effectively tuned. Owing to the large number of exposed active sites on the carbon nanosheets, the synthesized FeNi-NC catalysts exhibit high electrocatalytic activity in both ORR (E1/2 = 0.852 V) and OER (ηj=10 = 359 mV). The construction of rechargeable zinc-air batteries resulted in a high power density of 135.78 mW cm−2, a better specific capacitance of 726.9 Wh kgZn−1 and 210 h enduring durability. More importantly, density functional theory (DFT) calculations indicate that the electronic interactions between Fe/Ni and nitrogen-doped carbon matrices play a pivotal role in enhancing the electrocatalytic performance of functional groups. These interactions effectively disrupt the electronic neutrality of carbon atoms, thereby accelerating the kinetics of the reaction. This research provides a new method for the preparation of single atom catalysts with bifunctional activities.