OH Reaction Research Articles

Unveiling the Critical Pathways of Hydroxyl Radical Formation in Breakpoint Chlorination: The Role of Trichloramine and Dichloramine Interactions.

Chlorination of ammonia or chloramine-containing waters induces breakpoint chlorination reactions, producing a hydroxyl radical (•OH), but enhances the formation of undesirable N-nitrosamines. The prevailing view attributes •OH formation to a nitrosyl intermediate derived from the hydrolysis of dichloramine, but this pathway is unlikely at neutral or acidic pH. This study reveals a novel mechanism where •OH is generated via interactions between trichloramine (NCl3) and dichloramine (NHCl2), which also form nitrosation agents. Our experiments demonstrated that the NCl3-NHCl2 interaction degrades micropollutants with kinetics 2-3 times faster than breakpoint chlorination. Using electron paramagnetic resonance, we detected •OH in the NCl3-NHCl2 reaction. Micropollutant removal was unimpaired under low dissolved oxygen (O2(aq)) conditions, aligning with negligible O2(aq) changes during the NCl3-NHCl2 reaction and suggesting O2(aq) does not participate in •OH formation. Using benzene as a probe in 18O-labeled H2O, we confirmed water contributes to the oxygen source of •OH in NCl3-NHCl2 interactions, through which parallel reactions occur, leading to the formation of one mole of •OH alongside 1.92 mol of N2. A kinetic model developed in this study accurately predicted •OH and N2 and demonstrated the NCl3-NHCl2 interaction as the primary pathway for •OH formation in breakpoint chlorination, providing new insights into breakpoint chemistry.

NEIVAv1.0: Next-generation Emissions InVentory expansion of Akagi et al. (2011) version 1.0

Abstract. Accurate representation of fire emissions is critical for modeling the in-plume, near-source, and remote effects of biomass burning (BB) on atmospheric composition, air quality, and climate. In recent years application of advanced instrumentation has significantly improved knowledge of the compounds emitted from fires, which, coupled with a large number of recent laboratory and field campaigns, has facilitated the emergence of new emission factor (EF) compilations. The Next-generation Emissions InVentory expansion of Akagi (NEIVA) version 1.0 is one such compilation in which the EFs for 14 globally relevant fuel and fire types have been updated to include data from recent studies, with a focus on gaseous non-methane organic compounds (NMOC_g). The data are stored in a series of connected tables that facilitate flexible querying from the individual study level to recommended averages of all laboratory and field data by fire type. The querying features are enabled by assignment of unique identifiers to all compounds and constituents, including thousands of NMOC_g. NEIVA also includes chemical and physical property data and model surrogate assignments for three widely used chemical mechanisms for each NMOC_g. NEIVA EF datasets are compared with recent publications and other EF compilations at the individual compound level and in the context of overall volatility distributions and hydroxyl (OH) reactivity (OHR) estimates. The NMOC_g in NEIVA include ∼4–8 times more compounds with improved representation of intermediate volatility organic compounds, resulting in much lower overall volatility (lowest-volatility bin shifted by as much as 3 orders of magnitude) and significantly higher OHR (up to 90 %) than other compilations. These updates can strongly impact model predictions of the effects of BB on atmospheric composition and chemistry.

Reaction between peracetic acid and carbonyl oxide: Quantitative kinetics and insight into implications in the atmosphere

Peracetic acid (PAA, CH3C(O)OOH) is one of the most abundant organic peroxyacid in the atmosphere. PAA is often assumed to be removed by hydroxyl radical in the gas phase of troposphere, but its reaction rate is quite low. Here, we investigated the new reaction between PAA and carbonyl oxide (CH2OO) by using quantum chemical methods, reaction kinetics in combination with atmospheric modeling. We first performed W3X-L calculations close to CCSDT(Q)/CBS accuracy with the reaction systems containing eight carbon and oxygen atoms. The present findings show that the post-CCSD(T) contribution is about 0.50 kcal mol-1, which is important for obtaining quantitative relative enthalpy of activation at 0 K. We find that the recrossing effect reduces the rate constant by an order of magnitude for the mechanism of the hydrogen-shift coupled carbon-oxygen addition at low temperature. The calculated results reveal that the anharmonicity increases the rate constants of CH2OO + CH3C(O)OOH by a factor of 6.27 at 298 K. The present findings uncover that the PAA + CH2OO reaction is a dominant pathway for PAA sinks in the gas phase of troposphere at the lower nighttime OH concentrations at 298 K, since the rate of PAA + CH2OO is even an order of magnitude higher than the rate of the PAA + OH reaction. Moreover, atmospheric modeling simulations unveil that CH2OO can make certain contribution to the reduction of PAA in the Amazon.

Hydroxyl radical oxidation of chemical contaminants on indoor surfaces and dust

Humans are widely exposed to semivolatile organic contaminants in indoor environments. Many contaminants have long lifetimes following partitioning to the large surface reservoirs present indoors, which leads to long exposure times to gas-phase oxidants and multiphase chemistry. Studies have shown selective multiphase oxidation of organics on indoor surfaces, but the presence of hydroxyl radicals with nonselective reactivity and evidence of multiphase OH radical reactivity toward common indoor contaminants indicates that there may be additional unknown transformation chemistry indoors. We screened genuine indoor samples for 60 OH radical oxidation products of the common plasticizer and endocrine-disrupting contaminant bis(2-ethylhexyl) phthalate (DEHP) identified in laboratory experiments using nontargeted high-resolution mass spectrometry. At least 30 and 10 of these products are observed in indoor dust and DEHP films exposed to ambient indoor conditions, respectively, indicating that multiphase OH reactions occur indoors. Using the PROTEX model and a multimedia indoor chemical fate model, we demonstrate that these products have long indoor lifetimes and cause a higher potential for human exposure than DEHP. Some of these products are more active endocrine disruptors than DEHP itself, but most have unknown toxicities. Coexposure to all oxidation products will likely have an additive effect, leading to higher human health risks from indoor organic contaminants than previously thought. Due to the nonselective reactivity of OH radicals, it is likely that most indoor contaminants follow similar chemistry, and further study is needed to understand the prevalence and human health implications of such multiphase chemistry.

Experimental and theoretical investigation of benzothiazole oxidation by OH in air and the role of O2.

Benzothiazole (BTH) and its derivatives are amongst a group of emerging contaminants that are widely distributed in the environment due to their extensive use in many different consumer products. In air, reaction with the hydroxyl radical (OH) is expected to be a major loss process for BTH in the gas phase, but the kinetics and mechanisms are unknown. Here, we report a combination of experiments and theory to determine both the rate constant and products of the reaction of OH with the smallest member of the series, benzothiazole, in the gas phase. The mechanism first involves an attack by OH on BTH to produce several OHBTH intermediates. This is followed by O2 reactions with OHBTH, leading to several stable products successfully predicted by theory. Relative rate studies at 1 atm in air and 298 K using benzene as a reference gave a rate constant for the BTH + OH reaction of 2.1 ± 0.1 × 10-12 (1σ) cm3 per molecule per s, which translates to a lifetime in air of 5.5 days at 1 × 106 OH cm-3. Four hydroxybenzothiazole products reflecting attack on different carbon atoms of the benzene ring were measured (n-OHBTH, where n = 4, 5, 6, 7), with the relative product yields well predicted by the calculated formation energies of the pre-reaction OH⋯BTH complex. Attack of OH on the -CH of the thiazole ring leads to the formation of 2-OHBTH, representing a smaller fraction of the overall reaction, and is shown to proceed through a more complex mechanism than attack on the benzene ring. A theoretical approach to predicting chromatographic retention times of the products based on solvation free energies (ΔGsolv) was successful for most of the products. These studies illustrate how the powerful combination of experiment and theory can be used to predict products of atmospheric oxidation of emerging contaminants and ultimately used to assess their impacts on the environment.

OH Radical Oxidation of Organosulfates in the Atmospheric Aqueous Phase.

Organosulfates (OS, ROSO3-), ubiquitous constituents of atmospheric particulate matter (PM), influence both the physicochemical and climatic properties of PM. Although the formation pathways of OS have been extensively researched, only a few studies have investigated the atmospheric fate of this class of compounds. Here, to better understand the reactivity and transformation of OS under cloudwater- and aerosol-relevant conditions, we investigate the hydroxyl radical (OH) oxidation bimolecular rate constants (kOS+OHII) and products of five atmospherically relevant OS as a function of pH and ionic strength: methyl sulfate (MeS), ethyl sulfate (EtS), propyl sulfate (PrS), hydroxyacetone sulfate (HaS) and phenyl sulfate (PhS). Our results show that OS are oxidized by OH with kOS+OHII between 108 - 109 M-1 s-1, which corresponds to atmospheric lifetimes of minutes in aqueous aerosol to days in cloudwater. We find that kOS+OHII increases with carbon chain length (MeS < EtS < PrS) and aromaticity (PrS < PhS), but does not depend on solution pH (2, 9). In addition, we find that whereas the OH reactivity of the aliphatic OS studied here decreases by ∼2× with increasing ionic strength (0-15 M), the reactivity of PhS decreases by ∼10×. The oxidation of EtS and PrS produced organic peroxides (ROOH) as first-generation oxidation products, which subsequently photolyzed; the oxidation of PhS resulted in hydroxylated aromatic products. These results highlight the need for inclusion of OS loss pathways in atmospheric models, and suggest caution in using ambient OS concentration measurements alone to estimate their production rates.

Interaction between marine and terrestrial biogenic volatile organic compounds: Non-linear effect on secondary organic aerosol formation

Biogenic volatile organic compounds (BVOCs) are the largest source of secondary organic aerosols (SOA) globally. However, the complex interactions between marine and terrestrial BVOCs remain unclear, inhibiting our in-depth understanding of the SOA formation in the coastal areas and its environmental impacts. Here, we performed smog chamber experiments with mixed α-pinene (a typical monoterpene) and dimethyl sulfide (DMS, a typical marine emission BVOC) to investigate their possible interactions and subsequent SOA formation. It is found that DMS has a non-linear effect on SOA generation: The mass concentration and yield of SOA show increasing and then decreasing trends with the increase of the initial concentration of DMS. The increasing trend can be attributed to OH regeneration from isomerization of the CH3SCH2OO radical together with acid-catalyzed heterogeneous reactions by the oxidation of DMS, while the decreasing trend is explained by the less contribution of isomerization reaction and the high OH reactivity that inhibits the formation of low volatility products. The results from infrared spectra and mass spectra together reveal the contribution of sulfur-containing molecules in the mixed system. Moreover, the mass spectra results indicate that acidic products generated by DMS photooxidation enhance the O:C ratio, while organosulfates are produced to contribute to the formation of mixed SOA. In addition, the trends in relative abundance of highly oxygenated organic molecules (HOMs) with C8 - C10 multiple functional groups in different mixed systems agree well with the turning point of the SOA yield. The findings of this study have significant implications for understanding binary or more complex systems in the atmosphere in the coastal areas.

Hyaluronic acid modified Cu/Mn-doped metal-organic framework nanocatalyst for chemodynamic therapy

Chemodynamic therapy (CDT) is a new method for cancer treatment that produces highly toxic reactive oxygen species (ROS) in the tumor microenvironment to induce cancer cell apoptosis or necrosis. However, the therapeutic effect of CDT is often hindered by intracellular H2O2deficiency and the activity of antioxidants such as glutathione (GSH). In this study, a nano-catalyst HCM was developed using a self-assembled Cu/Mn-doped metal-organic framework, and its surface was modified with hyaluronic acid to construct a tumor-targeting CDT therapeutic agent with improved the efficiency and specificity. Three substances HHTP (2, 3, 6, 7, 10, 11-hexahydroxybenzophenanthrene), Cu2+, and Mn2+were shown to be decomposed and released under weakly acidic conditions in tumor cells. HHTP produces exogenous H2O2in the presence of oxygen to increase the H2O2content in tumors, Cu2+reduces GSH content and generates Cu+in the tumor, and Cu+and Mn2+catalyze H2O2to produce ∙OH in a Fenton-like reaction. Together, these three factors change the tumor microenvironment and improve the efficiency of ROS production. HCM showed selective and efficient cytotoxicity to cancer cells, and could effectively inhibit tumor growthin vivo, indicating a good CDT effect.

Characteristics of Ozone Photochemical Reaction and Emission Reduction Strategies in Summer and Autumn in Shangqiu

Recently, ozone （O3） pollution in Shangqiu has become increasingly prominent, especially in summer and autumn, crucially affecting the local environmental air quality. Based on the monitoring data of O3 pollution days from the Environmental Monitoring Station in June and September 2022 （representing summer and autumn） in Shangqiu, an observation-based model （OBM） was used to study the causes and photochemical reaction characteristics of O3 pollution in the city and precursor emission reduction strategies were studied. The observation results indicated that during summer in Shangqiu, the ρ（O3） and O3 daily maximum 8 h moving concentrations [ρ（MDA8-O3）] were 149.7 μg·m-3 and 195.4 μg·m-3, whereas in autumn, ρ（O3） and ρ（MDA8-O3） were 119.8 μg·m-3 and 173.9 μg·m-3, respectively； the O3 concentration in summer was significantly higher than that in autumn. Ozone sensitivity research showed that the generation of O3 in summer and autumn in Shangqiu was controlled by volatile organic compounds （VOCs）. Among them, oxygen-containing volatile organic compounds （OVOCs）, aromatic hydrocarbons, and alkenes contributed the most to the ozone generation potential （OFP） and ·OH reactivity （L·OH）, and the control must have been strengthened. The OBM simulation results indicated that the maximum O3 generation rates in summer and autumn were 23.0×10-9 h-1 and 13.6×10-9 h-1, with maximum net generation rates of 17.4×10-9 h-1 and 10.4×10-9 h-1 and the maximum and maximum net generation rates of O3 in summer were 1.68 times higher than those in autumn, indicating that the photochemical reactions in summer were significantly stronger than those in autumn. Compared with that in summer, the generation of O3 in autumn was greatly influenced by regional inputs from other regions or cities, with a maximum input of 14.2×10-9 h-1. The prevention and control of O3 pollution in the summer and autumn seasons in Shangqiu should mainly focus on controlling VOCs. The reduction ratio of VOCs/nitrogen oxides （NOx） in autumn should be greater than that in summer and the reduction ratios of 3∶1 in summer and 4∶1 in autumn could be adopted for control.

Atmospheric Chemistry of Chloroprene Initiated by OH Radicals: Combined Ab Initio/DFT Calculations and Kinetics Analysis.

Chloroprene (CP; CH2═C(Cl)-CH═CH2) is a significant toxic airborne pollutant, often originating from anthropogenic activities. However, the environmental fate of CP is incompletely understood. High level CCSD(T)/aug-cc-pVTZ//M06-2X/aug-cc-pVTZ calculations combined with kinetic modeling were employed here to glean new insight into the reaction mechanism, energies, and kinetics of the reaction of CP with OH radical (•OH). We report the energies of four different addition pathways and six different abstraction pathways. The •OH attack on the terminal C1 atom of the =CH2 group (which is directly attached to the =CCl moiety), leading to the formation of HOCH2-•C(Cl)-CH═CH2, was found to be a major path. The barrier height for the formation of the corresponding transition state was found to be -1.9 kcal mol-1 below that of the starting CP + •OH reactants. Rate coefficients were calculated for addition and abstraction pathways involving the CP + •OH reaction under pre-equilibrium approximation conditions, employing a combination of canonical variational transition state theory and small curvature tunneling. The overall rate coefficient for the reaction of CP + •OH at 298 K was found to be 1.4 × 10-10 cm3 molecule-1 s-1. The thermochemistry of the possible channels and atmospheric implications are provided. In addition, the fate of HOCH2-•C(Cl)-CH═CH2 in the presence of 3O2 was investigated. We found the reaction of the CP-derived peroxy radical adduct with HO2 and NO to make contributions to the formation of products such as formaldehyde, HO2 radical, Cl atom, HOCH2C(OOH)(Cl)CH═CH2, HOCH2C(O)Cl, ClC(O)CH═CH2, HOCH2C(O)CH═CH2, and HC(O) radical.

Analysis of Ozone Pollution and Precursor Control Strategies in the Pearl River Delta During Summer and Autumn Transition Season

To analyze the causes of ozone pollution in the Pearl River Delta （PRD） Region during the summer and autumn transition seasons, a case study was carried out in Guangzhou, which is located in the center of the PRD Region, to analyze the ozone photochemical production and destruction pathways as well as emission reduction scenarios using a box model based on comprehensive observation. The results showed that the stagnant meteorological conditions and high temperature during the observation period were suitable for the photochemical production of ozone, which led to widespread and prolonged ozone pollution. Aromatic hydrocarbons （AHs） contributed the most to the ozone formation potential （OFP）, and m/p-xylene, toluene, and o-xylene were the major three VOC species contributing to the OFP. Box model analysis revealed that the averaged net O3 production rate during the polluted period was 23.2×10-9 h-1 and the peak reached 39.2×10-9 h-1. The HO2·+NO and NO2+·OH reaction pathways contributed the most to the local photochemical ozone production （51.2%） and destruction （47.0%）, respectively. Observed ozone concentration was primarily controlled by both the local photochemical O3 production and the export-dominated transport. The RIR and EKMA analyses showed that O3 formation in Guangzhou during the summer-autumn transition seasons was mainly a VOC-limited regime and AHs showed the greatest sensitivity to O3 production. Toluene, m/p-xylene, o-xylene, n-butane, and propylene were the five key components affecting O3 generation. The analysis of reduction scenarios showed that reducing anthropogenic VOC emissions was the most favorable way to reduce O3 concentrations； however, if NOx emission was controlled after reducing VOCs, the O3 concentration would rebound in a short time. Our results suggested that the synergistic reduction of VOCs and NOx while mainly focusing on VOCs alleviation should be implemented to continuously reduce ozone concentrations in the future.

Biogenic Volatile Organic Compound Emission and Its Response to Land Cover Changes in China During 2001–2020 Using an Improved High‐Precision Vegetation Data Set

AbstractBiogenic volatile organic compounds (BVOCs) are regarded as important precursors for ozone and secondary organic aerosol, mainly from vegetation emissions. In the context of the expanding trend of vegetation greening, the development of high‐precision vegetation data and accurate BVOC emission estimates are essential to develop effective air pollution control measures. In this study, by integrating the multi‐source vegetation cover data, we established a high‐resolution vegetation distribution (HRVD) data set to develop a high spatio‐temporal resolution emission inventory and investigated the impact of different land cover data sets on emission simulation and impact of land cover change on BVOC emissions during 2001–2020. The annual total BVOC emissions in China for 2020 was 15.66 Tg, which were mainly from trees. The emissions simulated by CNLUCC and MODIS data sets were 1.53% and 1.72% higher than those simulated by HRVD data sets, respectively. The spatial distribution of emission differences was consistent with that of land cover differences. The simulated BVOC emissions by the HRVD data set had the best accuracy as they improved the bias between modeling and observation from 69.06% to 65.35% and decreased the underprediction of observations by a factor of 2.13 compared with simulation by MEGAN default vegetation data. The annual BVOC emissions caused by changing vegetation distribution and LAIv (LAI of vegetation covered surfaces) enhanced at a rate of 72.06 Gg yr−1 during 2001–2020. LAIv was the main driver of emission variations. The total OH reactivity of the resulted BVOC emissions increased at a rate of 1.59 s−1 yr−1, with isoprene contributed the most.

Exploration of radical chemistry, precursor sensitivity and O3 control strategies in a provincial capital city, northwestern China

As the core city in northwestern China, Xi'an has suffered from serious O3 pollution in recent years. An observational model, coupled with the Master Chemical Mechanism (V3.3.1) and comprehensive data, analyzed atmospheric oxidation capacity (AOC), O3 formation mechanism, precursor sensitivity and control strategies in Xi'an. The study examined two periods (period I and II), with notable temperature and humidity differences. Despite lower precursor levels in period I, an O3 episode (peak value: 102.68 ppb) occurred only in period I, highlighting the crucial influence of meteorological conditions. Higher removal rate of primary pollutants occurs in period I, but meteorological conditions may not alter the dominant factor of AOC. Period I exhibited markedly high OH reactivity, with aromatics, alkenes, and NOx being the main contributors. HONO photolysis (50.78%) in the morning and O3 photolysis (34.13%) in the afternoon were the main HOx sources in period I, while HONO photolysis (62.86–80.68%) was significant at daytime for period II. Higher temperatures in period I accelerated all reaction rates involved in radical cycling, especially emphasizing RO2 + NO → RO + NO2. The results of sensitivity analysis showed that O3 sensitivity regime is VOC-limited in Xi'an, but the specific reactive species target VOC reductions emissions exhibited discrepancies for two distinct periods. A 20% decrease in VOCs and a 50% decrease in NOx (VOCs/NOx = 0.4) was proposed to be the optimal solution to achieve the O3 control target in period I. This study enhances our understanding of O3 formation under different meteorological conditions and provides scientific evidence for O3 pollution abatement policies in northwestern China, with potential applicability to other cities in this region and similar countries.

Effect of direct water injection on knock suppressing mechanism in a high compression ratio gasoline engine

ABSTRACT A low capacity, boosted gasoline engine is an effective approach to enhancing fuel economy. However, knock combustion poses significant limitations to the practical development of these engines. This study investigated the chemical kinetics and macroscopic properties of engines equipped with direct water injection (DWI) at high compression ratios (CRs) to address knock issues. The results indicated that the generation and consumption pathways of OH and CH2O remain unaffected by water injection. Although water exhibited an opposing effect on the sensitive reactions of OH and CH2O, the production reaction rates of OH and CH2O decrease with water injection. Knock index values at each monitoring point approached zero when the water injection quality exceeds 30%. Additionally, knock suppression effectiveness improved with the advancement of water injection timing. The simulation results indicated that the knock index at high CR decreased from 13.61 to 0.27 when the water/fuel ratio exceeded 30%. The indicated specific fuel consumption decreased by 29.3%, and indicated power increased by 41.8% compared to the original engine. Although NOx and CO emissions increased because of the high CR, the water injection coupled with the compression ratio strategy limited the increase in emissions. These findings indicated that DWI coupled with high CR was advantageous to enhancing fuel economy and reducing emissions in low capacity gasoline engines.

Unveiling the Influence of Water Molecules for NF3 Removal by the Reaction of NF3 with OH: A DFT Study.

The removal of nitrogen trifluoride (NF3) is of significant importance in atmospheric chemistry, as NF3 is an important anthropogenic greenhouse gas. However, the radical species OH and O(1D) in atmospheric conditions are nonreactive towards NF3. It is necessary to explore possible ways to remove NF3 in atmosphere. Therefore, the participation of water molecules in the reaction of NF3 with OH was discussed, as water is abundant in the atmosphere and can form very stable complexes due to its ability to act as both a hydrogen bond donor and acceptor. Systemic DFT calculations carried out at the CBS-QB3 and ωB97XD/aug-cc-pVTZ level of theory suggest that water molecules could affect the NF3 + OH reaction as well. The energy barrier of the SN2 mechanism was decreased by 8.52 kcal/mol and 10.58 kcal/mol with the assistance of H2O and (H2O)2, respectively. Moreover, the presence of (H2O)2 not only reduced the energy barrier of the reaction, but also changed the product channels, i.e., formation of NF2O + (H2O)2-HF instead of NF2OH + (H2O)2-F. Therefore, the removal of NF3 by reaction with OH is possible in the presence of water molecules. The results presented in this study should provide useful information on the atmospheric chemistry of NF3.

Controllable synthesis of NiCoMo-LDH with nanofloral structure assisted by monodisperse spherical silica for asymmetric supercapacitor

Traditional layered double hydroxides (LDH) have disadvantages such as small layer spacing, insufficient active sites and poor electrical conductivity, which seriously restricts their future utilization in the realm of energy storage. In this paper, a controlled synthesis strategy of tercomponent metal NiCoMo-LDH is proposed by using the structural advantages of metal-organic skeleton (MOF) templates, combining structural regulation and atom doping. On the basis of the synthesis of Ni-MOF 74, Co and Mo atoms are introduced for a small amount of doping, and the monodisperse spherical SiO2 is inserted to adjust the pore structure of NiCoMo-MOF, expand the lamellar spacing, and effectively avoid the accumulation and agglomeration of lamella. Finally, NiCoMo-LDH cathode material with loose porous and coarsely curled nanosphere structure was synthesized through the chemical reaction of OH− with SiO2 and the destruction of the skeleton structure of MOF. The specific capacitance of the material is 1423.3 F·g−1 at 0.5 A·g−1, and after 5000 cycles of charging and discharging, 80.0% of the original specific capacitance is sustained. Moreover, NiCoMo-LDH//AC ASC possesses a high energy density of 39.1 Wh·kg−1 at the power density 400 W·kg−1. Combined with density functional theory (DFT) calculation, the fact that metal doping can not only effectively improve the conductivity of electrode materials has been further proved, but also accelerate the electron/ion migration rate, which successfully reveal the synergistic enhancement mechanism of electrochemical properties of materials.

Fundamental Invariant Neural Network (FI-NN) Potential Energy Surface for the OH + CH3OH Reaction with Analytical Forces.

The hydrogen abstraction reaction of OH + CH3OH plays a great role in combustion and atmospheric and interstellar chemistry and has been extensively studied theoretically and experimentally. Theoretically, the numerical gradients with respect to the Cartesian coordinates of atoms in molecular simulations on our recent potential energy surface (PES) for the title reaction trained using the permutationally invariant polynomial neural network (PIP-NN) approach hinder the extensive calculation because of the unaffordable computation cost. To address this issue, we in this work report a new full-dimensional accurate analytical PES for the title reaction using the fundamental invariant neural network (FI-NN) approach based on 140,192 points of the quality UCCSD(T)-F12a/AVTZ. Besides, the spin-orbit (SO) corrections of OH in the entrance channel were determined at the level of complete active space self-consistent field with the AVTZ basis set. As a compromise between computational cost and efficiency, the Δ-machine learning approach was employed to construct the SO-corrected PES. Based on this new FI-NN PES with analytical forces, thermal rate coefficients and various dynamic properties, including the integral cross sections, the differential cross sections, and the product energy partitioning, were determined by running a total of 5.5 million trajectories. The use of analytical gradients of the FI-NN PES accelerated simulations and about 99% of computation cost was saved, compared to that for the PIP-NN PES with numerical gradients. Such a significant acceleration is achieved mainly by replacing PIPs with FIs.

Synergistic ROS Generation via Core-Shell Nanostructures with Increased Lattice Microstrain Combined with Single-Atom Catalysis for Enhanced Tumor Suppression.

This study emphasizes the innovative application of FePt and Cu core-shell nanostructures with increased lattice microstrain, coupled with Au single-atom catalysis, in significantly enhancing •OH generation for catalytic tumor therapy. The combination of core-shell with increased lattice microstrain and single-atom structures introduces an unexpected boost in hydroxyl radical (•OH) production, representing a pivotal advancement in strategies for enhancing reactive oxygen species. The creation of a core-shell structure, FePt@Cu, showcases a synergistic effect in •OH generation that surpasses the combined effects of FePt and Cu individually. Incorporating atomic Au with FePt@Cu/Au further enhances •OH production. Both FePt@Cu and FePt@Cu/Au structures boost the O2 → H2O2 → •OH reaction pathway and catalyze Fenton-like reactions. This enhancement is underpinned by DFT theoretical calculations revealing a reduced O2 adsorption energy and energy barrier, facilitated by lattice mismatch and the unique catalytic activity of single-atom Au. Notably, the FePt@Cu/Au structure demonstrates remarkable efficacy in tumor suppression and exhibits biodegradable properties, allowing for rapid excretion from the body. This dual attribute underscores its potential as a highly effective and safe cancer therapeutic agent.

A Novel Cerium Oxide/Gold/Carbon Nanocomposite-Based Electrochemical Sensor for Detecting Hydroxyl Radicals

Hydroxyl radicals (•OH), a type of reactive oxygen species (ROS), play a crucial role in maintaining the normal physiological processes of human cells. Nevertheless, an excessive accumulation of these radicals may perturb cellular mechanisms, so triggering the onset of severe diseases, including cancer, neurological disorders, and heart disease. The detection of •OH is thus of utmost importance in the early diagnosis of these disorders. The combination of an electrochemical methodology with a recognition system is considered as a promising approach for the detection of •OH. This is primarily due to its capacity to provide fast and direct readings without the need for any preliminary sample preparation. This study presents the development of a new electrochemical sensor for the detection of •OH. The sensor was developed by modifying a screen-printed carbon electrode (SPCE) with a nanocomposite consisting of cerium oxide nanoclusters (CeOx), gold nanoparticles (AuNPs), and a highly conductive carbon. The synthesis of AuNPs supported by carbon was carried out using a deposition-precipitation process. Subsequently, the meticulous deposition of CeOx nanoclusters onto the AuNPs was achieved by the use of surface organometallic chemistry (SOMC). Energy dispersive X-ray spectroscopy (EDS) and transmission electron microscopy (TEM) were applied to assess the distribution of AuNPs on the carbon substrate and their subsequent embellishment with CeOx nanoclusters. The actual loadings of Ce and Au present in the nanocomposite were measured using inductively coupled plasma optical emission spectroscopy (ICP-OES). Cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS) were employed to analyze the electrochemical responses resulting from the interaction of the CeOx-Au/Carbon nanocomposite with •OH. The CV results demonstrated that the proposed sensor exhibited the capability to effectively identify the presence of •OH in the Fenton reaction, with a notably low limit of detection of 58 µM. The sensor demonstrated a linear correlation between the current response and the concentration of •OH, within the range of 0.05 to 5 mM. Compared to a sensor modified with CeOx/Carbon, the CeOx-Au/Carbon-modified sensor exhibited enhanced electrochemical performance, as demonstrated by an increased current response and a reduced peak potential difference when detecting •OH radicals. Furthermore, the EIS studies showed that the sensor could distinguish •OH from other comparable ROS, such as hydrogen peroxide (H2O2).

Coupling Electro-Fenton and Electrocoagulation of Aluminum-Air Batteries for Enhanced Tetracycline Degradation: Improving Hydrogen Peroxide and Power Generation.

Electro-Fenton (EF) technology has shown great potential in environmental remediation. However, developing efficient heterogeneous EF catalysts and understanding the relevant reaction mechanisms for pollutant degradation remain challenging. We propose a new system that combines aluminum-air battery electrocoagulation (EC) with EF. The system utilizes dual electron reduction of O2 to generate H2O2 in situ on the air cathodes of aluminum-air batteries and the formation of primary cells to produce electricity. Tetracycline (TC) is degraded by ·OH produced by the Fenton reaction. Under optimal conditions, the system exhibits excellent TC degradation efficiency and higher H2O2 production. The TC removal rate by the reaction system using a graphite cathode reached nearly 100% within 4 h, whereas the H2O2 yield reached 127.07 mg/L within 24 h. The experimental results show that the novel EF and EC composite system of aluminum-air batteries, through the electroflocculation mechanism and ·OH and EF reactions, with EC as the main factor, generates multiple •OH radicals that interact to efficiently remove TC. This work provides novel and important insights into EF technology, as well as new strategies for TC removal.