Peroxymonosulfate(PMS)-assisted visible-light photocatalytic degradation of organic pollutants using graphitic carbon nitride(g-C3N4)presents a promising and environmentally friendly approach.However,pristine g-...Peroxymonosulfate(PMS)-assisted visible-light photocatalytic degradation of organic pollutants using graphitic carbon nitride(g-C3N4)presents a promising and environmentally friendly approach.However,pristine g-C3N4 suffers from limited visible-light absorption and low charge-carrier mobility.In this study,a phosphorus-doped tubular carbon nitride(5P-TCN)was synthesized via a precursor self-assembly method using phosphoric acid and melamine as raw materials,eliminating the need for organic solvents or templates.The 5P-TCN catalyst demonstrated enhanced visible-light absorption,improved charge transfer capability,and a 5.25-fold increase in specific surface area(31.092 m2/g),which provided abundant active sites to efficiently drive the PMS-assisted photocatalytic reaction.The 5P-TCN/vis/PMS system exhibited exceptional degradation performance for organic pollutants across a broad pH range(3–9),achieving over 92%degradation of Rhodamine B(RhB)within 15 min.Notably,the system retained>98%RhB degradation efficiency after three consecutive operational cycles,demonstrating robust operational stability and reusability.Moreover,key parameters influencing,active radi-cals,degradation pathways,and potential mechanisms for RhB degradation were systematically investigated.This work proposes a green and cost-effective strategy for developing high-efficiency photocatalysts,while demon-strating the exceptional capability of a PMS-assisted photocatalytic system for rapid degradation of RhB.展开更多
Groundwater is a key part of the terrestrial ecosystem,but it is vulnerable to pollution in the context of chemical industry development.Treating contaminated groundwater is challenging due to its stable water quality...Groundwater is a key part of the terrestrial ecosystem,but it is vulnerable to pollution in the context of chemical industry development.Treating contaminated groundwater is challenging due to its stable water quality,hidden contamination,and complex treatment requirements.Current research focuses on advanced treatment technologies,among which the advanced oxidation process(AOPs) of peroxomonosulfate(PMS) has great potential.Although there are many reviews of PMS-based AOP,most of them focus on surface water.This review aims to explore the activation reaction of PMS to groundwater by in-situ chemical oxidation(ISCO) technology,further study the reaction mechanism,compare the treatment effect of characteristic pollutants in the groundwater of the chemical industry park,propose new activation methods and catalyst selection,and provide guidance for future groundwater treatment research.展开更多
Fenton-like technology based on peroxymonosulfate activation has shown great potential in refractory organics degradation.In this work,single Fe atom catalysts were synthesized through facile ball milling and exhibite...Fenton-like technology based on peroxymonosulfate activation has shown great potential in refractory organics degradation.In this work,single Fe atom catalysts were synthesized through facile ball milling and exhibited very high performance in peroxymonosulfate activation.The Fe single-atom filled an N vacancy on the triazine ring edge of C3N4,as confirmed through X-ray absorption fine structure,density functional calculation and elec-tron paramagnetic resonance.The SAFe0.4–C3N4/PMS system could completely remove phenol(20 mg/L)within 10 min and its first-order kinetic constant was 12.3 times that of the Fe3O4/PMS system.Under different ini-tial pH levels and in various anionic environments,SAFe0.4–C3N4 still demonstrated excellent catalytic activity,achieving a removal rate of over 90%for phenol within 12 min.In addition,SAFe0.4–C3N4 exhibited outstanding selectivity in reaction systems with different pollutants,showing excellent degradation effects on electron-rich pollutants only.Hydroxyl radicals(•OH),singlet oxygen(1O2)and high-valent iron oxide(Fe(Ⅳ)=O)were de-tected in the SAFe0.4–C3N4/PMS system through free radical capture experiments.Further experiments on the quenching of active species and a methyl phenyl sulfoxide probe confirmed that 1O2 and Fe(Ⅳ)=O played dom-inant roles.Additionally,the change in the current response after adding PMS and phenol in succession proved that a direct electron transfer path between organic matter and the catalyst surface was unlikely to exist in the SAFe0.4–C3N4/PMS/Phenol degradation system.This study provides a new demonstration of the catalytic mech-anism of single-atom catalysts.展开更多
The adsorption of PMS and the associated transfer of photogenerated carriers are prerequisites for photo-Fenton activation.In this work,we constructed an S-scheme Vo-ZF@TCN heterojunction with the characteristics of i...The adsorption of PMS and the associated transfer of photogenerated carriers are prerequisites for photo-Fenton activation.In this work,we constructed an S-scheme Vo-ZF@TCN heterojunction with the characteristics of interlayer and in-plane multi-level built-in electric fields(BIEF).It was found that the BIEF amplitude of the in-plane heterojunction was~2.7 times that of a traditional heterojunction.The strong BIEF promotes the directional,rapid,and efficient transfer of photogenerated charge carriers,enabling the photostimulated synergistic activation of PMS for the degradation of organic pollutants.The rational design of redox ends promotes the formation of electron-deficient Vo-Fe,which creates Lewis acid adsorption sites.This design constructs a composite site for PMS adsorption and carrier transfer.We elucidated that the directional migration of electrons and holes causes the spatial separation of PMS radical and non-radical activation sites,regulating the activation pathways by altering the migration direction of PMS through adsorption.This study provides new insights into the regulation of PMS activation pathways and enriches the design strategies for efficient photogenerated carrier transport and transfer.展开更多
摘要Peroxymonosulfate(PMS)-assisted visible-light photocatalytic degradation of organic pollutants using graphitic carbon nitride(g-C3N4)presents a promising and environmentally friendly approach.However,pristine g-C3N4 suffers from limited visible-light absorption and low charge-carrier mobility.In this study,a phosphorus-doped tubular carbon nitride(5P-TCN)was synthesized via a precursor self-assembly method using phosphoric acid and melamine as raw materials,eliminating the need for organic solvents or templates.The 5P-TCN catalyst demonstrated enhanced visible-light absorption,improved charge transfer capability,and a 5.25-fold increase in specific surface area(31.092 m2/g),which provided abundant active sites to efficiently drive the PMS-assisted photocatalytic reaction.The 5P-TCN/vis/PMS system exhibited exceptional degradation performance for organic pollutants across a broad pH range(3–9),achieving over 92%degradation of Rhodamine B(RhB)within 15 min.Notably,the system retained>98%RhB degradation efficiency after three consecutive operational cycles,demonstrating robust operational stability and reusability.Moreover,key parameters influencing,active radi-cals,degradation pathways,and potential mechanisms for RhB degradation were systematically investigated.This work proposes a green and cost-effective strategy for developing high-efficiency photocatalysts,while demon-strating the exceptional capability of a PMS-assisted photocatalytic system for rapid degradation of RhB.
基金supported by the National Key Research and Development Program of China (No.2023YFC3708005)the National Natural Science Foundation of China (Nos.21872102,22172080)the Fundamental Research Funds for the Central Universities (Nankai University,No.63241208)。
摘要Groundwater is a key part of the terrestrial ecosystem,but it is vulnerable to pollution in the context of chemical industry development.Treating contaminated groundwater is challenging due to its stable water quality,hidden contamination,and complex treatment requirements.Current research focuses on advanced treatment technologies,among which the advanced oxidation process(AOPs) of peroxomonosulfate(PMS) has great potential.Although there are many reviews of PMS-based AOP,most of them focus on surface water.This review aims to explore the activation reaction of PMS to groundwater by in-situ chemical oxidation(ISCO) technology,further study the reaction mechanism,compare the treatment effect of characteristic pollutants in the groundwater of the chemical industry park,propose new activation methods and catalyst selection,and provide guidance for future groundwater treatment research.
基金supported by the National Natural Science Foundation of China(Nos.22406081,22276086,22306086)the Natural Science Foundation of Jiangxi Province(No.20232BAB213029),all of which are greatly acknowledged by the authors.
摘要Fenton-like technology based on peroxymonosulfate activation has shown great potential in refractory organics degradation.In this work,single Fe atom catalysts were synthesized through facile ball milling and exhibited very high performance in peroxymonosulfate activation.The Fe single-atom filled an N vacancy on the triazine ring edge of C3N4,as confirmed through X-ray absorption fine structure,density functional calculation and elec-tron paramagnetic resonance.The SAFe0.4–C3N4/PMS system could completely remove phenol(20 mg/L)within 10 min and its first-order kinetic constant was 12.3 times that of the Fe3O4/PMS system.Under different ini-tial pH levels and in various anionic environments,SAFe0.4–C3N4 still demonstrated excellent catalytic activity,achieving a removal rate of over 90%for phenol within 12 min.In addition,SAFe0.4–C3N4 exhibited outstanding selectivity in reaction systems with different pollutants,showing excellent degradation effects on electron-rich pollutants only.Hydroxyl radicals(•OH),singlet oxygen(1O2)and high-valent iron oxide(Fe(Ⅳ)=O)were de-tected in the SAFe0.4–C3N4/PMS system through free radical capture experiments.Further experiments on the quenching of active species and a methyl phenyl sulfoxide probe confirmed that 1O2 and Fe(Ⅳ)=O played dom-inant roles.Additionally,the change in the current response after adding PMS and phenol in succession proved that a direct electron transfer path between organic matter and the catalyst surface was unlikely to exist in the SAFe0.4–C3N4/PMS/Phenol degradation system.This study provides a new demonstration of the catalytic mech-anism of single-atom catalysts.
基金supported by the National Natural Science Foundation of China(Grant No.22076068,22106053)the Senior Talent Fund of Jiangsu University(23JDG012).
摘要The adsorption of PMS and the associated transfer of photogenerated carriers are prerequisites for photo-Fenton activation.In this work,we constructed an S-scheme Vo-ZF@TCN heterojunction with the characteristics of interlayer and in-plane multi-level built-in electric fields(BIEF).It was found that the BIEF amplitude of the in-plane heterojunction was~2.7 times that of a traditional heterojunction.The strong BIEF promotes the directional,rapid,and efficient transfer of photogenerated charge carriers,enabling the photostimulated synergistic activation of PMS for the degradation of organic pollutants.The rational design of redox ends promotes the formation of electron-deficient Vo-Fe,which creates Lewis acid adsorption sites.This design constructs a composite site for PMS adsorption and carrier transfer.We elucidated that the directional migration of electrons and holes causes the spatial separation of PMS radical and non-radical activation sites,regulating the activation pathways by altering the migration direction of PMS through adsorption.This study provides new insights into the regulation of PMS activation pathways and enriches the design strategies for efficient photogenerated carrier transport and transfer.