Enhancing the corrosion resistance of carriers within Fenton-like systems and inhibiting the migration and aggregation of single atoms in reaction environments are essential for maintaining both high activity and stab...Enhancing the corrosion resistance of carriers within Fenton-like systems and inhibiting the migration and aggregation of single atoms in reaction environments are essential for maintaining both high activity and stability at catalytic sites,thus meeting fundamental requirements for practical application.The Fenton-like process of activating various strong oxidants by silicon-based single atom catalysts(SACs)prepared based on silicon-based materials(mesoporous silica,silicon-based minerals,and organosilicon materials)has unique advantages such as structural stability(especially important under strong oxidation conditions)and environmental protection.In this paper,the preparation strategies for the silicon-based SACs were assessed first,and the structural characteristics of various silicon-based SACs are systematically discussed,their application process and mechanism in Fenton-like process to achieve water purification are investigated,and the progress of Fenton-like process in density functional theory(DFT)of siliconbased derived single atom catalysts is summarized.In this paper,the preparation strategies and applications of silicon-based derived SACs are analyzed in depth,and their oxidation activities and pathways to different pollutants in water are reviewed.In addition,this paper also summarizes the device design and application of silicon-based derived SACs,and prospects the future development of silicon-based SACs in Fenton-like applications.展开更多
Refractory organic pollutants in water threaten human health and environmental safety,and advanced oxidation processes (AOPs) are effective for the degradation of these pollutants.Catalysts play vital role in AOPs,and...Refractory organic pollutants in water threaten human health and environmental safety,and advanced oxidation processes (AOPs) are effective for the degradation of these pollutants.Catalysts play vital role in AOPs,and Ce-based catalysts have exhibited excellent performance.Recently,the development and application of Ce-based catalysts in various AOPs have been reported.Our study conducts the first review in this rapid growing field.This paper clarifies the variety and properties of Ce-based catalysts.Their applications in different AOP systems (catalytic ozonation,photodegradation,Fenton-like reactions,sulfate radicalbased AOPs,and catalytic sonochemistry) are discussed.Different Ce-based catalysts suit different reaction systems and produce different active radicals.Finally,future research directions of Ce-based catalysts in AOP systems are suggested.展开更多
The degradation of the anti-inflammatory ibuprofen(IBP)was evaluated by several advanced oxidation processes.IBP was treated by single ozonation and oxidation with hydrogen peroxide(H_(2)O_(2)),as well as a combinatio...The degradation of the anti-inflammatory ibuprofen(IBP)was evaluated by several advanced oxidation processes.IBP was treated by single ozonation and oxidation with hydrogen peroxide(H_(2)O_(2)),as well as a combination of these treatments.In order to improve the efficiency,the presence of catalysts such as original carbon nanotubes,labelled as CNT,and iron oxide supported on carbon nanotubes,named as Fe/CNT sample,was considered.The evolution of IBP degradation,mineralization and toxicity of the solutions was assessed.The formation of intermediates was also monitored.In the non-catalytic processes,IBP was faster removed by single ozonation,whereas no significant total organic carbon(TOC)removal was achieved.Oxidation with H_(2)O_(2) did not present satisfactory results.When ozone and H_(2)O_(2) were combined,a higher mineralization was attained(70%after 180 min of reaction).On the other hand,in the catalytic processes,this combined process allowed the fastest IBP degradation.In terms of mineralization degree,the presence of Fe/CNT increases the removal rate in the first hour of reaction,achieving a TOC removal of 85%.Four compounds were detected as by-products.All treated solutions presented lower toxicity than the initial solution,suggesting that the released intermediates during applied processes are less toxic.展开更多
S and Co co-doped carbon catalysts were prepared via pyrolysis of MOF-71 and thiourea mixtures at 800℃at a mass ratio of MOF-71 to thiourea of 1:0.1 to effectively activate peroxymonosulfate(PMS)for methylene blue(MB...S and Co co-doped carbon catalysts were prepared via pyrolysis of MOF-71 and thiourea mixtures at 800℃at a mass ratio of MOF-71 to thiourea of 1:0.1 to effectively activate peroxymonosulfate(PMS)for methylene blue(MB)degradation.The effects of two different mixing routes were identified on the MB degradation performance.Particularly,the catalyst obtained by the alcohol solvent evaporation(MOF-AEP)mixing route could degrade 95.60%MB(50 mg/L)within 4 min(degradation rate:K=0.78 min^(-1)),which was faster than that derived from the direct grinding method(MOF-DGP,80.97%,K=0.39 min^(-1)).X-ray photoelectron spectroscopy revealed that the Co-S content of MOF-AEP(43.39at%)was less than that of MOF-DGP(54.73at%),and the proportion of C-S-C in MOF-AEP(13.56at%)was higher than that of MOF-DGP(10.67at%).Density functional theory calculations revealed that the adsorption energy of Co for PMS was -2.94 eV when sulfur was doped as C-S-C on the carbon skeleton,which was higher than that when sulfur was doped next to cobalt in the form of Co-S bond(-2.86 eV).Thus,the C-S-C sites might provide more contributions to activate PMS compared with Co-S.Furthermore,the degradation parameters,including pH and MOF-AEP dosage,were investigated.Finally,radical quenching experiments and electron paramagnetic resonance(EPR)measurements revealed that ^(1)O_(2)might be the primary catalytic species,whereas·O~(2-)might be the secondary one in degrading MB.展开更多
Owing to outstanding hydrophilicity and ionic interaction,layered double hydroxides(LDHs)have emerged as a promising carrier for high performance catalysts.However,the synthesis of new specialized catalytic LDHs for d...Owing to outstanding hydrophilicity and ionic interaction,layered double hydroxides(LDHs)have emerged as a promising carrier for high performance catalysts.However,the synthesis of new specialized catalytic LDHs for degradation of antibiotics still faces some challenges.In this study,a CoFe_(2)O_(4)/MgAl-LDH composite catalyst was synthesized using a hydrothermal coprecipitation method.Comprehensive characterization reveals that the surface of MgAl-LDH is covered with nanometer CoFe_(2)O_(4) particles.The specific surface area of CoFe_(2)O_(4)/MgAl-LDH is 82.84 m^(2)·g^(-)1,which is 2.34 times that of CoFe_(2)O_(4).CoFe_(2)O_(4)/MgAl-LDH has a saturation magnetic strength of 22.24 A·m^(2)·kg^(-1) facilitating efficient solid-liquid separation.The composite catalyst was employed to activate peroxymonosulfate(PMS)for the efficient degradation of tetracycline hydrochloride(TCH).It is found that the catalytic performance of CoFe_(2)O_(4)/MgAl-LDH significantly exceeds that of CoFe_(2)O_(4).The maximum TCH removal reaches 98.2%under the optimal conditions([TCH]=25 mg/L,[PMS]=1.5 mmol/L,CoFe_(2)O_(4)/MgAl-LDH=0.20 g/L,pH 7,and T=25℃).Coexisting ions in the solution,such as SO_(4)^(2-),Cl-,H_(2)PO_(4)^(-),and CO_(3)^(2-),have a negligible effect on catalytic performance.Cyclic tests demonstrate that the catalytic performance of CoFe_(2)O_(4)/MgAl-LDH remains 67.2%after five cycles.Mechanism investigations suggest that O_(2)^(•-)and ^(1)O_(2) produced by CoFe_(2)O_(4)/MgAl-LDH play a critical role in the catalytic degradation.展开更多
This study focuses on the synthesis of metal-based biochar catalysts and their catalytic activation of peroxymonosulfate(PMS,HSO5−)for the degradation of three different wastewater model pollutants employing advanced ...This study focuses on the synthesis of metal-based biochar catalysts and their catalytic activation of peroxymonosulfate(PMS,HSO5−)for the degradation of three different wastewater model pollutants employing advanced oxidation processes(AOP).Iron,copper,and two different cobalt-based catalysts were prepared and evaluated.The catalysts were supported on a biochar obtained from the pyrolysis of woody pruning wastes.They were characterized by C,H,and N elemental analysis,X-Ray diffraction(XRD),Fourier-transform infrared spectroscopy(FTIR),and scanning electron microscope(SEM).The metal content in each catalyst was determined by means of atomic absorption spectroscopy(AAS).The degradation reac-tions of benzoic acid(BA),catechol(C),and cinnamic acid(CA)were carried out in a lab scale batch glass reactor and were followed by UV-Visible spectroscopy(UV-Vis).A colorimetric technique was employed to verify the presence of oxidant during the reaction progress.The catalyst/oxidant optimal ratio was determined for the cobalt catalysts.The mineralization degree of the pollutants after the degradations was verified by means of total organic carbon(TOC)content in the residual liquids.After 4 h of reaction,the maximum mineralization was reached when C was treated with a cobalt-based catalyst(>80%),and its stability was evaluated through successive cycles of use.展开更多
Single-atom catalysts(SACs)have been widely recognized as state-of-the-art catalysts in environment remediation because of their exceptional performance,100%metal atomic utilization,almost no secondary pollution,and r...Single-atom catalysts(SACs)have been widely recognized as state-of-the-art catalysts in environment remediation because of their exceptional performance,100%metal atomic utilization,almost no secondary pollution,and robust structures.Most recently,the activation of persulfate with carbon-based SACs in advanced oxidation processes(AOPs)raises tremendous interest in the degradation of emerging contaminants in wastewater,owning to its efficient and versatile reactive oxidant species(ROS)generation.However,the comprehensive and critical review unraveling the underlying relationship between structures of carbon-based SACs and the corresponding generated ROS is still rare.Herein,we systematically summarize the fundamental understandings and intrinsic mechanisms between single metal atom active sites and produced ROS during AOPs.The types of emerging contaminants are firstly elaborated,presenting the prior pollutants that need to be degraded.Then,the preparation and characterization methods of carbon-based SACs are overviewed.The underlying material structure–ROS type relationship in persulfate-based AOPs is discussed in depth to expound the catalytic mechanisms.Finally,we briefly conclude the current development of carbon-based SACs in AOPs and propose the prospects for rational design and synthesis of carbon-based SACs with on-demand catalytic performances in AOPs in future research.展开更多
基金supported by National Natural Science Foundation of China(No.52170086)Natural Science Foundation of Shandong Province(No.ZR2021ME013)+1 种基金Natural science Foundation of Shaanxi province(No.2024JC-YBQN-0252)Special Scientific Research Project of Hanzhong City-Shaanxi University of Technology Co-construction State Key Laboratory(No.SXJ2106)。
文摘Enhancing the corrosion resistance of carriers within Fenton-like systems and inhibiting the migration and aggregation of single atoms in reaction environments are essential for maintaining both high activity and stability at catalytic sites,thus meeting fundamental requirements for practical application.The Fenton-like process of activating various strong oxidants by silicon-based single atom catalysts(SACs)prepared based on silicon-based materials(mesoporous silica,silicon-based minerals,and organosilicon materials)has unique advantages such as structural stability(especially important under strong oxidation conditions)and environmental protection.In this paper,the preparation strategies for the silicon-based SACs were assessed first,and the structural characteristics of various silicon-based SACs are systematically discussed,their application process and mechanism in Fenton-like process to achieve water purification are investigated,and the progress of Fenton-like process in density functional theory(DFT)of siliconbased derived single atom catalysts is summarized.In this paper,the preparation strategies and applications of silicon-based derived SACs are analyzed in depth,and their oxidation activities and pathways to different pollutants in water are reviewed.In addition,this paper also summarizes the device design and application of silicon-based derived SACs,and prospects the future development of silicon-based SACs in Fenton-like applications.
基金supported by National Water Pollution Control and Treatment Science and Technology Major Project (No.2018ZX07110003)the National Natural Science Foundation of China (No.51779068)。
文摘Refractory organic pollutants in water threaten human health and environmental safety,and advanced oxidation processes (AOPs) are effective for the degradation of these pollutants.Catalysts play vital role in AOPs,and Ce-based catalysts have exhibited excellent performance.Recently,the development and application of Ce-based catalysts in various AOPs have been reported.Our study conducts the first review in this rapid growing field.This paper clarifies the variety and properties of Ce-based catalysts.Their applications in different AOP systems (catalytic ozonation,photodegradation,Fenton-like reactions,sulfate radicalbased AOPs,and catalytic sonochemistry) are discussed.Different Ce-based catalysts suit different reaction systems and produce different active radicals.Finally,future research directions of Ce-based catalysts in AOP systems are suggested.
基金financially supported by Base Funding–UIDB/50020/2020 of the Associate Laboratory LSRE-LCM–funded by national funds through FCT/MCTES(PIDDAC)Project PTDC/EAM-AMB/31337/2017–POCI-01-0145-FEDER-031337–funded by FEDER funds through COMPETE2020–Programa Operacional Competitividade e Internacionalização(POCI)+4 种基金with financial support of FCT/MCTES through national funds(PIDDAC)by NORTE-01-0247-FEDER-069836co-funded by the European Regional Development Fund(ERDF),through the North Portugal Regional Operational Programme(NORTE2020),under the PORTUGAL 2020 Partnership AgreementFCT funding under DL57/2016 Transitory Norm ProgrammeFCT funding under the Scientific Employment Stimulus–Institutional Call CEECINST/00049/2018
文摘The degradation of the anti-inflammatory ibuprofen(IBP)was evaluated by several advanced oxidation processes.IBP was treated by single ozonation and oxidation with hydrogen peroxide(H_(2)O_(2)),as well as a combination of these treatments.In order to improve the efficiency,the presence of catalysts such as original carbon nanotubes,labelled as CNT,and iron oxide supported on carbon nanotubes,named as Fe/CNT sample,was considered.The evolution of IBP degradation,mineralization and toxicity of the solutions was assessed.The formation of intermediates was also monitored.In the non-catalytic processes,IBP was faster removed by single ozonation,whereas no significant total organic carbon(TOC)removal was achieved.Oxidation with H_(2)O_(2) did not present satisfactory results.When ozone and H_(2)O_(2) were combined,a higher mineralization was attained(70%after 180 min of reaction).On the other hand,in the catalytic processes,this combined process allowed the fastest IBP degradation.In terms of mineralization degree,the presence of Fe/CNT increases the removal rate in the first hour of reaction,achieving a TOC removal of 85%.Four compounds were detected as by-products.All treated solutions presented lower toxicity than the initial solution,suggesting that the released intermediates during applied processes are less toxic.
基金financially supported by the National Natural Science Foundation of China(Nos.51602018 and 51902018)the Natural Science Foundation of Beijing Municipality(No.2154052)+3 种基金the China Postdoctoral Science Foundation(No.2014M560044)the Fundamental Research Funds for the Central Universities(No.FRF-MP-20-22)USTB Research Center for International People-to-people Exchange in Science,Technology and Civilization(No.2022KFYB007)Education and Teaching Reform Foundation at University of Science and Technology Beijing(Nos.2023JGC027,KC2022QYW06,and KC2022TS09)。
文摘S and Co co-doped carbon catalysts were prepared via pyrolysis of MOF-71 and thiourea mixtures at 800℃at a mass ratio of MOF-71 to thiourea of 1:0.1 to effectively activate peroxymonosulfate(PMS)for methylene blue(MB)degradation.The effects of two different mixing routes were identified on the MB degradation performance.Particularly,the catalyst obtained by the alcohol solvent evaporation(MOF-AEP)mixing route could degrade 95.60%MB(50 mg/L)within 4 min(degradation rate:K=0.78 min^(-1)),which was faster than that derived from the direct grinding method(MOF-DGP,80.97%,K=0.39 min^(-1)).X-ray photoelectron spectroscopy revealed that the Co-S content of MOF-AEP(43.39at%)was less than that of MOF-DGP(54.73at%),and the proportion of C-S-C in MOF-AEP(13.56at%)was higher than that of MOF-DGP(10.67at%).Density functional theory calculations revealed that the adsorption energy of Co for PMS was -2.94 eV when sulfur was doped as C-S-C on the carbon skeleton,which was higher than that when sulfur was doped next to cobalt in the form of Co-S bond(-2.86 eV).Thus,the C-S-C sites might provide more contributions to activate PMS compared with Co-S.Furthermore,the degradation parameters,including pH and MOF-AEP dosage,were investigated.Finally,radical quenching experiments and electron paramagnetic resonance(EPR)measurements revealed that ^(1)O_(2)might be the primary catalytic species,whereas·O~(2-)might be the secondary one in degrading MB.
基金University Synergy Innovation Program of Anhui Province(GXXT-2022-083)Science and Technology Plan Project of Wuhu City,China(2023kx12)Anhui Provincial Department of Education New Era Education Project(2023xscx070)。
文摘Owing to outstanding hydrophilicity and ionic interaction,layered double hydroxides(LDHs)have emerged as a promising carrier for high performance catalysts.However,the synthesis of new specialized catalytic LDHs for degradation of antibiotics still faces some challenges.In this study,a CoFe_(2)O_(4)/MgAl-LDH composite catalyst was synthesized using a hydrothermal coprecipitation method.Comprehensive characterization reveals that the surface of MgAl-LDH is covered with nanometer CoFe_(2)O_(4) particles.The specific surface area of CoFe_(2)O_(4)/MgAl-LDH is 82.84 m^(2)·g^(-)1,which is 2.34 times that of CoFe_(2)O_(4).CoFe_(2)O_(4)/MgAl-LDH has a saturation magnetic strength of 22.24 A·m^(2)·kg^(-1) facilitating efficient solid-liquid separation.The composite catalyst was employed to activate peroxymonosulfate(PMS)for the efficient degradation of tetracycline hydrochloride(TCH).It is found that the catalytic performance of CoFe_(2)O_(4)/MgAl-LDH significantly exceeds that of CoFe_(2)O_(4).The maximum TCH removal reaches 98.2%under the optimal conditions([TCH]=25 mg/L,[PMS]=1.5 mmol/L,CoFe_(2)O_(4)/MgAl-LDH=0.20 g/L,pH 7,and T=25℃).Coexisting ions in the solution,such as SO_(4)^(2-),Cl-,H_(2)PO_(4)^(-),and CO_(3)^(2-),have a negligible effect on catalytic performance.Cyclic tests demonstrate that the catalytic performance of CoFe_(2)O_(4)/MgAl-LDH remains 67.2%after five cycles.Mechanism investigations suggest that O_(2)^(•-)and ^(1)O_(2) produced by CoFe_(2)O_(4)/MgAl-LDH play a critical role in the catalytic degradation.
基金funded by SGCyT-UNS M24/Q075,PICTO COVIAR 2017-0112Agregando Valor VT42-UNS11738 research Grants.
文摘This study focuses on the synthesis of metal-based biochar catalysts and their catalytic activation of peroxymonosulfate(PMS,HSO5−)for the degradation of three different wastewater model pollutants employing advanced oxidation processes(AOP).Iron,copper,and two different cobalt-based catalysts were prepared and evaluated.The catalysts were supported on a biochar obtained from the pyrolysis of woody pruning wastes.They were characterized by C,H,and N elemental analysis,X-Ray diffraction(XRD),Fourier-transform infrared spectroscopy(FTIR),and scanning electron microscope(SEM).The metal content in each catalyst was determined by means of atomic absorption spectroscopy(AAS).The degradation reac-tions of benzoic acid(BA),catechol(C),and cinnamic acid(CA)were carried out in a lab scale batch glass reactor and were followed by UV-Visible spectroscopy(UV-Vis).A colorimetric technique was employed to verify the presence of oxidant during the reaction progress.The catalyst/oxidant optimal ratio was determined for the cobalt catalysts.The mineralization degree of the pollutants after the degradations was verified by means of total organic carbon(TOC)content in the residual liquids.After 4 h of reaction,the maximum mineralization was reached when C was treated with a cobalt-based catalyst(>80%),and its stability was evaluated through successive cycles of use.
基金The authors would like to acknowledge the financial support of the China Postdoctoral Science Foundation(2022M711687 and 2022M721691)Key Laboratory for Organic Electronics&Information Displays(GZR2022010010)+3 种基金Nanjing University of Posts and Telecommunications(Start-up Grant:NY221005)the Special Professor Fund of Jiangsu Province(RK030STP21007 and RK030STP22001)Natural Science Foundation of Jiangsu Province(SBK2022044384)National Natural Science Foundation of China(22276100).
文摘Single-atom catalysts(SACs)have been widely recognized as state-of-the-art catalysts in environment remediation because of their exceptional performance,100%metal atomic utilization,almost no secondary pollution,and robust structures.Most recently,the activation of persulfate with carbon-based SACs in advanced oxidation processes(AOPs)raises tremendous interest in the degradation of emerging contaminants in wastewater,owning to its efficient and versatile reactive oxidant species(ROS)generation.However,the comprehensive and critical review unraveling the underlying relationship between structures of carbon-based SACs and the corresponding generated ROS is still rare.Herein,we systematically summarize the fundamental understandings and intrinsic mechanisms between single metal atom active sites and produced ROS during AOPs.The types of emerging contaminants are firstly elaborated,presenting the prior pollutants that need to be degraded.Then,the preparation and characterization methods of carbon-based SACs are overviewed.The underlying material structure–ROS type relationship in persulfate-based AOPs is discussed in depth to expound the catalytic mechanisms.Finally,we briefly conclude the current development of carbon-based SACs in AOPs and propose the prospects for rational design and synthesis of carbon-based SACs with on-demand catalytic performances in AOPs in future research.
