The factors and mechanisms of oxidative degradation of three organophosphorus pesticides (dichlorvos, methamidophos and phoxim) were studied with sodium percarbonate (SPC) as a solid oxidant. The result showed tha...The factors and mechanisms of oxidative degradation of three organophosphorus pesticides (dichlorvos, methamidophos and phoxim) were studied with sodium percarbonate (SPC) as a solid oxidant. The result showed that SPC has highly activity in degrading these organophosphous pesticides. The most efficient degradation of pesticides occurred under basic conditions and the degradation rates increased with time extension and high temperature. The degradation of organophosphorus pesticides was expected to get even better results at lower initial concentration. Furthermore, we analyzed the intermediate products by NMP, spectrometry. On the basis of the analytical result, the oxidative degradation mechanism was proposed for each organophosphous pesticide. It is significant to understand the environment chemistry of organophosphorus pesticides in environmental system.展开更多
As an active metabolite of venlafaxine and emerging antidepressant,Odesmethylvenlafaxine(ODVEN) was widely detected in different water bodies,which caused potential harm to human health and environmental safety.In thi...As an active metabolite of venlafaxine and emerging antidepressant,Odesmethylvenlafaxine(ODVEN) was widely detected in different water bodies,which caused potential harm to human health and environmental safety.In this study,the comparative work on the ODVEN degradation by UV(254 nm) and UV-LED(275 nm) activated sodium percarbonate(SPC) systems was systematically performed.The higher removal rate of ODVEN can be achieved under UV-LED direct photolysis(14.99%) than UV direct photolysis(4.57%) due to the higher values of photolysis coefficient at the wavelength 275nm.Significant synergistic effects were observed in the UV/SPC(80.38%) and UV-LED/SPC(53.57%) systems and the former exhibited better performance for the elimination of ODVEN.The degradation of ODVEN all followed the pseudo-first-order kinetics well in these processes,and the pseudo-first-order rate constant(kobs) increased with increasing SPC concentration.Radicals quenching experiments demonstrated that both ·OH and CO_(3)·-were involved in the degradation of ODVEN and the second-order rate constant of ODVEN with CO_(3)·-(1.58 × 10^(8)(mol/L)-1sec-1) was reported for the first time based on competitive kinetic method.The introduction of HA,Cl-,NO_(3)-and HCO_(3)-inhibited the ODVEN degradation to varying degrees in the both processes.According to quantum chemical calculation,radical addition at the ortho-position of the phenolic hydroxyl group was confirmed to be the main reaction pathways for the oxidation of ODVEN by·OH.In addition,the oxidation of ODVEN may involve the demethylation,H-abstraction,OH^(-)addition and C-N bond cleavage.Eventually,the UV-LED/SPC process was considered to be more cost-effective compared to the UV/SPC process,although the UV/SPC process possessed a higher removal rate of ODVEN.展开更多
The performance of sodium percarbonate (SPC) activated with ferrous ion (Fe(Ⅱ) with the addition of formic acid (FA) to stimulate the degradation of carbon tetrachloride (CT) was investigated. Results showed...The performance of sodium percarbonate (SPC) activated with ferrous ion (Fe(Ⅱ) with the addition of formic acid (FA) to stimulate the degradation of carbon tetrachloride (CT) was investigated. Results showed that CT could be entirely reduced within 15 min in the system at a variety of SPC/Fe(Ⅱ)/FA/CT molar ratios in experimental level. Scavenging tests indicated that carbon dioxide radical anion (CO2-) was the dominant reactive oxygen species responsible for CT degradation. CT degradation rate, to a large extent, increased with increasing dosages of chemical agents and the optimal molar ratio of SPC/Fe(Ⅱ)/FAJCT was set as 60/60/60/1. The initial concentration of CT can hardly affect the CT removal, while CT degradation was favorable in the pH range of 3.0-9.0, but apparently inhibited at pH 12. C1- and HCO3 of high concentration showed negative impact on CT removal. Cl- released from CT was detected and the results confirmed nearly complete mineralization ofCT. CT degradation was proposed by reductive C-C1 bond splitting. This study demonstrated that SPC activated with Fe(Ⅱ) with the addition of FA may be promising technique for CT remediation in contaminated groundwater.展开更多
Sodium percarbonate(Na_(2)CO_(3)·1.5H_(2)O_(2),SPC)has been extensively employed as a solid substitute of H_(2)O_(2)for Fenton process in water treatment,because of its high stability during the production,transp...Sodium percarbonate(Na_(2)CO_(3)·1.5H_(2)O_(2),SPC)has been extensively employed as a solid substitute of H_(2)O_(2)for Fenton process in water treatment,because of its high stability during the production,transport,storage and usage.In addition,SPC can be applied in a wider range of work pH,it is also applied as a buffer in Fenton reaction for preventing a drop in pH.Herein,we have synthesized basic copper molybdate(BCM)nanoblocks with the molecular formula of Cu_(3)(MoO_(4))_(2)(OH)_(2)as an efficient and heterogeneous catalyst for antibiotics degradation via percarbonate activation.First,fully physical characterizations confirmed BCM nanocomposite exhibited a structure of nanoblocks.We also found that BCM/SPC system could work in a much wider pH range,compared with H_(2)O_(2).Then,BCM/SPC system presented a good anti-interference ability for natural organic matter in OTC degradation.EPR results and Quenching tests confirmed that the co-presence of·CO_(3)-,·O_(2)-,1O_(2)and·OH in BCM/SPC system.展开更多
A new process for the Pd/Cu co-catalyzed homocoupling reaction of terminal alkynes was developed. The reaction was carried out in aqueous media with sodium percarbonate as both a clean oxidant and a base. Meanwhile, a...A new process for the Pd/Cu co-catalyzed homocoupling reaction of terminal alkynes was developed. The reaction was carried out in aqueous media with sodium percarbonate as both a clean oxidant and a base. Meanwhile, a palladium complex immobilized on a synthetic PS-PEG400-PPh2 resin was used as the catalyst, which may be recovered by simple filtration and reused for several times with high activity.展开更多
Sodium percarbonate(SPC)and peroxymonocarbonate(PMC)have been widely used in modified Fenton reactions because of their multiple superior features,such as a wide pH range and environmental friendliness.This broad revi...Sodium percarbonate(SPC)and peroxymonocarbonate(PMC)have been widely used in modified Fenton reactions because of their multiple superior features,such as a wide pH range and environmental friendliness.This broad review is intended to provide the fundamental information,status and progress of SPC and PMC based decontamination technologies according to the peer-reviewed papers in the last two decades.Both SPC and PMC can directly decompose various pollutants.The degradation efficiency will be enhanced and the target contaminants will be expanded after the activation of SPC and PMC.The most commonly used catalysts for SPC activation are iron compounds while cobalt composi-tions are applied to activate PMC in homogenous and heterogeneous catalytical systems.The generation and participation of hydroxyl,superoxide and/or carbonate radicals are involved in the activated SPC and PMC system.The reductive radicals,such as carbon dioxide and hydroxyethyl radicals,can be generated when formic acid or methanol is added in the Fe(II)/SPC system,which can reduce target contaminants.SPC can also be activated by energy,tetraacetylethylenediamine,ozone and buffered alkaline to generate different reactive radicals for pollutant decomposition.The SPC and activated SPC have been assessed for application in-situ chemical oxidation and sludge dewatering treatment.The challenges and prospects of SPC and PMC based decontamination technologies are also addressed in the last section.展开更多
文摘The factors and mechanisms of oxidative degradation of three organophosphorus pesticides (dichlorvos, methamidophos and phoxim) were studied with sodium percarbonate (SPC) as a solid oxidant. The result showed that SPC has highly activity in degrading these organophosphous pesticides. The most efficient degradation of pesticides occurred under basic conditions and the degradation rates increased with time extension and high temperature. The degradation of organophosphorus pesticides was expected to get even better results at lower initial concentration. Furthermore, we analyzed the intermediate products by NMP, spectrometry. On the basis of the analytical result, the oxidative degradation mechanism was proposed for each organophosphous pesticide. It is significant to understand the environment chemistry of organophosphorus pesticides in environmental system.
基金supported by the National Natural Science Foundation of China (Nos.51978618,51878582)the Natural Science Foundation of Zhejiang Province (Nos.LY21E080018,LY18E080036)+1 种基金Guiding Project of Fujian Province of China (No.2021Y0041)Foundation of Key Laboratory of Yangtze River Water Environment and Ministry of Education (Tongji University),China (No.YRWEF201901)。
文摘As an active metabolite of venlafaxine and emerging antidepressant,Odesmethylvenlafaxine(ODVEN) was widely detected in different water bodies,which caused potential harm to human health and environmental safety.In this study,the comparative work on the ODVEN degradation by UV(254 nm) and UV-LED(275 nm) activated sodium percarbonate(SPC) systems was systematically performed.The higher removal rate of ODVEN can be achieved under UV-LED direct photolysis(14.99%) than UV direct photolysis(4.57%) due to the higher values of photolysis coefficient at the wavelength 275nm.Significant synergistic effects were observed in the UV/SPC(80.38%) and UV-LED/SPC(53.57%) systems and the former exhibited better performance for the elimination of ODVEN.The degradation of ODVEN all followed the pseudo-first-order kinetics well in these processes,and the pseudo-first-order rate constant(kobs) increased with increasing SPC concentration.Radicals quenching experiments demonstrated that both ·OH and CO_(3)·-were involved in the degradation of ODVEN and the second-order rate constant of ODVEN with CO_(3)·-(1.58 × 10^(8)(mol/L)-1sec-1) was reported for the first time based on competitive kinetic method.The introduction of HA,Cl-,NO_(3)-and HCO_(3)-inhibited the ODVEN degradation to varying degrees in the both processes.According to quantum chemical calculation,radical addition at the ortho-position of the phenolic hydroxyl group was confirmed to be the main reaction pathways for the oxidation of ODVEN by·OH.In addition,the oxidation of ODVEN may involve the demethylation,H-abstraction,OH^(-)addition and C-N bond cleavage.Eventually,the UV-LED/SPC process was considered to be more cost-effective compared to the UV/SPC process,although the UV/SPC process possessed a higher removal rate of ODVEN.
文摘The performance of sodium percarbonate (SPC) activated with ferrous ion (Fe(Ⅱ) with the addition of formic acid (FA) to stimulate the degradation of carbon tetrachloride (CT) was investigated. Results showed that CT could be entirely reduced within 15 min in the system at a variety of SPC/Fe(Ⅱ)/FA/CT molar ratios in experimental level. Scavenging tests indicated that carbon dioxide radical anion (CO2-) was the dominant reactive oxygen species responsible for CT degradation. CT degradation rate, to a large extent, increased with increasing dosages of chemical agents and the optimal molar ratio of SPC/Fe(Ⅱ)/FAJCT was set as 60/60/60/1. The initial concentration of CT can hardly affect the CT removal, while CT degradation was favorable in the pH range of 3.0-9.0, but apparently inhibited at pH 12. C1- and HCO3 of high concentration showed negative impact on CT removal. Cl- released from CT was detected and the results confirmed nearly complete mineralization ofCT. CT degradation was proposed by reductive C-C1 bond splitting. This study demonstrated that SPC activated with Fe(Ⅱ) with the addition of FA may be promising technique for CT remediation in contaminated groundwater.
基金Financial support from the NSFC(Nos.21972073,22136003,21805166 and 22206188)the 111 Project of China(No.D20015)and Natural Science Foundation of Hubei Province,China(No.2022CFB275)is gratefully acknowledged。
文摘Sodium percarbonate(Na_(2)CO_(3)·1.5H_(2)O_(2),SPC)has been extensively employed as a solid substitute of H_(2)O_(2)for Fenton process in water treatment,because of its high stability during the production,transport,storage and usage.In addition,SPC can be applied in a wider range of work pH,it is also applied as a buffer in Fenton reaction for preventing a drop in pH.Herein,we have synthesized basic copper molybdate(BCM)nanoblocks with the molecular formula of Cu_(3)(MoO_(4))_(2)(OH)_(2)as an efficient and heterogeneous catalyst for antibiotics degradation via percarbonate activation.First,fully physical characterizations confirmed BCM nanocomposite exhibited a structure of nanoblocks.We also found that BCM/SPC system could work in a much wider pH range,compared with H_(2)O_(2).Then,BCM/SPC system presented a good anti-interference ability for natural organic matter in OTC degradation.EPR results and Quenching tests confirmed that the co-presence of·CO_(3)-,·O_(2)-,1O_(2)and·OH in BCM/SPC system.
基金Project supported by the National Natural Science Foundation of China (Nos. 20332030, 20572027, 20625205).
文摘A new process for the Pd/Cu co-catalyzed homocoupling reaction of terminal alkynes was developed. The reaction was carried out in aqueous media with sodium percarbonate as both a clean oxidant and a base. Meanwhile, a palladium complex immobilized on a synthetic PS-PEG400-PPh2 resin was used as the catalyst, which may be recovered by simple filtration and reused for several times with high activity.
基金supported by the Beijing Natural Science Foun-dation(No.8202029)the National Key R&D Program of China(No.2018YFD0900805)+1 种基金the National Natural Science Founda-tion of China(Nos.U19A20107 and 21307005)Beijing Ad-vanced Innovation Program for Land Surface Science.
文摘Sodium percarbonate(SPC)and peroxymonocarbonate(PMC)have been widely used in modified Fenton reactions because of their multiple superior features,such as a wide pH range and environmental friendliness.This broad review is intended to provide the fundamental information,status and progress of SPC and PMC based decontamination technologies according to the peer-reviewed papers in the last two decades.Both SPC and PMC can directly decompose various pollutants.The degradation efficiency will be enhanced and the target contaminants will be expanded after the activation of SPC and PMC.The most commonly used catalysts for SPC activation are iron compounds while cobalt composi-tions are applied to activate PMC in homogenous and heterogeneous catalytical systems.The generation and participation of hydroxyl,superoxide and/or carbonate radicals are involved in the activated SPC and PMC system.The reductive radicals,such as carbon dioxide and hydroxyethyl radicals,can be generated when formic acid or methanol is added in the Fe(II)/SPC system,which can reduce target contaminants.SPC can also be activated by energy,tetraacetylethylenediamine,ozone and buffered alkaline to generate different reactive radicals for pollutant decomposition.The SPC and activated SPC have been assessed for application in-situ chemical oxidation and sludge dewatering treatment.The challenges and prospects of SPC and PMC based decontamination technologies are also addressed in the last section.