Radical Yield Research Articles

Synergistic Degradation of Methylene Blue by Hydrodynamic Cavitation Combined with Hydrogen Peroxide/Vitamin C System.

In this study, a new combined process of hydrodynamic cavitation (HC) and a hydrogen peroxide/vitamin C (H2O2/Vc) system was proposed for the degradation of methylene blue (MB) in wastewater. An impact-jet hydraulic cavitator was used as the cavitation generation equipment, and H2O2/Vc was selected as a homogeneous oxidation system. The degradation characteristics of MB were investigated. The results showed that the degradation effect of HC in combination with the H2O2/Vc system was more effective than that of the individual HC or H2O2/Vc system. A maximum degradation rate of 87.8% was achieved under the following conditions: H2O2 concentration of 0.03 mol/L, Vc concentration of 0.021 mol/L, inlet pressure of 0.3 MPa, initial solution concentration of 4 μmol/L, solution volume of 150 mL, and reaction time of 10 min. The synergy index was 1.615, indicating a synergistic effect between the HC and H2O2/Vc system. The data of the hydroxyl radical (·OH) yield under the conditions of HC, the H2O2/Vc system, and the HC + H2O2/Vc system were fitted and analyzed. A correlation equation for ·OH yield was established, further revealing the synergistic mechanism of the HC and H2O2/Vc system. The intermediate products of MB degradation were detected based on LC-MS, and three possible degradation pathways of MB degradation were proposed. The combined process of HC and H2O2/Vc systems exhibited relatively low energy efficiency and operating cost, indicating that it was in line with the development direction of wastewater treatment.

Computational study of the supramolecular complexation of azocompounds with cucurbit[7]uril: effects on the production and release of free radicals.

An inclusion complex between 2,2'-azobis(2-methylpropionamidine) dihydrochloride (AAPH), a widely employed azocompound, and cucurbit[7]util (CB[7]), has shown an increased yield of radicals derived from the homolytic cleavage of the azo bond. Aimed to get insights about the formation of complexes and their effect on the yield of radicals production, complexes of CB[7] with seven azocompounds were studied by computational methods. Molecular electrostatic surfaces and structural analysis showed that the inclusion of symmetrical azocompounds inside of CB[7] depends mainly on the charge density and position of the functional groups at the main chain of the azoderivative. Analysis of non-covalent interactions and thermodynamic outcomes revealed that positively charged azocompounds with amidinium or imidazolium groups presented strong favorable interactions (multiple hydrogen bonds) with the oxygens of CB[7] portals. Additionally, carbon-centered radicals generated from the complexes (azocompounds@CB[7]) were corroborated using the electron localization function (ELF). Results evidenced that the strength of the interactions and the level of inclusion (partial or complete) between the azocompound and CB[7] determined the final orientation of the radicals (located out- or inside of the CB[7] cavity). Obtained results could be employed to design new supramolecular systems based on the properties of azocomplound@CB[7] complexes for new scientific or industrial applications. First-principles calculations at B3LYP-D3BJ/6-311g(d,p) level theory in the gas phase and in solvent (PCM, water) were performed in Gaussian 16 software package. The dispersion energy correction was included through the Grimme's dispersion with Becke-Johnson damping D3(BJ). Thermodynamical data and the minimum character of all structures were obtained from vibrational frequency calculations. NBO, Multiwfn, Chemcraft, and NCIPLOT software were used to perform population analysis, analyze outcomes, visualize data, and display non-covalent interactions respectively.

Constructing novel metal-free HCOF-Ph@g-C3N4 heterojunctions through molecular expansion to enhance photogenerated carrier involved molecular oxygen activation and photocatalytic hydrogen evolution

Modification of covalent organic frameworks (COFs) have exceptional stability as well as tunable structures is the key to efficient photocatalysts. In this study, hyper-crosslinked COF-Ph was constructed with g-C3N4 to obtain a novel HCOF-Ph@g-C3N4 heterojunction, and the lamellar mesoporous of g-C3N4 was successfully embedded into the pores of 3D HCOF-Ph. The synthetic strategy greatly enhanced the photocatalytic properties and molecular oxygen activation capability of the catalyst. 10 mg of HCOF-Ph@g-C3N4 heterojunction could completely degrade 30 mg/L of tetracycline (TC) within 14 min, and the rate of hydrogen generation reached 9214.69 μmol g−1 h−1. The active species in this process of photocatalysis were verified through tests with free radical trapping and ESR spectra. In addition, the molecular oxygen activation capacity of heterojunction interface and the yield of superoxide radicals were examined by 3,3′,5,5′-tetramethylbenzidine (TMB) oxidation and degradation of nitrotetrazolium nlue chloride (NBT) experiments, respectively. We found that the molecular expansion strategy can change molecule energy band structure to improve absorption of sunlight, and the efficient segregation of the photogenerated charge were ensured by the complementary energy band structure between g-C3N4 and HCOF-Ph. This study created an efficient molecular expansion method for the synthesis of COF-based catalysts with potential uses in the energy and environmental fields.

Contact-Electro-Catalysis Through Electret Behavior to Facilitate Electron Transfer.

Contact-electro-catalysis (CEC) usually uses polymer dielectrics as its catalysts under mechanical stimulation conditions, which although has a decent catalytic dye degradation effect still warrants performance improvement. A carrier separation promotion strategy based on an internal electric field by polarization can effectively improve ferroelectric material performance in photocatalysis and piezocatalysis. Therefore, carrier separation as a necessary process of CEC also can be promoted and is largely expected to improve CEC performance theoretically. However, the carrier separation enhancement by the internal electric field strategy has not been achieved in the CEC experiment yet, because of the difficulty of building an internal electric field in an inert polymer dielectric. Herein, a polytetrafluoroethylene (PTFE) dielectric was charged through an electret process, which was believed to establish an internal electric field for CEC catalysts proved by KPFM, XPS, and triboelectric nanogenerator voltage output analysis. The fastest degradation rate of methyl orange reached over 90% at 1.5 h, while the hydroxyl free radical (•OH) yield of the PTFE electret was nearly three times that of the original PTFE. Density functional theory (DFT) calculations verified that the potential barrier of interatomic electron transfer between PTFE and H2O was reduced by 37% under the internal electric field. The electret strategy used herein to optimize the PTFE catalyst provides a base for the use of other general plastics in CEC and facilitates the production of easily prepared, easily recyclable, and inexpensive polymer dielectric catalysts that can promote large-scale pollutant degradation via CEC.

Electro-activated periodate for organic contaminants degradation: Insights into the pH-dependent mechanism of active species

Although electro-activated periodate (PI) has demonstrated significant efficiency in degrading emerging contaminants (ECs), there has been limited research investigating the pH-dependence of active species generation and pollutant degradation. A graphite felt-based electrochemical system (GF-PI) was chosen to deeply explored. It exhibited significant differences in contaminants removal under different pH conditions. Notably, an interesting result is found that the GF-PI system at pH=3 exhibited exceptional removal performance specifically for phenolic contaminants, such as bisphenol A (BPA) and acetaminophen (ACT), whereas it displayed poor efficiency for other compounds, including sulfamethoxazole (SMX), carbamazepine (CBZ), benzoic acid (BA), and atrazine (ATZ). However, there is no selectivity for contaminants removal in pH=4, 7, and 9 system. The experiment of probe capture and quenching are conducted to thoroughly investigate the variety of reactive oxygen species (ROSs) generated. It has been proven that hypoiodous acid (HOI) is the main active species in the system with pH=3. In addition, the system with pH=4 exhibits the highest degradation efficiency and TOC removal efficiency, despite the low yield of hydroxyl radical (·OH), indicating that the iodate radical (IO3·) plays a pivotal role. Under neutral and alkaline conditions, ·OH, IO3·, and singlet oxygen (1O2) are the main active species. Moreover, the system exhibits remarkable stability, anti-interference capabilities, and cost-effectiveness, indicating the superiority for treatment of authentic wastewater. Additionally, the degradation intermediates and biotoxicity of SMX are evaluated through multiple measures. A comprehensive understanding of pH is indispensable in electro-activated PI system for treatment of emerging organic contaminants.

Optimizing Ultrasonic‐Assisted Extraction for Enhanced Yield of Phenolic Compounds and Antioxidant Activity in Cold Brew Coffee

ABSTRACTThis study aimed to identify the best conditions for ultrasonic‐assisted extraction (UAE) of DPPH and phenolic compounds from cold brew coffee using Box‐Behnken Design (BBD) and Response Surface Methodology (RSM). It explored the effects of solid‐liquid ratio (5%–15%), extraction time (40–50 min), and ultrasonic power (70%–80%) on these compounds, finding that all factors significantly influenced the outcomes. Statistical analysis showed the data fit a quadratic polynomial model well, with R2 values of 0.9981 for phenolic compounds and 0.9799 for DPPH radicals. Using 3D surface and contour plots from these models, the optimal extraction conditions for these compounds from cold brew coffee were determined. The highest yields of total phenolic compounds and DPPH radical were obtained when samples were extracted at a 10% solid–liquid ratio, 45 min extraction time, and 75% ultrasonic power. Under these optimal conditions, total phenolic compounds and DPPH radical were 64.10 ± 0.31 gGAE/mL and 61.90 ± 0.14%, respectively, with a maximum caffeine content of 213.13 ± 0.23 mg/L. Gamma irradiation at kGy also reduced cold brew coffee's microbial content. This research may be a new alternative for producing cold brew coffee that will save time and help extend the shelf life.

Quantification of Free Radicals from Vaping Electronic Cigarettes Containing Nicotine Salt Solutions with Different Organic Acid Types and Concentrations.

Electronic (e-) cigarette formulations containing nicotine salts from a range of organic acid conjugates and pH values have dominated the commercial market. The acids in the nicotine salt formulations may alter the redox environment in e-cigarettes, impacting free radical formation in e-cigarette aerosol. Here, the generation of aerosol mass and free radicals from a fourth-generation e-cigarette device was evaluated at 2 wt % nicotine salts (pH 7, 30:70 mixture propylene glycol to vegetable glycerin) across eight organic acids used in e-liquids: benzoic acid (BA), salicylic acid (SLA), lactic acid (LA), levulinic acid (LVA), succinic acid (SA), malic acid (MA), tartaric acid (TA), and citric acid (CA). Furthermore, 2 wt % BA nicotine salts were studied at the following nicotine to acid ratios: 1:2 (pH 4), 1:1 (pH 7), and 2:1 (pH 8), in comparison with freebase nicotine (pH 10). Radical yields were quantified by spin-trapping and electron paramagnetic resonance (EPR) spectroscopy. The EPR spectra of free radicals in the nicotine salt aerosol matched those generated from the Fenton reaction, which are primarily hydroxyl (OH) radicals and other reactive oxygen species (ROS). Although the aerosol mass formation was not significantly different for most of the tested nicotine salts and acid concentrations, notable ROS yields were observed only from BA, CA, and TA under the study conditions. The e-liquids with SLA, LA, LVA, SA, and MA produced less ROS than the 2 wt % freebase nicotine e-liquid, suggesting that organic acids may play dual roles in the production and scavenging of ROS. For BA nicotine salts, it was found that the ROS yield increased with a higher acid concentration (or a lower nicotine to acid ratio). The observation that BA nicotine salts produce the highest ROS yield in aerosol generated from a fourth-generation vape device, which increases with acid concentration, has important implications for ROS-mediated health outcomes that may be relevant to consumers, manufacturers, and regulatory agencies.

Critical Role of Mineral Fe(IV) Formation in Low Hydroxyl Radical Yields during Fe(II)-Bearing Clay Mineral Oxygenation.

In subsurface environments, Fe(II)-bearing clay minerals can serve as crucial electron sources for O2 activation, leading to the sequential production of O2•-, H2O2, and •OH. However, the observed •OH yields are notably low, and the underlying mechanism remains unclear. In this study, we investigated the production of oxidants from oxygenation of reduced Fe-rich nontronite NAu-2 and Fe-poor montmorillonite SWy-3. Our results indicated that the •OH yields are dependent on mineral Fe(II) species, with edge-surface Fe(II) exhibiting significantly lower •OH yields compared to those of interior Fe(II). Evidence from in situ Raman and Mössbauer spectra and chemical probe experiments substantiated the formation of structural Fe(IV). Modeling results elucidate that the pathways of Fe(IV) and •OH formation respectively consume 85.9-97.0 and 14.1-3.0% of electrons for H2O2 decomposition during oxygenation, with the Fe(II)edge/Fe(II)total ratio varying from 10 to 90%. Consequently, these findings provide novel insights into the low •OH yields of different Fe(II)-bearing clay minerals. Since Fe(IV) can selectively degrade contaminants (e.g., phenol), the generation of mineral Fe(IV) and •OH should be taken into consideration carefully when assessing the natural attenuation of contaminants in redox-fluctuating environments.

Experimental and chemical kinetics study on the flammability limit of CO2/C3H6 mixture working fluid at variable initial temperature

CO2/C3H6 mixture has a wide range of applications in refrigeration systems, heat pumps and Organic Rankine Cycle (ORC) systems, but its flammability safety needs to be considered. An experimental and computational investigation has been conducted on the determination of the flammability limits of CO2/C3H6 and on the understanding of associated limit phenomena in general. We tested the flammable zone of CO2/C3H6 at variable initial temperature. The accuracy of the prediction model of calculation adiabatic flame temperature were verified based on the experimental data. Meanwhile, a high-speed camera was used to record the process of CO2 suppression of flame propagation near flammability limit. Furthermore, based on kinetic numerical calculation, the effect of CO2 chemical and thermal on the flammability limit of C3H6 were analyzed. The results show that the thermal effect of CO2 is greater than that of chemical effect near the flammability limit. The theory of chemical reactivity inhibition reduces the yield and molar ratio of key radicals. The addition of CO2 can inhibit the activity of the dominant chain and increase the activity of the dominant chain termination reaction in the global combustion kinetics. Results of this study provide theoretical guidance for the safe application of CO2/C3H6 mixture.

Unusual enhancement of the radical production in the X-ray irradiated aqueous-organic systems containing W(VI) in homogeneous and nanoparticle forms

The metal and oxide nanoparticles (NPs) containing various elements with high atomic number (Z) are considered as prospective sensitizers for the production of radicals upon X-ray irradiation of aqueous solutions, which can be used for different applications in medical treatment and material modification. The common basis for the sensitizing effect in oxygen-free systems is concerned with increase of the absorbed dose due to the presence of high-Z atoms (known as physical enhancement, relatively insensitive to the NP size). In this work we report the first experimental evidence for extra enhancement of the radical yield in a model oxygen-free aqueous organic system irradiated with X-rays (45 kVp) in the presence of W(VI) compounds, both in homogeneous solutions of Na2WO4 and in the form of ultra-small NPs of WO3. Meanwhile, in the case of larger WO3 NPs the radical yield is consistent with physical enhancement mechanism. In the case of systems containing HfO2 NPs only physical enhancement was observed, independent of the NP size. Unusually large enhancement of radical production and size effect for W(VI) in homogeneous and NP forms was tentatively attributed to the radiation-chemical processes involving intermediate formation of metastable W(V) due to reactions of hydrated electron.

Cyclodextrin-boosted photocatalytic oxidation for efficient bisphenol A removal

Wastewater contains various high-risk trace organic pollutants, such as antibiotics and endocrine disruptors, which seriously restrict wastewater reuse. Cyclodextrin-based functional materials show great potential in the removal of trace pollutants because of their adsorption catalytic synergy. Clarifying the synergistic mechanism of cyclodextrin in oxidation is the key issue in confined catalytic oxidation process design. In this work, we fabricated a BiOIO3@BiOBr/β-CD heterojunction photocatalyst to study the synergistic mechanism of cyclodextrin in the photocatalytic oxidation process. The synergistic mechanism of cyclodextrin was investigated by combining radical chemistry, electrochemistry, spectroscopy, and time-dependent density functional theory. Results showed that the excited intermediate free radicals played an important role in promoting the photocatalytic degradation process. The heterojunction photocatalyst loaded with β-cyclodextrin (β-CD) at the electronic end (C[Cat.] = 0.2 mg/mL) removed about 97% of bisphenol A (BPA) within 30 min, and the first-order kinetic constant (kCDBIB = 0.112 min−1) was about twice that of the unloaded β-CD (kBIB = 0.057 min−1). Cyclodextrin loading improved the photocatalytic performance of the heterojunction and stimulated the intermediate to increase the free radical yield and regulate the reaction path.

Multiscale Modeling of Plutonium Radiation Chemistry in Nitric Acid Solutions. 1. Cobalt-60 Gamma Irradiation of Pu(IV).

Careful manipulation of the plutonium oxidation states is essential in the study and utilization of its rich redox chemistry. To achieve this level of control, a comprehensive mechanistic understanding of radiation-induced plutonium redox chemistry is critical due to the unavoidable exposure of plutonium to ionizing radiation fields, both inherent and from in-process applications. To this end, we have developed an experimentally evaluated multiscale computer model for the prediction of gamma radiation-induced Pu(IV) redox chemistry in concentrated nitric acid solutions (1.0, 3.0, and 6.0 M). Under these acidic, aqueous solution conditions, cobalt-60 gamma irradiation afforded marginal net conversion of Pu(IV) to Pu(VI), the extent of which was dependent on the concentration of HNO3 and absorbed gamma dose. Multiscale calculations, which are in excellent agreement with experimental data, indicate that this observation is due to a combination of inherent plutonium disproportionation reactions and several radiation-induced processes, including redox cycling between Pu(IV) and Pu(III), as achieved by the reduction of Pu(IV) by nitrous acid and hydrogen peroxide, the oxidation of Pu(III) by nitrate and hydroxyl radicals, and the sequential oxidation of Pu(IV) to Pu(V) and Pu(VI) by the remaining available yield of nitrate radicals.

Degradation mechanisms of antibiotics in UV222/H2O2 and UV222/persulfate systems: Dual roles of inorganic anions

Advanced oxidation processes based on KrCl* excimer lamps (UV222-AOPs) have recently received widespread attention in water treatment due to their high radical yields. In this investigation, the degradation of two typical antibiotics, florfenicol (FLO) and ciprofloxacin (CIP), by UV222 and its combination with hydrogen peroxide (H2O2) or persulfate (PDS) were studied, respectively. The dual effects of inorganic anions on the degradation performance of UV222/UV222-AOPs were determined. It was found that NO3– significantly enhanced the photolysis of CIP, and the degradation rate constants increased from 1.03 × 10-4 mJ−1 cm2 (without NO3–) to 2.56 × 10-4 mJ−1 cm2 (with 1 mM NO3–). However, NO3– markedly inhibited the photolysis of FLO, leading to a decrease in the degradation rate constants from 1.18 × 10-3 mJ−1 cm2 (without NO3–) to 5.27 × 10-4 mJ−1 cm2 (with 1 mM NO3–). HCO3– was found to have a certain promoting effect on the photolysis of FLO and CIP, and SO42- has a negligible effect on the photolysis of both antibiotics. The above three inorganic ions decelerated the degradation of CIP and FLO in UV222-AOP, where NO3– exerted the most inhibition. Through LC-MS analysis and ECOSAR model, the main transformation products were individually determined and evaluated for toxicity. In addition, the performance of UV222-AOPs and UV254-AOPs in reclaimed wastewater (RWW) treatment were compared, and the steady-state concentration of radicals was measured. This study provided novel insight into the application of UV222-AOPs in RWW treatment.

Computational modeling of a surfatron mode microwave plasma in NH3/N2 for remote radical generation in a silicon native oxide cleaning process

Plasma-produced NxHy radicals facilitate the removal of native oxide layers in a semiconductor wafer surface. A remote microwave excited plasma with a NH3–N2 feed gas is used commonly to produce the active radicals. We perform a three-dimensional modeling of a microwave excited plasma operating in a surfatron mode. The device consists of a rectangular waveguide intersecting a quartz tube through which the feed gas flows. We discuss the propagation of a polarized 2.45 GHz microwave from the waveguide into the quartz tube where power is deposited into the plasma. The plasma–wave interaction is found to be highly three dimensional, with a propagating surface mode of the wave established along the dielectric tube plasma interface. Significant heating occurs on the side of the tube that directly faces the incident wave. As the flow carries the plasma-produced species down the tube, species radial profiles become increasingly diffusion controlled and axisymmetric. The dominant radicals that exit the tube are H2 and NH2, with nearly complete conversion of the feed gases to product species. The gas temperature rises above this inlet feed gas temperature and increases with increasing wave power. However, the gas temperature increase is not consequential to the overall radical yield from the plasma. The parametric study with changing pressure and input power illustrates the role of specific chemical reactions in the overall remote plasma process.

Electron-catalytic conversion of carbon dioxide into formaldehyde and methanol

Since the mid-19th century, there has been a steady increase in the amount of CO2 in the atmosphere, leading to global warming due to the greenhouse effect. CO2 can be utilized to obtain a large number of organic compounds. The formation of these compounds depends on the methods of CO2 processing, which include biological, thermal conversion, photochemical, and plasma methods. Most of these methods involve the use of catalysts. One of the plasma methods is the electron-catalytic method using a barrier discharge. Studies on the catalytic conversion of CO2 into methanol and formaldehyde were carried out on a laboratory setup consisting of two sources of low-temperature plasma – dischargers, one of which contains a heterogeneous catalyst. Water vapor was used as the source of hydrogen. The formation of methanol and formaldehyde was investigated under different operating modes of the setup. The effect of sample aging for a day was determined. As a result, there is an increase in the concentration of methanol in the sample from 5.8% to 49.74% and formaldehyde from 4.1% to 50.01% for different operating modes of the setup. The observed results are explained by a sharp increase in the yield of oxygen-containing radicals and , which are formed by the interaction of ozone, formed from CO2 in the discharge zone, with aqueous solutions.

Adsorption effects of electron scavengers and inorganic ions on catalysts for catalytic oxidation of sulfamethoxazole in radiation treatment

This study aimed to investigate adsorption effects of electron scavengers (H2O2 and S2O82−) on oxidation performance for mineralization of sulfamethoxazole (SMX) in radiation treatment using catalysts (Al2O3, TiO2). Hydrogen peroxide (H2O2, 1 mM) as an electron scavenger showed weak adsorption onto catalysts (0.012 mmol g−1-Al2O3 and 0.004 mmol g−1-TiO2, respectively), leading to an increase in TOC removal efficiency of SMX within the absorbed dose of 30 kGy by 12.3% with Al2O3 and by 8.0% with TiO2. The weak adsorption of H2O2 onto the catalyst allowed it to act as an electron scavenger, promoting indirect decomposition reactions. However, high adsorption of S2O82− (1 mM) onto Al2O3 (0.266 mmol g−1-Al2O3) showed a decrease in TOC removal efficiency of SMX from 76.2% to 30.2% within the absorbed dose of 30 kGy. The high adsorption of S2O82− onto the catalyst inhibited direct decomposition reaction by reducing adsorption of SMX on catalysts. TOC removal efficiency for Al2O3 without electron scavengers in an acidic condition was higher than that in a neutral or alkaline condition. However, TOC removal efficiency for Al2O3 with S2O82− was higher in a neutral condition than in other pH conditions. This indicates that the pH of a solution plays a critical role in the catalytic oxidation performance by determining surface charges of catalysts and yield of reactive radicals produced from water radiolysis. In the radiocatalytic system, H2O2 enhances the oxidation performance of catalysts (Al2O3 and TiO2) over a wide pH range (3–11). Meanwhile, S2O82− is not suitable with Al2O3 in acidic conditions because of its strong adsorption onto Al2O3 in this study.

One-step in-situ construction engineering of ZnO-Zn2SnO4 heterojunction for deeply photocatalytic oxidation of nitric oxide

The generation of hazardous intermediates during the process of photocatalytic nitric oxide (NO) oxidation presents a tough issue. Herein, a one-step microwave strategy was employed to introduce oxygen vacancies (OVs) into zinc oxide-zinc stannate (ZnO-Zn2SnO4) heterojunction, resulting in an improvement in the photocatalytic efficiency for NO removal. The construction ZnO-Zn2SnO4 heterojunction with the OVs (ZSO-3) owns a significant contribution towards highly efficient electron transfer efficiency (99.7%), which renders ZSO-3 to exert a deep oxidation of NO-to-nitrate (NO3−) rather than NO-to-nitrite (NO2−) or NO-to-nitrogen dioxide (NO2). Based on the solid supports of experimental and simulated calculations, it can be found that OVs play an irreplaceable role in activating small molecules such as NO and O2. Moreover, the enhanced adsorption capacity of small molecules, which guarantees the high yield of active radical due to the formation of S-scheme heterojunction. This work illuminates a novel viewpoint on one-step in-situ route to prepare Zn2SnO4-based heterojunction photocatalyst with deep oxidation ability of NO-to-NO3−.

Reactive Oxygen Species Formation and Peroxide and Carbonyl Decomposition in Aqueous Photolysis of Secondary Organic Aerosols.

The mechanism and kinetics of reactive oxygen species (ROS) formation when atmospheric secondary organic aerosol (SOA) is exposed to solar radiation are poorly understood. In this study, we combined an in situ UV-vis irradiation system with electron paramagnetic resonance (EPR) spectroscopy to characterize the photolytic formation of ROS in aqueous extracts of SOA formed by the oxidation of isoprene, α-pinene, α-terpineol, and toluene. We observed substantial formation of free radicals, including •OH, superoxide (HO2•), and organic radicals (R•/RO•) upon irradiation. Compared to dark conditions, the radical yield was enhanced by a factor of ∼30 for •OH and by a factor of 2-10 for superoxide radicals, and we observed the emergence of organic radicals. Total peroxide measurements showed substantial decreases of peroxide contents after photoirradiation, indicating that organic peroxides can be an important source of the observed radicals. A liquid chromatography interfaced with high-resolution mass spectrometry was used to detect a number of organic radicals in the form of adducts with a spin trap, BMPO. The types of detected radicals and aqueous photolysis of model compounds indicated that photolysis of carbonyls by Norrish type I mechanisms plays an important role in the organic radical formation. The photolytic ROS formation serves as the driving force for cloud and fog processing of SOA.

Crystal Plane Regulation Promotes the Oriented Conversion of Radicals in Heterogeneous Persulfate Catalyzed Oxidation Process.

In heterogeneous persulfate-catalyzed oxidation systems, the mechanism underlying the crystal plane effects of the catalyst on the selective conversion of reactive oxygen species (ROS) remains ambiguous. In this study, nano-Co3O4 catalysts with varying crystallinity and exposure levels of (111) crystal planes are prepared via a hydrothermal method. Compared to low crystalline catalysts, high crystallinity catalysts predominantly expose (111) planes containing higher concentrations of Co2+ and oxygen vacancies (Ov), resulting in an increase degradation efficiency of p-nitrobenzaldehyde (4-NBA) from 74.5% to 100%. Radical quenching experiments and EPR characterization reveal that the degradation of 4-NBA occurs through a radical pathway, and quantification of radicals demonstrates that increasing exposure levels of (111) planes effectively promote radical yield (CSO4•- increase from 18.2 to 172.8 µm and C•OH increase from 1 to 58.9 µm). Furthermore, XPS and DFT calculations indicate that high crystallinity catalyst possesses more Ov active sites on (111) planes. The presence of Ov not only facilitates the adsorption of PMS molecules but also enhances electron transfer from Co2+ to PMS, leading to directed formation and efficient transformation of radicals. This study presents a novel strategy for promoting efficient radical formation in persulfate-activated systems.

Influence of interactions between bubbles on physico-chemical effects of acoustic cavitation

Ultrasound technology has been extensively used as one of the efficient and economic methodology to achieve the desired outcomes in many applications by harnessing the physico-chemical effects of acoustic cavitation. However, the cavitation-associated effects, primarily determined by the oscillatory dynamics of cavitation bubbles, are considerably complex and still remain poorly understood. The main objective of this study was to perform a numerical analysis of the acoustic cavitation (i.e., the cavitation dynamics, the resultant temperature, pressure and chemical yields within collapsing bubbles), particularly focusing on the influence of the interactions between bubbles. A comprehensive model was developed to simulate the acoustic cavitation dynamics via combining the influences of mass transfer, heat conduction and chemical reactions as well as the interaction effects between bubbles. The results demonstrated that only the large bubble exerts a greater impact on the small one in a two-bubble system. Specifically, within parameter ranges covered this study, there are noticeable decreases in the expansion ratio of the small bubble, the resultant temperature, pressure and molar yields of free radicals, hence weakening the cavitation intensity and cavitation- associated physico-chemical effects. Moreover, the influences of the interactions between bubbles were further assessed quantitatively under various parameters, such as the ultrasound amplitude PA and frequency f, the distance between bubbles d0, the initial radius of the large bubble R20, as well as the liquid properties (e.g., surface tension σ and viscosity μ). It was found that the suppression effect can be amplified when subjected to ultrasound with an increased PA and/or a decreased f, probably due to a stronger cavitation intensity under this condition. Additionally, the suppression effect is also enhanced with a decrease in d0, σ and μ, but with R20 increasing. This study can contribute to deepening knowledge about acoustic cavitation and the resultant physical and/or chemical effects, potentially further facilitating the ultrasound-assisted various applications involving acoustic cavitation.