Hexafluoropropylene oxide(HFPO)is a crucial fluorinated chemical mainly synthesized from hexafluoropropylene(HFP)through the oxidation of oxygen.However,the reaction network and kinetic characteristics are not fully u...Hexafluoropropylene oxide(HFPO)is a crucial fluorinated chemical mainly synthesized from hexafluoropropylene(HFP)through the oxidation of oxygen.However,the reaction network and kinetic characteristics are not fully understood yet,resulting in a lack of theoretical basis for synthesis process improvement.Here,the free radical reaction mechanism and complete reaction network involved in the noncatalytic oxidation of HFP to synthesize HFPO was explored by density functional theory.Transition state theory was employed to calculate the intrinsic reaction rate constants for elementary reactions.Based on theoretical reaction rate ratios,reaction pathways were selected,and a simplified reaction network was derived.It was found that byproducts were formed owing to the decomposition of HFPO and subsequent reactions with excessive oxygen while oxygen tended to participate more in the main reaction under oxygen-deficient conditions.The variations in reaction pathways occurring at different HFP/oxygen molar ratios was well elucidated by comparing with experimental data.This research establishes a robust theoretical foundation for optimizing and regulating the synthesis of HFPO.展开更多
Pavement runoff sampling points were set up on the main roads of Chengdu city.Six rainfall-runoff events from July to September in 2017 were sampled by synchronous observation of rainfall,runoff and pollution.The conc...Pavement runoff sampling points were set up on the main roads of Chengdu city.Six rainfall-runoff events from July to September in 2017 were sampled by synchronous observation of rainfall,runoff and pollution.The concentration changes of copper,lead,zinc,chromium and cadmium in the runoff process were monitored,and the pollution emission regularity and initial scouring effect were studied.The results show that the emission regularity of pavement runoff pollution is closely related to rainfall characteristics and pollutant occurrence,and the concentration of dissolved heavy metals reaches its peak at the initial stage of runoff.The peak time of particulate heavy metal concentration lagged slightly behind that of rainfall intensity.There is a big difference between the strength of initial scouring degree and dissolved heavy metals the stronger the initial scouring degree of total heavy metals,the weaker the dissolved heavy metals.Reducing pavement runoff in the early stage of rainfall is an effective means to control heavy metal pollution.展开更多
基金supported by the National Key Research&Development Program of China(2021YFB3803200)the National Natural Science Foundation of China(22288102).
文摘Hexafluoropropylene oxide(HFPO)is a crucial fluorinated chemical mainly synthesized from hexafluoropropylene(HFP)through the oxidation of oxygen.However,the reaction network and kinetic characteristics are not fully understood yet,resulting in a lack of theoretical basis for synthesis process improvement.Here,the free radical reaction mechanism and complete reaction network involved in the noncatalytic oxidation of HFP to synthesize HFPO was explored by density functional theory.Transition state theory was employed to calculate the intrinsic reaction rate constants for elementary reactions.Based on theoretical reaction rate ratios,reaction pathways were selected,and a simplified reaction network was derived.It was found that byproducts were formed owing to the decomposition of HFPO and subsequent reactions with excessive oxygen while oxygen tended to participate more in the main reaction under oxygen-deficient conditions.The variations in reaction pathways occurring at different HFP/oxygen molar ratios was well elucidated by comparing with experimental data.This research establishes a robust theoretical foundation for optimizing and regulating the synthesis of HFPO.
文摘Pavement runoff sampling points were set up on the main roads of Chengdu city.Six rainfall-runoff events from July to September in 2017 were sampled by synchronous observation of rainfall,runoff and pollution.The concentration changes of copper,lead,zinc,chromium and cadmium in the runoff process were monitored,and the pollution emission regularity and initial scouring effect were studied.The results show that the emission regularity of pavement runoff pollution is closely related to rainfall characteristics and pollutant occurrence,and the concentration of dissolved heavy metals reaches its peak at the initial stage of runoff.The peak time of particulate heavy metal concentration lagged slightly behind that of rainfall intensity.There is a big difference between the strength of initial scouring degree and dissolved heavy metals the stronger the initial scouring degree of total heavy metals,the weaker the dissolved heavy metals.Reducing pavement runoff in the early stage of rainfall is an effective means to control heavy metal pollution.
