Particulate matter with diameters of 2.5 μm or smaller(PM_(2.5)) and ozone(O_3) are major pollutants in the urban atmosphere. PM_(2.5) can affect O_3 by altering the photolysis rate and heterogeneous reactions. Howev...Particulate matter with diameters of 2.5 μm or smaller(PM_(2.5)) and ozone(O_3) are major pollutants in the urban atmosphere. PM_(2.5) can affect O_3 by altering the photolysis rate and heterogeneous reactions. However, these two processes and their relative importance remain uncertain. In this paper, with Nanjing in China as the target city, we investigate the characteristics and mechanism of interactions between particles and O_3 based on ground observations and numerical modeling.In 2008, the average concentrations of PM_(2.5) and O_3 at Caochangmen station are 64.6 ± 47.4 μg m^(-3) and 24.6 ± 22.8 ppb,respectively, while at Pukou station they are 94.1 ± 63.4 μg m^(-3) and 16.9 ± 14.9 ppb. The correlation coefficient between PM_(2.5) and O_3 is -0.46. In order to understand the reaction between PM_(2.5) and O_3, we construct a box model, in which an aerosol optical property model, ultraviolet radiation model, gas phase chemistry model, and heterogeneous chemistry model,are coupled. The model is employed to investigate the relative contribution of the aforementioned two processes, which vary under different particle concentrations, scattering capability and VOCs/NOxratios(VOCs: volatile organic compounds;NOx: nitric oxide and nitrogen dioxide). Generally, photolysis rate effect can cause a greater O_3 reduction when the particle concentrations are higher, while heterogeneous reactions dominate O_3 reduction with low-level particle concentrations.Moreover, in typical VOC-sensitive regions, O_3 can even be increased by heterogeneous reactions. In Nanjing, both processes lead to O_3 reduction, and photolysis rate effect is dominant. Our study underscores the importance of photolysis rate effect and heterogeneous reactions for O_3, and such interaction processes should be fully considered in future atmospheric chemistry modeling.展开更多
The heterogeneous Fenton reaction can generate highly reactive hydroxyl radicals（·OH）from reactions between recyclable solid catalysts and H2O2 at acidic or even circumneutral pH.Hence,it can effectively oxidiz...The heterogeneous Fenton reaction can generate highly reactive hydroxyl radicals（·OH）from reactions between recyclable solid catalysts and H2O2 at acidic or even circumneutral pH.Hence,it can effectively oxidize refractory organics in water or soils and has become a promising environmentally friendly treatment technology.Due to the complex reaction system,the mechanism behind heterogeneous Fenton reactions remains unresolved but fascinating,and is crucial for understanding Fenton chemistry and the development and application of efficient heterogeneous Fenton technologies.Iron-based materials usually possess high catalytic activity,low cost,negligible toxicity and easy recovery,and are a superior type of heterogeneous Fenton catalysts.Therefore,this article reviews the fundamental but important interfacial mechanisms of heterogeneous Fenton reactions catalyzed by iron-based materials..OH,hydroperoxyl radicals/superoxide anions（HO2./O2^-.）and high-valent iron are the three main types of reactive oxygen species（ROS）,with different oxidation reactivity and selectivity.Based on the mechanisms of ROS generation,the interfacial mechanisms of heterogeneous Fenton systems can be classified as the homogeneous Fenton mechanism induced by surface-leached iron,the heterogeneous catalysis mechanism,and the heterogeneous reaction-induced homogeneous mechanism.Different heterogeneous Fenton systems catalyzed by characteristic iron-based materials are comprehensively reviewed.Finally,related future research directions are also suggested.展开更多
The oxidation of hydrocarbons to produce high value-added compounds(ketones or alcohols)using oxygen in air as the only oxidant is an efficient synthetic strategy from both environmental and economic views.Herein,we s...The oxidation of hydrocarbons to produce high value-added compounds(ketones or alcohols)using oxygen in air as the only oxidant is an efficient synthetic strategy from both environmental and economic views.Herein,we successfully synthesized cobalt single atom site catalysts(Co SACs)with high metal loading of 23.58 wt.%supported on carbon nitride(CN),which showed excellent catalytic properties for oxidation of ethylbenzene in air.Moreover,Co SACs show a much higher turn-over frequency(19.6 h^(−1))than other reported non-noble catalysts under the same condition.Comparatively,the as-obtained nanosized or homogenous Co catalysts are inert to this reaction.Co SACs also exhibit high selectivity(97%)and stability(unchanged after five runs)in this reaction.DFT calculations reveal that Co SACs show a low energy barrier in the first elementary step and a high resistance to water,which result in the robust catalytic performance for this reaction.展开更多
The task assignment problem of multiple heterogeneous unmanned aerial vehicles （UAVs）, concerned with cooperative decision making and control, is studied in this paper. The heterogeneous vehicles have different oper...The task assignment problem of multiple heterogeneous unmanned aerial vehicles （UAVs）, concerned with cooperative decision making and control, is studied in this paper. The heterogeneous vehicles have different operational capabilities and kinematic constraints, and carry limited resources （e.g., weapons） onboard. They are designated to perform multiple consecutive tasks cooperatively on multiple ground targets. The problem becomes much more complicated because of these terms of heterogeneity. In order to tackle the challenge, we modify the former genetic algorithm with multi-type genes to stochastically search a best solution. Genes of chromo- somes are different, and they are assorted into several types according to the tasks that must be performed on targets. Different types of genes are processed specifically in the improved genetic operators including initialization, crossover, and mutation. We also present a mirror representation of vehicles to deal with the limited resource constraint. Feasible chromosomes that vehicles could perform tasks using their limited resources under the assignment are created and evolved by genetic operators. The effect of the proposed algorithm is demonstrated in numerical simulations. The results show that it effectively provides good feasible solutions and finds an optimal one.展开更多
基金supported by the National Key Basic Research & Development Program of China (Grant Nos. 2016YFC0203303, 2016YFC0208504 and 2014CB441203)the National Natural Science Foundation of China (Grant Nos. 91544230, 41575145 and 41621005)the EU 7th Framework Marie Curie Actions IRSES project: REQUA (Grant No. PIRSESGA-2013-612671)
文摘Particulate matter with diameters of 2.5 μm or smaller(PM_(2.5)) and ozone(O_3) are major pollutants in the urban atmosphere. PM_(2.5) can affect O_3 by altering the photolysis rate and heterogeneous reactions. However, these two processes and their relative importance remain uncertain. In this paper, with Nanjing in China as the target city, we investigate the characteristics and mechanism of interactions between particles and O_3 based on ground observations and numerical modeling.In 2008, the average concentrations of PM_(2.5) and O_3 at Caochangmen station are 64.6 ± 47.4 μg m^(-3) and 24.6 ± 22.8 ppb,respectively, while at Pukou station they are 94.1 ± 63.4 μg m^(-3) and 16.9 ± 14.9 ppb. The correlation coefficient between PM_(2.5) and O_3 is -0.46. In order to understand the reaction between PM_(2.5) and O_3, we construct a box model, in which an aerosol optical property model, ultraviolet radiation model, gas phase chemistry model, and heterogeneous chemistry model,are coupled. The model is employed to investigate the relative contribution of the aforementioned two processes, which vary under different particle concentrations, scattering capability and VOCs/NOxratios(VOCs: volatile organic compounds;NOx: nitric oxide and nitrogen dioxide). Generally, photolysis rate effect can cause a greater O_3 reduction when the particle concentrations are higher, while heterogeneous reactions dominate O_3 reduction with low-level particle concentrations.Moreover, in typical VOC-sensitive regions, O_3 can even be increased by heterogeneous reactions. In Nanjing, both processes lead to O_3 reduction, and photolysis rate effect is dominant. Our study underscores the importance of photolysis rate effect and heterogeneous reactions for O_3, and such interaction processes should be fully considered in future atmospheric chemistry modeling.
基金supported by the National Natural Science Foundation of China (Nos. 21107125, 21577160, 51221892, 51290282 and 41201498)
文摘The heterogeneous Fenton reaction can generate highly reactive hydroxyl radicals（·OH）from reactions between recyclable solid catalysts and H2O2 at acidic or even circumneutral pH.Hence,it can effectively oxidize refractory organics in water or soils and has become a promising environmentally friendly treatment technology.Due to the complex reaction system,the mechanism behind heterogeneous Fenton reactions remains unresolved but fascinating,and is crucial for understanding Fenton chemistry and the development and application of efficient heterogeneous Fenton technologies.Iron-based materials usually possess high catalytic activity,low cost,negligible toxicity and easy recovery,and are a superior type of heterogeneous Fenton catalysts.Therefore,this article reviews the fundamental but important interfacial mechanisms of heterogeneous Fenton reactions catalyzed by iron-based materials..OH,hydroperoxyl radicals/superoxide anions（HO2./O2^-.）and high-valent iron are the three main types of reactive oxygen species（ROS）,with different oxidation reactivity and selectivity.Based on the mechanisms of ROS generation,the interfacial mechanisms of heterogeneous Fenton systems can be classified as the homogeneous Fenton mechanism induced by surface-leached iron,the heterogeneous catalysis mechanism,and the heterogeneous reaction-induced homogeneous mechanism.Different heterogeneous Fenton systems catalyzed by characteristic iron-based materials are comprehensively reviewed.Finally,related future research directions are also suggested.
基金This work was supported by the National Key R&D Program of China(Nos.2018YFA0702003 and 2016YFA0202801)the National Natural Science Foundation of China(Nos.21890383,21671117,21871159,and 21901135)+2 种基金Science and Technology Key Project of Guangdong Province of China(No.2020B010188002)Beijing Municipal Science&Technology Commission(No.Z191100007219003)China Postdoctoral Science Foundation(No.2018M640114).
文摘The oxidation of hydrocarbons to produce high value-added compounds(ketones or alcohols)using oxygen in air as the only oxidant is an efficient synthetic strategy from both environmental and economic views.Herein,we successfully synthesized cobalt single atom site catalysts(Co SACs)with high metal loading of 23.58 wt.%supported on carbon nitride(CN),which showed excellent catalytic properties for oxidation of ethylbenzene in air.Moreover,Co SACs show a much higher turn-over frequency(19.6 h^(−1))than other reported non-noble catalysts under the same condition.Comparatively,the as-obtained nanosized or homogenous Co catalysts are inert to this reaction.Co SACs also exhibit high selectivity(97%)and stability(unchanged after five runs)in this reaction.DFT calculations reveal that Co SACs show a low energy barrier in the first elementary step and a high resistance to water,which result in the robust catalytic performance for this reaction.
文摘The task assignment problem of multiple heterogeneous unmanned aerial vehicles （UAVs）, concerned with cooperative decision making and control, is studied in this paper. The heterogeneous vehicles have different operational capabilities and kinematic constraints, and carry limited resources （e.g., weapons） onboard. They are designated to perform multiple consecutive tasks cooperatively on multiple ground targets. The problem becomes much more complicated because of these terms of heterogeneity. In order to tackle the challenge, we modify the former genetic algorithm with multi-type genes to stochastically search a best solution. Genes of chromo- somes are different, and they are assorted into several types according to the tasks that must be performed on targets. Different types of genes are processed specifically in the improved genetic operators including initialization, crossover, and mutation. We also present a mirror representation of vehicles to deal with the limited resource constraint. Feasible chromosomes that vehicles could perform tasks using their limited resources under the assignment are created and evolved by genetic operators. The effect of the proposed algorithm is demonstrated in numerical simulations. The results show that it effectively provides good feasible solutions and finds an optimal one.
