Synergistic Catalysis of SO42-/TiO2-CNT for the CO2 Desorption Process with Low Energy Consumption.

To address the issue of high energy consumption associated with monoethanolamine (MEA) regeneration in the CO2 capture process, solid acid catalysts have been widely investigated due to their performance in accelerating carbamate decomposition. The recently discovered carbon nanotube (CNT) catalyst presents efficient catalytic activity for bicarbonate decomposition. In this paper, bifunctional catalysts SO42-/TiO2-CNT (STC) were prepared, which could simultaneously catalyze carbamate and bicarbonate decomposition, and outstanding catalytic performance has been exhibited. STC significantly increased the CO2 desorption amount by 82.3% and decreased the relative heat duty by 46% compared to the MEA-CO2 solution without catalysts. The excellent stability of STC was confirmed by 15 cyclic absorption-desorption experiments, showing good practical feasibility for decreasing energy consumption in an industrial CO2 capture process. Furthermore, associated with the results of experimental characterization and theoretical calculations, the synergistic catalysis of STC catalysts via proton and charge transfer was proposed. This work demonstrated the potential of STC catalysts in improving the efficiency of amine regeneration processes and reducing energy consumption, contributing to the design of more effective and economical catalysts for carbon capture.

Spontaneous Degradation of the "Forever Chemicals" Perfluoroalkyl and Polyfluoroalkyl Substances (PFASs) on Water Droplet Surfaces.

Because of their innate chemical stability, the ubiquitous perfluoroalkyl and polyfluoroalkyl substances (PFASs) have been dubbed "forever chemicals" and have attracted considerable attention. However, their stability under environmental conditions has not been widely verified. Herein, perfluorooctanoic acid (PFOA), a widely used and detected PFAS, was found to be spontaneously degraded in aqueous microdroplets under room temperature and atmospheric pressure conditions. This unexpected fast degradation occurred via a unique multicycle redox reaction of PFOA with interfacial reactive species on the droplet surface. Similar degradation was observed for other PFASs. This study extends the current understanding of the environmental fate and chemistry of PFASs and provides insight into aid in the development of effective methods for removing PFASs.

Kinase PIM1 governs ferroptosis to reduce retinal microvascular endothelial cell dysfunction triggered by high glucose.

Previous studies have implicated targeting Pim-1 proto-oncogene, serine/threonine kinase (PIM1) as a preventive measure against high glucose-induced cellular stress and apoptosis. This study aimed to reveal the potential role and regulatory mechanism of PIM1 in diabetic retinopathy. Human retinal microvascular endothelial cells (hRMECs) underwent high glucose induction, and fluctuations in PIM1 levels were assessed. By overexpressing PIM1, its effects on the levels of inflammatory factors, oxidative stress indicators, migration and tube formation abilities, tight junction protein expression levels, and ferroptosis in hRMECs were identified. Afterwards, hRMECs were treated with the ferroptosis-inducing agent erastin, and the effect of erastin on the above PIM1 regulatory functions was focused on. PIM1 was downregulated upon high glucose, and its overexpression inhibited the inflammatory response, oxidative stress, cell migration, and tube formation potential in hRMECs, whereas elevated tight junction protein levels. Furthermore, PIM1 overexpression reduced intracellular iron ion levels, lipid peroxidation, and levels of proteins actively involved in ferroptosis. Erastin treatment reversed the impacts of PIM1 on hRMECs, suggesting the mediation of ferroptosis in PIM1 regulation. The current study has yielded critical insights into the role of PIM1 in ameliorating high glucose-induced hRMEC dysfunction through the inhibition of ferroptosis.

HIO3-HIO2-Driven Three-Component Nucleation: Screening Model and Cluster Formation Mechanism.

Iodine oxoacids (HIO3 and HIO2)-driven nucleation has been suggested to efficiently contribute to new particle formation (NPF) in marine atmospheres. Abundant atmospheric nucleation precursors may further enhance HIO3-HIO2-driven nucleation through various multicomponent nucleation mechanisms. However, the specific enhancing potential (EP) of different precursors remains largely unknown. Herein, the EP-based screening model of precursors and enhancing mechanism of the precursor with the highest EP on HIO3-HIO2 nucleation were investigated. The formation free energies (ΔG), as critical parameters for evaluating EP, were calculated for the dimers of 63 selected precursors with HIO2. Based on the ΔG values, (1) a quantitative structure-activity relationship model was developed for evaluating ΔG of other precursors and (2) atmospheric concentrations of 63 (precursor)1(HIO2)1 dimer clusters were assessed to identify the precursors with the highest EP for HIO3-HIO2-driven nucleation by combining with earlier results for the nucleation with HIO3 as the partner. Methanesulfonic acid (MSA) was found to be one of the precursors with the highest EP. Finally, we found that MSA can effectively enhance HIO3-HIO2 nucleation at atmospheric conditions by studying larger MSA-HIO3-HIO2 clusters. These results augment our current understanding of HIO3-HIO2 and MSA-driven nucleation and may suggest a larger impact of HIO2 in atmospheric aerosol nucleation.

Iodine oxoacids enhance nucleation of sulfuric acid particles in the atmosphere.

The main nucleating vapor in the atmosphere is thought to be sulfuric acid (H2SO4), stabilized by ammonia (NH3). However, in marine and polar regions, NH3 is generally low, and H2SO4 is frequently found together with iodine oxoacids [HIOx, i.e., iodic acid (HIO3) and iodous acid (HIO2)]. In experiments performed with the CERN CLOUD (Cosmics Leaving OUtdoor Droplets) chamber, we investigated the interplay of H2SO4 and HIOx during atmospheric particle nucleation. We found that HIOx greatly enhances H2SO4(-NH3) nucleation through two different interactions. First, HIO3 strongly binds with H2SO4 in charged clusters so they drive particle nucleation synergistically. Second, HIO2 substitutes for NH3, forming strongly bound H2SO4-HIO2 acid-base pairs in molecular clusters. Global observations imply that HIOx is enhancing H2SO4(-NH3) nucleation rates 10- to 10,000-fold in marine and polar regions.

An overlooked oxidation mechanism of toluene: computational predictions and experimental validations.

Secondary organic aerosols (SOAs) influence the Earth's climate and threaten human health. Aromatic hydrocarbons (AHs) are major precursors for SOA formation in the urban atmosphere. However, the revealed oxidation mechanism dramatically underestimates the contribution of AHs to SOA formation, strongly suggesting the importance of seeking additional oxidation pathways for SOA formation. Using toluene, the most abundant AHs, as a model system and the combination of quantum chemical method and field observations based on advanced mass spectrometry, we herein demonstrate that the second-generation oxidation of AHs can form novel epoxides (TEPOX) with high yield. Such TEPOX can further react with H2SO4 or HNO3 in the aerosol phase to form less-volatile compounds including novel non-aromatic and ring-retaining organosulfates or organonitrates through reactive uptakes, providing new candidates of AH-derived organosulfates or organonitrates for future ambient observation. With the newly revealed mechanism, the chemistry-aerosol box modeling revealed that the SOA yield of toluene oxidation can reach up to 0.35, much higher than 0.088 based on the original mechanism under the conditions of pH = 2 and 0.1 ppbv NO. This study opens a route for the formation of reactive uptake SOA precursors from AHs and significantly fills the current knowledge gap for SOA formation in the urban atmosphere.

Nonacid Carbon Materials as Catalysts for Monoethanolamine Energy-Efficient Regeneration.

In the CO2 capture process, solid acid catalysts have been widely adopted to decrease energy consumption in the amine regeneration process owing to abundant acid sites. However, acid sites unavoidably degenerate in the basic amine solution. To address the challenge, nonacid carbon materials including carbon molecular sieves, porous carbon, carbon nanotubes, and graphene are first proposed to catalyze amine regeneration. It is found that carbon materials can significantly increase the CO2 desorption amount by 47.1-72.3% and reduce energy consumption by 32-42%. In 20 stability experiments, CO2 loading was stable with the max difference value of 0.01 mol CO2/mol monoethanolamine (MEA), and no obvious increase in the relative heat duty (the maximum difference is 4%) occurred. The stability of carbon materials is superior to excellent solid acid catalysts, and the desorption performance is comparable. According to the results of theoretical calculation and experimental characterization, the electron-transfer mechanism of nonacid carbon materials is proposed, which is not only beneficial for MEA regeneration but also the probable reason for the stable catalytic activity. Owing to the excellent catalytic performance of carbon nanotube (CNT) in the HCO3- decomposition, nonacid carbon materials are quite promising to enhance the desorption performance of novel blend amines, which will further reduce the cost of carbon capture in the industry. This study provides a new strategy to develop stable catalysts used for amine energy-efficient regeneration.

The contribution of industrial emissions to ozone pollution: identified using ozone formation path tracing approach.

Wintertime meteorological conditions are usually unfavorable for ozone (O3) formation due to weak solar irradiation and low temperature. Here, we observed a prominent wintertime O3 pollution event in Shijiazhuang (SJZ) during the Chinese New Year (CNY) in 2021. Meteorological results found that the sudden change in the air pressure field, leading to the wind changing from northwest before CNY to southwest during CNY, promotes the accumulation of air pollutants from southwest neighbor areas of SJZ and greatly inhibits the diffusion and dilution of local pollutants. The photochemical regime of O3 formation is limited by volatile organic compounds (VOCs), suggesting that VOCs play an important role in O3 formation. With the developed O3 formation path tracing (OFPT) approach for O3 source apportionment, it has been found that highly reactive species, such as ethene, propene, toluene, and xylene, are key contributors to O3 production, resulting in the mean O3 production rate (PO3) during CNY being 3.7 times higher than that before and after CNY. Industrial combustion has been identified as the largest source of the PO3 (2.6 ± 2.2 ppbv h-1), with the biggest increment (4.8 times) during CNY compared to the periods before and after CNY. Strict control measures in the industry should be implemented for O3 pollution control in SJZ. Our results also demonstrate that the OFPT approach, which accounts for the dynamic variations of atmospheric composition and meteorological conditions, is effective for O3 source apportionment and can also well capture the O3 production capacity of different sources compared with the maximum incremental reactivity (MIR) method.

Enhancement of Atmospheric Nucleation Precursors on Iodic Acid-Induced Nucleation: Predictive Model and Mechanism.

Iodic acid (IA) has recently been recognized as a key driver for new particle formation (NPF) in marine atmospheres. However, the knowledge of which atmospheric vapors can enhance IA-induced NPF remains limited. The unique halogen bond (XB)-forming capacity of IA makes it difficult to evaluate the enhancing potential (EP) of target compounds on IA-induced NPF based on widely studied sulfuric acid systems. Herein, we employed a three-step procedure to evaluate the EP of potential atmospheric nucleation precursors on IA-induced NPF. First, we evaluated the EP of 63 precursors by simulating the formation free energies (ΔG) of the IA-containing dimer clusters. Among all dimer clusters, 44 contained XBs, demonstrating that XBs are frequently formed. Based on the calculated ΔG values, a quantitative structure-activity relationship model was developed for evaluating the EP of other precursors. Second, amines and O/S-atom-containing acids were found to have high EP, with diethylamine (DEA) yielding the highest potential to enhance IA-induced nucleation by combining both the calculated ΔG and atmospheric concentration of considered 63 precursors. Finally, by studying larger (IA)1-3(DEA)1-3 clusters, we found that the IA-DEA system with merely 0.1 ppt (2.5×106 cm-3) DEA yields comparable nucleation rates to that of the IA-iodous acid system.

Counterintuitive Oxidation of Alcohols at Air-Water Interfaces.

This study shows that the oxidation of alcohols can rapidly occur at air-water interfaces. It was found that methanediols (HOCH2OH) orient at air-water interfaces with a H atom of the -CH2- group pointing toward the gaseous phase. Counterintuitively, gaseous hydroxyl radicals do not prefer to attack the exposed -CH2- group but the -OH group that forms hydrogen bonds with water molecules at the surface via a water-promoted mechanism, leading to the formation of formic acids. Compared with gaseous oxidation, the water-promoted mechanism at the air-water interface significantly lowers free-energy barriers from ∼10.7 to ∼4.3 kcal·mol-1 and therefore accelerates the formation of formic acids. The study unveils a previously overlooked source of environmental organic acids that are bound up with aerosol formation and water acidity.

Atmospheric Sulfuric Acid-Multi-Base New Particle Formation Revealed through Quantum Chemistry Enhanced by Machine Learning.

The formation of molecular clusters and secondary aerosols in the atmosphere has a significant impact on the climate. Studies typically focus on the new particle formation (NPF) of sulfuric acid (SA) with a single base molecule (e.g., dimethylamine or ammonia). In this work, we examine the combinations and synergy of several bases. Specifically, we used computational quantum chemistry to perform configurational sampling (CS) of (SA)0-4(base)0-4 clusters with five different types of bases: ammonia (AM), methylamine (MA), dimethylamine (DMA), trimethylamine (TMA), and ethylenediamine (EDA). Overall, we studied 316 different clusters. We used a traditional multilevel funnelling sampling approach augmented by a machine-learning (ML) step. The ML made the CS of these clusters possible by significantly enhancing the speed and quality of the search for the lowest free energy configurations. Subsequently, the cluster thermodynamics properties were evaluated at the DLPNO-CCSD(T0)/aug-cc-pVTZ//ωB97X-D/6-31++G(d,p) level of theory. The calculated binding free energies were used to evaluate the cluster stabilities for population dynamics simulations. The resultant SA-driven NPF rates and synergies of the studied bases are presented to show that DMA and EDA act as nucleators (although EDA becomes weak in large clusters), TMA acts as a catalyzer, and AM/MA is often overshadowed by strong bases.

Critical Role of Iodous Acid in Neutral Iodine Oxoacid Nucleation.

Nucleation of neutral iodine particles has recently been found to involve both iodic acid (HIO3) and iodous acid (HIO2). However, the precise role of HIO2 in iodine oxoacid nucleation remains unclear. Herein, we probe such a role by investigating the cluster formation mechanisms and kinetics of (HIO3)m(HIO2)n (m = 0-4, n = 0-4) clusters with quantum chemical calculations and atmospheric cluster dynamics modeling. When compared with HIO3, we find that HIO2 binds more strongly with HIO3 and also more strongly with HIO2. After accounting for ambient vapor concentrations, the fastest nucleation rate is predicted for mixed HIO3-HIO2 clusters rather than for pure HIO3 or HIO2 ones. Our calculations reveal that the strong binding results from HIO2 exhibiting a base behavior (accepting a proton from HIO3) and forming stronger halogen bonds. Moreover, the binding energies of (HIO3)m(HIO2)n clusters show a far more tolerant choice of growth paths when compared with the strict stoichiometry required for sulfuric acid-base nucleation. Our predicted cluster formation rates and dimer concentrations are acceptably consistent with those measured by the Cosmic Leaving Outdoor Droplets (CLOUD) experiment. This study suggests that HIO2 could facilitate the nucleation of other acids beyond HIO3 in regions where base vapors such as ammonia or amines are scarce.

Amine-Enhanced Methanesulfonic Acid-Driven Nucleation: Predictive Model and Cluster Formation Mechanism.

Atmospheric amines are considered to be an effective enhancer for methanesulfonic acid (MSA)-driven nucleation. However, out of the 195 detected atmospheric amines, the enhancing potential (EP) has so far only been studied for five amines. This severely hinders the understanding of the contribution of amines to MSA-driven nucleation. Herein, a two-step procedure was employed to probe the EP of various amines on MSA-driven nucleation. Initially, the formation free energies (ΔG) of 50 MSA-amine dimer clusters were calculated. Based on the calculated ΔG values, a robust quantitative structure-activity relationship (QSAR) model was built and utilized to predict the ΔG values of the remaining 145 amines. The QSAR model identified two guanidino-containing compounds as the potentially strongest enhancer for MSA-driven nucleation. Second, the EP of guanidino-containing compounds was studied by employing larger clusters and selecting guanidine (Gud) as a representative. The results indicate that Gud indeed has the strongest EP. The Gud-MSA system presents a unique clustering mechanism, proceeding via the initial formation of the (Gud)1(MSA)1 cluster, and subsequently by cluster collisions with either a (Gud)1(MSA)1 or (Gud)2(MSA)2 cluster. The developed QSAR model and the identification of amines with the strongest EP provide a foundation for comprehensively evaluating the contribution of atmospheric amines to MSA-driven nucleation.

Potential Application of Machine-Learning-Based Quantum Chemical Methods in Environmental Chemistry.

It is an important topic in environmental sciences to understand the behavior and toxicology of chemical pollutants. Quantum chemical methodologies have served as useful tools for probing behavior and toxicology of chemical pollutants in recent decades. In recent years, machine learning (ML) techniques have brought revolutionary developments to the field of quantum chemistry, which may be beneficial for investigating environmental behavior and toxicology of chemical pollutants. However, the ML-based quantum chemical methods (ML-QCMs) have only scarcely been used in environmental chemical studies so far. To promote applications of the promising methods, this Perspective summarizes recent progress in the ML-QCMs and focuses on their potential applications in environmental chemical studies that could hardly be achieved by the conventional quantum chemical methods. Potential applications and challenges of the ML-QCMs in predicting degradation networks of chemical pollutants, searching global minima for atmospheric nanoclusters, discovering heterogeneous or photochemical transformation pathways of pollutants, as well as predicting environmentally relevant end points with wave functions as descriptors are introduced and discussed.

Mechanistic Understanding of Superoxide Radical-Mediated Degradation of Perfluorocarboxylic Acids.

Perfluorocarboxylic acids (PFCAs) exhibit strong persistence in sunlit surface waters and in radical-based treatment processes, where superoxide radical (O2•-) is an important and abundant reactive oxygen species. Given that the role of O2•- during the transformation of PFCAs remains largely unknown, we investigated the kinetics and mechanisms of O2•--mediated PFCAs attenuation through complementary experimental and theoretical approaches. The aqueous-phase rate constants between O2•- and C3-C8 PFCAs were measured using a newly designed in situ spectroscopic system. Mechanistically, bimolecular nucleophilic substitution (SN2) is most likely to be thermodynamically feasible, as indicated by density functional theory calculations at the CBS-QB3 level of theory. This pathway was then investigated by ab initio molecular dynamics simulation with free-energy samplings. As O2•- approaches PFCA, the C-F bond at the alpha carbon is spontaneously stretched, leading to the bond cleavage. The solvation mechanism for O2•--mediated PFCA degradation was also elucidated. Our results indicated that although the less polar solvent enhanced the nucleophilicity of O2•-, it also decreased the desolvation process of PFCAs, resulting in reduced kinetics. With these quantitative and mechanistic results, we achieved a defined picture of the O2•--initiated abatement of PFCAs in natural and engineered waters.

Atmospheric Autoxidation of Organophosphate Esters.

Organophosphate esters (OPEs), widely used as flame retardants and plasticizers, have frequently been identified in the atmosphere. However, their atmospheric fate and toxicity associated with atmospheric transformations are unclear. Here, we performed quantum chemical calculations and computational toxicology to investigate the reaction mechanism of peroxy radicals of OPEs (OPEs-RO2•), key intermediates in determining the atmospheric chemistry of OPEs, and the toxicity of the reaction products. TMP-RO2• (R1) and TCPP-RO2• (R2) derived from trimethyl phosphate and tris(2-chloroisopropyl) phosphate, respectively, are selected as model systems. The results indicate that R1 and R2 can follow an H-shift-driven autoxidation mechanism under low NO concentration ([NO]) conditions, clarifying that RO2• from esters can follow an autoxidation mechanism. The unexpected autoxidation mechanism can be attributed to the distinct role of the ─(O)3P(═O) phosphate-ester group in facilitating the H-shift of OPEs-RO2• from commonly encountered ─OC(═O)─ and ─ONO2 ester groups in the atmosphere. Under high [NO] conditions, NO can mediate the autoxidation mechanism to form organonitrates and alkoxy radical-related products. The products from the autoxidation mechanism have low volatility and aquatic toxicity compared to their corresponding parent compounds. The proposed autoxidation mechanism advances our current understanding of the atmospheric RO2• chemistry and the environmental risk of OPEs.

Organic acid-ammonia ion-induced nucleation pathways unveiled by quantum chemical calculation and kinetics modeling: A case study of 3-methyl-1,2,3-butanetricarboxylic acid.

Nucleation of organic acids (OAs) and H2SO4 is an important source for new particle formation in the atmosphere. However, it is still unclear whether organic acids can produce nanoparticles independent of H2SO4. In this study, 3-methyl-1,2,3-butanetricarboxylic acid (MBTCA) was adopted as a model of OAs. Pathways of clustering from MBTCA, ammonia and ions (NH4+ and NO3-) to form a 1.9 nm nucleus were investigated by quantum chemical calculation and kinetic modeling. Results show recombination of charged clusters/ions plays an essential role in the nucleation processes. Cluster formation rates increase by a factor of 103 when NH3 increases from 2.6 × 108 molecules·cm-3 (under clean conditions) to 2.6 × 1011 molecules·cm-3 (under polluted conditions), as NH3 can stabilize MBTCA clusters and change ion compositions from H3O+ to NH4+. Although the proposed new mechanism cannot compete with H2SO4-NH3-H2O or H2SO4-OA nucleation currently, it may be important in the future with the decline of SO2 concentration.

Heterogeneous Formation of HONO Catalyzed by CO2.

Gas-phase nitrous acid (HONO) is a major precursor of hydroxyl radicals that dominate atmospheric oxidizing capacity. Nevertheless, pathways of HONO formation remain to be explored. This study unveiled an important CO2-catalysis mechanism of HONO formation, using Born-Oppenheimer molecular dynamics simulations and free-energy samplings. In the mechanism, HCO3- formed from CO2 hydrolysis reacts with NO2 dimers to produce HONO at water surfaces, and simultaneously, itself reconverts back to CO2 via intermediates OC(O)ONO- and HOC(O)ONO. A flow system experiment was performed to confirm the new mechanism, which indicated that HONO concentrations with CO2 injections were increased by 29.4-68.5%. The new mechanism can be extended to other humid surfaces. Therefore, this study unveiled a previously overlooked vital role of CO2 that catalyzes formation of HONO and affects atmospheric oxidizing capacity.

Atmospheric Chemistry of Allylic Radicals from Isoprene: A Successive Cyclization-Driven Autoxidation Mechanism.

The atmospheric chemistry of isoprene has broad implications for regional air quality and the global climate. Allylic radicals, taking 13-17% yield in the isoprene oxidation by •Cl, can contribute as much as 3.6-4.9% to all possible formed intermediates in local regions at daytime. Considering the large quantity of isoprene emission, the chemistry of the allylic radicals is therefore highly desirable. Here, we investigated the atmospheric oxidation mechanism of the allylic radicals using quantum chemical calculations and kinetics modeling. The results indicate that the allylic radicals can barrierlessly combine with O2 to form peroxy radicals (RO2•). Under ≤100 ppt NO and ≤50 ppt HO2• conditions, the formed RO2• mainly undergo two times "successive cyclization and O2 addition" to finally form the product fragments 2-alkoxy-acetaldehyde (C2H3O2•) and 3-hydroperoxy-2-oxopropanal (C3H4O4). The presented reaction illustrates a novel successive cyclization-driven autoxidation mechanism. The formed 3-hydroperoxy-2-oxopropanal product is a new isomer of the atmospheric C3H4O4 family and a potential aqueous-phase secondary organic aerosol precursor. Under >100 ppt NO condition, NO can mediate the cyclization-driven autoxidation process to form C5H7NO3, C5H7NO7, and alkoxy radical-related products. The proposed novel autoxidation mechanism advances our current understanding of the atmospheric chemistry of both isoprene and RO2•.