Current research on heterogeneous advanced oxidation processes(HAOPs)predominantly emphasizes catalyst iteration and innovation.Significant efforts have been made to regulate the electron structure and optimize the el...Current research on heterogeneous advanced oxidation processes(HAOPs)predominantly emphasizes catalyst iteration and innovation.Significant efforts have been made to regulate the electron structure and optimize the electron distribution,thereby increasing the catalytic activity.However,this focus often overshadows an equally essential aspect of HAOPs:the adsorption effect.Adsorption is a critical initiator for triggering the interaction of oxidants and contaminants with heterogeneous catalysts.The efficacy of these interactions is influenced by a variety of physicochemical properties,including surface chemistry and pore sizes,which determine the affinities between contaminants and material surfaces.This dispar ity in affinity is pivotal because it underpins the selective removal of contaminants,especially in complex waste streams containing diverse contaminants and competing matrices.Consequently,understanding and mastering these interfacial interactions is fundamentally indispensable not only for improving pro cess efficiency but also for enhancing the selectivity of contaminant removal.Herein,we highlight the importance of adsorption-driven interfacial interactions for fundamentally elucidating the catalytic mechanisms of HAOPs.Such interactions dictate the overall performance of the treatment processes by balancing the adsorption,reaction,and desorption rates on the catalyst surfaces.Elucidating the adsorption effect not only shifts the paradigm in understanding HAOPs but also improves their practical ity in water treatment and wastewater decontamination.Overall,we propose that revisiting adsorption driven interfacial interactions holds great promise for optimizing catalytic processes to develop effective HAOP strategies.展开更多
Coupling adsorption and in-situ Fenton-like oxidation process was developed for Methylene blue(MB) using refined iron-containing lowgrade attapulgite(ATP) clay, and the removal mechanism was investigated. The MB was i...Coupling adsorption and in-situ Fenton-like oxidation process was developed for Methylene blue(MB) using refined iron-containing lowgrade attapulgite(ATP) clay, and the removal mechanism was investigated. The MB was initially adsorbed on the porous ATPs, and then the enriched MB was removed by the H2O2-assisted Fenton-like oxidation with the iron-containing ATP catalyst. Under optimal conditions, the ATP powder exhibits the maximum removal efficiency of 100% with negligible iron leaching(1.5 mg L^(-1)) and no sludge formation. Furthermore,polysulfone/ATP(PSF/ATP) pellets were fabricated through a water-induced phase separation process to construct a fixed-bed reactor(FBR) for continuous contaminant removal. For the first cycle, the maximum adsorption capacity was 15.5 L with an outlet MB concentration of1.973 mg L-1(< 2 mg L^(-1), GB4287-2012) using the PSF/ATP pellets containing 50.0 g of ATP powders, and the maximum Fenton-like oxidation capacity was 35.5 L with the outlet concentration of 0.831 mg L^(-1). After five cycles, the total treated volume of the MB solution was ca. 255 L, and the efficiency remained above 99%. After 10 h of continuous treatment towards practical resin industrial wastewater, the chemical oxygen demand(COD) removal efficiency was still measured at 83.05%, costing 0.398 $ m^(-3). These results demonstrate the practical applicability of iron-containing low-grade ATP clay for textile water treatment.展开更多
Manganese oxides are known as one type of semiconductors,but their photocatalysis characteristics have not been deeply explored.In this study,photocatalytic degradation of phenol using several synthesized manganese ox...Manganese oxides are known as one type of semiconductors,but their photocatalysis characteristics have not been deeply explored.In this study,photocatalytic degradation of phenol using several synthesized manganese oxides,i.e,acidic birnessite （BIR-H）,alkaline birnessite （BIR-OH）,cryptomelane （CRY） and todorokite （TOD）,were comparatively investigated.To elucidate phenol degradation mechanisms,X-ray diffraction （XRD）,ICP-AES （inductively coupled plasma-atomic emission spectroscopy）,TEM （transmission electronic microscope）,N 2 physisorption at 77 K and UV-visible diffuse reflectance spectroscopy （UV-Vis DRS） were employed to characterize the structural,compositional,morphological,specific surface area and optical absorption properties of the manganese oxides.After 12 hr of UV-Vis irradiation,the total organic carbon （TOC） removal rate reached 62.1%,43.1%,25.4%,and 22.5% for cryptomelane,acidic birnessite,todorokite and alkaline birnessite,respectively.Compared to the reactions in the dark condition,UV- Vis exposure improved the TOC removal rates by 55.8%,31.9%,23.4% and 17.9%.This suggests a weak ability of manganese oxides to degrade phenol in the dark condition,while UV-Vis light irradiation could significantly enhance phenol degradation.The manganese minerals exhibited photocatalytic activities in the order of：CRY BIR-H TOD BIR-OH.There may be three possible mechanisms for photochemical degradation：（1） direct photolysis of phenol;（2） direct oxidation of phenol by manganese oxides;（3） photocatalytic oxidation of phenol by manganese oxides.Photocatalytic oxidation of phenol appeared to be the dominant mechanism.展开更多
Oxidation treatment on the adsorption and the stability of Hg on activated carbon （AC） was inrestigated. Both MnO2-AC and FeCl3-AC were produced during oxidation treatment. The measurement of modified AC＇s mercury ...Oxidation treatment on the adsorption and the stability of Hg on activated carbon （AC） was inrestigated. Both MnO2-AC and FeCl3-AC were produced during oxidation treatment. The measurement of modified AC＇s mercury adsorption capacity was conducted in a simulated coal-fired flue gas by adsorbing test apparatus. TCLP and column leaching methods were used to test the stability of mercury adsorbed on ACs. The results indicate that the oxidation treatment changed the pore structure of the AC and modified the carbon surface by creating chemical components such as MnO4^-, Mn^4＋, O, NO^3-, Fe^3＋, Cl^-, etc. The Hg sorption capacity on MnO2-AC or FeCl3-AC was about three times higher than that of untreated carbon. In addition, the mercury control cost of each of the formers was about the half cost of the untreated carbon. The stability of Hg absorption was studied, it found that mercury adsorbed on the oxidation treated AC was not better than that of untreated carbon. It could concluded that the insoluble form of Hg is very important to the stability of mercury adsorbed on AC. This study suggests that the FeCl3-AC is the best absorbent for Hg with high adsorption capacity, better Hg adsorption stability in leaching environment, and lower cost among the three ACs tested.展开更多
Bioaerosol emissions from wastewater and wastewater treatment processes are a significant subgroup of atmospheric aerosols. Most previous work has focused on the evaluation of their biological risks. In this study, ho...Bioaerosol emissions from wastewater and wastewater treatment processes are a significant subgroup of atmospheric aerosols. Most previous work has focused on the evaluation of their biological risks. In this study, however, the adsorption method was applied to reduce airborne microorganisms generated from a pilot scale wastewater treatment facility with oxidation ditch. Results showed adsorption on granule activated carbon （GAC） was an efficient method for the purification of airborne microorganisms. The GAC itself had a maximum adsorption capacity of 2217 CFU/g for airborne bacteria and 225 CFU/g for fungi with a flow rate of 1.50 m^3/hr. Over 85% of airborne bacteria and fungi emitted from the oxidation ditch were adsorbed within 80 hr of continuous operation mode. Most of them had a particle size of 0.65-4.7 μm. Those airborne microorganisms with small particle size were apt to be adsorbed. The SEM/EDAX, BET and Boehm＇s titration methods were applied to analyse the physicochemical characteristics of the GAC. Relationships between GAC surface characteristics and its adsorption performance demonstrated that porous structure, large surface area, and hydrophobicity rendered GAC an effective absorber of airborne microorganisms. Two regenerate methods, ultraviolet irradiation and high pressure vapor, were compared for the regeneration of used activated carbon. High pressure vapor was an effective technique as it totally destroyed the microorganisms adhered to the activated carbon. Microscopic observation was also carried out to investigate original and used adsorbents.展开更多
Metal oxide catalysts are widely employed in propane dehydrogenation(PDH)for propylene synthesis,requiring sequential reduction-reaction-regeneration cycles.However,the eff ect of water present in the inlet gas or rea...Metal oxide catalysts are widely employed in propane dehydrogenation(PDH)for propylene synthesis,requiring sequential reduction-reaction-regeneration cycles.However,the eff ect of water present in the inlet gas or reactor on the catalytic per-formance of various metal oxides remains insuffi ciently understood.This study examines the infl uence of water on supported metal oxide catalysts,specifi cally CoO x/Al_(2)O_(3),VO x/Al_(2)O_(3),and an industrial analog CrO x/Al_(2)O_(3) catalyst.By combining titration experiments,in situ Fourier transform infrared spectroscopy,kinetic analysis,and isotopic techniques,we demon-strate that even trace amounts of water can markedly suppress PDH performance via dissociative adsorption on the oxide surface.Methanol pretreatment eff ectively scavenges adsorbed water,recovering Lewis acid-base sites and consequently restoring PDH activity.This work underscores the profound inhibitory role of trace water in PDH over metal oxide catalysts and illustrates the potential of methanol pretreatment as an effective strategy to mitigate this limitation.展开更多
The indiscriminate use and disposal of ciprofloxacin(CIP)have led to its detection in water globally,which pose a huge risk to public health and water environment.Herein,(Zn-Al)LDHs modified 3D reduced graphene oxide ...The indiscriminate use and disposal of ciprofloxacin(CIP)have led to its detection in water globally,which pose a huge risk to public health and water environment.Herein,(Zn-Al)LDHs modified 3D reduced graphene oxide nanocomposite((Zn-Al)LDHs/3D-rGO)was synthesized through a feasible onepot hydrothermal method for CIP removal.The highly distributed(Zn-Al)LDHs flakes on the surface of 3D-rGO endow the resulted(Zn-Al)LDHs/3D-rGO with an excellent adsorption performance for CIP.The adsorption results showed that the adsorption process could be well interpreted by Temkin isothermal model and the pseudo second-order kinetics model.The maximal adsorption capacity of 20.01 mg·g^(-1)for CIP could be achieved under the optimal conditions optimized by response surface methodology(RSM).The inhibitory effect of co-existing ions on CIP adsorption were also discussed.The probable adsorption mechanism might be ascribed toπ-πinteractions,hydrogen bonding,electrostatic,and surface complexation.Regeneration tests showed that the obtained 3D porous material also possessed pronounced recyclability.The obtained(Zn-Al)LDHs/3D-rGO holds a great potential for removal of CIP from actual wastewater.展开更多
The long term exposure of arsenic via drinking water has resulted in wide occurrence of arsenisim globally, and the oxidation of the non-ionic arsenite(As(Ⅲ)) to negatively-charged arsenate(As(Ⅴ)) is of crucial impo...The long term exposure of arsenic via drinking water has resulted in wide occurrence of arsenisim globally, and the oxidation of the non-ionic arsenite(As(Ⅲ)) to negatively-charged arsenate(As(Ⅴ)) is of crucial importance for the promising removal of arsenic. The chemical oxidants of ozone, chlorine, chlorine dioxide, and potassium permanganate may achieve this goal;however, their application in developing countries is sometimes restricted by the complicate operation and high cost. This review paper focuses on the heterogeneous oxidation of As(Ⅲ) by solid oxidants such as manganese oxide, and the adsorption of As(Ⅴ)accordingly. Manganese oxide may be prepared by both chemical and biological methods to achieve good oxidation performance towards As(Ⅲ). Additionally, manganese oxide may be combined with other metal oxides, e.g., iron oxide, to improve the adsorption capability towards As(Ⅴ). Furthermore, manganese oxide may be coated onto porous materials of metal organic frameworks to develop novel adsorbents for arsenic removal. To achieve the application in engineering works, the adsorbents granulation may be achieved by drying and calcination, agglomeration, and the active components may also be in situ coated onto the porous materials to maintain the oxidation and adsorption activities as much as possible. The novel adsorbents with heterogeneous oxidation and adsorption capability may be carefully designed for the removal of arsenic in household purifiers, community-level decentralized small systems, and the large-scale drinking water treatment plants(DWTPs).This review provides insight into the fundamental studies on novel adsorbents, the development of innovative technologies, and the demonstration engineering works involved in the heterogeneous oxidation and adsorption, and may be practically valuable for the arsenic pollution control globally.展开更多
Antimony（Sb）, which can be toxic at relatively low concentrations, may co-exist with Mn（Ⅱ）and/or Fe（Ⅱ） in some groundwater and surface water bodies. Here we investigated the potential oxidation and adsorption ...Antimony（Sb）, which can be toxic at relatively low concentrations, may co-exist with Mn（Ⅱ）and/or Fe（Ⅱ） in some groundwater and surface water bodies. Here we investigated the potential oxidation and adsorption pathways of Sb（Ⅲ and V） species in the presence of Mn（Ⅱ） and Mn-oxidizing bacteria, with or without Fe（Ⅱ）. Batch experiments were conducted to determine the oxidation and adsorption characteristics of Sb species in the presence of biogenic Mn oxides（BMOs）, which were formed in-situ via the oxidation of Mn（Ⅱ） by a Mn-oxidizing bacterium（Pseudomonas sp. QJX-1）. Results indicated that Sb（Ⅲ） ions could be oxidized to Sb（V） ions by BMO, but only Sb（V） originating from Sb（Ⅲ） oxidation was adsorbed effectively by BMO. Introduced Fe（Ⅱ） was chemically oxidized to Fe OOH, the precipitates of which mixed with BMO to form a new compound, biogenic Fe–Mn oxides（BFMO）. The BMO part of the BFMO mainly oxidized and the Fe OOH of the BFMO mainly adsorbed the Sb species. In aquatic solutions containing both As（Ⅲ） and Sb（Ⅲ）, the BFMO that formed in-situ preferentially oxidized Sb over As but adsorbed As more efficiently. Chemical analysis and reverse transcription real-time polymerase chain reaction revealed that the presence of Fe（Ⅱ）, As（Ⅲ） and Sb（Ⅲ） accelerated the oxidation of Mn（Ⅱ） but inhibited the activity of Mn-oxidizing bacteria. These results provide significant insights into the biogeochemical pathways of Sb, Mn（Ⅱ） in aquatic ecosystems, with or without Fe（Ⅱ）.展开更多
Magnetic Fe3 O4@Cu/Ce microspheres were successfully prepared by one-step solvothermal approach and further utilized to remediate toxic arsenic(As(Ⅲ)) pollution. The effects of Cu/Ce elements co-doping on the crystal...Magnetic Fe3 O4@Cu/Ce microspheres were successfully prepared by one-step solvothermal approach and further utilized to remediate toxic arsenic(As(Ⅲ)) pollution. The effects of Cu/Ce elements co-doping on the crystal structure, catalytic oxidation and adsorption behaviors of magnetic microspheres were researched systematically. The results showed that with the aid of Cu/Ce elements, the grain size reduced, lattice defects increased, and the oxygen vacancies and surface hydroxyl groups were improved. Therefore, Cu/Ce elements endowed magnetic Fe3 O4@Cu/Ce microspheres with excellent As(III) removal performance, whose maximum adsorption capacity reached 139.19 mg/g. The adsorption mechanism mainly involved catalytic oxidant co-adsorption. This research developed a feasible strategy for the preparation of high efficiency magnetic adsorbent to enhance the removal of As(Ⅲ).展开更多
A greater part of water-solnble organic substances, accounting for 6070To of the total, could be adsorbedby soils, which included strongly and weekly reducing substances, positively and negatively charged substancesan...A greater part of water-solnble organic substances, accounting for 6070To of the total, could be adsorbedby soils, which included strongly and weekly reducing substances, positively and negatively charged substancesand substances containing amido. There existed a tendency of decrease in adsorption of the negativelycharged organic substances by the soil from South China to North China, with expression as Coulombianadsorption. A simultaneous reduction of iron and manganese appeared with clear voltammetric behavioursupon oxidation of water-soluble organic substances. Complexation of organic ligands with ferrons iron andmanganous manganese was proved by differential pulse voltammetric method, with disappearance of oxidationpeaks of ferrous iron and manganous manganese at 0.00 V and 0.35 V and occurrence of Fe`+-complex andMn￣2+ -complex at 0.75 V and 1.2 V respectively, whose peak potentials shifted backward.展开更多
The available data have shown that acid-leached clays had sites for adsorption of impurities in oils. Data obtained on residual impurities in cotton and sunflower-seed oils bleached with the same clay materials produc...The available data have shown that acid-leached clays had sites for adsorption of impurities in oils. Data obtained on residual impurities in cotton and sunflower-seed oils bleached with the same clay materials produced linear Langmuir and Freundlich isotherms. The increase in constant, k with increase in both temperature of thermal activation and concentration of acid used to leach the clay, suggests that bleaching efficiency increased. The value of n decreased with increase in temperature of activation and concentration of acid used to leach the clay suggesting that bleaching capacity increased. The mineral compositions of the clays influenced their surface, structural and bleaching properties.展开更多
The hardness,wettability,and electrochemical properties of Ti6Al4V alloy surfaces treated with anodic oxidation and plasma oxidation as well as the viabilities of the different cell lines on the obtained surfaces were...The hardness,wettability,and electrochemical properties of Ti6Al4V alloy surfaces treated with anodic oxidation and plasma oxidation as well as the viabilities of the different cell lines on the obtained surfaces were investigated.The anodic oxidation was performed for 10 min under 100 V potential,and it resulted in a 0.95μm thick nanoporous anatase-TiO2 structure.On the other hand,plasma oxidation was carried out at 650℃ for 1 h and resulted in a dense rutile-TiO2 structure with a thickness of 1.2μm.While a hardness of HV0.025823 and roughness of^220 nm were obtained by plasma oxidation,those obtained by anodic oxidation were HV0.025512 and^130 nm,respectively.The anodic oxidation process created a more hydrophilic surface with a contact angle of 87.2°.Both oxidation processes produced similar properties in terms of corrosion behavior and showed better resistance than the as-received state in a certain range of potential.Moreover,the surface treatments led to no significant change in the protein adsorption levels,which indicates that the difference in viability between the osteoblast and fibroblast cells was not due to the difference in surface protein adsorption.Given all the factors,the surfaces obtained by anodic oxidation treatment revealed higher cell viability than those obtained by plasma oxidation(p=0.05).展开更多
In-situ oxidation of solid phase was considered to investigate adsorption behavior under different geochemical parameters like pH, initial concentration and ionic strength. Pumice tuff, a potential host rock for low a...In-situ oxidation of solid phase was considered to investigate adsorption behavior under different geochemical parameters like pH, initial concentration and ionic strength. Pumice tuff, a potential host rock for low and intermediate radioactive wastes, has been affected by the redox zone. The characterization of the fresh and oxidized tuff was performed by X-ray diffractometer, scanning electron microscope and mercury intrusion porosimetry. In order to compare the difference of distribution coefficient (K<sub>d</sub>) in fresh and oxidized pumice tuffs, a batch adsorption study was carried out at the range of pH (4 - 12), ionic strength (0.003, 0.1, 1.0 and 3.0 mol/dm<sup>3</sup>) and initial cesium concentration (10<sup>dž</sup>, 10<sup>LJ</sup>, 10<sup>Lj</sup> and 10<sup>lj</sup> mol/dm<sup>3</sup>). Based on experimental K<sub>d</sub> values, ionic strength was found to be the most influential factor, whereas the effects of pH, initial Cs concentration and weathering condition of pumice tuff were negligible. The recalculated K<sub>d</sub> values suggest that the existing surface complexation model is applicable to explain the sorption coefficients through the wide range of solution conditions.展开更多
A novel adsorbent based on iron oxide dispersed over activated carbon （AC） were prepared, and used for phosphate removal from aqueous solutions. The influence of pre-oxidation treatment on the physical, chemical and...A novel adsorbent based on iron oxide dispersed over activated carbon （AC） were prepared, and used for phosphate removal from aqueous solutions. The influence of pre-oxidation treatment on the physical, chemical and phosphate adsorption properties of iron-containing AC were determined. Two series of ACs, non-oxidized and oxidized carbon modified by iron （denoted as AC-Fe and AC/O- Fe）, resulted in a maximum impregnated iron of 4.03% and 7.56%, respectively. AC/O-Fe showed 34.0%46.6% higher phosphate removal efficiency than the AC-Fe did. This was first attributed to the moderate pre-oxidation of raw AC by nitric acid, achieved by dosing Fe（II） after a pre-oxidation, to obtain higher iron loading, which is favorable for phosphate adsorption. Additionally, the in-situ formed active site on the surface of carbon, which was derived from the oxidation of Fe（II） by nitric acid dominated the remarkably high efficiency with respect to the removal of phosphate. The activation energy for adsorption was calculated to be 10.53 and 18.88 kJ/mol for AC-Fe and AC/O- Fe, respectively. The results showed that the surface mass transfer and intra-parficle diffusion were simultaneously occurring during the process and contribute to the adsorption mechanism.展开更多
The alkali-metal Na adsorption on Si(100)2×1 surface and its promoted oxidation and Si oxide growth have been investigated by means of thermal desorption,work function,Auger electron spectroscopy and photoemissio...The alkali-metal Na adsorption on Si(100)2×1 surface and its promoted oxidation and Si oxide growth have been investigated by means of thermal desorption,work function,Auger electron spectroscopy and photoemission electron spectroscopy.The experimental data showed that there was a new state,interface electron state,near the Fermi level after the deposition of Na atoms.It was found that the presence of Na always caused an increase of the oxygen initial uptake whereas the promotion of Si oxide growth was observed only at the coverage of Na greater than 0.5 ML.A new mechanism of Na-promoted Si oxide growth is suggested in this paper.展开更多
To solve the problem of polymer-bearing effluent of crude oil not reaching the standard,deep treatment system of Fenton oxidation-activated carbon adsorption is established in one refinery,and the most suitable condit...To solve the problem of polymer-bearing effluent of crude oil not reaching the standard,deep treatment system of Fenton oxidation-activated carbon adsorption is established in one refinery,and the most suitable condition of Fenton oxidation reaction is determined.Operation results show that CODCrconcentration of effluent treated by the system could be lower than 50 mg/L,and ammonia nitrogen content is less than 3 mg/L,which meets design requirement.展开更多
Hausmannite is a common low valence Mn oxide mineral,with a distorted spinel structure,in surficial sediments.Although natural Mn oxides often contain various impurities of transitional metals(TMs),few studies have ad...Hausmannite is a common low valence Mn oxide mineral,with a distorted spinel structure,in surficial sediments.Although natural Mn oxides often contain various impurities of transitional metals(TMs),few studies have addressed the effect and related mechanism of TM doping on the reactivity of hausmannite with metal pollutants.Here,the reactivity of cobalt(Co)doped hausmannite with aqueous As(Ⅲ)and As(Ⅴ)was studied.Co doping decreased the point of zero charge of hausmannite and its adsorption capacity for As(Ⅴ).Despite a reduction of the initial As(Ⅲ)oxidation rate,Co-doped hausmannite could effectively oxidize As(Ⅲ)to As(Ⅴ),followed by the adsorption and fixation of a large amount of As(Ⅴ)on the mineral surface.Arsenic K-edge EXAFS analysis of the samples after As(Ⅴ)adsorption and As(Ⅲ)oxidation revealed that only As(Ⅴ)was adsorbed on the mineral surface,with an average As-Mn distance of 3.25–3.30 A,indicating the formation of bidentate binuclear complexes.These results provide new insights into the interaction mechanism between TMs and low valence Mn oxides and their effect on the geochemical behaviors of metal pollutants.展开更多
In order to investigate the effects of pre-oxidation conditions on adsorption performance of activated carbon fibers （ ACFs ）, electrospun polyacrylonitrile （ PAN ） fiber webs were adopted as precursors for prepar...In order to investigate the effects of pre-oxidation conditions on adsorption performance of activated carbon fibers （ ACFs ）, electrospun polyacrylonitrile （ PAN ） fiber webs were adopted as precursors for preparing ACFs. Firstly, the webs were stabilized under different pre-oxidation conditions; secondly, the pre-oxidative fibers were chemically activated by high temperature treatment in nitrogen. Pre-oxidation temperature, heating rate, and treatment time are the main factors on affecting the adsorption performance of the ACFs. Scanning electron microscope （ SEM）, differential scanning calorimeter （DSC）, and Fourier transform infrared spectroscopy （FTIR） were used to characterize the structure and property of the pre-oxldatlve fibers, and the dynamic benzene adsorption capacity of benzene of ACFs was measured. The results indicate that the moderate pre-oxidation condition is necessary to prepare the ACFs with better adsorption capacity, and the optimal oxidation conditions are to increase from room temperature to 230 ~C with a heating rate of 0.75 ~C ~ min -1 held at the peak temperature for 30min.展开更多
The fate of 2-nitrobenzaldehyde(2-NBA)is of interest in atmospheric chemistry as it is a semi-volatile organic compound with high photosensitivity.This study presents a quantum chemical study of the gas-phase reaction...The fate of 2-nitrobenzaldehyde(2-NBA)is of interest in atmospheric chemistry as it is a semi-volatile organic compound with high photosensitivity.This study presents a quantum chemical study of the gas-phase reactions of 2-NBA photo-excitation and OH-oxidation in the absence and presence of small TiO_(2) clusters.To further understand the unknown photolysis mechanism,the photo-reaction pathways of ground singlet state and the lying excited triplet state of 2-NBA were investigated including the initial and subsequent reactions of proton transfer,direct CO,NO_(2),and HCO elimination routes in the presence of O_(2) and NO.Meanwhile,the OH-mediated degradation of 2-NBA proceeded via five H-extraction and six OH-addition channels by indirect mechanism,which follows a succession of reaction steps initiated by the formation of weakly stable intermediate complexes.The H-extraction from the-CHO group was the dominant pathway with a negative activation energy of-1.22 kcal/mol.The calculated rate coefficients at 200–600 K were close to the experimental data in literature within 308-352 K,and the kinetic negative temperature independence was found in both experimental literature and computational results.Interestingly,2-NBA was favored to be captured onto small TiO_(2) clusters via six adsorption configurations formed via various combination of three types of bonds of Ti…O,Ti…C,and O…H between the molecularly adsorbed 2-NBA and TiO_(2) clusters.Comparison indicted that the chemisorptions of aldehyde oxygen have largest energies.The results suggested adsorption conformations have a respectable impact on the catalysis barrier.This study is significant for understanding the atmospheric chemistry of 2-nitrobenzaldehyde.展开更多
基金supported by the National Key Research and Development Program of China(2022YFC3205300)the National Natural Science Foundation of China(22176124).
文摘Current research on heterogeneous advanced oxidation processes(HAOPs)predominantly emphasizes catalyst iteration and innovation.Significant efforts have been made to regulate the electron structure and optimize the electron distribution,thereby increasing the catalytic activity.However,this focus often overshadows an equally essential aspect of HAOPs:the adsorption effect.Adsorption is a critical initiator for triggering the interaction of oxidants and contaminants with heterogeneous catalysts.The efficacy of these interactions is influenced by a variety of physicochemical properties,including surface chemistry and pore sizes,which determine the affinities between contaminants and material surfaces.This dispar ity in affinity is pivotal because it underpins the selective removal of contaminants,especially in complex waste streams containing diverse contaminants and competing matrices.Consequently,understanding and mastering these interfacial interactions is fundamentally indispensable not only for improving pro cess efficiency but also for enhancing the selectivity of contaminant removal.Herein,we highlight the importance of adsorption-driven interfacial interactions for fundamentally elucidating the catalytic mechanisms of HAOPs.Such interactions dictate the overall performance of the treatment processes by balancing the adsorption,reaction,and desorption rates on the catalyst surfaces.Elucidating the adsorption effect not only shifts the paradigm in understanding HAOPs but also improves their practical ity in water treatment and wastewater decontamination.Overall,we propose that revisiting adsorption driven interfacial interactions holds great promise for optimizing catalytic processes to develop effective HAOP strategies.
基金supported by Gansu Cuihua Technology Co.,Ltd.(H2020292)Science and Technology Planning of Baiyin City,Fundamental Research Funds for the Central Universities (buctrc202208)+2 种基金Engineering Research Center of Non-metallic Minerals of Zhejiang Province and the Beijing Engineering Center for Hierarchical Catalysts. Central Government Guiding Funds for Local Science and Technology Development (2022ZY015)Nanjiang Technology Project(2023AB028)Open Laboratory of State Key Laboratory of Organic and Inorganic Composites (oic-202301006)。
文摘Coupling adsorption and in-situ Fenton-like oxidation process was developed for Methylene blue(MB) using refined iron-containing lowgrade attapulgite(ATP) clay, and the removal mechanism was investigated. The MB was initially adsorbed on the porous ATPs, and then the enriched MB was removed by the H2O2-assisted Fenton-like oxidation with the iron-containing ATP catalyst. Under optimal conditions, the ATP powder exhibits the maximum removal efficiency of 100% with negligible iron leaching(1.5 mg L^(-1)) and no sludge formation. Furthermore,polysulfone/ATP(PSF/ATP) pellets were fabricated through a water-induced phase separation process to construct a fixed-bed reactor(FBR) for continuous contaminant removal. For the first cycle, the maximum adsorption capacity was 15.5 L with an outlet MB concentration of1.973 mg L-1(< 2 mg L^(-1), GB4287-2012) using the PSF/ATP pellets containing 50.0 g of ATP powders, and the maximum Fenton-like oxidation capacity was 35.5 L with the outlet concentration of 0.831 mg L^(-1). After five cycles, the total treated volume of the MB solution was ca. 255 L, and the efficiency remained above 99%. After 10 h of continuous treatment towards practical resin industrial wastewater, the chemical oxygen demand(COD) removal efficiency was still measured at 83.05%, costing 0.398 $ m^(-3). These results demonstrate the practical applicability of iron-containing low-grade ATP clay for textile water treatment.
基金supported by the National Natural Sci-ence Foundation of China(No.40830527,40771102)the New Century Excellent Talents in University of China(No.NCET-09-0399)
文摘Manganese oxides are known as one type of semiconductors,but their photocatalysis characteristics have not been deeply explored.In this study,photocatalytic degradation of phenol using several synthesized manganese oxides,i.e,acidic birnessite （BIR-H）,alkaline birnessite （BIR-OH）,cryptomelane （CRY） and todorokite （TOD）,were comparatively investigated.To elucidate phenol degradation mechanisms,X-ray diffraction （XRD）,ICP-AES （inductively coupled plasma-atomic emission spectroscopy）,TEM （transmission electronic microscope）,N 2 physisorption at 77 K and UV-visible diffuse reflectance spectroscopy （UV-Vis DRS） were employed to characterize the structural,compositional,morphological,specific surface area and optical absorption properties of the manganese oxides.After 12 hr of UV-Vis irradiation,the total organic carbon （TOC） removal rate reached 62.1%,43.1%,25.4%,and 22.5% for cryptomelane,acidic birnessite,todorokite and alkaline birnessite,respectively.Compared to the reactions in the dark condition,UV- Vis exposure improved the TOC removal rates by 55.8%,31.9%,23.4% and 17.9%.This suggests a weak ability of manganese oxides to degrade phenol in the dark condition,while UV-Vis light irradiation could significantly enhance phenol degradation.The manganese minerals exhibited photocatalytic activities in the order of：CRY BIR-H TOD BIR-OH.There may be three possible mechanisms for photochemical degradation：（1） direct photolysis of phenol;（2） direct oxidation of phenol by manganese oxides;（3） photocatalytic oxidation of phenol by manganese oxides.Photocatalytic oxidation of phenol appeared to be the dominant mechanism.
基金The National Natural Science Foundation of China (No. 50476056) the Hi-Tech Research and Development Program (863) ofChina (No. 2005AA520080)
文摘Oxidation treatment on the adsorption and the stability of Hg on activated carbon （AC） was inrestigated. Both MnO2-AC and FeCl3-AC were produced during oxidation treatment. The measurement of modified AC＇s mercury adsorption capacity was conducted in a simulated coal-fired flue gas by adsorbing test apparatus. TCLP and column leaching methods were used to test the stability of mercury adsorbed on ACs. The results indicate that the oxidation treatment changed the pore structure of the AC and modified the carbon surface by creating chemical components such as MnO4^-, Mn^4＋, O, NO^3-, Fe^3＋, Cl^-, etc. The Hg sorption capacity on MnO2-AC or FeCl3-AC was about three times higher than that of untreated carbon. In addition, the mercury control cost of each of the formers was about the half cost of the untreated carbon. The stability of Hg absorption was studied, it found that mercury adsorbed on the oxidation treated AC was not better than that of untreated carbon. It could concluded that the insoluble form of Hg is very important to the stability of mercury adsorbed on AC. This study suggests that the FeCl3-AC is the best absorbent for Hg with high adsorption capacity, better Hg adsorption stability in leaching environment, and lower cost among the three ACs tested.
基金supported by the National Natural Science Foundation of China (No.50921064, 50978249)
文摘Bioaerosol emissions from wastewater and wastewater treatment processes are a significant subgroup of atmospheric aerosols. Most previous work has focused on the evaluation of their biological risks. In this study, however, the adsorption method was applied to reduce airborne microorganisms generated from a pilot scale wastewater treatment facility with oxidation ditch. Results showed adsorption on granule activated carbon （GAC） was an efficient method for the purification of airborne microorganisms. The GAC itself had a maximum adsorption capacity of 2217 CFU/g for airborne bacteria and 225 CFU/g for fungi with a flow rate of 1.50 m^3/hr. Over 85% of airborne bacteria and fungi emitted from the oxidation ditch were adsorbed within 80 hr of continuous operation mode. Most of them had a particle size of 0.65-4.7 μm. Those airborne microorganisms with small particle size were apt to be adsorbed. The SEM/EDAX, BET and Boehm＇s titration methods were applied to analyse the physicochemical characteristics of the GAC. Relationships between GAC surface characteristics and its adsorption performance demonstrated that porous structure, large surface area, and hydrophobicity rendered GAC an effective absorber of airborne microorganisms. Two regenerate methods, ultraviolet irradiation and high pressure vapor, were compared for the regeneration of used activated carbon. High pressure vapor was an effective technique as it totally destroyed the microorganisms adhered to the activated carbon. Microscopic observation was also carried out to investigate original and used adsorbents.
基金supported by the National Key R&D Program of China(No.2023YFA1507800)the National Science Foundation of China(Nos.22121004,22122808,22478279,and 22108201)+1 种基金the Haihe Laboratory of Sustainable Chemical Trans-formations,the Program of Introducing Talents of Discipline to Uni-versities(No.BP0618007)the XPLORER PRIZE.
文摘Metal oxide catalysts are widely employed in propane dehydrogenation(PDH)for propylene synthesis,requiring sequential reduction-reaction-regeneration cycles.However,the eff ect of water present in the inlet gas or reactor on the catalytic per-formance of various metal oxides remains insuffi ciently understood.This study examines the infl uence of water on supported metal oxide catalysts,specifi cally CoO x/Al_(2)O_(3),VO x/Al_(2)O_(3),and an industrial analog CrO x/Al_(2)O_(3) catalyst.By combining titration experiments,in situ Fourier transform infrared spectroscopy,kinetic analysis,and isotopic techniques,we demon-strate that even trace amounts of water can markedly suppress PDH performance via dissociative adsorption on the oxide surface.Methanol pretreatment eff ectively scavenges adsorbed water,recovering Lewis acid-base sites and consequently restoring PDH activity.This work underscores the profound inhibitory role of trace water in PDH over metal oxide catalysts and illustrates the potential of methanol pretreatment as an effective strategy to mitigate this limitation.
基金support from Basic research project of Education Department of Liaoning Province(LJKZ0256)Special Fund for Basic Scientific Research of Liaoning Province(LJKZSYLUGX027).
文摘The indiscriminate use and disposal of ciprofloxacin(CIP)have led to its detection in water globally,which pose a huge risk to public health and water environment.Herein,(Zn-Al)LDHs modified 3D reduced graphene oxide nanocomposite((Zn-Al)LDHs/3D-rGO)was synthesized through a feasible onepot hydrothermal method for CIP removal.The highly distributed(Zn-Al)LDHs flakes on the surface of 3D-rGO endow the resulted(Zn-Al)LDHs/3D-rGO with an excellent adsorption performance for CIP.The adsorption results showed that the adsorption process could be well interpreted by Temkin isothermal model and the pseudo second-order kinetics model.The maximal adsorption capacity of 20.01 mg·g^(-1)for CIP could be achieved under the optimal conditions optimized by response surface methodology(RSM).The inhibitory effect of co-existing ions on CIP adsorption were also discussed.The probable adsorption mechanism might be ascribed toπ-πinteractions,hydrogen bonding,electrostatic,and surface complexation.Regeneration tests showed that the obtained 3D porous material also possessed pronounced recyclability.The obtained(Zn-Al)LDHs/3D-rGO holds a great potential for removal of CIP from actual wastewater.
基金supported by the National Natural Science Foundation of China (No. 51925807)。
文摘The long term exposure of arsenic via drinking water has resulted in wide occurrence of arsenisim globally, and the oxidation of the non-ionic arsenite(As(Ⅲ)) to negatively-charged arsenate(As(Ⅴ)) is of crucial importance for the promising removal of arsenic. The chemical oxidants of ozone, chlorine, chlorine dioxide, and potassium permanganate may achieve this goal;however, their application in developing countries is sometimes restricted by the complicate operation and high cost. This review paper focuses on the heterogeneous oxidation of As(Ⅲ) by solid oxidants such as manganese oxide, and the adsorption of As(Ⅴ)accordingly. Manganese oxide may be prepared by both chemical and biological methods to achieve good oxidation performance towards As(Ⅲ). Additionally, manganese oxide may be combined with other metal oxides, e.g., iron oxide, to improve the adsorption capability towards As(Ⅴ). Furthermore, manganese oxide may be coated onto porous materials of metal organic frameworks to develop novel adsorbents for arsenic removal. To achieve the application in engineering works, the adsorbents granulation may be achieved by drying and calcination, agglomeration, and the active components may also be in situ coated onto the porous materials to maintain the oxidation and adsorption activities as much as possible. The novel adsorbents with heterogeneous oxidation and adsorption capability may be carefully designed for the removal of arsenic in household purifiers, community-level decentralized small systems, and the large-scale drinking water treatment plants(DWTPs).This review provides insight into the fundamental studies on novel adsorbents, the development of innovative technologies, and the demonstration engineering works involved in the heterogeneous oxidation and adsorption, and may be practically valuable for the arsenic pollution control globally.
基金supported by the National Natural Science Foundation of China(Nos.51290282,51578537,51420105012)the National Water Pollution Control and Treatment Science and Technology Major Project(No.2014ZX07405003)
文摘Antimony（Sb）, which can be toxic at relatively low concentrations, may co-exist with Mn（Ⅱ）and/or Fe（Ⅱ） in some groundwater and surface water bodies. Here we investigated the potential oxidation and adsorption pathways of Sb（Ⅲ and V） species in the presence of Mn（Ⅱ） and Mn-oxidizing bacteria, with or without Fe（Ⅱ）. Batch experiments were conducted to determine the oxidation and adsorption characteristics of Sb species in the presence of biogenic Mn oxides（BMOs）, which were formed in-situ via the oxidation of Mn（Ⅱ） by a Mn-oxidizing bacterium（Pseudomonas sp. QJX-1）. Results indicated that Sb（Ⅲ） ions could be oxidized to Sb（V） ions by BMO, but only Sb（V） originating from Sb（Ⅲ） oxidation was adsorbed effectively by BMO. Introduced Fe（Ⅱ） was chemically oxidized to Fe OOH, the precipitates of which mixed with BMO to form a new compound, biogenic Fe–Mn oxides（BFMO）. The BMO part of the BFMO mainly oxidized and the Fe OOH of the BFMO mainly adsorbed the Sb species. In aquatic solutions containing both As（Ⅲ） and Sb（Ⅲ）, the BFMO that formed in-situ preferentially oxidized Sb over As but adsorbed As more efficiently. Chemical analysis and reverse transcription real-time polymerase chain reaction revealed that the presence of Fe（Ⅱ）, As（Ⅲ） and Sb（Ⅲ） accelerated the oxidation of Mn（Ⅱ） but inhibited the activity of Mn-oxidizing bacteria. These results provide significant insights into the biogeochemical pathways of Sb, Mn（Ⅱ） in aquatic ecosystems, with or without Fe（Ⅱ）.
基金Project(2018YFC1802204)supported by the National Key R&D Program of ChinaProject(51634010)supported by the Key Project of National Natural Science Foundation of ChinaProject(2018SK2026)supported by the Key R&D Program of Hunan Province,China。
文摘Magnetic Fe3 O4@Cu/Ce microspheres were successfully prepared by one-step solvothermal approach and further utilized to remediate toxic arsenic(As(Ⅲ)) pollution. The effects of Cu/Ce elements co-doping on the crystal structure, catalytic oxidation and adsorption behaviors of magnetic microspheres were researched systematically. The results showed that with the aid of Cu/Ce elements, the grain size reduced, lattice defects increased, and the oxygen vacancies and surface hydroxyl groups were improved. Therefore, Cu/Ce elements endowed magnetic Fe3 O4@Cu/Ce microspheres with excellent As(III) removal performance, whose maximum adsorption capacity reached 139.19 mg/g. The adsorption mechanism mainly involved catalytic oxidant co-adsorption. This research developed a feasible strategy for the preparation of high efficiency magnetic adsorbent to enhance the removal of As(Ⅲ).
文摘A greater part of water-solnble organic substances, accounting for 6070To of the total, could be adsorbedby soils, which included strongly and weekly reducing substances, positively and negatively charged substancesand substances containing amido. There existed a tendency of decrease in adsorption of the negativelycharged organic substances by the soil from South China to North China, with expression as Coulombianadsorption. A simultaneous reduction of iron and manganese appeared with clear voltammetric behavioursupon oxidation of water-soluble organic substances. Complexation of organic ligands with ferrons iron andmanganous manganese was proved by differential pulse voltammetric method, with disappearance of oxidationpeaks of ferrous iron and manganous manganese at 0.00 V and 0.35 V and occurrence of Fe`+-complex andMn￣2+ -complex at 0.75 V and 1.2 V respectively, whose peak potentials shifted backward.
文摘The available data have shown that acid-leached clays had sites for adsorption of impurities in oils. Data obtained on residual impurities in cotton and sunflower-seed oils bleached with the same clay materials produced linear Langmuir and Freundlich isotherms. The increase in constant, k with increase in both temperature of thermal activation and concentration of acid used to leach the clay, suggests that bleaching efficiency increased. The value of n decreased with increase in temperature of activation and concentration of acid used to leach the clay suggesting that bleaching capacity increased. The mineral compositions of the clays influenced their surface, structural and bleaching properties.
基金This work was financially supported by Erzincan Binali Yıldırım University Research Fund(No.FBA-2018-547).
文摘The hardness,wettability,and electrochemical properties of Ti6Al4V alloy surfaces treated with anodic oxidation and plasma oxidation as well as the viabilities of the different cell lines on the obtained surfaces were investigated.The anodic oxidation was performed for 10 min under 100 V potential,and it resulted in a 0.95μm thick nanoporous anatase-TiO2 structure.On the other hand,plasma oxidation was carried out at 650℃ for 1 h and resulted in a dense rutile-TiO2 structure with a thickness of 1.2μm.While a hardness of HV0.025823 and roughness of^220 nm were obtained by plasma oxidation,those obtained by anodic oxidation were HV0.025512 and^130 nm,respectively.The anodic oxidation process created a more hydrophilic surface with a contact angle of 87.2°.Both oxidation processes produced similar properties in terms of corrosion behavior and showed better resistance than the as-received state in a certain range of potential.Moreover,the surface treatments led to no significant change in the protein adsorption levels,which indicates that the difference in viability between the osteoblast and fibroblast cells was not due to the difference in surface protein adsorption.Given all the factors,the surfaces obtained by anodic oxidation treatment revealed higher cell viability than those obtained by plasma oxidation(p=0.05).
文摘In-situ oxidation of solid phase was considered to investigate adsorption behavior under different geochemical parameters like pH, initial concentration and ionic strength. Pumice tuff, a potential host rock for low and intermediate radioactive wastes, has been affected by the redox zone. The characterization of the fresh and oxidized tuff was performed by X-ray diffractometer, scanning electron microscope and mercury intrusion porosimetry. In order to compare the difference of distribution coefficient (K<sub>d</sub>) in fresh and oxidized pumice tuffs, a batch adsorption study was carried out at the range of pH (4 - 12), ionic strength (0.003, 0.1, 1.0 and 3.0 mol/dm<sup>3</sup>) and initial cesium concentration (10<sup>dž</sup>, 10<sup>LJ</sup>, 10<sup>Lj</sup> and 10<sup>lj</sup> mol/dm<sup>3</sup>). Based on experimental K<sub>d</sub> values, ionic strength was found to be the most influential factor, whereas the effects of pH, initial Cs concentration and weathering condition of pumice tuff were negligible. The recalculated K<sub>d</sub> values suggest that the existing surface complexation model is applicable to explain the sorption coefficients through the wide range of solution conditions.
基金supported by the Major Science and Technology Program forWater Pollution Control and Treatment(No.2012ZX07102-004)
文摘A novel adsorbent based on iron oxide dispersed over activated carbon （AC） were prepared, and used for phosphate removal from aqueous solutions. The influence of pre-oxidation treatment on the physical, chemical and phosphate adsorption properties of iron-containing AC were determined. Two series of ACs, non-oxidized and oxidized carbon modified by iron （denoted as AC-Fe and AC/O- Fe）, resulted in a maximum impregnated iron of 4.03% and 7.56%, respectively. AC/O-Fe showed 34.0%46.6% higher phosphate removal efficiency than the AC-Fe did. This was first attributed to the moderate pre-oxidation of raw AC by nitric acid, achieved by dosing Fe（II） after a pre-oxidation, to obtain higher iron loading, which is favorable for phosphate adsorption. Additionally, the in-situ formed active site on the surface of carbon, which was derived from the oxidation of Fe（II） by nitric acid dominated the remarkably high efficiency with respect to the removal of phosphate. The activation energy for adsorption was calculated to be 10.53 and 18.88 kJ/mol for AC-Fe and AC/O- Fe, respectively. The results showed that the surface mass transfer and intra-parficle diffusion were simultaneously occurring during the process and contribute to the adsorption mechanism.
文摘The alkali-metal Na adsorption on Si(100)2×1 surface and its promoted oxidation and Si oxide growth have been investigated by means of thermal desorption,work function,Auger electron spectroscopy and photoemission electron spectroscopy.The experimental data showed that there was a new state,interface electron state,near the Fermi level after the deposition of Na atoms.It was found that the presence of Na always caused an increase of the oxygen initial uptake whereas the promotion of Si oxide growth was observed only at the coverage of Na greater than 0.5 ML.A new mechanism of Na-promoted Si oxide growth is suggested in this paper.
文摘To solve the problem of polymer-bearing effluent of crude oil not reaching the standard,deep treatment system of Fenton oxidation-activated carbon adsorption is established in one refinery,and the most suitable condition of Fenton oxidation reaction is determined.Operation results show that CODCrconcentration of effluent treated by the system could be lower than 50 mg/L,and ammonia nitrogen content is less than 3 mg/L,which meets design requirement.
基金supported by the Key science and Technology Projects of Inner Mongolia Autonomous Region(No.2019ZD001)the National Natural Science Foundation of China(Nos.42077015,41771267 and 41877030)+1 种基金the National Key Research and Development Program of China(No.2016YFD0800403)the Fundamental Research Funds for the Central Universities(No.103-510320036)。
文摘Hausmannite is a common low valence Mn oxide mineral,with a distorted spinel structure,in surficial sediments.Although natural Mn oxides often contain various impurities of transitional metals(TMs),few studies have addressed the effect and related mechanism of TM doping on the reactivity of hausmannite with metal pollutants.Here,the reactivity of cobalt(Co)doped hausmannite with aqueous As(Ⅲ)and As(Ⅴ)was studied.Co doping decreased the point of zero charge of hausmannite and its adsorption capacity for As(Ⅴ).Despite a reduction of the initial As(Ⅲ)oxidation rate,Co-doped hausmannite could effectively oxidize As(Ⅲ)to As(Ⅴ),followed by the adsorption and fixation of a large amount of As(Ⅴ)on the mineral surface.Arsenic K-edge EXAFS analysis of the samples after As(Ⅴ)adsorption and As(Ⅲ)oxidation revealed that only As(Ⅴ)was adsorbed on the mineral surface,with an average As-Mn distance of 3.25–3.30 A,indicating the formation of bidentate binuclear complexes.These results provide new insights into the interaction mechanism between TMs and low valence Mn oxides and their effect on the geochemical behaviors of metal pollutants.
文摘In order to investigate the effects of pre-oxidation conditions on adsorption performance of activated carbon fibers （ ACFs ）, electrospun polyacrylonitrile （ PAN ） fiber webs were adopted as precursors for preparing ACFs. Firstly, the webs were stabilized under different pre-oxidation conditions; secondly, the pre-oxidative fibers were chemically activated by high temperature treatment in nitrogen. Pre-oxidation temperature, heating rate, and treatment time are the main factors on affecting the adsorption performance of the ACFs. Scanning electron microscope （ SEM）, differential scanning calorimeter （DSC）, and Fourier transform infrared spectroscopy （FTIR） were used to characterize the structure and property of the pre-oxldatlve fibers, and the dynamic benzene adsorption capacity of benzene of ACFs was measured. The results indicate that the moderate pre-oxidation condition is necessary to prepare the ACFs with better adsorption capacity, and the optimal oxidation conditions are to increase from room temperature to 230 ~C with a heating rate of 0.75 ~C ~ min -1 held at the peak temperature for 30min.
基金supported by the National Natural Science Foundation of China(No.22006101)the Natural Science Foundation of Liaoning Province(No.2023-MS-250)+3 种基金the Basic Scientific Research Foundation Project of Liaoning Province(No.LJKQZ20222283)the National Natural Science Foundation of China-Liaoning Joint Fund(No.U1908204)the Doctoral Research Start-up Fund of Shenyang Normal University(No.BS202124,No.BS202016)the Basic Scientific Research Project of Universities in Liaoning Province(No.LQN202007)。
文摘The fate of 2-nitrobenzaldehyde(2-NBA)is of interest in atmospheric chemistry as it is a semi-volatile organic compound with high photosensitivity.This study presents a quantum chemical study of the gas-phase reactions of 2-NBA photo-excitation and OH-oxidation in the absence and presence of small TiO_(2) clusters.To further understand the unknown photolysis mechanism,the photo-reaction pathways of ground singlet state and the lying excited triplet state of 2-NBA were investigated including the initial and subsequent reactions of proton transfer,direct CO,NO_(2),and HCO elimination routes in the presence of O_(2) and NO.Meanwhile,the OH-mediated degradation of 2-NBA proceeded via five H-extraction and six OH-addition channels by indirect mechanism,which follows a succession of reaction steps initiated by the formation of weakly stable intermediate complexes.The H-extraction from the-CHO group was the dominant pathway with a negative activation energy of-1.22 kcal/mol.The calculated rate coefficients at 200–600 K were close to the experimental data in literature within 308-352 K,and the kinetic negative temperature independence was found in both experimental literature and computational results.Interestingly,2-NBA was favored to be captured onto small TiO_(2) clusters via six adsorption configurations formed via various combination of three types of bonds of Ti…O,Ti…C,and O…H between the molecularly adsorbed 2-NBA and TiO_(2) clusters.Comparison indicted that the chemisorptions of aldehyde oxygen have largest energies.The results suggested adsorption conformations have a respectable impact on the catalysis barrier.This study is significant for understanding the atmospheric chemistry of 2-nitrobenzaldehyde.
