The air quality model CMAQ-MADRID (Community Multiscale Air Quality-Model of Aerosol Dynamics, Reaction, Ionization and Dissolution) was employed to simulate summer O3 formation in Beijing China, in order to explore...The air quality model CMAQ-MADRID (Community Multiscale Air Quality-Model of Aerosol Dynamics, Reaction, Ionization and Dissolution) was employed to simulate summer O3 formation in Beijing China, in order to explore the impacts of four heterogeneous reactions on O3 formation in an urban area. The results showed that the impacts were obvious and exhibited the characteristics of a typical response of a VOC-limited regime in the urban area. For the four heterogeneous reactions considered, the NO2 and HO2 heterogeneous reactions have the most severe impacts on O3 formation. During the O3 formation period, the NO2 heterogeneous reaction increased new radical creation by 30%, raising the atmospheric activity as more NO→NO2 conversion occurred, thus causing the O3 to rise. The increase of O3 peak concentration reached a maximum value of 67 ppb in the urban area. In the morning hours, high NO titration reduced the effect of the photolysis of HONO, which was produced heterogeneously at night in the surface layer. The NO2 heterogeneous reaction in the daytime is likely one of the major reasons causing the O3 increase in the Beijing urban area. The HO2 heterogeneous reaction accelerated radical termination, resulting in a decrease of the radical concentration by 44% at the most. O3 peak concentration decreased by a maximum amount of 24 ppb in the urban area. The simulation results were improved when the heterogeneous reactions were included, with the O3 and HONO model results close to the observations.展开更多
The variations of sulfate formation and optical coefficients during SO2 heterogeneous reactions on hematite surface under different SO2 concentrations were examined using in situ diffuse reflectance infrared Fourier t...The variations of sulfate formation and optical coefficients during SO2 heterogeneous reactions on hematite surface under different SO2 concentrations were examined using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and ion chromatograph (IC). Laboratory experiments revealed that within ambient SO2 of 0.51-18.6 ppmv, sulfate product, producing velocity, absorption and backward scattering coefficients showed an increasing trend with SO2 concentration. Under given SO2 concentration, the velocity of sulfate producing performed an evolution of initial increasing, midterm decreasing and final stabilizing. The reactive uptake and Brunaner-Emmett-Teller (BET) uptake coefficients of heterogeneous reactions rose with SOz and exhibited high reactivities. Considering global warming, this result is important for the knowledge of heterogeneous reactions of SO2 on mineral particle surface in the atmosphere and the assessment of their impacts on radiative forcing.展开更多
Oxidized starch powder and cationic starch solution were reacted with alkyl ketene dimer(AKD) under heterogeneous conditions at 70℃ for 12 h.The AKD molecules reacted with starch hydroxyl groups to form β-keto ester...Oxidized starch powder and cationic starch solution were reacted with alkyl ketene dimer(AKD) under heterogeneous conditions at 70℃ for 12 h.The AKD molecules reacted with starch hydroxyl groups to form β-keto ester linkages under the above conditions.The reaction products were separated into CHCl_3-soluble and CHCl_3-insoluble fractions.FT-IR spectroscopy,SEM,Xray diffraction,and TG-DTA analyses of the CHCl_3-insoluble fraction indicated that β-keto ester substituents were introduced to hydroxyl groups on the starch surfaces.The results indicated that hydrogen bonds between the starch molecules were disrupted under heterogeneous conditions upon heating.The activity and accessibility of hydroxyl groups were enhanced,as a result of which β-keto ester bonds were produced between AKD and starch.Based on these results,we speculate that the β-keto esters which existed in the sheets sized by AKD emulsions were generated by the reaction between AKD and starch.展开更多
The homogeneous and heterogeneous reactions in the boundary-layer of a flat surface are considered. The autocatalysts are assumed to be of regular sizes, while the solution is a dilute nanofluid. The heat release due ...The homogeneous and heterogeneous reactions in the boundary-layer of a flat surface are considered. The autocatalysts are assumed to be of regular sizes, while the solution is a dilute nanofluid. The heat release due to the chemical reactions is taken into account. The Buongiorno’s model is used to describe the behaviors of this reaction system. This configuration makes the current model be different from all previous publications. Multiple solutions are given numerically to the rescaled nonlinear system, whose stability is verified. The results show that the strength coefficients of the homogeneous and heterogeneous reactions are key factors to cause the appearance of the multiple solutions in the distribution of the chemical reactions. Nanofluids enhance the diffusion of heat and help maintain the stability of chemical reactions.展开更多
Heterogeneous reaction of mineral aerosols and atmospheric polluting gases play an important role in atmospheric chemistry.In this study,the reactions of NO_(2) with or without SO_(2) mixture gas on the surface of α-...Heterogeneous reaction of mineral aerosols and atmospheric polluting gases play an important role in atmospheric chemistry.In this study,the reactions of NO_(2) with or without SO_(2) mixture gas on the surface of α-Fe_(2)O_(3) particles under dry conditions were studied.The effects of sodium dodecyl sulfate(SDS)and the heterogeneous reaction under both dark and UV irradiation conditions were investigated.The infrared spectrum analyzed by the two-dimensional correlation spectroscopy(2D-COS)was used to obtain the products formation sequences.The results showed that UV irradiation can promote the production of nitrate.The 2D-COS analysis indicated SDS changed the sequence order of nitrate and nitrite species during reactions.In oxidation conditions,the final product of heterogeneous reaction of NO_(2) and α-Fe_(2)O_(3) was monodentate nitrate.Only the heterogenous reaction of NO_(2) and α-Fe_(2)O_(3) containing SDS(FOS)without UV light,the final product was bidentate nitrate.SDS was the catalysis agent supply and photoresist to the system.With surface active compounds,the environmental lifetime of heterogeneous reactions between trace gases and aerosols extends.Surfactants,ultraviolet light,and the types of gases involved in the reaction all have complex effects on the aerosol aging process.This study provided a reference for subsequent heterogeneous reaction studies and the formation of aerosols.展开更多
Heterogeneous reaction of NO_(2) with mineral dust aerosol may play important roles in troposphere chemistry,and has been investigated by a number of laboratory studies.However,the influence of mineralogy on this reac...Heterogeneous reaction of NO_(2) with mineral dust aerosol may play important roles in troposphere chemistry,and has been investigated by a number of laboratory studies.However,the influence of mineralogy on this reaction has not been well understood,and its impact on aerosol hygroscopicity is not yet clear.This work investigated heterogeneous reactions of NO_(2)(∼10 ppmv)with K-feldspar,illite,kaolinite,montmorillonite and Arizona Test Dust(ATD)at room temperature as a function of relative humidity(<1%to 80%)and reaction time(up to 24 hr).Heterogeneous reactivity towards NO_(2) was low for illite,kaolinite,montmorillonite and ATD,and uptake coefficients of NO_(2),γ(NO_(2)),were determined to be around or smaller than 1×10^(−8);K-feldspar exhibited higher reactivity towards NO_(2),and CaCO_(3) is most reactive among the nine mineral dust samples considered in this and previous work.After heterogeneous reaction with NO_(2) for 24 hr,increase in hygroscopicity was nearly insignificant for illite,kaolinite and montmorillonite,and small but significant for K-feldspar;in addition,large increase in hygroscopicity was observed for ATD,although the increase in hygroscopicity was still smaller than CaCO_(3).展开更多
Mineral dust is an important type of ice nucleating particles in the troposphere;however,the effects of heterogeneous reactions on ice nucleation(IN)activities of mineral dust remain to be elucidated.A droplet-freezin...Mineral dust is an important type of ice nucleating particles in the troposphere;however,the effects of heterogeneous reactions on ice nucleation(IN)activities of mineral dust remain to be elucidated.A droplet-freezing apparatus(Guangzhou Institute of Geochemistry Ice Nucleation Apparatus,GIGINA)was developed in thiswork to measure IN activities of atmospheric particles in the immersion freezingmode,and its performancewas validated by a series of experimental characterizations.This apparatus was then employed to measure IN activities of feldspar and Arizona Test Dust(ATD)particles before and after heterogeneous reaction with NO_(2)(10±0.5 ppmv)at 40%relative humidity.The surface coverage of nitrate,θ(NO_(3)^(−)),increased to 3.1±0.2 for feldspar after reaction with NO_(2) for 6 hr,and meanwhile the active site density per unit surface area(ns)at-20℃ was reduced from 92±5 to<1.0 cm^(−2) by about two orders of magnitude;however,no changes in nitrate content or IN activities were observed for further increase in reaction time(up to 24 hr).Both nitrate content and IN activities changed continuously with reaction time(up to 24 hr)for ATD particles;after reaction with NO_(2) for 24 hr,θ(NO_(3)^(−))increased to 1.4±0.1 and ns at-20℃ was reduced from 20±4 to 9.7±1.9 cm^(−2) by a factor of∼2.Our work suggests that heterogeneous reaction with NO_(2),an abundant reactive nitrogen species in the troposphere,may significantly reduce IN activities of mineral dust in the immersion freezing mode.展开更多
Soot particles,composed of elemental carbon and organic compounds,have attracted widespread attention in recent years due to their significant impacts on climate,the environment and human health.Soot has been found to...Soot particles,composed of elemental carbon and organic compounds,have attracted widespread attention in recent years due to their significant impacts on climate,the environment and human health.Soot has been found to be chemically and physically active in atmospheric aging processes,which leads to alterations in its composition,morphology,hygroscopicity and optical properties and thus changes its environmental and health effects.The heterogeneous reactions on soot also have a significant impact on the transformation of gaseous pollutants into secondary aerosols.Therefore,the interactions between soot and atmospheric substances have been widely investigated to better understand the environmental behaviors of soot.In this review,we systematically summarize the progress and developments in the heterogeneous chemistry on soot over the past_(3)0 years.Atmospheric trace constituents such as NO_(2),O_(3),SO_(2),N_(2)O_(5),HNO_(3),H_(2)SO_(4),OH radical,HO_(2)radical,peroxyacetyl nitrate etc.,are presented in detail from the aspect of their heterogeneous reactions on soot.The possible mechanisms and the effects of environmental conditions on these heterogeneous reactions are also addressed.Further,the impacts of the heterogeneous reactions of soot on the atmospheric environment are discussed,and some aspects of soot-related research which require further investigation are proposed as well.展开更多
The studies on heterogeneous reactions over montmorillonite, which is a typical 2:1 layered aluminosilicate, will benefit to the Understanding of heterogeneous reactions on clay minerals. Montmorillonite can be class...The studies on heterogeneous reactions over montmorillonite, which is a typical 2:1 layered aluminosilicate, will benefit to the Understanding of heterogeneous reactions on clay minerals. Montmorillonite can be classified as sodium montmorillonite or calcium montmorillonite depending on the cation presented between the different layers. Using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), the heterogeneous reaction mechanism of NO2 on the surface of montmorillonite was firstly investigated. Results showed that the reaction of NO2 on the surface of sodium and calcium montmorillonite fit a first-order kinetics, and the reaction duration of calcium montmorillonite was longer than that of sodium montmorillonite under the dry condition. For either sodium or calcium montmorillonite, the uptake coefficient decreased as humidity increased.展开更多
Heterogeneous reactions on the aerosol particle surface in the atmosphere play important roles in air pollution, climate change, and global biogeochemical cycles. However, the reported uptake coefficients of heterogen...Heterogeneous reactions on the aerosol particle surface in the atmosphere play important roles in air pollution, climate change, and global biogeochemical cycles. However, the reported uptake coefficients of heterogeneous reactions usually have large variations and may not be relevant to real atmospheric conditions. One of the major reasons for this is the use of bulk samples in laboratory experiments, while particles in the atmosphere are suspended individually. A number of technologies have been developed recently to study heterogeneous reactions on the surfaces of individual particles. Precise measurements on the reactive surface area, volume, and morphology of individual particles are necessary for calculating the uptake coefficient, quantifying reactants and products, and understanding the reaction mechanism better. In this study, for the first time we used synchrotron radiation X-ray computed tomography(XCT) and micro-Raman spectrometry to measure individual CaCO_3 particle morphology, with sizes ranging from 3.5–6.5 μm. Particle surface area and volume were calculated using a reconstruction method based on software threedimensional(3-D) rendering. The XCT was first validated with high-resolution fieldemission scanning electron microscopy(FE-SEM) to acquire accurate CaCO_3 particle surface area and volume estimates. Our results showed an average difference of only 6.1% in surface area and 3.2% in volume measured either by micro-Raman spectrometry or X-ray tomography. X-ray tomography and FE-SEM can provide more morphological details of individual Ca CO3 particles than micro-Raman spectrometry. This study demonstrated that X-ray computed tomography and micro-Raman spectrometry can precisely measure the surface area, volume, and morphology of an individual particle.展开更多
Sea salt particles containing NaCl are among the most abundant particulate masses in coastal atmosphere. Reactions involving sea salt particles potentially generate Cl radicals, which are released into coastal atmosph...Sea salt particles containing NaCl are among the most abundant particulate masses in coastal atmosphere. Reactions involving sea salt particles potentially generate Cl radicals, which are released into coastal atmosphere. Cl radicals play an important role in the nitrogen and O3 cycles, sulfitr chemistry and particle formation in the troposphere of the polluted coastal regions. This paper aimed at .the heterogeneous reaction between gaseous HNO3 .and solid NaCl. The mech.anis.m was in.vestigatedby density functional theory (DFT). The results imply that water molecules induce the surface reconstruction, which is essential for the heterogeneous reaction. The surface reconstruction on the defective (710) surface has a barrier of 10.24 kcal.mol-1 and is endothermic by 9.69 kcal.mol-1, whereas the reconstruction on the clean (100) surface has a barrier of 18.46 kcal.mol-1 and isendothermic by 12.96 kcal.mol-1. The surface reconstruction involved in water-adsorbed (710) surface is more energetically favorable. In comparison, water molecules adsorbed on NaCl (100) surface likely undergo water diffusion or desorption. Further, it reveals that the coordination number of the Cl-out is reduced after the surface reconstruction, which assists Clout to accept the proton from HNO3. HCl is released from heterogeneous reactions between gaseous HNO3 and solid NaCl and can react with OH free radicals to produce atomic Cl radicals. The results will offer further insights into the impact of gaseous HNO3 on the air quality of the coastal areas.展开更多
Despite the heterogeneous reaction of sulfur dioxide(SO_(2))on mineral dust particles significantly affects the atmospheric environment,the effect of acidic gases on the formation of sulfite and sulfate from this reac...Despite the heterogeneous reaction of sulfur dioxide(SO_(2))on mineral dust particles significantly affects the atmospheric environment,the effect of acidic gases on the formation of sulfite and sulfate from this reaction is not particularly clear.In this work,using the in-situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)technique,we employed a mineral dust particle model(CaCO_(3))combined with NO_(2)and acetic acid to investigate their effects on the heterogeneous reaction of SO_(2)on CaCO_(3)particles.Itwas found that water vapor can promote the formation of sulfite and simulated radiation can facilitate the oxidation of sulfite to sulfate.The addition of NO_(2)or acetic acid to the reaction system altered the production of sulfate and sulfite accordingly.There was a synergistic effect between NO_(2)and SO_(2)that promoted the oxidation of sulfite to sulfate,and a competitive effect between acetic acid and SO_(2)that inhibited the formation of sulfite.Moreover,light and water vapor can also affect the heterogeneous reaction of SO_(2)with the coexistence ofmultiple gases.These findings improve our understanding of the effects of organic and inorganic gases and environmental factors on the formation of sulfite and sulfate in heterogeneous reactions.展开更多
The present study reveals the effect of homogeneous/hetereogeneous reaction on stagnation point flow of Williamson fluid in the presence of magnetohydrodynamics and heat generation/absorption coefficient over a stretc...The present study reveals the effect of homogeneous/hetereogeneous reaction on stagnation point flow of Williamson fluid in the presence of magnetohydrodynamics and heat generation/absorption coefficient over a stretching cylinder. Further the effects of variable thermal conductivity and thermal stratification are also considered. The governing partial differential equations are converted to ordinary differential equations with the help of similarity transformation.The system of coupled non-linear ordinary differential equations is then solved by shooting technique. MATLAB shooting code is validated by comparison with the previously published work in limiting case. Results are further strengthened when the present results are compared with MATLAB built-in function bvp4c. Effects of prominent parameters are deliberated graphically for the velocity, temperature and concentration profiles. Skin-friction coefficient and Nusselt number for the different parameters are investigated with the help of tables.展开更多
The heterogeneous reaction of SO_(2) on mineral dust surfaces is generally considered as an important chemical pathway for secondary sulfate formation in the troposphere.To this day,there are no reported studies that ...The heterogeneous reaction of SO_(2) on mineral dust surfaces is generally considered as an important chemical pathway for secondary sulfate formation in the troposphere.To this day,there are no reported studies that assess the impact of atmospheric CO_(2) in sulfate production on mineral dust surfaces.In this work,we investigate the impact of CO_(2) on SO_(2) uptake on dust proxy aluminum oxide particles using a diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS).CO_(2) is demonstrated to suppress the heterogeneous oxidation of SO_(2) on alpha-Al2 O_(3).Compared to that measured in the CO_(2)-free case,the uptake coefficient is decreased by nearly 57%when Al_(2)O_(3) particles are exposed to the gas flow with atmospheric CO_(2) at a relative humidity(RH)of 25%.It is also found that there is a balance between the yield of active moiety-OH provided by AI(OH)3(CO)(OH)2 clusters and the loss of basic hydroxyl group on aluminum oxide surfaces blocked by CO_(2)-derived(bi)carbonate species.This work,for the first time,reveals a negative effect of atmospheric CO_(2) on the sulfate formation,which potentially decreases solarradiation scattering and further exacerbates global warming.展开更多
The reaction kinetics of the heterogeneous oxidation of toluene with Mn 3+ was studied by considering the effects of disproportionation of Mn 3+ in reaction system, a 'parallel' modulus was set up. A...The reaction kinetics of the heterogeneous oxidation of toluene with Mn 3+ was studied by considering the effects of disproportionation of Mn 3+ in reaction system, a 'parallel' modulus was set up. And then the concentration of Mn 3+ in disproportionation and the concentration of benzaldehyde in oxidation were respectively determined in turn, the rate constant, order and pseudo activation energy of the heterogeneous oxidation were obtained by mathematical deduction and the kinetic equation was concluded. In addition, the reaction mechanism was analyzed. It shows that the results are completely consistent with modulus.展开更多
The reactions of gas-phase anthracene and suspended anthracene particles with O3 and O3-NO were conducted in a 200-L reaction chamber, respectively. The secondary organic aerosol (SOA) formations from gas-phase reac...The reactions of gas-phase anthracene and suspended anthracene particles with O3 and O3-NO were conducted in a 200-L reaction chamber, respectively. The secondary organic aerosol (SOA) formations from gas-phase reactions of anthracene with O3 and O3-NO were observed. Meanwhile, the size distributions and mass concentrations of SOA were monitored with a scanning mobility particle sizer (SMPS) during the formation processes. The rapid exponential growths of SOA reveal that the atmospheric lifetimes of gas-phase anthracene towards O3 and O3-NO are less than 20.5 and 4.34 hr, respectively. The particulate oxidation products from homogeneous and heterogeneous reactions were analyzed with a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS). Gas chromatograph/mass spectrometer (GC/MS) analyses of oxidation products of anthracene were carried out for assigning the time-of-flight (TOF) mass spectra of products from homogeneous and heterogeneous reactions. Anthrone, anthraquinone, 9,10- dihydroxyanthracene, and 1,9,10-trihydroxyanthracene were the ozonation products of anthracene, while anthrone, anthraquinone, 9-nitroanthracene, and 1,8-dihydroxyanthraquinone were the main products of anthracene with O3-NO.展开更多
MnFe1.4Ru0.45Cu0.15O4 was an effective heterogeneous catalyst for the oxidation of various types of alcohols to the corresponding carbonyl compounds using atmospheric pressure of oxygen under mild conditions. Further...MnFe1.4Ru0.45Cu0.15O4 was an effective heterogeneous catalyst for the oxidation of various types of alcohols to the corresponding carbonyl compounds using atmospheric pressure of oxygen under mild conditions. Furthermore, this catalyst was also effective towards alcohol oxidation using water as solvent instead of toluene.展开更多
The possibility of carrying out a purely heterogeneous Heck reaction in practice without Pd leaching has been previously considered by a number of research groups but no general consent has yet arrived. Here, the reac...The possibility of carrying out a purely heterogeneous Heck reaction in practice without Pd leaching has been previously considered by a number of research groups but no general consent has yet arrived. Here, the reaction was, for the first time, evaluated by a simple computational approach. Modelling experiments were performed on one of the initial catalytic steps: phenyl halides attachment on Pd (111) to (100) and (111) to (111) ridges of a Pd crystal. Three surface structures of resulting were identified as possible reactive intermediates. Following potential energy minimisation calculations based on a universal force field, the relative stabilities of these surface species were then determined. Results showed the most stable species to be one in which a Pd ridge atom is removed from the Pd crystal structure, suggesting Pd leaching induced by phenyl halides is energetically favourable.展开更多
The Weather Research and Forecasting/Chemistry model (WRF-Chem) was updated by including pho- toexeited nitrogen dioxide (NO2) molecules, heterogeneous reactions on aerosol surfaces, and direct emissions of nitrou...The Weather Research and Forecasting/Chemistry model (WRF-Chem) was updated by including pho- toexeited nitrogen dioxide (NO2) molecules, heterogeneous reactions on aerosol surfaces, and direct emissions of nitrous acid (HONO) in the Carbon-Bond Mechanism Z (CBM-Z). Five simulations were conducted to assess the effects of each new component and the three additional HONO sources on concentrations of major chemical components. We calculated percentage changes of major aerosol components and concentration ratios of gas NOy (NOyg) to NOy and particulate nitrates (NO3-) to NOy due to the three additional HONO sources in the North China Plain in August of 2007. Our results indicate that when the three additional HONO sources are included, WRF-Chem can reasonably reproduce the HONO observations. Heterogeneous reactions on aerosol surfaces are a key contributor to concentrations of HONO, nitrates (NO3-), ammonium (NH+), and PM2.5 (concentration of particulate matter of ≤2.5 um in the ambient air) across the North China Plain. The three additional HONO sources produced a -5% -20% increase in monthly mean daytime concentration ratios of NO3-/NOy, a -15%- 52% increase in maximum hourly mean concentration ratios of NO3-/NOy, and a -10% -50% increase in monthly mean concentrations of NOx and NH+ across large areas of the North China Plain. For the Bohai Bay, the largest hourly increases of NO3- exceeded 90%, of NH+ exceeded 80%, and of PM2.5 exceeded 40%, due to the three additional HONO sources. This implies that the three additional HONO sources can aggravate regional air pollution, further impair visibility, and enhance the incidence of haze in some industrialized regions with high emissions of NOx and particulate matter under favorable meteorological conditions.展开更多
Aerosol samples were collected in summer in Macao, a coastal city of the Pearl River Delta Region in China. Morphology, size, elemental composition, and mixing state of individual aerosol particles were determined by ...Aerosol samples were collected in summer in Macao, a coastal city of the Pearl River Delta Region in China. Morphology, size, elemental composition, and mixing state of individual aerosol particles were determined by scanning electron microscopy coupled energy dispersive X-ray (SEM/EDX) and transmission electron microscopy (TEM). Based on the morphologies of 5711 aerosol particles, they consist of soot (32%), mineral (17%), secondary-(22%), and unknown fine particles (29%). The sizes of these particles were mostly distributed between 0.1 and 0.4 μm. Compositions of 202 mineral particles were obtained by SEM/EDX. Mineral particles were mainly classified into three types: Si-rich, Ca-rich, and Na-rich. The compositions of typical mineral particles can indicate their sources in sampling location. For example, mineral particles, collected along the main street, were associated with trace amounts of heavy metals, such as Zn, Ti, Mn, Ba, Pb, and As. TEM observations indicate that most Na-rich particles were aged sea salt particles (e.g., Na2SO4 and NaNO3) which formed through heterogeneous chemical reactions between sea salt and acidic gases. Additionally, aging time of soot was short in Macao due to high humidity, high temperature, and high levels of sunlight in Macao. Most of soot and fine mineral dust particles were internally mixed with secondary particles.展开更多
文摘The air quality model CMAQ-MADRID (Community Multiscale Air Quality-Model of Aerosol Dynamics, Reaction, Ionization and Dissolution) was employed to simulate summer O3 formation in Beijing China, in order to explore the impacts of four heterogeneous reactions on O3 formation in an urban area. The results showed that the impacts were obvious and exhibited the characteristics of a typical response of a VOC-limited regime in the urban area. For the four heterogeneous reactions considered, the NO2 and HO2 heterogeneous reactions have the most severe impacts on O3 formation. During the O3 formation period, the NO2 heterogeneous reaction increased new radical creation by 30%, raising the atmospheric activity as more NO→NO2 conversion occurred, thus causing the O3 to rise. The increase of O3 peak concentration reached a maximum value of 67 ppb in the urban area. In the morning hours, high NO titration reduced the effect of the photolysis of HONO, which was produced heterogeneously at night in the surface layer. The NO2 heterogeneous reaction in the daytime is likely one of the major reasons causing the O3 increase in the Beijing urban area. The HO2 heterogeneous reaction accelerated radical termination, resulting in a decrease of the radical concentration by 44% at the most. O3 peak concentration decreased by a maximum amount of 24 ppb in the urban area. The simulation results were improved when the heterogeneous reactions were included, with the O3 and HONO model results close to the observations.
基金supported by the National Natural Science Foundation of China (No. 40533017, 20377008,40605001)the National Key Technology R&D Program(No. 2006BAC12B001)the State Key Laboratory of Atmospheric Boundary Layer Physics and Atmospheric Chemistry (LAPC-KF-2006-05) of China
文摘The variations of sulfate formation and optical coefficients during SO2 heterogeneous reactions on hematite surface under different SO2 concentrations were examined using in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) and ion chromatograph (IC). Laboratory experiments revealed that within ambient SO2 of 0.51-18.6 ppmv, sulfate product, producing velocity, absorption and backward scattering coefficients showed an increasing trend with SO2 concentration. Under given SO2 concentration, the velocity of sulfate producing performed an evolution of initial increasing, midterm decreasing and final stabilizing. The reactive uptake and Brunaner-Emmett-Teller (BET) uptake coefficients of heterogeneous reactions rose with SOz and exhibited high reactivities. Considering global warming, this result is important for the knowledge of heterogeneous reactions of SO2 on mineral particle surface in the atmosphere and the assessment of their impacts on radiative forcing.
基金financial support from Shandong Province Education Department(Grant No.J14 LC11)National Natural Science Foundation of China(Grant No.21406126 and 21576146)+2 种基金Department of Science and Technology of Shandong Province(Grant No.2014 GSF116001)973(Grant No.2014 CB460610)Department of Science and Technology of Shandong Province(Grant No.2015 ZDXX0403 B03)
文摘Oxidized starch powder and cationic starch solution were reacted with alkyl ketene dimer(AKD) under heterogeneous conditions at 70℃ for 12 h.The AKD molecules reacted with starch hydroxyl groups to form β-keto ester linkages under the above conditions.The reaction products were separated into CHCl_3-soluble and CHCl_3-insoluble fractions.FT-IR spectroscopy,SEM,Xray diffraction,and TG-DTA analyses of the CHCl_3-insoluble fraction indicated that β-keto ester substituents were introduced to hydroxyl groups on the starch surfaces.The results indicated that hydrogen bonds between the starch molecules were disrupted under heterogeneous conditions upon heating.The activity and accessibility of hydroxyl groups were enhanced,as a result of which β-keto ester bonds were produced between AKD and starch.Based on these results,we speculate that the β-keto esters which existed in the sheets sized by AKD emulsions were generated by the reaction between AKD and starch.
基金the National Natural Science Foundation of China(Nos.11872241 and11432009)。
文摘The homogeneous and heterogeneous reactions in the boundary-layer of a flat surface are considered. The autocatalysts are assumed to be of regular sizes, while the solution is a dilute nanofluid. The heat release due to the chemical reactions is taken into account. The Buongiorno’s model is used to describe the behaviors of this reaction system. This configuration makes the current model be different from all previous publications. Multiple solutions are given numerically to the rescaled nonlinear system, whose stability is verified. The results show that the strength coefficients of the homogeneous and heterogeneous reactions are key factors to cause the appearance of the multiple solutions in the distribution of the chemical reactions. Nanofluids enhance the diffusion of heat and help maintain the stability of chemical reactions.
基金supported by the National Natural Science Foundation of China(Nos.41807304 and 22206130)。
文摘Heterogeneous reaction of mineral aerosols and atmospheric polluting gases play an important role in atmospheric chemistry.In this study,the reactions of NO_(2) with or without SO_(2) mixture gas on the surface of α-Fe_(2)O_(3) particles under dry conditions were studied.The effects of sodium dodecyl sulfate(SDS)and the heterogeneous reaction under both dark and UV irradiation conditions were investigated.The infrared spectrum analyzed by the two-dimensional correlation spectroscopy(2D-COS)was used to obtain the products formation sequences.The results showed that UV irradiation can promote the production of nitrate.The 2D-COS analysis indicated SDS changed the sequence order of nitrate and nitrite species during reactions.In oxidation conditions,the final product of heterogeneous reaction of NO_(2) and α-Fe_(2)O_(3) was monodentate nitrate.Only the heterogenous reaction of NO_(2) and α-Fe_(2)O_(3) containing SDS(FOS)without UV light,the final product was bidentate nitrate.SDS was the catalysis agent supply and photoresist to the system.With surface active compounds,the environmental lifetime of heterogeneous reactions between trace gases and aerosols extends.Surfactants,ultraviolet light,and the types of gases involved in the reaction all have complex effects on the aerosol aging process.This study provided a reference for subsequent heterogeneous reaction studies and the formation of aerosols.
基金supported by the National Natural Science Foundation of China(No.42022050)Guangdong Foundation for Program of Science and Technology Research(Nos.2019B121205006 and 2020B1212060053)+1 种基金the Guangdong Science and Technology Department(No.2017GC010501)CAS Pioneer Hundred Talents program.
文摘Heterogeneous reaction of NO_(2) with mineral dust aerosol may play important roles in troposphere chemistry,and has been investigated by a number of laboratory studies.However,the influence of mineralogy on this reaction has not been well understood,and its impact on aerosol hygroscopicity is not yet clear.This work investigated heterogeneous reactions of NO_(2)(∼10 ppmv)with K-feldspar,illite,kaolinite,montmorillonite and Arizona Test Dust(ATD)at room temperature as a function of relative humidity(<1%to 80%)and reaction time(up to 24 hr).Heterogeneous reactivity towards NO_(2) was low for illite,kaolinite,montmorillonite and ATD,and uptake coefficients of NO_(2),γ(NO_(2)),were determined to be around or smaller than 1×10^(−8);K-feldspar exhibited higher reactivity towards NO_(2),and CaCO_(3) is most reactive among the nine mineral dust samples considered in this and previous work.After heterogeneous reaction with NO_(2) for 24 hr,increase in hygroscopicity was nearly insignificant for illite,kaolinite and montmorillonite,and small but significant for K-feldspar;in addition,large increase in hygroscopicity was observed for ATD,although the increase in hygroscopicity was still smaller than CaCO_(3).
基金supported by the National Natural Science Foundation of China(No.42022050)the Guangdong Basic and Applied Basic Research Fund Committee(No.2020B1515130003)+3 种基金the Guangdong Foundation for Program of Science and Technology Research(Nos.2019B121205006 and 2020B1212060053)the Guangdong Science and Technology Department(No.2017GC010501)the CAS Pioneer Hundred Talents program.We would like to thank Ryan Sullivan(Carnegie Mellon University,USA)the Nadine Borduas-Dedekind(University of British Columbia,Canada)for sharing their original data.
文摘Mineral dust is an important type of ice nucleating particles in the troposphere;however,the effects of heterogeneous reactions on ice nucleation(IN)activities of mineral dust remain to be elucidated.A droplet-freezing apparatus(Guangzhou Institute of Geochemistry Ice Nucleation Apparatus,GIGINA)was developed in thiswork to measure IN activities of atmospheric particles in the immersion freezingmode,and its performancewas validated by a series of experimental characterizations.This apparatus was then employed to measure IN activities of feldspar and Arizona Test Dust(ATD)particles before and after heterogeneous reaction with NO_(2)(10±0.5 ppmv)at 40%relative humidity.The surface coverage of nitrate,θ(NO_(3)^(−)),increased to 3.1±0.2 for feldspar after reaction with NO_(2) for 6 hr,and meanwhile the active site density per unit surface area(ns)at-20℃ was reduced from 92±5 to<1.0 cm^(−2) by about two orders of magnitude;however,no changes in nitrate content or IN activities were observed for further increase in reaction time(up to 24 hr).Both nitrate content and IN activities changed continuously with reaction time(up to 24 hr)for ATD particles;after reaction with NO_(2) for 24 hr,θ(NO_(3)^(−))increased to 1.4±0.1 and ns at-20℃ was reduced from 20±4 to 9.7±1.9 cm^(−2) by a factor of∼2.Our work suggests that heterogeneous reaction with NO_(2),an abundant reactive nitrogen species in the troposphere,may significantly reduce IN activities of mineral dust in the immersion freezing mode.
基金This work was financially supported by the National Natural Science Foundation of China(22122610,22188102,41877304,21777171).
文摘Soot particles,composed of elemental carbon and organic compounds,have attracted widespread attention in recent years due to their significant impacts on climate,the environment and human health.Soot has been found to be chemically and physically active in atmospheric aging processes,which leads to alterations in its composition,morphology,hygroscopicity and optical properties and thus changes its environmental and health effects.The heterogeneous reactions on soot also have a significant impact on the transformation of gaseous pollutants into secondary aerosols.Therefore,the interactions between soot and atmospheric substances have been widely investigated to better understand the environmental behaviors of soot.In this review,we systematically summarize the progress and developments in the heterogeneous chemistry on soot over the past_(3)0 years.Atmospheric trace constituents such as NO_(2),O_(3),SO_(2),N_(2)O_(5),HNO_(3),H_(2)SO_(4),OH radical,HO_(2)radical,peroxyacetyl nitrate etc.,are presented in detail from the aspect of their heterogeneous reactions on soot.The possible mechanisms and the effects of environmental conditions on these heterogeneous reactions are also addressed.Further,the impacts of the heterogeneous reactions of soot on the atmospheric environment are discussed,and some aspects of soot-related research which require further investigation are proposed as well.
基金supported by the National Natural Science Foundation of China (No. 41005071,40490265,20637020)the National Basic Research Program of China(No. 2002CB410802 )the Special Fund of State Key Joint Laboratory of Environment Simulation and Pollution Control (No. 09K01ESPCP)
文摘The studies on heterogeneous reactions over montmorillonite, which is a typical 2:1 layered aluminosilicate, will benefit to the Understanding of heterogeneous reactions on clay minerals. Montmorillonite can be classified as sodium montmorillonite or calcium montmorillonite depending on the cation presented between the different layers. Using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), the heterogeneous reaction mechanism of NO2 on the surface of montmorillonite was firstly investigated. Results showed that the reaction of NO2 on the surface of sodium and calcium montmorillonite fit a first-order kinetics, and the reaction duration of calcium montmorillonite was longer than that of sodium montmorillonite under the dry condition. For either sodium or calcium montmorillonite, the uptake coefficient decreased as humidity increased.
基金supported by the Chinese Ministry of Science and Technology(No.2008AA062503)the National Natural Science Foundation Committee of China(Nos.41421064,20637020)the China Postdoctoral Science Foundation(No.20100470166)
文摘Heterogeneous reactions on the aerosol particle surface in the atmosphere play important roles in air pollution, climate change, and global biogeochemical cycles. However, the reported uptake coefficients of heterogeneous reactions usually have large variations and may not be relevant to real atmospheric conditions. One of the major reasons for this is the use of bulk samples in laboratory experiments, while particles in the atmosphere are suspended individually. A number of technologies have been developed recently to study heterogeneous reactions on the surfaces of individual particles. Precise measurements on the reactive surface area, volume, and morphology of individual particles are necessary for calculating the uptake coefficient, quantifying reactants and products, and understanding the reaction mechanism better. In this study, for the first time we used synchrotron radiation X-ray computed tomography(XCT) and micro-Raman spectrometry to measure individual CaCO_3 particle morphology, with sizes ranging from 3.5–6.5 μm. Particle surface area and volume were calculated using a reconstruction method based on software threedimensional(3-D) rendering. The XCT was first validated with high-resolution fieldemission scanning electron microscopy(FE-SEM) to acquire accurate CaCO_3 particle surface area and volume estimates. Our results showed an average difference of only 6.1% in surface area and 3.2% in volume measured either by micro-Raman spectrometry or X-ray tomography. X-ray tomography and FE-SEM can provide more morphological details of individual Ca CO3 particles than micro-Raman spectrometry. This study demonstrated that X-ray computed tomography and micro-Raman spectrometry can precisely measure the surface area, volume, and morphology of an individual particle.
基金This work was supported by the National High Technology Research & Development Program of China (No. 2012AA06A301) and the National Natural Science Foundation of China (Grant Nos. 21337001 and 21177076).
文摘Sea salt particles containing NaCl are among the most abundant particulate masses in coastal atmosphere. Reactions involving sea salt particles potentially generate Cl radicals, which are released into coastal atmosphere. Cl radicals play an important role in the nitrogen and O3 cycles, sulfitr chemistry and particle formation in the troposphere of the polluted coastal regions. This paper aimed at .the heterogeneous reaction between gaseous HNO3 .and solid NaCl. The mech.anis.m was in.vestigatedby density functional theory (DFT). The results imply that water molecules induce the surface reconstruction, which is essential for the heterogeneous reaction. The surface reconstruction on the defective (710) surface has a barrier of 10.24 kcal.mol-1 and is endothermic by 9.69 kcal.mol-1, whereas the reconstruction on the clean (100) surface has a barrier of 18.46 kcal.mol-1 and isendothermic by 12.96 kcal.mol-1. The surface reconstruction involved in water-adsorbed (710) surface is more energetically favorable. In comparison, water molecules adsorbed on NaCl (100) surface likely undergo water diffusion or desorption. Further, it reveals that the coordination number of the Cl-out is reduced after the surface reconstruction, which assists Clout to accept the proton from HNO3. HCl is released from heterogeneous reactions between gaseous HNO3 and solid NaCl and can react with OH free radicals to produce atomic Cl radicals. The results will offer further insights into the impact of gaseous HNO3 on the air quality of the coastal areas.
基金supported by the National Natural Science Foundation of China(No.91644214)Youth Innovation Program of Universities in Shandong Province(No.2019KJD007)Fundamental Research Fund of Shandong University(No.2020QNQT012)
文摘Despite the heterogeneous reaction of sulfur dioxide(SO_(2))on mineral dust particles significantly affects the atmospheric environment,the effect of acidic gases on the formation of sulfite and sulfate from this reaction is not particularly clear.In this work,using the in-situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)technique,we employed a mineral dust particle model(CaCO_(3))combined with NO_(2)and acetic acid to investigate their effects on the heterogeneous reaction of SO_(2)on CaCO_(3)particles.Itwas found that water vapor can promote the formation of sulfite and simulated radiation can facilitate the oxidation of sulfite to sulfate.The addition of NO_(2)or acetic acid to the reaction system altered the production of sulfate and sulfite accordingly.There was a synergistic effect between NO_(2)and SO_(2)that promoted the oxidation of sulfite to sulfate,and a competitive effect between acetic acid and SO_(2)that inhibited the formation of sulfite.Moreover,light and water vapor can also affect the heterogeneous reaction of SO_(2)with the coexistence ofmultiple gases.These findings improve our understanding of the effects of organic and inorganic gases and environmental factors on the formation of sulfite and sulfate in heterogeneous reactions.
文摘The present study reveals the effect of homogeneous/hetereogeneous reaction on stagnation point flow of Williamson fluid in the presence of magnetohydrodynamics and heat generation/absorption coefficient over a stretching cylinder. Further the effects of variable thermal conductivity and thermal stratification are also considered. The governing partial differential equations are converted to ordinary differential equations with the help of similarity transformation.The system of coupled non-linear ordinary differential equations is then solved by shooting technique. MATLAB shooting code is validated by comparison with the previously published work in limiting case. Results are further strengthened when the present results are compared with MATLAB built-in function bvp4c. Effects of prominent parameters are deliberated graphically for the velocity, temperature and concentration profiles. Skin-friction coefficient and Nusselt number for the different parameters are investigated with the help of tables.
基金the National Natural Science Foundation of China(Nos.21976030 and21677037)Ministry of Science and Technology of China(Nos.2016YFE0112200 and 2016YFC0202700)the Natural Science Foundation of Shanghai(Nos.19ZR1471200 and 17ZR1440200)。
文摘The heterogeneous reaction of SO_(2) on mineral dust surfaces is generally considered as an important chemical pathway for secondary sulfate formation in the troposphere.To this day,there are no reported studies that assess the impact of atmospheric CO_(2) in sulfate production on mineral dust surfaces.In this work,we investigate the impact of CO_(2) on SO_(2) uptake on dust proxy aluminum oxide particles using a diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS).CO_(2) is demonstrated to suppress the heterogeneous oxidation of SO_(2) on alpha-Al2 O_(3).Compared to that measured in the CO_(2)-free case,the uptake coefficient is decreased by nearly 57%when Al_(2)O_(3) particles are exposed to the gas flow with atmospheric CO_(2) at a relative humidity(RH)of 25%.It is also found that there is a balance between the yield of active moiety-OH provided by AI(OH)3(CO)(OH)2 clusters and the loss of basic hydroxyl group on aluminum oxide surfaces blocked by CO_(2)-derived(bi)carbonate species.This work,for the first time,reveals a negative effect of atmospheric CO_(2) on the sulfate formation,which potentially decreases solarradiation scattering and further exacerbates global warming.
文摘The reaction kinetics of the heterogeneous oxidation of toluene with Mn 3+ was studied by considering the effects of disproportionation of Mn 3+ in reaction system, a 'parallel' modulus was set up. And then the concentration of Mn 3+ in disproportionation and the concentration of benzaldehyde in oxidation were respectively determined in turn, the rate constant, order and pseudo activation energy of the heterogeneous oxidation were obtained by mathematical deduction and the kinetic equation was concluded. In addition, the reaction mechanism was analyzed. It shows that the results are completely consistent with modulus.
基金supported by the funding for Creative Research Groups of China (No. 50921064)the China Postdoctoral Science Foundation Funded Project (No. 2011M500433)the President Fund of GUCAS (No. Y25102GN00)
文摘The reactions of gas-phase anthracene and suspended anthracene particles with O3 and O3-NO were conducted in a 200-L reaction chamber, respectively. The secondary organic aerosol (SOA) formations from gas-phase reactions of anthracene with O3 and O3-NO were observed. Meanwhile, the size distributions and mass concentrations of SOA were monitored with a scanning mobility particle sizer (SMPS) during the formation processes. The rapid exponential growths of SOA reveal that the atmospheric lifetimes of gas-phase anthracene towards O3 and O3-NO are less than 20.5 and 4.34 hr, respectively. The particulate oxidation products from homogeneous and heterogeneous reactions were analyzed with a vacuum ultraviolet photoionization aerosol time-of-flight mass spectrometer (VUV-ATOFMS). Gas chromatograph/mass spectrometer (GC/MS) analyses of oxidation products of anthracene were carried out for assigning the time-of-flight (TOF) mass spectra of products from homogeneous and heterogeneous reactions. Anthrone, anthraquinone, 9,10- dihydroxyanthracene, and 1,9,10-trihydroxyanthracene were the ozonation products of anthracene, while anthrone, anthraquinone, 9-nitroanthracene, and 1,8-dihydroxyanthraquinone were the main products of anthracene with O3-NO.
文摘MnFe1.4Ru0.45Cu0.15O4 was an effective heterogeneous catalyst for the oxidation of various types of alcohols to the corresponding carbonyl compounds using atmospheric pressure of oxygen under mild conditions. Furthermore, this catalyst was also effective towards alcohol oxidation using water as solvent instead of toluene.
文摘The possibility of carrying out a purely heterogeneous Heck reaction in practice without Pd leaching has been previously considered by a number of research groups but no general consent has yet arrived. Here, the reaction was, for the first time, evaluated by a simple computational approach. Modelling experiments were performed on one of the initial catalytic steps: phenyl halides attachment on Pd (111) to (100) and (111) to (111) ridges of a Pd crystal. Three surface structures of resulting were identified as possible reactive intermediates. Following potential energy minimisation calculations based on a universal force field, the relative stabilities of these surface species were then determined. Results showed the most stable species to be one in which a Pd ridge atom is removed from the Pd crystal structure, suggesting Pd leaching induced by phenyl halides is energetically favourable.
基金supported by the National Natural Science Foundation of China (Grant Nos. 41175105 and 40905055)the Key Project of Chinese Academy of Sciences (Grant No. kzcx1-yw-06-04)
文摘The Weather Research and Forecasting/Chemistry model (WRF-Chem) was updated by including pho- toexeited nitrogen dioxide (NO2) molecules, heterogeneous reactions on aerosol surfaces, and direct emissions of nitrous acid (HONO) in the Carbon-Bond Mechanism Z (CBM-Z). Five simulations were conducted to assess the effects of each new component and the three additional HONO sources on concentrations of major chemical components. We calculated percentage changes of major aerosol components and concentration ratios of gas NOy (NOyg) to NOy and particulate nitrates (NO3-) to NOy due to the three additional HONO sources in the North China Plain in August of 2007. Our results indicate that when the three additional HONO sources are included, WRF-Chem can reasonably reproduce the HONO observations. Heterogeneous reactions on aerosol surfaces are a key contributor to concentrations of HONO, nitrates (NO3-), ammonium (NH+), and PM2.5 (concentration of particulate matter of ≤2.5 um in the ambient air) across the North China Plain. The three additional HONO sources produced a -5% -20% increase in monthly mean daytime concentration ratios of NO3-/NOy, a -15%- 52% increase in maximum hourly mean concentration ratios of NO3-/NOy, and a -10% -50% increase in monthly mean concentrations of NOx and NH+ across large areas of the North China Plain. For the Bohai Bay, the largest hourly increases of NO3- exceeded 90%, of NH+ exceeded 80%, and of PM2.5 exceeded 40%, due to the three additional HONO sources. This implies that the three additional HONO sources can aggravate regional air pollution, further impair visibility, and enhance the incidence of haze in some industrialized regions with high emissions of NOx and particulate matter under favorable meteorological conditions.
基金supported by the National Basic Research Program (973) of China (No.2006CB403701)the Macao Foundation for Development of Science and Technology (No.023/2006/A)+3 种基金the State Key Laboratory of Coal Resources and Safe Mining (China University of Mining and Technology) (No.SKLCRSM09KFB04)the China Postdoctoral Science Foundation Funded Project(No.20090461213)the Shandong Postdoctoral Science Innovation Foundation (No.200902016)the Independent Innovation Foundation of Shandong University
文摘Aerosol samples were collected in summer in Macao, a coastal city of the Pearl River Delta Region in China. Morphology, size, elemental composition, and mixing state of individual aerosol particles were determined by scanning electron microscopy coupled energy dispersive X-ray (SEM/EDX) and transmission electron microscopy (TEM). Based on the morphologies of 5711 aerosol particles, they consist of soot (32%), mineral (17%), secondary-(22%), and unknown fine particles (29%). The sizes of these particles were mostly distributed between 0.1 and 0.4 μm. Compositions of 202 mineral particles were obtained by SEM/EDX. Mineral particles were mainly classified into three types: Si-rich, Ca-rich, and Na-rich. The compositions of typical mineral particles can indicate their sources in sampling location. For example, mineral particles, collected along the main street, were associated with trace amounts of heavy metals, such as Zn, Ti, Mn, Ba, Pb, and As. TEM observations indicate that most Na-rich particles were aged sea salt particles (e.g., Na2SO4 and NaNO3) which formed through heterogeneous chemical reactions between sea salt and acidic gases. Additionally, aging time of soot was short in Macao due to high humidity, high temperature, and high levels of sunlight in Macao. Most of soot and fine mineral dust particles were internally mixed with secondary particles.