Triclosan(TCS) poses harmful risks to ecosystems and human health owing to its endocrine-disrupting effects.Therefore,developing an efficient and sustainable technology to degrade TCS is urgently needed.Herein,cobalt ...Triclosan(TCS) poses harmful risks to ecosystems and human health owing to its endocrine-disrupting effects.Therefore,developing an efficient and sustainable technology to degrade TCS is urgently needed.Herein,cobalt oxyhydroxide @covalent organic frameworks(CoOOH@COFs) S-scheme heterojunction was synthesized,which combined the visible-light-driven photocatalysis and peroxymonosulfate(PMS) activation to synergistically generate abundant reactive oxygen species(ROSs) for TCS degradation.The degradation efficiency of TCS reached 100 % within 8 min in the Vis-CoOOH@COFs/PMS system,and the reaction rate constant was 0.456 min^(-1),which was nearly 1.90 and 2.85 times that of single Co OOH and COFs,and2.36 times that under dark condition,respectively.The density functional theory(DFT) calculations confirmed the energy band bending of CoOOH@COFs and S-scheme charge transport from COFs to Co OOH.Both experimental and theoretical analyses indicated that Co OOH@COFs in photocatalytic-PMS activation systems synergistically facilitated photo-generated carrier separation,enhanced interfacial electron transfer,accelerated PMS activation,and generated multiple ROSs.In particular,photogenerated electrons(e^(-))accelerated the Co(Ⅲ)/Co(Ⅱ) redox cycle,while the PMS captured the e-,which significantly decreased the charge combination of Co OOH@COFs.Radicals(O_(2)^(·-),^(·)OH,and SO_(4)^(·-)) and non-radicals(such as ^(1)O_(2),h^(+),and e^(-)) were both presented in the Vis-CoOOH@COFs/PMS system,with O_(2)^(-) playing a dominant role in TCS degradation.Furthermore,the pathway of TCS degradation and toxicity of intermediates were explored by DFT calculation and transformation product identification.Importantly,the environmentally friendly CoOOH@COFs S-scheme heterojunction exhibited excellent stability and reusability.In conclusion,this study innovatively designed an S-scheme heterojunction in the photocatalytic-PMS activation system,providing guidance and theoretical support for efficient and eco-friendly wastewater treatment.展开更多
Cobalt-based catalysts were regarded as highly effective for pollutant degradation through peroxymono-sulfate activation.Nevertheless,conventional synthesis methods for cobalt-based catalysts were associ-ated with iss...Cobalt-based catalysts were regarded as highly effective for pollutant degradation through peroxymono-sulfate activation.Nevertheless,conventional synthesis methods for cobalt-based catalysts were associ-ated with issues of cobalt ion leakage,which posed a risk of secondary environmental contamination.Addressing this issue,a novel cobalt-based catalyst,CoS nanoparticles,was biosynthesized by Shewanella algae and designated as SA@CoS.SA@CoS,a nanoflower coated with proteins/peptides,contained a sig-nificant number of sulfur vacancies.Compared to chemically synthesized CoS,SA@CoS exhibited lower cobalt ion release(0.13 mg/L)and higher catalytic activity.Based on this,SA@CoS was employed to de-grade Rhodamine B(RhB)and tetracycline(TC)by activating peroxymonosulfate.The results indicated that the degradation efficiencies of RhB and TC could reach 99.9%and 90.5%within 10 min,respec-tively.Further analyses revealed that both radical(·O_(2)^(-),·OH and SO_(4)^(·-))and non-radical(_(1)O_(2))pathways were involved in the degradation of RhB and TC,with the non-radical pathway dominating the degra-dation process.This work not only offered a facile approach for the biosynthesis of stable cobalt-based catalysts,but also underscored the immense potential of biogenic nano-catalysts in the realm of environ-mental remediation.展开更多
The regulation of peroxymonosulfate(PMS)activation by constructing oxygen vacancy and heterogeneous interface catalytic is crucial towards the oxidation of refractory pollutants still remains a major hurdle.This work ...The regulation of peroxymonosulfate(PMS)activation by constructing oxygen vacancy and heterogeneous interface catalytic is crucial towards the oxidation of refractory pollutants still remains a major hurdle.This work demonstrates a strategy to constructed ethylene glycol(EG)well-coupled S-scheme heterojunction of NiFe_(2)O_(4-x)/NiS with oxygen vacancy(VO)-modified to efficiently achieve pollutant removal by activating PMS through photoexcitation,a 99%PMS decomposition efficiency is achieved.Photoassisted Kelvin probe force microscopy and in-situ electron spin resonance verify the establishment of a charge-transfer pathway consistent in NiFe_(2)O_(4-x)/NiS with an S-scheme heterojunction,which dramatically provides abundant active sites and distinct charge transport pathway for organic pollutant oxidation.The S-scheme NiFe_(2)O_(4-x)/NiS heterojunction in the photo-Fenton-like system exhibited significantly enhanced degradation rate(0.15 min^(-1))at a low PMS dosage of 0.1 g/L,which is 19 times greater than that of the pristine NiS(0.0077 min^(-1)).Density functional theory calculations confirmed that VO in NiFe_(2)O_(4-x)/NiS efficiently promoted PMS adsorption and lowered the energy barrier for electron transfer.Moreover,in-situ experiments and experimental evidence offer mechanistic insights into the PMS activation through photoexcitation,unraveling a dual-pathway activation mechanism involving reduction and oxidation processes over NiFe_(2)O_(4-x)/NiS during the reaction.This work emphasizes the potential of vacancy engineering synergistic S-scheme heterojunction in developing efficient catalysts for regulating PMS activation,providing a promising solution the cost-effective and efficient treatment of organic wastewater.展开更多
The influence of electronic structure on the performance of catalysts for peroxymonosulfate(PMS)activation remains ambiguous.In this study,the 3d electron configuration of Fe(Ⅲ)in AgFeO_(2) was atomically regulated u...The influence of electronic structure on the performance of catalysts for peroxymonosulfate(PMS)activation remains ambiguous.In this study,the 3d electron configuration of Fe(Ⅲ)in AgFeO_(2) was atomically regulated using cobalt doping.The amount of PMS adsorbed and the catalytic performance were positively correlated with the total effective magnetic moment and the ratios of high-spin Fe(Ⅲ)and eg filling within the catalysts.These 3d electron regulations favor PMS adsorption and electron transfer owing to the lower PMS adsorption energy,increased electronic states near the Fermi level,and reduced dz^(2) orbital occupancy.Benefiting from fine tailoring of the electron configuration,the AgFe_(0.80)Co_(0.20)O_(2) catalyst exhibited outstanding catalytic PMS activation and favorable application potential,achieving efficient pharmaceutical wastewater treatment and more than 80%ofloxacin removal after 72 h of continuous-flow operation.Notably,this study offers a comprehensive understanding for the influence mechanism of electronic structure regulation on PMS activation,providing design guidance for the development of efficient heterogeneous Fenton-like catalytic systems.展开更多
An environmentally friendly Mn‐oxide‐supported metal‐organic framework(MOF),Mn3O4/ZIF‐8,was successfully prepared using a facile solvothermal method,with a formation mechanism proposed.The composite was characteri...An environmentally friendly Mn‐oxide‐supported metal‐organic framework(MOF),Mn3O4/ZIF‐8,was successfully prepared using a facile solvothermal method,with a formation mechanism proposed.The composite was characterized using X‐ray diffraction,scanning electron microscopy,transmission electron microscopy,X‐ray photoelectron microscopy,and Fourier‐transform infrared spectroscopy.After characterization,the MOF was used to activate peroxymonosulfate(PMS)for degradation of the refractory pollutant rhodamine B(RhB)in water.The composite prepared at a0.5:1mass ratio of Mn3O4to ZIF‐8possessed the highest catalytic activity with negligible Mn leaching.The maximum RhB degradation of approximately98%was achieved at0.4g/L0.5‐Mn/ZIF‐120,0.3g/L PMS,and10mg/L initial RhB concentration at a reaction temperature of23°C.The RhB degradation followed first‐order kinetics and was accelerated with increased0.5‐Mn/ZIF‐120and PMS dosages,decreased initial RhB concentration,and increased reaction temperature.Moreover,quenching tests indicated that?OH was the predominant radical involved in the RhB degradation;the?OH mainly originated from SO4??and,hence,PMS.Mn3O4/ZIF‐8also displayed good reusability for RhB degradation in the presence of PMS over five runs,with a RhB degradation efficiency of more than96%and Mn leaching of less than5%for each run.Based on these findings,a RhB degradation mechanism was proposed.展开更多
Peroxymonosulfate(PMS)activation in heterogeneous processes is a promising water treatment technology.Nevertheless,the high energy consumption and low efficiency during the reaction are ineluctable,due to electron cyc...Peroxymonosulfate(PMS)activation in heterogeneous processes is a promising water treatment technology.Nevertheless,the high energy consumption and low efficiency during the reaction are ineluctable,due to electron cycling rate limitation.Herein,a new strategy is proposed based on a quantum dots(QDs)/PMS system.Co-ZnS QDs are synthesized by a water phase coprecipitation method.The inequivalent lattice-doping of Co for Zn leads to the generation of surface sulfur vacancies(SVs),which modulates the surface of the catalyst to form an electronic nonequilibrium surface.Astonishingly,the plasticizer micropollutants can be completely degraded within only tens of seconds in the Co-Zn S QDs/PMS system due to this type of surface modulation.The interfacial reaction mechanism is revealed that pollutants tend to be adsorbed on the cobalt metal sites as the electron donors,where the internal electrons of pollutants are captured by the metal species and transferred to the surface SVs.Meanwhile,PMS adsorbed on the SVs is reduced to radicals by capturing electrons,achieving effective electron recovery.Dissolved oxygen(DO)molecules are also easily attracted to catalyst defects and are reduced to O_(2)^(·-),further promoting the degradation of pollutants.展开更多
The Z-scheme heterostructure for photocatalyst can effectively prolong the lifetime of photogenerated carriers and retain a higher conduction/valence band position,promoting the synergistic coupling of photocatalysis ...The Z-scheme heterostructure for photocatalyst can effectively prolong the lifetime of photogenerated carriers and retain a higher conduction/valence band position,promoting the synergistic coupling of photocatalysis and peroxymonosulfate(PMS) activation.In order to fully utilize the luminous energy and realize the efficient activation of PMS,this work achieved successful construction of NiCo_(2)O_(4)/BiOCl/Bi_(24)O_(31)Br_(10) ternary Z-scheme heterojunction by simultaneously synthesizing BiOCl and NiCo_(2)O_(4) with NiCl_(2) and CoCl_(2) as the precursors.The intercalated BiOCl could serve as a carrier migration ladder to further achieve the spatial separation of electron-hole pairs,so that the oxidation and reduction processes separately occurred in different regions.Compared with the reported catalysts,the as-prepared composites exhibited the enhanced removal efficiency for tetracycline hydrochloride(TCH) in the visible light/PMS system,with a degradation efficiency of 85.30%in 2 min,and possessed good stability.Z-scheme heterojunction was shown to be beneficial for maximizing the superiority of photo-assisted Fenton-like reaction system.The experimental and characterization results confirmed that both non-radicals(^(1)O_(2)) and radicals(SO_(5)^(·-) and SO_(4)^(·-)) were involved in the reaction process and the SO_(5)^(·-)generated by the oxidation of PMS played a crucial role in the TCH degradation.The possible reaction mechanism was finally proposed.This study provided new insight into the Z-scheme heterostructure to promote the photo-assisted Fenton-like reaction.展开更多
Morphology and dispersity are key factors for activating peroxymonosulfate(PMS).In this study,we designed a recyclable open-type NiCo_(2)O_(4) hollow microsphere via a simple hydrothermal method with the assistance of...Morphology and dispersity are key factors for activating peroxymonosulfate(PMS).In this study,we designed a recyclable open-type NiCo_(2)O_(4) hollow microsphere via a simple hydrothermal method with the assistance of an NH_(3) vesicle.The physical structure and chemical properties were characterized using techniques such as scanning electron microscope(SEM),transmission electron microscope(TEM),X-ray diffraction(XRD),N2 adsorption and X-ray photoelectron spectroscopy(XPS).The test results confirm that the inner and outer surfaces of open-type NiCo_(2)O_(4) hollow-sphere can be efficiently utilized because of the hole on the surface of the catalyst,which can minimize the diffusion resistance of the reactants and products.Under optimized conditions,the total orga nic carbon(TOC) removal efficiency of rhodamine B(RhB) can reach up to 80% in 40 min,which is almost 50% shorter than the reported values.The reactive radicals were identified and the proposed reaction mechanism was well described.Moreover,the disturbances of HCO_(3)^(-),NO_(3)^(-),Cl^(-)and H_(2) PO_(4)^(-)were further investigated.As a result,HCO_(3)-and NO_(3)-suppressed the reaction while Cl-and H_(2) PO4-had a double effect on reaction.展开更多
Formaldehyde(FA),as an important chemical raw material,has been widely used in many fields.However,the discharge of a large amount of FA-containing wastewater poses a serious threat to the environment and human health...Formaldehyde(FA),as an important chemical raw material,has been widely used in many fields.However,the discharge of a large amount of FA-containing wastewater poses a serious threat to the environment and human health.Recently,the in-situ hydrogen energy release technology of hydrogen-containing stable liquid has been extensively explored due to its safe storage.Exploring a robust method to achieve FA removal and synchronous in-situ hydrogen release from FA containing wastewater is of great significant for environmental protection and energy crisis alleviation.Here,we have innovatively introduced peroxymonosulfate(PMS)activation technology into FA removal and hydrogen production simultaneously.The composite of nitrogen doped carbon coating Co_(9)S_(8)nanotubes(Co_(9)S_(8)@N-C)is employed as a proof of concept for FA decomposition and simultaneously hydrogen production based on PMS activation system.As expected,the Co_(9)S_(8)@N-C/PMS system presents much superior hydrogen production efficiency and satisfactory FA removal rate towards FA wastewater than those of common catalysis,photocatalysis and Fenton reaction in the basic condition in a wide range of FA concentration.The hydrogen yield reaches a value as high as 471μmol within 60 min,corresponding to a FA degradation rate of 30%with an initial FA concentration of 0.722 mol L^(-1).Characterizations and density functional theory(DFT)calculations suggest that the free radical process dominated by superoxide radical(O_(2)·^(-))and nonradical process dominated by singlet oxygen(^(1)O_(2)),which are induced by Co_(9)S_(8)@N-C/PMS system,are responsible for highly efficient hydrogen production via FA degradation.These generated O_(2)·^(-)and ^(1)O_(2)can extract·H from FA to form·OOH intermediate,which can further combine with the·H from water to produce hydrogen.This study provides an applicable technique for environmental purification and new energy development based on FA containing wastewater.展开更多
Herein,a novel MoS_(2)-stainless steel composite material was first synthetized via a 3D printing method(3DP MoS_(2)-SS)for peroxymonosulfate(PMS)activation and organics degradation.Compared with MoS_(2)-SS powder/PMS...Herein,a novel MoS_(2)-stainless steel composite material was first synthetized via a 3D printing method(3DP MoS_(2)-SS)for peroxymonosulfate(PMS)activation and organics degradation.Compared with MoS_(2)-SS powder/PMS system(0.37 g/(m^(2)/min)),4.3-fold higher k_(FLO)/S_(BET)value was obtained in 3DP MoS_(2)-SS/PMS system(1.60 g/(m^(2)/min),resulting from the superior utilization of active sites.We observed that 3DP MoS_(2)-SS significantly outperformed the 3DP SS due to the enhanced electron transfer rate and increased active sites.Moreover,Mo^(4+)facilitated the Fe^(2+)/Fe^(3+)cycle,resulting in the rapid degradation of florfenicol(FLO).Quenching experiments and electron paramagnetic resonance spectra indicated that·OH,SO_(4)·^(-),O_(2)·^(-)and^(1)O_(2)were involved in the degradation of FLO.The effect of influencing factors on the degradation of FLO were evaluated,and the optimized degradation efficiency of 98.69%was achieved at 1 mM PMS and pH of 3.0.Six degradation products were detected by UPLC/MS analyses and several possible degradation pathways were proposed to be the cleavage of C-N bonds,dechlorination,hydrolysis,defluorination and hydroxylation.In addition,3DP MoS_(2)-SS/PMS system also demonstrated superior degradation performance for 2-chlorophenol,acetaminophen,ibuprofen and carbamazepine.This study provided deep insights into the MoS_(2)-SS catalyst prepared by 3DP technology for PMS activation and FLO-polluted water treatment.展开更多
Emerging organic pollutants(EoPs)in water are of great concern due to their high environmental risk,so urgent technologies are needed for effective removal of those pollutants.Herein,a heterogeneous advanced oxidation...Emerging organic pollutants(EoPs)in water are of great concern due to their high environmental risk,so urgent technologies are needed for effective removal of those pollutants.Herein,a heterogeneous advanced oxidation process(AoP)of peroxymonosulfate(PMS)activation by functional material was developed for degradation of a typical antibiotic,gatifloxacin(GAT).The reactive species including sulfate radical(SO^(4)^(·-))and singlet oxygen(^(1)O_(2))in this AOP were regulated by interlayered ions(Na^(+)/H^(+))of titanate nanotubes that supported on Co(OH)_(2)hollow microsphere.Both the Na-type(NaTi-CoHS)and H-type(HTi-CoHS)materials achieved efficient PMS activation for GAT degradation,and HTi-CoHS even exhibited a relatively high degradation efficiency of 96.6%within 5 min.Co(OH)_(2)was considered the key component for generation of SO_(4)^(·-)after PMS activation,while hydrogen titanate nanotubes(H-TNTs)promoted the transformation of peroxysulfate radical(SO_(5)^(·-))to ^(1)O_(2) by hydrogen bond interaction.Therefore,when the interlayer ion of TNTs transformed from Na^(+) to H^(+),more ^(1)O_(2) was produced for organic pollutant degradation.H-TNTs with lower symmetry preferred to adsorb PMS molecules to achieve interlayer electron transport through hydrogen bonding,rather than electrostatic interaction of Na^(+) for Na-TNTs.In addition,the degradation pathway of GAT mainly proceeded by the cleavage of C-N bond at the 8 N site of the piperazine ring,which was confirmed by condensed Fukui index and mass spectrographic analysis.This work gives new sights into the regulation of reactive species in AoPs by the composition of material and promotes the understanding of pollutant degradation mechanisms in water treatment process.展开更多
Designing efficient and sustainable catalyst for peroxymonosulfate(PMS)activation and refractory 2,4,6-trichlorophenol(2,4,6-TCP)removal is an imminent task.This study synthesized a novelγ-MnO_(2)/NF catalyst,which h...Designing efficient and sustainable catalyst for peroxymonosulfate(PMS)activation and refractory 2,4,6-trichlorophenol(2,4,6-TCP)removal is an imminent task.This study synthesized a novelγ-MnO_(2)/NF catalyst,which has advantages in saving manganese dioxide demand and reducing manganese leaching.Theγ-MnO_(2)/NF+PMS oxidation system achieved a 0.219 min^(−1)2,4,6-TCP apparent rate constant at 20℃,and removed>90%of 2,4,6-TCP at the 5th cycle.Both free radical identification and DFT calculations revealed that•OH and SO_(4)^(•−),rather than 1O_(2),were the dominant reactive species duringγ-MnO_(2)/NF+PMS oxidation.The results indicated that the inner-sphere complexation betweenγ-MnO_(2)/NF and PMS facilitated the formation of•OH and SO_(4)^(•−).To fill the research gap in the molecular-level dissimilarities between•OH and SO_(4)^(•−)in 2,4,6-TCP degradation mechanism,experimental testing and quantum chemical analysis methods were used.The DFT calculation found that the HAA reaction at H13 site and RAF reaction at C1 site were more favorable for both•OH and SO_(4)^(•−).For most reaction sites,SO_(4)^(•−)demonstrates greater energy barriers and substrate selectivity than•OH,attributed to steric constraints.The•OH acted as the predominant oxidative agents responsible for 2,4,6-TCP decomposition.Combining DFT calculation and intermediate identification,potential degradation routes of 2,4,6-TCP were proposed.The ecotoxicity assays verified a substantial reduction in acute toxicity of the treated 2,4,6-TCP solution.This study opens up new avenues for activating PMS withγ-MnO_(2)/NF,and helps to select preferred radical oxidation processes for optimal 2,4,6-TCP removal in practical engineering.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
Biochar-based transition metal catalysts have been identified as excellent peroxymonosulfate(PMS)activators for producing radicals used to degrade organic pollutants.However,the radical-dominated pathways for PMS acti...Biochar-based transition metal catalysts have been identified as excellent peroxymonosulfate(PMS)activators for producing radicals used to degrade organic pollutants.However,the radical-dominated pathways for PMS activation severely limit their practical applications in the degradation of organic pollutants from wastewater due to side reactions between radicals and the coexisting anions.Herein,bimetallic Fe/Mn-loaded hydroxyl-rich biochar(FeMn-OH-BC)is synthesized to activate PMS through nonradical-dominated pathways.The as-prepared FeMn-OH-BC exhibits excellent catalytic activity for degrading tetracycline at broad pH conditions ranging from 5 to 9,and about 85.0%of tetracycline is removed in 40 min.Experiments on studying the influences of various anions(HCO_(3)^(−),NO_(3)^(−),and H_(2)PO_(4)^(−))show that the inhibiting effect is negligible,suggesting that the FeMn-OHBC based PMS activation is dominated by nonradical pathways.Electron paramagnetic resonance measurements and quenching tests provide direct evidence to confirm that 1O2 is the major reactive oxygen species generated from FeMn-OH-BC based PMS activation.Theoretical calculations further reveal that the FeMn-OH sites in FeMn-OH-BC are dominant active sites for PMS activation,which have higher adsorption energy and stronger oxidative activity towards PMS than OH-BC sites.This work provides a new route for driving PMS activation by biochar-based transition metal catalysts through nonradical pathways.展开更多
Heterogeneous advanced oxidation processes(AOPs)based on non-radical reactive species are considered as a powerful technology for wastewater purification due to their long half-lives and high adaptation in a wide pH r...Heterogeneous advanced oxidation processes(AOPs)based on non-radical reactive species are considered as a powerful technology for wastewater purification due to their long half-lives and high adaptation in a wide pH range.Herein,we fabricate surface Co defect-rich spinel ZnCo_(2)O_(4)porous nanosheets,which can generate≡CoIV=O and ^(1)O_(2) over a wide pH range of 3.81-10.96 by the formation of amphoteric≡Zn(OH)2 in peroxymonosulfate(PMS)activation process.Density functional theory(DFT)calculations show Co defect-rich ZnCo_(2)O_(4)possesses much stronger adsorption ability and more electron transfer to PMS.Moreover,the adsorption mode changes from terminal oxygen Co-O-Co to Co-O,accelerating the polarization of adjacent oxygen,which is beneficial to the generation of≡CoIV=O and Generating ^(1)O_(2) .Co defect-rich ZnCo_(2)O_(4)porous nanosheets exhibit highly active PMS activation activity and stability in p-nitrophenol(PNP)degradation,whose toxicity of degradation intermediates is significant reduction.The Co defect-rich ZnCo_(2)O_(4)nanosheet catalyst sponge/PMS system achieved stable and efficient removal of PNP with a removal efficiency higher than 93%over 10 h.This work highlights the development of functional catalyst and provides an atomic-level understanding into non-radical PMS activation process in wastewater treatment.展开更多
The adsorption of peroxymonosulfate(PMS)is crucial for PMS activation in the heterogeneous advanced oxidation processes.However,the investigation of PMS adsorption on the piezocatalysts still remains insufficient.In t...The adsorption of peroxymonosulfate(PMS)is crucial for PMS activation in the heterogeneous advanced oxidation processes.However,the investigation of PMS adsorption on the piezocatalysts still remains insufficient.In this work,bismuth oxychloride(BiO Cl)nanosheets were prepared as the piezocatalysts for PMS activation under ultrasonic vibration to remove carbamazepine(CBZ)in aqueous solutions.Up to92.5%of CBZ was degraded for 40 min in Bi OCl piezo-activated PMS system with the reaction rate constant of 0.0741 min-1,being 1.63 times that of the sum of BiOCl piezocatalysis,BiOCl-activated PMS,and vibration-activated PMS.PMS adsorption on the surface of BiOCl was specifically studied by comparing the microscopic structure change of the fresh and used Bi OCl.The results suggested that the piezoelectric field of Bi OCl was able to promote the tight adsorption of PMS on the surface,thus facilitating the fast activation of PMS through electrons transfer to produce reactive species(HO·,SO_(4)·-,O_(2)·-,1O_(2)).This work presents an in-depth understanding for the role of piezoelectric effect on the adsorption and activation of PMS.展开更多
In this study,supported Pd catalysts were prepared and used as heterogeneous catalysts for the activation of peroxymonosulfate(PMS)which successfully degrade bisphenol F(BPF).Among the supported catalysts(i.e.,Pd/SiO_...In this study,supported Pd catalysts were prepared and used as heterogeneous catalysts for the activation of peroxymonosulfate(PMS)which successfully degrade bisphenol F(BPF).Among the supported catalysts(i.e.,Pd/SiO_(2),Pd/CeO_(2),Pd/TiO_(2)and Pd/Al2O3),Pd/TiO_(2)exhibited the highest catalytic activity due to the high isoelectric point and high Pd0 content.Pd/TiO_(2)prepared by the deposition method leads to high Pd dispersion,which are the key factors for efficient BPF degradation.The influencing factors were investigated during the reaction process and two possible degradation pathways were proposed.Density functional theory(DFT)calculations demonstrate that stronger BPF adsorption and BPF degradation with lower reaction barrier occurs on smaller Pd particles.The catalytic activities are strongly dependent on the structural features of the catalysts.Both experiments and theoretical calculations prove that the reaction is actuated by electron transfer rather than radicals.展开更多
Rational tuning of crystallographic surface and metal doping were effective to enhance the catalytic performance of metal organic frameworks,but limited work has been explored for achieving modulation of crystal facet...Rational tuning of crystallographic surface and metal doping were effective to enhance the catalytic performance of metal organic frameworks,but limited work has been explored for achieving modulation of crystal facets and metal doping in a single system.MIL-68(In)was promising for photocatalytic applications due to its low toxicity and excellent photoresponsivity.However,its catalytic activity was constrained by severe carrier recombination and a lack of active sites.Herein,increased(001)facet ratio and active sites exposure were simultaneously realized by cobalt doping in MIL-68(In)through a one-pot solvothermal strategy.Optimized MIL-68(In/Co)-2.5 exhibited remarkable catalytic performance in comparison with pristine MIL-68(In)and other MIL-68(In/Co).The reaction kinetic constant and degradation efficiency of MIL-68(In/Co)were approximately twice and 17%higher than the pristine MIL-68(In)in 36 min reaction,respectively.Density functional theory calculations revealed that Co dopant could modulate the orientation of MIL-68(In)facets,facilitate the exchange of electrons and reduce the adsorption energy of peroxymonosulfate(PMS).This work provides a novel pathway for improvement of In-based MOFs in PMS/vis system,it also promotes the profound comprehension of the correlation between crystal facet regulation and catalytic activation in the PMS/vis system.展开更多
The degradation of organic pollutants in water is a critical environmental challenge.The iron-doped MoS_(2) catalysts have demonstrated potential in activating peroxymonosulfate(PMS)for environmental remediation,but t...The degradation of organic pollutants in water is a critical environmental challenge.The iron-doped MoS_(2) catalysts have demonstrated potential in activating peroxymonosulfate(PMS)for environmental remediation,but they face challenges such as poor conductivity,limited electron transfer efficiency,and a scarcity of active sites.To address these issues,we successfully synthesized a nano-flowers FeS/MoS_(2) composite derived from polyoxometalates(NH_(4))_(3)[Fe(III)Mo_(6)O_(24)H_(6)]⋅6H_(2)O(denoted as FeMo6)as the bimetallic precursors.This synthesis strategy enhances the interaction between FeS and MoS_(2),thereby facilitating electron transfer.Notably,the introduction of sulfur vacancies in FeS/MoS_(2) exposes additional Mo4t active sites,promoting the redox cycle of Fe^(2+)/Fe^(3+) and accelerating the regeneration of Fe^(2+),which in turn enhances PMS activation.Therefore,a catalytic oxidation system of FeS/MoS_(2)/PMS is presented that primarily relies on SO_(4)^(⋅-)and⋅OH,with ^(1)O_(2) as a supplementary oxidant.This system exhibits exceptional degradation efficiency for p-chlorophenol(4-CP),achieving 100% degradation within 10 min over a wide pH range of 2.4–8.4.The robust performance and wide applicability of FeS/MoS_(2) catalyst make it a promising candidate in advanced oxidation processes(AOPs)for environmental remediation.展开更多
Metal-based perovskite oxides have contributed significantly to the advanced oxidation processes(AOPs)due to their diverse active sites and excellent compositional/structural flexibility.In this study,we specially des...Metal-based perovskite oxides have contributed significantly to the advanced oxidation processes(AOPs)due to their diverse active sites and excellent compositional/structural flexibility.In this study,we specially designed a perovskite oxide with abundant oxygen vacancies,SrCo_(0.8)Fe_(0.2)O_(3)(SCF),and firstly applied it as a catalyst in peroxymonosulfate(PMS) activation towards organic pollutants degradation.The result revealed that the prepared SCF catalyst exhibited excellent performance on organic compounds degradation.Besides,SCF showed much better activity than La_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3)(LSCF) in terms of reaction rate and stability for the degradation of the organic compounds.Based on the analysis of scanning electron microscope,transmission electron microscope,X-ray diffraction,N_(2) adsorption-desorption,X-ray photoelectron spectroscopy and electron paramagnetic resonance,it was confirmed that the perovskite catalysts with high content of Sr doping at A-site could effectively create a defect-rich surface and optimize its physicochemical properties,which was responsible for the excellent heterogeneous catalytic activity of SCF.SCF can generate three highly active species:~1 O_(2),SO_(4)^(-)· and ·OH in PMS activation,revealing the degradation process of organic compounds was a coupled multiple active species in both radical and nonradical pathway.Moreover,it was mainly in a radical pathway in the degradation through PMS activation on SCF and SO_(4)^(-)· radicals produced were the dominant species in SCF/PMS system.This study demonstrated that perovskite-type catalysts could enrich OVs efficiently by doping strategy and regulate the PMS activation towards sulfate radical-based AOPs.展开更多
文摘Triclosan(TCS) poses harmful risks to ecosystems and human health owing to its endocrine-disrupting effects.Therefore,developing an efficient and sustainable technology to degrade TCS is urgently needed.Herein,cobalt oxyhydroxide @covalent organic frameworks(CoOOH@COFs) S-scheme heterojunction was synthesized,which combined the visible-light-driven photocatalysis and peroxymonosulfate(PMS) activation to synergistically generate abundant reactive oxygen species(ROSs) for TCS degradation.The degradation efficiency of TCS reached 100 % within 8 min in the Vis-CoOOH@COFs/PMS system,and the reaction rate constant was 0.456 min^(-1),which was nearly 1.90 and 2.85 times that of single Co OOH and COFs,and2.36 times that under dark condition,respectively.The density functional theory(DFT) calculations confirmed the energy band bending of CoOOH@COFs and S-scheme charge transport from COFs to Co OOH.Both experimental and theoretical analyses indicated that Co OOH@COFs in photocatalytic-PMS activation systems synergistically facilitated photo-generated carrier separation,enhanced interfacial electron transfer,accelerated PMS activation,and generated multiple ROSs.In particular,photogenerated electrons(e^(-))accelerated the Co(Ⅲ)/Co(Ⅱ) redox cycle,while the PMS captured the e-,which significantly decreased the charge combination of Co OOH@COFs.Radicals(O_(2)^(·-),^(·)OH,and SO_(4)^(·-)) and non-radicals(such as ^(1)O_(2),h^(+),and e^(-)) were both presented in the Vis-CoOOH@COFs/PMS system,with O_(2)^(-) playing a dominant role in TCS degradation.Furthermore,the pathway of TCS degradation and toxicity of intermediates were explored by DFT calculation and transformation product identification.Importantly,the environmentally friendly CoOOH@COFs S-scheme heterojunction exhibited excellent stability and reusability.In conclusion,this study innovatively designed an S-scheme heterojunction in the photocatalytic-PMS activation system,providing guidance and theoretical support for efficient and eco-friendly wastewater treatment.
基金supported by the National Natural Science Foundation of China(No.42376204)the Shandong Provin-cial Natural Science Foundation(No.ZR2022MD023)+3 种基金the Interna-tional Partnership Program by Chinese Academy of Sciences(No.058GJHZ2023058FN)the Young Elite Scientists Sponsorship Pro-gram by CAST(No.YESS20210201)the Key R&D Program of Shan-dong Province,China(Nos.2022CXPT027 and 2023CXPT008)Guangxi Science and Technology Program(Guike AA23026007).
文摘Cobalt-based catalysts were regarded as highly effective for pollutant degradation through peroxymono-sulfate activation.Nevertheless,conventional synthesis methods for cobalt-based catalysts were associ-ated with issues of cobalt ion leakage,which posed a risk of secondary environmental contamination.Addressing this issue,a novel cobalt-based catalyst,CoS nanoparticles,was biosynthesized by Shewanella algae and designated as SA@CoS.SA@CoS,a nanoflower coated with proteins/peptides,contained a sig-nificant number of sulfur vacancies.Compared to chemically synthesized CoS,SA@CoS exhibited lower cobalt ion release(0.13 mg/L)and higher catalytic activity.Based on this,SA@CoS was employed to de-grade Rhodamine B(RhB)and tetracycline(TC)by activating peroxymonosulfate.The results indicated that the degradation efficiencies of RhB and TC could reach 99.9%and 90.5%within 10 min,respec-tively.Further analyses revealed that both radical(·O_(2)^(-),·OH and SO_(4)^(·-))and non-radical(_(1)O_(2))pathways were involved in the degradation of RhB and TC,with the non-radical pathway dominating the degra-dation process.This work not only offered a facile approach for the biosynthesis of stable cobalt-based catalysts,but also underscored the immense potential of biogenic nano-catalysts in the realm of environ-mental remediation.
文摘The regulation of peroxymonosulfate(PMS)activation by constructing oxygen vacancy and heterogeneous interface catalytic is crucial towards the oxidation of refractory pollutants still remains a major hurdle.This work demonstrates a strategy to constructed ethylene glycol(EG)well-coupled S-scheme heterojunction of NiFe_(2)O_(4-x)/NiS with oxygen vacancy(VO)-modified to efficiently achieve pollutant removal by activating PMS through photoexcitation,a 99%PMS decomposition efficiency is achieved.Photoassisted Kelvin probe force microscopy and in-situ electron spin resonance verify the establishment of a charge-transfer pathway consistent in NiFe_(2)O_(4-x)/NiS with an S-scheme heterojunction,which dramatically provides abundant active sites and distinct charge transport pathway for organic pollutant oxidation.The S-scheme NiFe_(2)O_(4-x)/NiS heterojunction in the photo-Fenton-like system exhibited significantly enhanced degradation rate(0.15 min^(-1))at a low PMS dosage of 0.1 g/L,which is 19 times greater than that of the pristine NiS(0.0077 min^(-1)).Density functional theory calculations confirmed that VO in NiFe_(2)O_(4-x)/NiS efficiently promoted PMS adsorption and lowered the energy barrier for electron transfer.Moreover,in-situ experiments and experimental evidence offer mechanistic insights into the PMS activation through photoexcitation,unraveling a dual-pathway activation mechanism involving reduction and oxidation processes over NiFe_(2)O_(4-x)/NiS during the reaction.This work emphasizes the potential of vacancy engineering synergistic S-scheme heterojunction in developing efficient catalysts for regulating PMS activation,providing a promising solution the cost-effective and efficient treatment of organic wastewater.
文摘The influence of electronic structure on the performance of catalysts for peroxymonosulfate(PMS)activation remains ambiguous.In this study,the 3d electron configuration of Fe(Ⅲ)in AgFeO_(2) was atomically regulated using cobalt doping.The amount of PMS adsorbed and the catalytic performance were positively correlated with the total effective magnetic moment and the ratios of high-spin Fe(Ⅲ)and eg filling within the catalysts.These 3d electron regulations favor PMS adsorption and electron transfer owing to the lower PMS adsorption energy,increased electronic states near the Fermi level,and reduced dz^(2) orbital occupancy.Benefiting from fine tailoring of the electron configuration,the AgFe_(0.80)Co_(0.20)O_(2) catalyst exhibited outstanding catalytic PMS activation and favorable application potential,achieving efficient pharmaceutical wastewater treatment and more than 80%ofloxacin removal after 72 h of continuous-flow operation.Notably,this study offers a comprehensive understanding for the influence mechanism of electronic structure regulation on PMS activation,providing design guidance for the development of efficient heterogeneous Fenton-like catalytic systems.
基金supported by the National Key Research and Development Program of China (2016YFB0700504)~~
文摘An environmentally friendly Mn‐oxide‐supported metal‐organic framework(MOF),Mn3O4/ZIF‐8,was successfully prepared using a facile solvothermal method,with a formation mechanism proposed.The composite was characterized using X‐ray diffraction,scanning electron microscopy,transmission electron microscopy,X‐ray photoelectron microscopy,and Fourier‐transform infrared spectroscopy.After characterization,the MOF was used to activate peroxymonosulfate(PMS)for degradation of the refractory pollutant rhodamine B(RhB)in water.The composite prepared at a0.5:1mass ratio of Mn3O4to ZIF‐8possessed the highest catalytic activity with negligible Mn leaching.The maximum RhB degradation of approximately98%was achieved at0.4g/L0.5‐Mn/ZIF‐120,0.3g/L PMS,and10mg/L initial RhB concentration at a reaction temperature of23°C.The RhB degradation followed first‐order kinetics and was accelerated with increased0.5‐Mn/ZIF‐120and PMS dosages,decreased initial RhB concentration,and increased reaction temperature.Moreover,quenching tests indicated that?OH was the predominant radical involved in the RhB degradation;the?OH mainly originated from SO4??and,hence,PMS.Mn3O4/ZIF‐8also displayed good reusability for RhB degradation in the presence of PMS over five runs,with a RhB degradation efficiency of more than96%and Mn leaching of less than5%for each run.Based on these findings,a RhB degradation mechanism was proposed.
基金financially supported by the National Natural Science Foundation of China(Nos.52070046,52122009,51808140and 51838005)the Introduced of Innovative R&D Team Project under the“Pearl River Talent Recruitment Program”of Guangdong Province(No.2019ZT08L387)+1 种基金the Guangdong Province Universities and Colleges Pearl River Scholar Funded Scheme(Young Scholar)the support from the BL14W1beamline of Shanghai Synchrotron Radiation Facility(SSRF,China)。
文摘Peroxymonosulfate(PMS)activation in heterogeneous processes is a promising water treatment technology.Nevertheless,the high energy consumption and low efficiency during the reaction are ineluctable,due to electron cycling rate limitation.Herein,a new strategy is proposed based on a quantum dots(QDs)/PMS system.Co-ZnS QDs are synthesized by a water phase coprecipitation method.The inequivalent lattice-doping of Co for Zn leads to the generation of surface sulfur vacancies(SVs),which modulates the surface of the catalyst to form an electronic nonequilibrium surface.Astonishingly,the plasticizer micropollutants can be completely degraded within only tens of seconds in the Co-Zn S QDs/PMS system due to this type of surface modulation.The interfacial reaction mechanism is revealed that pollutants tend to be adsorbed on the cobalt metal sites as the electron donors,where the internal electrons of pollutants are captured by the metal species and transferred to the surface SVs.Meanwhile,PMS adsorbed on the SVs is reduced to radicals by capturing electrons,achieving effective electron recovery.Dissolved oxygen(DO)molecules are also easily attracted to catalyst defects and are reduced to O_(2)^(·-),further promoting the degradation of pollutants.
基金financially supported by the National Natural Science Foundation of China(Nos.52170079 and U20A20322)the Programme of Introducing Talents of Discipline to Universities,China(No.B16020)。
文摘The Z-scheme heterostructure for photocatalyst can effectively prolong the lifetime of photogenerated carriers and retain a higher conduction/valence band position,promoting the synergistic coupling of photocatalysis and peroxymonosulfate(PMS) activation.In order to fully utilize the luminous energy and realize the efficient activation of PMS,this work achieved successful construction of NiCo_(2)O_(4)/BiOCl/Bi_(24)O_(31)Br_(10) ternary Z-scheme heterojunction by simultaneously synthesizing BiOCl and NiCo_(2)O_(4) with NiCl_(2) and CoCl_(2) as the precursors.The intercalated BiOCl could serve as a carrier migration ladder to further achieve the spatial separation of electron-hole pairs,so that the oxidation and reduction processes separately occurred in different regions.Compared with the reported catalysts,the as-prepared composites exhibited the enhanced removal efficiency for tetracycline hydrochloride(TCH) in the visible light/PMS system,with a degradation efficiency of 85.30%in 2 min,and possessed good stability.Z-scheme heterojunction was shown to be beneficial for maximizing the superiority of photo-assisted Fenton-like reaction system.The experimental and characterization results confirmed that both non-radicals(^(1)O_(2)) and radicals(SO_(5)^(·-) and SO_(4)^(·-)) were involved in the reaction process and the SO_(5)^(·-)generated by the oxidation of PMS played a crucial role in the TCH degradation.The possible reaction mechanism was finally proposed.This study provided new insight into the Z-scheme heterostructure to promote the photo-assisted Fenton-like reaction.
基金supported by the Hebei Natural Science Foundation (No.B2020208064)the Double Tops Joint Fund of the Yunnan Science and Technology Bureau and Yunnan University (No.2019FY003025)Shijiazhuang Science and Technology Department (No.191240263A)。
文摘Morphology and dispersity are key factors for activating peroxymonosulfate(PMS).In this study,we designed a recyclable open-type NiCo_(2)O_(4) hollow microsphere via a simple hydrothermal method with the assistance of an NH_(3) vesicle.The physical structure and chemical properties were characterized using techniques such as scanning electron microscope(SEM),transmission electron microscope(TEM),X-ray diffraction(XRD),N2 adsorption and X-ray photoelectron spectroscopy(XPS).The test results confirm that the inner and outer surfaces of open-type NiCo_(2)O_(4) hollow-sphere can be efficiently utilized because of the hole on the surface of the catalyst,which can minimize the diffusion resistance of the reactants and products.Under optimized conditions,the total orga nic carbon(TOC) removal efficiency of rhodamine B(RhB) can reach up to 80% in 40 min,which is almost 50% shorter than the reported values.The reactive radicals were identified and the proposed reaction mechanism was well described.Moreover,the disturbances of HCO_(3)^(-),NO_(3)^(-),Cl^(-)and H_(2) PO_(4)^(-)were further investigated.As a result,HCO_(3)-and NO_(3)-suppressed the reaction while Cl-and H_(2) PO4-had a double effect on reaction.
基金the National Natural Science Foundation of China(Nos.21975193 and 51602237)the Fundamental Research Funds for the Central Universities,China(WUT:2021Ⅲ034JC)。
文摘Formaldehyde(FA),as an important chemical raw material,has been widely used in many fields.However,the discharge of a large amount of FA-containing wastewater poses a serious threat to the environment and human health.Recently,the in-situ hydrogen energy release technology of hydrogen-containing stable liquid has been extensively explored due to its safe storage.Exploring a robust method to achieve FA removal and synchronous in-situ hydrogen release from FA containing wastewater is of great significant for environmental protection and energy crisis alleviation.Here,we have innovatively introduced peroxymonosulfate(PMS)activation technology into FA removal and hydrogen production simultaneously.The composite of nitrogen doped carbon coating Co_(9)S_(8)nanotubes(Co_(9)S_(8)@N-C)is employed as a proof of concept for FA decomposition and simultaneously hydrogen production based on PMS activation system.As expected,the Co_(9)S_(8)@N-C/PMS system presents much superior hydrogen production efficiency and satisfactory FA removal rate towards FA wastewater than those of common catalysis,photocatalysis and Fenton reaction in the basic condition in a wide range of FA concentration.The hydrogen yield reaches a value as high as 471μmol within 60 min,corresponding to a FA degradation rate of 30%with an initial FA concentration of 0.722 mol L^(-1).Characterizations and density functional theory(DFT)calculations suggest that the free radical process dominated by superoxide radical(O_(2)·^(-))and nonradical process dominated by singlet oxygen(^(1)O_(2)),which are induced by Co_(9)S_(8)@N-C/PMS system,are responsible for highly efficient hydrogen production via FA degradation.These generated O_(2)·^(-)and ^(1)O_(2)can extract·H from FA to form·OOH intermediate,which can further combine with the·H from water to produce hydrogen.This study provides an applicable technique for environmental purification and new energy development based on FA containing wastewater.
基金supported by the Guangdong Province Enterprise Science and Technology Commissioner Project (No.GDKTP2021048000)the National Natural Science Foundation of China (No.41907292)+2 种基金the Guangdong Basic and Applied Basic Research Foundation (No.2019A1515110497)the Key-Area Research and Development Program of Guangdong Province (No.2020B090923002)the Guangdong Basic and Applied Basic Research Foundation (No.2019B1515130005)。
文摘Herein,a novel MoS_(2)-stainless steel composite material was first synthetized via a 3D printing method(3DP MoS_(2)-SS)for peroxymonosulfate(PMS)activation and organics degradation.Compared with MoS_(2)-SS powder/PMS system(0.37 g/(m^(2)/min)),4.3-fold higher k_(FLO)/S_(BET)value was obtained in 3DP MoS_(2)-SS/PMS system(1.60 g/(m^(2)/min),resulting from the superior utilization of active sites.We observed that 3DP MoS_(2)-SS significantly outperformed the 3DP SS due to the enhanced electron transfer rate and increased active sites.Moreover,Mo^(4+)facilitated the Fe^(2+)/Fe^(3+)cycle,resulting in the rapid degradation of florfenicol(FLO).Quenching experiments and electron paramagnetic resonance spectra indicated that·OH,SO_(4)·^(-),O_(2)·^(-)and^(1)O_(2)were involved in the degradation of FLO.The effect of influencing factors on the degradation of FLO were evaluated,and the optimized degradation efficiency of 98.69%was achieved at 1 mM PMS and pH of 3.0.Six degradation products were detected by UPLC/MS analyses and several possible degradation pathways were proposed to be the cleavage of C-N bonds,dechlorination,hydrolysis,defluorination and hydroxylation.In addition,3DP MoS_(2)-SS/PMS system also demonstrated superior degradation performance for 2-chlorophenol,acetaminophen,ibuprofen and carbamazepine.This study provided deep insights into the MoS_(2)-SS catalyst prepared by 3DP technology for PMS activation and FLO-polluted water treatment.
基金financially supported by the National Key Research and Development Program of China(No.2021YFA1202500)National Natural Science Foundation of China(NSFC)(Nos.52270053,52200083and 52200084)+3 种基金Beijing Nova Program(No.20220484215)China Postdoctoral Science Foundation(No.2021M700213)the Key Special Projects for Science and Technology of Inner Mongolia(No.2021EEDSCXSFQZD001)Emerging Engineering Interdisciplinary-Young Scholars Project,Peking University,the Fundamental Research Funds for the Central Universities.
文摘Emerging organic pollutants(EoPs)in water are of great concern due to their high environmental risk,so urgent technologies are needed for effective removal of those pollutants.Herein,a heterogeneous advanced oxidation process(AoP)of peroxymonosulfate(PMS)activation by functional material was developed for degradation of a typical antibiotic,gatifloxacin(GAT).The reactive species including sulfate radical(SO^(4)^(·-))and singlet oxygen(^(1)O_(2))in this AOP were regulated by interlayered ions(Na^(+)/H^(+))of titanate nanotubes that supported on Co(OH)_(2)hollow microsphere.Both the Na-type(NaTi-CoHS)and H-type(HTi-CoHS)materials achieved efficient PMS activation for GAT degradation,and HTi-CoHS even exhibited a relatively high degradation efficiency of 96.6%within 5 min.Co(OH)_(2)was considered the key component for generation of SO_(4)^(·-)after PMS activation,while hydrogen titanate nanotubes(H-TNTs)promoted the transformation of peroxysulfate radical(SO_(5)^(·-))to ^(1)O_(2) by hydrogen bond interaction.Therefore,when the interlayer ion of TNTs transformed from Na^(+) to H^(+),more ^(1)O_(2) was produced for organic pollutant degradation.H-TNTs with lower symmetry preferred to adsorb PMS molecules to achieve interlayer electron transport through hydrogen bonding,rather than electrostatic interaction of Na^(+) for Na-TNTs.In addition,the degradation pathway of GAT mainly proceeded by the cleavage of C-N bond at the 8 N site of the piperazine ring,which was confirmed by condensed Fukui index and mass spectrographic analysis.This work gives new sights into the regulation of reactive species in AoPs by the composition of material and promotes the understanding of pollutant degradation mechanisms in water treatment process.
基金supported by“Pioneer and Leading Goose+X”S&T Program of Zhejiang,China(No.2025C02230)the National Natural Science Foundation of China(Nos.52400110 and 52070111).
文摘Designing efficient and sustainable catalyst for peroxymonosulfate(PMS)activation and refractory 2,4,6-trichlorophenol(2,4,6-TCP)removal is an imminent task.This study synthesized a novelγ-MnO_(2)/NF catalyst,which has advantages in saving manganese dioxide demand and reducing manganese leaching.Theγ-MnO_(2)/NF+PMS oxidation system achieved a 0.219 min^(−1)2,4,6-TCP apparent rate constant at 20℃,and removed>90%of 2,4,6-TCP at the 5th cycle.Both free radical identification and DFT calculations revealed that•OH and SO_(4)^(•−),rather than 1O_(2),were the dominant reactive species duringγ-MnO_(2)/NF+PMS oxidation.The results indicated that the inner-sphere complexation betweenγ-MnO_(2)/NF and PMS facilitated the formation of•OH and SO_(4)^(•−).To fill the research gap in the molecular-level dissimilarities between•OH and SO_(4)^(•−)in 2,4,6-TCP degradation mechanism,experimental testing and quantum chemical analysis methods were used.The DFT calculation found that the HAA reaction at H13 site and RAF reaction at C1 site were more favorable for both•OH and SO_(4)^(•−).For most reaction sites,SO_(4)^(•−)demonstrates greater energy barriers and substrate selectivity than•OH,attributed to steric constraints.The•OH acted as the predominant oxidative agents responsible for 2,4,6-TCP decomposition.Combining DFT calculation and intermediate identification,potential degradation routes of 2,4,6-TCP were proposed.The ecotoxicity assays verified a substantial reduction in acute toxicity of the treated 2,4,6-TCP solution.This study opens up new avenues for activating PMS withγ-MnO_(2)/NF,and helps to select preferred radical oxidation processes for optimal 2,4,6-TCP removal in practical engineering.
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.
基金This work was financially supported by the talent starting-up project of research development fund of Zhejiang Agriculture and Forestry University(No.2034020103)the Overseas Expertise Introduction Project for Discipline Innovation(No.111 Project D18008).
文摘Biochar-based transition metal catalysts have been identified as excellent peroxymonosulfate(PMS)activators for producing radicals used to degrade organic pollutants.However,the radical-dominated pathways for PMS activation severely limit their practical applications in the degradation of organic pollutants from wastewater due to side reactions between radicals and the coexisting anions.Herein,bimetallic Fe/Mn-loaded hydroxyl-rich biochar(FeMn-OH-BC)is synthesized to activate PMS through nonradical-dominated pathways.The as-prepared FeMn-OH-BC exhibits excellent catalytic activity for degrading tetracycline at broad pH conditions ranging from 5 to 9,and about 85.0%of tetracycline is removed in 40 min.Experiments on studying the influences of various anions(HCO_(3)^(−),NO_(3)^(−),and H_(2)PO_(4)^(−))show that the inhibiting effect is negligible,suggesting that the FeMn-OHBC based PMS activation is dominated by nonradical pathways.Electron paramagnetic resonance measurements and quenching tests provide direct evidence to confirm that 1O2 is the major reactive oxygen species generated from FeMn-OH-BC based PMS activation.Theoretical calculations further reveal that the FeMn-OH sites in FeMn-OH-BC are dominant active sites for PMS activation,which have higher adsorption energy and stronger oxidative activity towards PMS than OH-BC sites.This work provides a new route for driving PMS activation by biochar-based transition metal catalysts through nonradical pathways.
基金supported by the National Natural Science Foundation of China(NSFC)(No.22308336).
文摘Heterogeneous advanced oxidation processes(AOPs)based on non-radical reactive species are considered as a powerful technology for wastewater purification due to their long half-lives and high adaptation in a wide pH range.Herein,we fabricate surface Co defect-rich spinel ZnCo_(2)O_(4)porous nanosheets,which can generate≡CoIV=O and ^(1)O_(2) over a wide pH range of 3.81-10.96 by the formation of amphoteric≡Zn(OH)2 in peroxymonosulfate(PMS)activation process.Density functional theory(DFT)calculations show Co defect-rich ZnCo_(2)O_(4)possesses much stronger adsorption ability and more electron transfer to PMS.Moreover,the adsorption mode changes from terminal oxygen Co-O-Co to Co-O,accelerating the polarization of adjacent oxygen,which is beneficial to the generation of≡CoIV=O and Generating ^(1)O_(2) .Co defect-rich ZnCo_(2)O_(4)porous nanosheets exhibit highly active PMS activation activity and stability in p-nitrophenol(PNP)degradation,whose toxicity of degradation intermediates is significant reduction.The Co defect-rich ZnCo_(2)O_(4)nanosheet catalyst sponge/PMS system achieved stable and efficient removal of PNP with a removal efficiency higher than 93%over 10 h.This work highlights the development of functional catalyst and provides an atomic-level understanding into non-radical PMS activation process in wastewater treatment.
基金financially supported by the National Natural Science Foundation of China(No.22006052)the Science and Technology Program of Guangzhou,China(No.202201020545)。
文摘The adsorption of peroxymonosulfate(PMS)is crucial for PMS activation in the heterogeneous advanced oxidation processes.However,the investigation of PMS adsorption on the piezocatalysts still remains insufficient.In this work,bismuth oxychloride(BiO Cl)nanosheets were prepared as the piezocatalysts for PMS activation under ultrasonic vibration to remove carbamazepine(CBZ)in aqueous solutions.Up to92.5%of CBZ was degraded for 40 min in Bi OCl piezo-activated PMS system with the reaction rate constant of 0.0741 min-1,being 1.63 times that of the sum of BiOCl piezocatalysis,BiOCl-activated PMS,and vibration-activated PMS.PMS adsorption on the surface of BiOCl was specifically studied by comparing the microscopic structure change of the fresh and used Bi OCl.The results suggested that the piezoelectric field of Bi OCl was able to promote the tight adsorption of PMS on the surface,thus facilitating the fast activation of PMS through electrons transfer to produce reactive species(HO·,SO_(4)·-,O_(2)·-,1O_(2)).This work presents an in-depth understanding for the role of piezoelectric effect on the adsorption and activation of PMS.
基金supported by the National Natural Science Foundation of China(NSFC)(No.21978137).
文摘In this study,supported Pd catalysts were prepared and used as heterogeneous catalysts for the activation of peroxymonosulfate(PMS)which successfully degrade bisphenol F(BPF).Among the supported catalysts(i.e.,Pd/SiO_(2),Pd/CeO_(2),Pd/TiO_(2)and Pd/Al2O3),Pd/TiO_(2)exhibited the highest catalytic activity due to the high isoelectric point and high Pd0 content.Pd/TiO_(2)prepared by the deposition method leads to high Pd dispersion,which are the key factors for efficient BPF degradation.The influencing factors were investigated during the reaction process and two possible degradation pathways were proposed.Density functional theory(DFT)calculations demonstrate that stronger BPF adsorption and BPF degradation with lower reaction barrier occurs on smaller Pd particles.The catalytic activities are strongly dependent on the structural features of the catalysts.Both experiments and theoretical calculations prove that the reaction is actuated by electron transfer rather than radicals.
基金supported by the National Natural Science Foundation of China(Nos.52100087,52170079,U20A20322)Science and Technology Development Program of Jilin Province,China(Nos.20220508100RC,20230402035GH).
文摘Rational tuning of crystallographic surface and metal doping were effective to enhance the catalytic performance of metal organic frameworks,but limited work has been explored for achieving modulation of crystal facets and metal doping in a single system.MIL-68(In)was promising for photocatalytic applications due to its low toxicity and excellent photoresponsivity.However,its catalytic activity was constrained by severe carrier recombination and a lack of active sites.Herein,increased(001)facet ratio and active sites exposure were simultaneously realized by cobalt doping in MIL-68(In)through a one-pot solvothermal strategy.Optimized MIL-68(In/Co)-2.5 exhibited remarkable catalytic performance in comparison with pristine MIL-68(In)and other MIL-68(In/Co).The reaction kinetic constant and degradation efficiency of MIL-68(In/Co)were approximately twice and 17%higher than the pristine MIL-68(In)in 36 min reaction,respectively.Density functional theory calculations revealed that Co dopant could modulate the orientation of MIL-68(In)facets,facilitate the exchange of electrons and reduce the adsorption energy of peroxymonosulfate(PMS).This work provides a novel pathway for improvement of In-based MOFs in PMS/vis system,it also promotes the profound comprehension of the correlation between crystal facet regulation and catalytic activation in the PMS/vis system.
基金financially supported by the National Natural Science Foundation of China(52063024 and 51868052)the Natural Science Foundation of Jiangxi Province(20192ACBL21046)the National Science Foundation of State Key Laboratory of Structural Chemistry(20160013).
文摘The degradation of organic pollutants in water is a critical environmental challenge.The iron-doped MoS_(2) catalysts have demonstrated potential in activating peroxymonosulfate(PMS)for environmental remediation,but they face challenges such as poor conductivity,limited electron transfer efficiency,and a scarcity of active sites.To address these issues,we successfully synthesized a nano-flowers FeS/MoS_(2) composite derived from polyoxometalates(NH_(4))_(3)[Fe(III)Mo_(6)O_(24)H_(6)]⋅6H_(2)O(denoted as FeMo6)as the bimetallic precursors.This synthesis strategy enhances the interaction between FeS and MoS_(2),thereby facilitating electron transfer.Notably,the introduction of sulfur vacancies in FeS/MoS_(2) exposes additional Mo4t active sites,promoting the redox cycle of Fe^(2+)/Fe^(3+) and accelerating the regeneration of Fe^(2+),which in turn enhances PMS activation.Therefore,a catalytic oxidation system of FeS/MoS_(2)/PMS is presented that primarily relies on SO_(4)^(⋅-)and⋅OH,with ^(1)O_(2) as a supplementary oxidant.This system exhibits exceptional degradation efficiency for p-chlorophenol(4-CP),achieving 100% degradation within 10 min over a wide pH range of 2.4–8.4.The robust performance and wide applicability of FeS/MoS_(2) catalyst make it a promising candidate in advanced oxidation processes(AOPs)for environmental remediation.
基金supported by the National Key Research and Development Program of China (Project No.2018YFB1502903)。
文摘Metal-based perovskite oxides have contributed significantly to the advanced oxidation processes(AOPs)due to their diverse active sites and excellent compositional/structural flexibility.In this study,we specially designed a perovskite oxide with abundant oxygen vacancies,SrCo_(0.8)Fe_(0.2)O_(3)(SCF),and firstly applied it as a catalyst in peroxymonosulfate(PMS) activation towards organic pollutants degradation.The result revealed that the prepared SCF catalyst exhibited excellent performance on organic compounds degradation.Besides,SCF showed much better activity than La_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3)(LSCF) in terms of reaction rate and stability for the degradation of the organic compounds.Based on the analysis of scanning electron microscope,transmission electron microscope,X-ray diffraction,N_(2) adsorption-desorption,X-ray photoelectron spectroscopy and electron paramagnetic resonance,it was confirmed that the perovskite catalysts with high content of Sr doping at A-site could effectively create a defect-rich surface and optimize its physicochemical properties,which was responsible for the excellent heterogeneous catalytic activity of SCF.SCF can generate three highly active species:~1 O_(2),SO_(4)^(-)· and ·OH in PMS activation,revealing the degradation process of organic compounds was a coupled multiple active species in both radical and nonradical pathway.Moreover,it was mainly in a radical pathway in the degradation through PMS activation on SCF and SO_(4)^(-)· radicals produced were the dominant species in SCF/PMS system.This study demonstrated that perovskite-type catalysts could enrich OVs efficiently by doping strategy and regulate the PMS activation towards sulfate radical-based AOPs.
