Peroxymonosulfate(PMS)activation and photocatalysis are effective technologies to remove organic pollutants,but the adsorption effect of the catalyst is usually unheeded in degradation process.Herein,a bifunctional ca...Peroxymonosulfate(PMS)activation and photocatalysis are effective technologies to remove organic pollutants,but the adsorption effect of the catalyst is usually unheeded in degradation process.Herein,a bifunctional catalyst of amorphous MoS_(x)(a-MoS_(x))with 3D layer-by-layer superstructure was synthesized by assembling basic active units[Mo_(3)S_(13)]^(2-)of MoS_(2).The large interlayer spacing and high exposure of active sites render a-MoS_(x)to have excellent synergy of adsorption and photo-assisted PMS activation for tetracycline(TC)degradation.Experiments and DFT calculation show that TC can be efficiently enriched on a-MoS_(x)by pore filling,π-πinteraction,hydrogen bonding and high adsorption energy.Subsequently,PMS can be quickly activated through electron transfer with a-MoS_(x),resulting in high TC degradation efficiency of 96.6%within 20 min.In addition,the synergistic mechanism of adsorption and photo-assisted PMS activation was explored,and the degradation pathway of TC was expounded.This work is inspirational for constructing bifunctional catalysts with superior synergistic adsorption and catalytic capabilities to remove refractory organic pollutants in water.展开更多
Eliminating highly concentrated antibiotic wastewater by transition metal catalyst-assisted AOPs is challenging.Herein,by varying the metal precursor composition(Co/Fe ratios of 1/1,1.5/2/3),alloyed Co_(7)Fe_(3)nanocr...Eliminating highly concentrated antibiotic wastewater by transition metal catalyst-assisted AOPs is challenging.Herein,by varying the metal precursor composition(Co/Fe ratios of 1/1,1.5/2/3),alloyed Co_(7)Fe_(3)nanocrystals or spinel-like CoFe_(2)O_(4)can be switched and both confined within the porous N-doped graphitic carbon fibers by electrospinning and controlled graphitization.Impressively,iron precursors played a dual role in working as reactive centers and main activators for the creation of porous carbon networks affording improved accessibility to catalytic sites and easy tetracycline(TC)diffusion effect.The catalytic activity of the resulting materials was closely related to surface metal valence and composition.Notably,the CoFe_(2)O_(4)exhibited a significant improvement in peroxymonosulfate(PMS)adsorption and activation,explained by the present electron-deficient Co and Fe synergetic sites together with the interesting Jahn-Teller effect.Fe_(1)Co_(2)/CNF demonstrated the highest efficiency in degrading TC,achieving a reaction rate constant of 0.4647 min^(-1)with a low activation energy of 9.3 kJ·mol^(-1),nearly a 7.5-fold enhancement compared to Fe_(1)Co_(3)/CNF(0.062 min^(-1)).The reaction mechanism and the role of reactive oxidative species revealed a synergy of·SO_(4)^(-),·OH,·O_(2)^(-)and^(1)O_(2).Wherein,·O_(2)^(-)plays a more dominant role in the degradation of TC than other reactive species.Additionally,a reinforced electron-transfer pathway in the Fe_(1)Co_(2)/CNF system during PMS interaction was demonstrated.Furthermore,the degradation routes of TC were unraveled,and the toxicity of various intermediate by-products was assessed.Importantly,our continuous flow-type TC degradation process and light-driven photothermal strengthened reaction process demonstrated consistent performance,thereby offering a promising approach for tackling highly concentrated antibiotic wastewater.展开更多
The nitrogen-doped carbon derived from graphitic carbon nitride(g-C_(3)N_(4))has been widely deployed in activating peroxymonosulfate(PMS)to remove organic pollutants.However,the instability of g-C_(3)N_(4)at high tem...The nitrogen-doped carbon derived from graphitic carbon nitride(g-C_(3)N_(4))has been widely deployed in activating peroxymonosulfate(PMS)to remove organic pollutants.However,the instability of g-C_(3)N_(4)at high temperature brings challenges to the preparation of materials.The nitrogen-doped graphitic carbon nanosheets(N-GC750)were synthesized by magnesium thermal denitrification.Magnesium undergoes the displacement reaction with small molecules produced by the pyrolysis of g-C_(3)N_(4),thereby effectively fixing carbon on the in-situ template of Mg_(3)N_(2)and avoiding direct product volatilization.N-GC750 exhibited excellent performance during the PMS activation process and bisphenol A(BPA,0.2 g/L)could be thoroughly removed in 30 min.A wide range of pH(3–11),temperature(10–40℃)and common anions were employed in studying the impact on system.Additionally,N-GC750 showed satisfactory reusability in cycle tests and promising applicability in real water samples.Quenching experiments and electron paramagnetic resonance(EPR)measurements indicated that singlet oxygen was the main active species coupled with partial electron transfer in N-GC750/PMS system.Furtherly,the oxidation products were identified,and their ecotoxicity was evaluated.This work is expected to provide a reference for the feasibility of preparing g-C_(3)N_(4)derived carbon materials and meaningful for PMS activation.展开更多
The multiple metal catalyst as a promising nanomaterial has shown excellent activity in the peroxymonosulfate(PMS)activation for pollutant degradation.However,the role of special sites and in-depth understanding of th...The multiple metal catalyst as a promising nanomaterial has shown excellent activity in the peroxymonosulfate(PMS)activation for pollutant degradation.However,the role of special sites and in-depth understanding of the PMS activation mechanism are not fully studied.In this study,a Cu-doped CoFe_(2)O_(4)nanocatalyst(0.5CCF)was synthesized by a sol-gel and calcination method,and used for PMS activation to remove Rhodamine B(RhB).The results showed that the Cu doping obviously enhanced the catalytic performance of CoFe_(2)O_(4),with 99.70%of RhB removed by 0.5CCF while 74.91%in the CoFe_(2)O_(4)within 15 min.Based on the X-ray photoelectron spectroscopy and electrochemical analysis,this could be ascribed to the more low valence of Co and Fe species generated on the 0.5CCF and faster electron transfers occurred in the 0.5CCF due to the Cu doping.In addition,Cu doping could provide more reaction sites for the 0.5CCF to activate PMS for RhB removal.The metal species and the surface hydroxyl were the reaction sites of PMS activation,and the surface hydroxyl played an important role in surface-bound reactive species generation.During the PMS activation,the Cu not only activated PMS to produce reactive oxygen species(ROS),but also regenerated Co^(2+)and Fe^(2+)to accelerate the PMS activation.The non-radical of ^(1)O_(2)was the main ROS with a 99.35%of contribution rate,and the SO_(5)^(·–)self-reaction was its major source.This study provides a new insight to enhance the PMS activation performance of multiple metal catalysts by Cu doping in wastewater treatment.展开更多
Due to the shortage of rational waste management,plastic waste has become increasingly serious,posing a serious threat to the environment and humans.The catalytic oxidation of polyethylene terephthalate(PET)waste has ...Due to the shortage of rational waste management,plastic waste has become increasingly serious,posing a serious threat to the environment and humans.The catalytic oxidation of polyethylene terephthalate(PET)waste has been reported to reduce environmental stress and produce valuable products.However,obtaining valuable chemicals from waste plastics under mild conditions driven by specific reactive oxygen species is a great challenge.Herein,N,P-doped Mo_(2)C@porous carbon was designed and employed in the peroxymonosulfate-based advanced oxidation reforming of PET hydrolysate.The ethylene glycol(EG)derived from PET fiber was catalytically oxidized to formate via singlet oxygen activation during the peroxymonosulfate-based advanced oxidation process.Compared with Mo_(2)C,the N,P-doped Mo_(2)C@porous carbon catalyst with a large specific surface area provides more active sites,which has the characteristic of high catalytic activity.It presents the tetracycline degradation efficiency of~80%under a wide pH range(6.8-10.6)and,further,the formate generation rate of~56.5 mmol_(gcat)−1 in the advanced oxidation reforming process of EG in 8 h.The detection and quenching experiments on the oxygen active species comprehensively confirmed that singlet oxygen is the key reactive oxygen species during the advanced catalytic oxidation reactions.This work provided a constructive demonstration for designing advanced oxidation catalysts to catalyze the reforming of waste PET fiber plastics into valuable chemicals.展开更多
Achieving efficient photocatalytic activation of peroxymonosulfate(PMS)degradation of pollutants through the regulation strategy of surface microstructure in catalysts remains a challenge.Herein,CuBi_(2)O_(4)nanorods(...Achieving efficient photocatalytic activation of peroxymonosulfate(PMS)degradation of pollutants through the regulation strategy of surface microstructure in catalysts remains a challenge.Herein,CuBi_(2)O_(4)nanorods(CBO NRs)and CuBi_(2)O_(4) microspheres(CBO Ms)were synthesized by simply regulating the alkalinity of the reaction solvent.Under fullespectrum irradiation,CBO Ms exhibited remarkable photocatalytic performance,removing 92.48%of tetracycline(TC)within 12 min,with the reaction rate constant reaching 0.2135 min^(-1),which is approximately 2.7 times that of CBO NRs(0.0798 min^(-1)).The exposure of oxygen vacancies on the surface of CBO Ms significantly promoted the generation and migration of photogenerated carriers internally,accelerated charge accumulation at the Cu active sites on the surface,and thereby enhanced the adsorption of CBO Ms on PMS.The charge density difference results confirmed the rapid transference of surfaceeenriched electrons to the PMS,facilitating further activation of PMS.Radical quenching experiment and EPR testing verified that both radical(SO_(4^(-)),·OH)and noneradical(^(1)O_(2))pathways were involved in the reaction system.This study offers novel insights into the design of catalysts for the photocatalytic activation of PMS to efficiently degrade environmental pollutants.展开更多
Photothermal material applied in environmental governance has attracted growing attention.By combining the Stober method and dopamine-triggered coating strategy,Co-Mn precursor was in situ incorporated into the poly d...Photothermal material applied in environmental governance has attracted growing attention.By combining the Stober method and dopamine-triggered coating strategy,Co-Mn precursor was in situ incorporated into the poly dopamine(PDA)layer over the surface of silica cores.Afterwards,a unique photothermal nanosphere with SiO_(2)core and thin carbon layer and dual Co-Mn oxides shell was allowed to form by sequential heat treatment in the inert atmosphere(SiO_(2)@CoMn/C).The bimetallic fraction of Co/Mn in the carbon layer and post-treatment calcination temperature was comprehensively tuned to optimize the peroxymonosulfate(PMS)activation performance of the catalyst.The state of bimetallic species was studied including their physical distribution,chemical valence,and interplay by various characterizations.Impressively,Co oxides appear as dominant monodispersed nanoparticles(~10 nm),while Mn with cluster-like morphology is observed to uniformly distribute over thin-layer carbon and adhered to the surface of SiO_(2)nanospheres(~250 nm).The calcined temperature could tune the oxidized state of Co species,leading to the optimization of the catalytic performance of introduced dual metal species.As a result,this obtained optimal catalyst integrated the advantages of exposed bimetallic CoMn species and N-doped thin carbon to deliver excellent catalytic PMS activation performance and photothermal synergetic catalytic mineralization ability for diversiform pollutants.Further reactions condition controls and anion interference studies were conducted to identify the adaptability of the optimal catalyst.Moreover,the application of solar-driven interfacial water evaporation using optimal SiO_(2)@Co_3Mn_1/C-600 catalyst was explored,showing a high water evaporation rate of 1.48 kg·m^(-2)·h^(-1)and an efficiency of 95.2%,further revealing a comprehensive governance functionality of obtained material in the complex pollution condition.展开更多
Sulfate radical anion(SO4*)based Fenton-like reaction have recently received a large quantity of attention owing to their strong oxidative capacity and high selectivity toward organic pollutants.However,the developmen...Sulfate radical anion(SO4*)based Fenton-like reaction have recently received a large quantity of attention owing to their strong oxidative capacity and high selectivity toward organic pollutants.However,the development of a high-efficient catalyst for activation of peroxymonosulfate(PMS)with a fast separation is still challengeable.Herein,magnetic mesoporous silica composites with a yolk-shell structure(Fe@void@mSiO2)have been prepared via a successive coating strategy,followed by a hightemperature in-situ treatment and demonstrated as a high-efficient and fast magnetic separable catalyst for the activation of PMS.The resultant material possesses a well-defined yolk-shell structure with high specific surface area(~495.0 m^2/g),uniform pore size(~6.9 nm)and super large magnetic susceptibility(~105 emu/g).Owing to the unique properties,the material possesses an excellent degradation activity for tetracyclines(TC),which is much higher than the commercialized Zero Valent Iron(ZVI)nanoparticles.Additionally,the catalyst is able to work over a broad pH range and be quickly recycled by using an external magnetic field.This research provides a promising strategy for the synthesis and design of multifunctional catalyst for the Fenton-like process.展开更多
The electron transfer mechanism in the process of peroxymonosulfate(PMS)activation using heterojunction catalyst was controversial.In this work,magnetic heterojunction Cu_(2)O/CoFe_(2)O_(4)(CC)was first synthesized to...The electron transfer mechanism in the process of peroxymonosulfate(PMS)activation using heterojunction catalyst was controversial.In this work,magnetic heterojunction Cu_(2)O/CoFe_(2)O_(4)(CC)was first synthesized to activate PMS.An innovative reaction mechanism based on built-in electric field-driven electron migration from Cu2O to CoFe2O4 and effective magnetic moment of CC for enhancing PMS activation was proposed.Meanwhile,the CC/PMS system was used for efficient removal of antibiotic tetracycline(TC).Under optimal conditions,98.0%TC could be removed using CC/PMS catalytic system after only 30 min.The catalytic activity was higher than that of Cu_(2)O/PMS and CoFe_(2)O_(4)/PMS.Meanwhile,the impact of solution pH on TC removal was insignificant,suggesting the pH-insensitive PMS activation ability of CC.Besides,the coexisting inorganic ions in the environment,such as HCO_(3)-,H_(2)PO4-,NO_(3)-,Cl-and humic acid(HA)as representative of natural organic matter,did not inhibit TC removal in CC/PMS system.Furthermore,CC/PMS system exhibited excellent reusability with more than94.0%TC removal after the 5th reuse.Electron paramagnetic resonance(EPR)tests and quenching experiments showed that O_(2)·-and 1O_(2) played vital roles in TC removal.The intermediate products and corresponding toxicity assessment revealed that this catalytic system could reduce TC toxicity.This work provided new insights into the PMS activation mechanism using heterogeneous magnetic catalysts,including transition metal oxide.展开更多
Catalysts that can rapidly degrade tetracycline(TC)in water without introducing secondary ion pollution have always been challenging.Herein,a cobalt-based catalyst(CoO_(x)@P-C)is prepared so that CoOx quantum particle...Catalysts that can rapidly degrade tetracycline(TC)in water without introducing secondary ion pollution have always been challenging.Herein,a cobalt-based catalyst(CoO_(x)@P-C)is prepared so that CoOx quantum particles(5e10 nm)are uniformly distributed on a linear substrate,and the outer layer is covered with a shell(P-C).The quantum particles of CoO_(x) provide many active sites for the reaction,which ensures the efficient degradation effect of the catalyst,and 30 mg/L TC can be completely degraded in only 5 min.The shell of the quantum particles'outer layer can effectively reduce ions'extravasation.The combination of the shell-like structure and the linear substrate greatly enhances the catalysis's stability and ensures that the catalyst is prepared into a film for practical application.The high catalytic activity of CoO_(x)@P-C is mainly due to the following factors:(1)Uniformly distributed ultra-small nanoparticles can provide many active sites.(2)The microenvironment formed by the core-shell structure enhances not only catalytic stability but also provides the driving force to improve the reaction rate.(3)The composite of CoO_(x) and P-C core-shell structure can accelerate electron transfer and generate many reactive oxygen species in a short time,which makes TC degrade extremely rapidly.展开更多
Resource recovery for the preparation of high-value-added products represents a promising strategy for reducing pollution and carbon emissions.In this study,stainless steel pickling wastewater was utilized as a metal ...Resource recovery for the preparation of high-value-added products represents a promising strategy for reducing pollution and carbon emissions.In this study,stainless steel pickling wastewater was utilized as a metal source to synthesize MIL-100(Fe),which was subsequently transformed into quasi-MIL-100(Fe)(Q350-MIL-100(Fe))through controlled pyrolysis at an optimized temperature of 350°C.The as-prepared Q350-MIL-100(Fe)demonstrated exceptional performance in activating peroxymonosulfate(PMS)under ultraviolet(UV)light irradiation,enabling the efficient degradation of various organic pollutants.Compared to pristine MIL-100(Fe),Q350-MIL-100(Fe)exhibited a 41.56-fold increase in the degradation rate constant for atrazine(ATZ),attributed to its narrower bandgap,abundant exposed active sites,and hierarchical porous structure.Furthermore,a self-constructed reactor employing Q350-MIL-100(Fe)/graphite felt(GF)as an immobilized catalyst achieved continuous and complete(100.0%)ATZ degradation for up to 96.0 hours.This work provides valuable insights into the sustainable utilization of industrial wastewater to produce high-value-added functional materials for environmental remediation,aligning with the dual goals of pollution control and resource recovery.展开更多
基金supported by the National Natural Science Foundation of China(Nos.52370073,12274115)Program for Science and Technology Innovation Team in Universities of Henan Province(No.24IRTSTHN017)+3 种基金Natural Science Foundation of Henan Province(No.212300410336)Program for Science and Technology Innovation Talent in Universities of Henan Province(No.23HASTIT027)Key Scientific and Technological Project of Henan Province(No.222102320188)Key Project of Science and Technology Research of Henan Provincial Department of Education(No.21A430008)。
文摘Peroxymonosulfate(PMS)activation and photocatalysis are effective technologies to remove organic pollutants,but the adsorption effect of the catalyst is usually unheeded in degradation process.Herein,a bifunctional catalyst of amorphous MoS_(x)(a-MoS_(x))with 3D layer-by-layer superstructure was synthesized by assembling basic active units[Mo_(3)S_(13)]^(2-)of MoS_(2).The large interlayer spacing and high exposure of active sites render a-MoS_(x)to have excellent synergy of adsorption and photo-assisted PMS activation for tetracycline(TC)degradation.Experiments and DFT calculation show that TC can be efficiently enriched on a-MoS_(x)by pore filling,π-πinteraction,hydrogen bonding and high adsorption energy.Subsequently,PMS can be quickly activated through electron transfer with a-MoS_(x),resulting in high TC degradation efficiency of 96.6%within 20 min.In addition,the synergistic mechanism of adsorption and photo-assisted PMS activation was explored,and the degradation pathway of TC was expounded.This work is inspirational for constructing bifunctional catalysts with superior synergistic adsorption and catalytic capabilities to remove refractory organic pollutants in water.
基金supported by the National Natural Science Foundation of China(No.21908085).
文摘Eliminating highly concentrated antibiotic wastewater by transition metal catalyst-assisted AOPs is challenging.Herein,by varying the metal precursor composition(Co/Fe ratios of 1/1,1.5/2/3),alloyed Co_(7)Fe_(3)nanocrystals or spinel-like CoFe_(2)O_(4)can be switched and both confined within the porous N-doped graphitic carbon fibers by electrospinning and controlled graphitization.Impressively,iron precursors played a dual role in working as reactive centers and main activators for the creation of porous carbon networks affording improved accessibility to catalytic sites and easy tetracycline(TC)diffusion effect.The catalytic activity of the resulting materials was closely related to surface metal valence and composition.Notably,the CoFe_(2)O_(4)exhibited a significant improvement in peroxymonosulfate(PMS)adsorption and activation,explained by the present electron-deficient Co and Fe synergetic sites together with the interesting Jahn-Teller effect.Fe_(1)Co_(2)/CNF demonstrated the highest efficiency in degrading TC,achieving a reaction rate constant of 0.4647 min^(-1)with a low activation energy of 9.3 kJ·mol^(-1),nearly a 7.5-fold enhancement compared to Fe_(1)Co_(3)/CNF(0.062 min^(-1)).The reaction mechanism and the role of reactive oxidative species revealed a synergy of·SO_(4)^(-),·OH,·O_(2)^(-)and^(1)O_(2).Wherein,·O_(2)^(-)plays a more dominant role in the degradation of TC than other reactive species.Additionally,a reinforced electron-transfer pathway in the Fe_(1)Co_(2)/CNF system during PMS interaction was demonstrated.Furthermore,the degradation routes of TC were unraveled,and the toxicity of various intermediate by-products was assessed.Importantly,our continuous flow-type TC degradation process and light-driven photothermal strengthened reaction process demonstrated consistent performance,thereby offering a promising approach for tackling highly concentrated antibiotic wastewater.
基金the Science and Technology Commission of Shanghai Municipality(Nos.21ZR1425200,18020500800,18JC1412900 and 19DZ2271100)。
文摘The nitrogen-doped carbon derived from graphitic carbon nitride(g-C_(3)N_(4))has been widely deployed in activating peroxymonosulfate(PMS)to remove organic pollutants.However,the instability of g-C_(3)N_(4)at high temperature brings challenges to the preparation of materials.The nitrogen-doped graphitic carbon nanosheets(N-GC750)were synthesized by magnesium thermal denitrification.Magnesium undergoes the displacement reaction with small molecules produced by the pyrolysis of g-C_(3)N_(4),thereby effectively fixing carbon on the in-situ template of Mg_(3)N_(2)and avoiding direct product volatilization.N-GC750 exhibited excellent performance during the PMS activation process and bisphenol A(BPA,0.2 g/L)could be thoroughly removed in 30 min.A wide range of pH(3–11),temperature(10–40℃)and common anions were employed in studying the impact on system.Additionally,N-GC750 showed satisfactory reusability in cycle tests and promising applicability in real water samples.Quenching experiments and electron paramagnetic resonance(EPR)measurements indicated that singlet oxygen was the main active species coupled with partial electron transfer in N-GC750/PMS system.Furtherly,the oxidation products were identified,and their ecotoxicity was evaluated.This work is expected to provide a reference for the feasibility of preparing g-C_(3)N_(4)derived carbon materials and meaningful for PMS activation.
基金supported by the National key research and development program of China (No.2016YFC04007022)the National Natural Science Foundation of China (No.21377041)the Guangdong Science and Technology Program (No.2020B121201003)。
文摘The multiple metal catalyst as a promising nanomaterial has shown excellent activity in the peroxymonosulfate(PMS)activation for pollutant degradation.However,the role of special sites and in-depth understanding of the PMS activation mechanism are not fully studied.In this study,a Cu-doped CoFe_(2)O_(4)nanocatalyst(0.5CCF)was synthesized by a sol-gel and calcination method,and used for PMS activation to remove Rhodamine B(RhB).The results showed that the Cu doping obviously enhanced the catalytic performance of CoFe_(2)O_(4),with 99.70%of RhB removed by 0.5CCF while 74.91%in the CoFe_(2)O_(4)within 15 min.Based on the X-ray photoelectron spectroscopy and electrochemical analysis,this could be ascribed to the more low valence of Co and Fe species generated on the 0.5CCF and faster electron transfers occurred in the 0.5CCF due to the Cu doping.In addition,Cu doping could provide more reaction sites for the 0.5CCF to activate PMS for RhB removal.The metal species and the surface hydroxyl were the reaction sites of PMS activation,and the surface hydroxyl played an important role in surface-bound reactive species generation.During the PMS activation,the Cu not only activated PMS to produce reactive oxygen species(ROS),but also regenerated Co^(2+)and Fe^(2+)to accelerate the PMS activation.The non-radical of ^(1)O_(2)was the main ROS with a 99.35%of contribution rate,and the SO_(5)^(·–)self-reaction was its major source.This study provides a new insight to enhance the PMS activation performance of multiple metal catalysts by Cu doping in wastewater treatment.
基金financially assisted by the Shanghai Committee of Science and Technology,China(No.21ZR1480000)the National Natural Science Foundation of China(No.52122312)the State Key Laboratory of Advanced Fiber Materials,Donghua University(No.KF2508).
文摘Due to the shortage of rational waste management,plastic waste has become increasingly serious,posing a serious threat to the environment and humans.The catalytic oxidation of polyethylene terephthalate(PET)waste has been reported to reduce environmental stress and produce valuable products.However,obtaining valuable chemicals from waste plastics under mild conditions driven by specific reactive oxygen species is a great challenge.Herein,N,P-doped Mo_(2)C@porous carbon was designed and employed in the peroxymonosulfate-based advanced oxidation reforming of PET hydrolysate.The ethylene glycol(EG)derived from PET fiber was catalytically oxidized to formate via singlet oxygen activation during the peroxymonosulfate-based advanced oxidation process.Compared with Mo_(2)C,the N,P-doped Mo_(2)C@porous carbon catalyst with a large specific surface area provides more active sites,which has the characteristic of high catalytic activity.It presents the tetracycline degradation efficiency of~80%under a wide pH range(6.8-10.6)and,further,the formate generation rate of~56.5 mmol_(gcat)−1 in the advanced oxidation reforming process of EG in 8 h.The detection and quenching experiments on the oxygen active species comprehensively confirmed that singlet oxygen is the key reactive oxygen species during the advanced catalytic oxidation reactions.This work provided a constructive demonstration for designing advanced oxidation catalysts to catalyze the reforming of waste PET fiber plastics into valuable chemicals.
基金the National Natural Science Foundation of China(NSFC No.22176151).
文摘Achieving efficient photocatalytic activation of peroxymonosulfate(PMS)degradation of pollutants through the regulation strategy of surface microstructure in catalysts remains a challenge.Herein,CuBi_(2)O_(4)nanorods(CBO NRs)and CuBi_(2)O_(4) microspheres(CBO Ms)were synthesized by simply regulating the alkalinity of the reaction solvent.Under fullespectrum irradiation,CBO Ms exhibited remarkable photocatalytic performance,removing 92.48%of tetracycline(TC)within 12 min,with the reaction rate constant reaching 0.2135 min^(-1),which is approximately 2.7 times that of CBO NRs(0.0798 min^(-1)).The exposure of oxygen vacancies on the surface of CBO Ms significantly promoted the generation and migration of photogenerated carriers internally,accelerated charge accumulation at the Cu active sites on the surface,and thereby enhanced the adsorption of CBO Ms on PMS.The charge density difference results confirmed the rapid transference of surfaceeenriched electrons to the PMS,facilitating further activation of PMS.Radical quenching experiment and EPR testing verified that both radical(SO_(4^(-)),·OH)and noneradical(^(1)O_(2))pathways were involved in the reaction system.This study offers novel insights into the design of catalysts for the photocatalytic activation of PMS to efficiently degrade environmental pollutants.
基金financially supported by the China National Natural Science Foundation(No.21908085)China Postdoctoral Science Foundation(No.2022M711686)Jiangsu Provincial Founds for the Young Scholars(No.BK20190961)。
文摘Photothermal material applied in environmental governance has attracted growing attention.By combining the Stober method and dopamine-triggered coating strategy,Co-Mn precursor was in situ incorporated into the poly dopamine(PDA)layer over the surface of silica cores.Afterwards,a unique photothermal nanosphere with SiO_(2)core and thin carbon layer and dual Co-Mn oxides shell was allowed to form by sequential heat treatment in the inert atmosphere(SiO_(2)@CoMn/C).The bimetallic fraction of Co/Mn in the carbon layer and post-treatment calcination temperature was comprehensively tuned to optimize the peroxymonosulfate(PMS)activation performance of the catalyst.The state of bimetallic species was studied including their physical distribution,chemical valence,and interplay by various characterizations.Impressively,Co oxides appear as dominant monodispersed nanoparticles(~10 nm),while Mn with cluster-like morphology is observed to uniformly distribute over thin-layer carbon and adhered to the surface of SiO_(2)nanospheres(~250 nm).The calcined temperature could tune the oxidized state of Co species,leading to the optimization of the catalytic performance of introduced dual metal species.As a result,this obtained optimal catalyst integrated the advantages of exposed bimetallic CoMn species and N-doped thin carbon to deliver excellent catalytic PMS activation performance and photothermal synergetic catalytic mineralization ability for diversiform pollutants.Further reactions condition controls and anion interference studies were conducted to identify the adaptability of the optimal catalyst.Moreover,the application of solar-driven interfacial water evaporation using optimal SiO_(2)@Co_3Mn_1/C-600 catalyst was explored,showing a high water evaporation rate of 1.48 kg·m^(-2)·h^(-1)and an efficiency of 95.2%,further revealing a comprehensive governance functionality of obtained material in the complex pollution condition.
基金the NSF of China(Nos.51822202 and 51772050)Shanghai Rising-Star Program(No.18QA1400100)+4 种基金Youth Top-notch Talent Support Program of ShanghaiScience and Technology Commission of Shanghai Municipality(No.19520713200)Shanghai Scientific and Technological Innovation Project(No.19JC1410400)DHU Distinguished Young Professor ProgramFundamental Research Funds for the Central Universities。
文摘Sulfate radical anion(SO4*)based Fenton-like reaction have recently received a large quantity of attention owing to their strong oxidative capacity and high selectivity toward organic pollutants.However,the development of a high-efficient catalyst for activation of peroxymonosulfate(PMS)with a fast separation is still challengeable.Herein,magnetic mesoporous silica composites with a yolk-shell structure(Fe@void@mSiO2)have been prepared via a successive coating strategy,followed by a hightemperature in-situ treatment and demonstrated as a high-efficient and fast magnetic separable catalyst for the activation of PMS.The resultant material possesses a well-defined yolk-shell structure with high specific surface area(~495.0 m^2/g),uniform pore size(~6.9 nm)and super large magnetic susceptibility(~105 emu/g).Owing to the unique properties,the material possesses an excellent degradation activity for tetracyclines(TC),which is much higher than the commercialized Zero Valent Iron(ZVI)nanoparticles.Additionally,the catalyst is able to work over a broad pH range and be quickly recycled by using an external magnetic field.This research provides a promising strategy for the synthesis and design of multifunctional catalyst for the Fenton-like process.
基金financially supported by the Science and Technology Research Program of Chongqing Municipal Education Commission(Nos.KJQN202204508 and KJQN201901401)Guizhou Province First-class Discipline(Group)Construction-Mining Engineering(No.XKTJ[2020]23)+5 种基金the National Natural Science Foundation of China(No.21906008)Science and Technology Fund Project of Guizhou Province(No.[2018]1415)Key Laboratory of Gas Prevention and Control in Coal Mines of Guizhou Province(No.KY[2019]054)Key Laboratory of Coalbed Methane Development and Utilization(No.52020-2018-03-06)Science and Technology Fund Project of Guizhou Province(No.[2018]1142)the Natural Science Foundation of Yongchuan District(No.2021yc-jckx20021)。
文摘The electron transfer mechanism in the process of peroxymonosulfate(PMS)activation using heterojunction catalyst was controversial.In this work,magnetic heterojunction Cu_(2)O/CoFe_(2)O_(4)(CC)was first synthesized to activate PMS.An innovative reaction mechanism based on built-in electric field-driven electron migration from Cu2O to CoFe2O4 and effective magnetic moment of CC for enhancing PMS activation was proposed.Meanwhile,the CC/PMS system was used for efficient removal of antibiotic tetracycline(TC).Under optimal conditions,98.0%TC could be removed using CC/PMS catalytic system after only 30 min.The catalytic activity was higher than that of Cu_(2)O/PMS and CoFe_(2)O_(4)/PMS.Meanwhile,the impact of solution pH on TC removal was insignificant,suggesting the pH-insensitive PMS activation ability of CC.Besides,the coexisting inorganic ions in the environment,such as HCO_(3)-,H_(2)PO4-,NO_(3)-,Cl-and humic acid(HA)as representative of natural organic matter,did not inhibit TC removal in CC/PMS system.Furthermore,CC/PMS system exhibited excellent reusability with more than94.0%TC removal after the 5th reuse.Electron paramagnetic resonance(EPR)tests and quenching experiments showed that O_(2)·-and 1O_(2) played vital roles in TC removal.The intermediate products and corresponding toxicity assessment revealed that this catalytic system could reduce TC toxicity.This work provided new insights into the PMS activation mechanism using heterogeneous magnetic catalysts,including transition metal oxide.
基金supported by the Joint Funds of the National Natural Science Foundation of China(U22A20140),the Independent Cultivation Program of Innovation Team of Ji'nan City(No.2019GXRC011),the Natural Science Foundation of Shandong Province(Grant No.ZR2021ME143,ZR2021MA073)and National Natural Science Foundation of China(Grant No.51908242)and.All the authors discussed the results and commented on the manuscript.
文摘Catalysts that can rapidly degrade tetracycline(TC)in water without introducing secondary ion pollution have always been challenging.Herein,a cobalt-based catalyst(CoO_(x)@P-C)is prepared so that CoOx quantum particles(5e10 nm)are uniformly distributed on a linear substrate,and the outer layer is covered with a shell(P-C).The quantum particles of CoO_(x) provide many active sites for the reaction,which ensures the efficient degradation effect of the catalyst,and 30 mg/L TC can be completely degraded in only 5 min.The shell of the quantum particles'outer layer can effectively reduce ions'extravasation.The combination of the shell-like structure and the linear substrate greatly enhances the catalysis's stability and ensures that the catalyst is prepared into a film for practical application.The high catalytic activity of CoO_(x)@P-C is mainly due to the following factors:(1)Uniformly distributed ultra-small nanoparticles can provide many active sites.(2)The microenvironment formed by the core-shell structure enhances not only catalytic stability but also provides the driving force to improve the reaction rate.(3)The composite of CoO_(x) and P-C core-shell structure can accelerate electron transfer and generate many reactive oxygen species in a short time,which makes TC degrade extremely rapidly.
基金supported by the National Natural Science Foundation of China(Nos.52370025 and 22176012)BUCEA Post Graduate Innovation Project(No.PG2024086).
文摘Resource recovery for the preparation of high-value-added products represents a promising strategy for reducing pollution and carbon emissions.In this study,stainless steel pickling wastewater was utilized as a metal source to synthesize MIL-100(Fe),which was subsequently transformed into quasi-MIL-100(Fe)(Q350-MIL-100(Fe))through controlled pyrolysis at an optimized temperature of 350°C.The as-prepared Q350-MIL-100(Fe)demonstrated exceptional performance in activating peroxymonosulfate(PMS)under ultraviolet(UV)light irradiation,enabling the efficient degradation of various organic pollutants.Compared to pristine MIL-100(Fe),Q350-MIL-100(Fe)exhibited a 41.56-fold increase in the degradation rate constant for atrazine(ATZ),attributed to its narrower bandgap,abundant exposed active sites,and hierarchical porous structure.Furthermore,a self-constructed reactor employing Q350-MIL-100(Fe)/graphite felt(GF)as an immobilized catalyst achieved continuous and complete(100.0%)ATZ degradation for up to 96.0 hours.This work provides valuable insights into the sustainable utilization of industrial wastewater to produce high-value-added functional materials for environmental remediation,aligning with the dual goals of pollution control and resource recovery.
