Metal-based catalysts with different site sizes(e.g.,metal nanoparticles(NPs)and single atom catalysts(SACs))demonstrated outstanding catalytic activities in versatile Fenton-like reactions.However,the surface/structu...Metal-based catalysts with different site sizes(e.g.,metal nanoparticles(NPs)and single atom catalysts(SACs))demonstrated outstanding catalytic activities in versatile Fenton-like reactions.However,the surface/structural instability is a critical issue,which will result in rapid passivation in Fenton-like reaction and fail in long-term operation.The catalytic stability of the catalysts with different metal sizes considering versatile peroxides(H_(2)O_(2),peroxymonosulfate(PMS),and peroxodisulfate(PDS))should be analyzed.In addition,strategies for catalyst regeneration and recyclability improvement are also important to realize the metal-based catalysts for practical applications.In this review,catalytic stability of catalysts with different metal sizes in the backgrounds of versatile peroxides and water matrixes in Fenton-like reactions were first evaluated.Regeneration of metal catalytic sites with different methods were also reviewed.Finally,major challenges and development of methods concerning the stability and regeneration of metal catalytic sites with different sizes were discussed to understand the future researches of metal catalytic sites in Fenton-like reactions.展开更多
The leaching and non-recoverability of mental ions have always limited the practical application of Fenton-like processes. For the first time, we synthesized molybdenum phosphide (MoP) with dual active sites for the d...The leaching and non-recoverability of mental ions have always limited the practical application of Fenton-like processes. For the first time, we synthesized molybdenum phosphide (MoP) with dual active sites for the degradation of diclofenac (DCF) in the Fenton-like process. The DCF degradation rate constant (k) of MoP + H_(2)O_(2) process was calculated to be 0.13 min^(-1) within 40 min, indicating a highly efficient catalytic ability of MoP. In addition, this catalyst exhibits a stable structure and good activity, which could apply in a broad pH range, different ions solution and real wastewater condition. Accordingly, this efficient catalytic capability may be attributed to the presence of the metal sites Mo^(δ+) and the electron-rich sites P^(δ-) in MoP, which could induce the generation of hydroxyl radical (^(·)OH) and superoxide radical (^(·)O_(2)^(-)) through electron transfer, resulting in the effective removal of DCF. This study provides an idea for the optimization of Fenton-like technologies and environmental remediation.展开更多
Regulating the photo-response region of iron metal-organic frameworks(Fe-MOFs)is a viable strategy for enhancing their practical application in the visible-light driven photo-Fenton-like process.This study developed a...Regulating the photo-response region of iron metal-organic frameworks(Fe-MOFs)is a viable strategy for enhancing their practical application in the visible-light driven photo-Fenton-like process.This study developed a novel pyrazine-based Fe-MOFs(MIL-101(Fe)-Pz)by substituting the 1,4-dicarboxybenzene acid ligands in typical MIL-101(Fe)with 2,5-pyrazinedicarboxylic acid(PzDC),in which sodium acetate was used as coordinative modulator to control the crystal size(2–3μm).The incorporation of Fe-pyridine N coordination structures originated from PzDC ligands gave MIL-101(Fe)-Pz narrowed band gap(1.45 eV)than MIL-101(Fe)(2.54 eV)resulting in improved visible-light adsorption capacity(λ>420 nm),and also increased the proportion of Fe(Ⅱ)in the Fe-clusters.Thus MIL-101(Fe)-Pz exhibited a synergistic enhanced photo-Fenton-like catalytic performance under visible-light irradiation.The MIL-101(Fe)-Pz/H_(2)O_(2)/Vis system could degrade 99%of sulfamethoxazolewithin 30min,whichwas 10-fold faster than that of the pristine MIL-101(Fe),it also effectively removed other organic micropollutants with high durability and stability.Mechanistic analysis revealed that the PzDC ligands substitution decreased the band gap of MIL-101(Fe),giving MIL-101(Fe)-Pz appropriate band structure(-0.40∼1.05 V vs.NHE)which can cover several light-driven process for the generation of reactive oxygen species,including Fe(Ⅲ)reduction and H_(2)O_(2) activation for accelerating•OH generation,as well as oxygen reduction reaction for generating H_(2)O_(2),O_(2)^(•−) and ^(1)O_(2).This study highlights the role of pyridine-N containing ligands in regulating the band structure of Fe-MOFs,providing valuable guidance for the design of Fe-MOFs photocatalysts.展开更多
Coupling adsorption and in-situ Fenton-like oxidation process was developed for Methylene blue(MB) using refined iron-containing lowgrade attapulgite(ATP) clay, and the removal mechanism was investigated. The MB was i...Coupling adsorption and in-situ Fenton-like oxidation process was developed for Methylene blue(MB) using refined iron-containing lowgrade attapulgite(ATP) clay, and the removal mechanism was investigated. The MB was initially adsorbed on the porous ATPs, and then the enriched MB was removed by the H2O2-assisted Fenton-like oxidation with the iron-containing ATP catalyst. Under optimal conditions, the ATP powder exhibits the maximum removal efficiency of 100% with negligible iron leaching(1.5 mg L^(-1)) and no sludge formation. Furthermore,polysulfone/ATP(PSF/ATP) pellets were fabricated through a water-induced phase separation process to construct a fixed-bed reactor(FBR) for continuous contaminant removal. For the first cycle, the maximum adsorption capacity was 15.5 L with an outlet MB concentration of1.973 mg L-1(< 2 mg L^(-1), GB4287-2012) using the PSF/ATP pellets containing 50.0 g of ATP powders, and the maximum Fenton-like oxidation capacity was 35.5 L with the outlet concentration of 0.831 mg L^(-1). After five cycles, the total treated volume of the MB solution was ca. 255 L, and the efficiency remained above 99%. After 10 h of continuous treatment towards practical resin industrial wastewater, the chemical oxygen demand(COD) removal efficiency was still measured at 83.05%, costing 0.398 $ m^(-3). These results demonstrate the practical applicability of iron-containing low-grade ATP clay for textile water treatment.展开更多
In this study,different types of small molecular carbon sources such as melamine,dicyandiamine,pyrocatechol,and o-phenylenediamine were used to regulate the surface structures of iron/nitrogen/carbonbased composites(F...In this study,different types of small molecular carbon sources such as melamine,dicyandiamine,pyrocatechol,and o-phenylenediamine were used to regulate the surface structures of iron/nitrogen/carbonbased composites(Fe-N/C),which were used to activate peroxymonosulfate(PMS).The relationship between different small molecular carbon sources and the electronic structure was investigated.The characteristics of metal-carrier interaction in the Fe-N/C were clarified.As a result,there were significant differences in the degradation efficiency of catalysts prepared with different small molecular carbon sources,which was related to the types of active sites.Density functional theory(DFT)and experiments results showed that the catalyst rich in C-O-C and FeN_(x)exhibited better catalytic activity,which may be attributed to the higher adsorption energy for PMS.The main active species for catalytic degradation of ofloxacin were identified as sulfate radical(SO_(4)^(·-))and hydroxyl radical(^(·)OH)by electron paramagnetic resonance(EPR)spectra.The introduction of different small molecular carbon sources can significantly affect the distribution and electronic structure of active sites on the catalyst surface,thereby regulating the generation and migration of radicals.展开更多
Most carbon-based catalysts utilized in Fenton-like systems face challenges such as structural instability,susceptibility to deactivation,and a tendency to disperse during operation.Wood-derived catalysts have garnere...Most carbon-based catalysts utilized in Fenton-like systems face challenges such as structural instability,susceptibility to deactivation,and a tendency to disperse during operation.Wood-derived catalysts have garnered considerable attention due to their well-defined structures,extensive pipeline networks,superior mechanical strength,and adaptability for device customization.However,there remains a paucity of research that systematically summarizes Fenton-like systems based on wood-derived catalysts.In this review,we first summarize the structural designs of wood-derived catalysts based on nano-metal sites and single-atom sites,while also outlining their advantages and limitations applied in Fenton-like systems.Furthermore,we evaluate catalytic modules of wood-derived catalysts for scale-up and continuous Fenton-like systems.Additionally,wood-inspired catalytic materials utilizing commercial textures and their applications in Fenton-like processes are also discussed.This paper aims to comprehensively explore the fundamental mechanisms(e.g.,characteristics of catalytic sites,catalytic performance,and mechanisms)of wood-based catalysts in Fenton-like chemistry,as well as their equipment designs and application scenarios,as well as providing the insights into future developments.展开更多
Although the powder Fenton-like catalysts have exhibited high catalytic performances towards pollutant degradation,they cannot be directly used for Fenton-like industrialization considering the problems of loss and re...Although the powder Fenton-like catalysts have exhibited high catalytic performances towards pollutant degradation,they cannot be directly used for Fenton-like industrialization considering the problems of loss and recovery.Therefore,the membrane fixation of catalyst is an important step to realize the actual application of Fenton-like catalysts.In this work,an efficient catalyst was developed with Co-N_(x)configuration facilely reconstructed on the surface of Co_(3)O_(4)(Co-N_(x)/Co_(3)O_(4)),which exhibited superior catalytic activity.We further fixed the highly efficient Co-N_(x)/Co_(3)O_(4)onto three kinds of organic membranes and one kind of inorganic ceramic membrane installing with the residual PMS treatment device to investigate its catalytic stability and sustainability.Results indicated that the inorganic ceramic membrane(CM)can achieve high water flux of 710 L m-2h-1,and the similar water flux can be achieved by Co-N_(x)/Co_(3)O_(4)/CM even without the pressure extraction.We also employed the Co-N_(x)/Co_(3)O_(4)/CM system to the wastewater secondary effluent,and the pollutant in complicated secondary effluent could be highly removed by the Co-N_(x)/Co_(3)O_(4)/CM system.This paper provides a new point of view for the application of metal-based catalysts with M-N_(x)coordination in catalytic reaction device.展开更多
The Fenton-like reaction between Cu^(2+)and H_(2)O_(2)was employed in chemical mechanical polishing to achieve efficient and high-quality processing of tungsten.The microstructure evolution and material removal rate o...The Fenton-like reaction between Cu^(2+)and H_(2)O_(2)was employed in chemical mechanical polishing to achieve efficient and high-quality processing of tungsten.The microstructure evolution and material removal rate of tungsten during polishing process were investigated via scanning electron microscopy,X-ray photoelectron spectroscopy,ultraviolet−visible spectrophotometry,and electrochemical experiments.The passivation behavior and material removal mechanism were discussed.Results show that the use of mixed H_(2)O_(2)+Cu(NO_(3))_(2)oxidant can achieve higher polishing efficiency and surface quality compared with the single oxidant Cu(NO_(3))_(2)or H_(2)O_(2).The increase in material removal rate is attributed to the rapid oxidation of W into WO_(3)via the chemical reaction between the substrate and hydroxyl radicals produced by the Fenton-like reaction.In addition,material removal rate and static etch rate exhibit significantly different dependencies on the concentration of Cu(NO_(3))_(2),while the superior oxidant for achieving the balance between polishing efficiency and surface quality is 0.5 wt.%H_(2)O_(2)+1.0 wt.%Cu(NO_(3))_(2).展开更多
Carbon dot(CD)is an edge-bound,nanometer-sized carbon material possessing unique optical and electronic properties,making it promising metal-free,environmentally benign.In this study,we identified a highly hydrophilic...Carbon dot(CD)is an edge-bound,nanometer-sized carbon material possessing unique optical and electronic properties,making it promising metal-free,environmentally benign.In this study,we identified a highly hydrophilic CD complexed with Fe(Ⅲ)via carboxyl groups to form CD-COOFeⅢ,which exhibited remarkably enhanced Fenton-like reaction performance boosted by visible light irradiation.CD-COOFeⅢenabled high activity in the visible region beyondλ>420 nm,and maintained stable oxidation efficiency in the presence of H_(2)O_(2)over at least ten cycles.The capacity of electrons transferred from photo-excited CD to reduce Fe(Ⅲ)was calculated to be 1.1 mmol/g of CD.Furthermore,the quantum yield(QY)of solarto-Fe(Ⅱ)conversion reached an impressive 87.7%.These findings not only suggest a viable strategy for efficient conversion of solar-to-chemical using a CD-COOFeⅢcomplex in visible light boosted Fenton-like oxidation reaction,but also provide insight for understanding the effect of nanosized artificial and/or natural carbon materials in iron recycling in a natural surface environment.展开更多
Asymmetric single-atom catalysts(ASACs)have attracted much attention owing to their excellent catalytic properties.However,the relationship between asymmetric coordination and the spin states of metal sites remains un...Asymmetric single-atom catalysts(ASACs)have attracted much attention owing to their excellent catalytic properties.However,the relationship between asymmetric coordination and the spin states of metal sites remains unclear.Additionally,the modulation of reactive oxygen species in Fenton-like reactions remains challenging.Herein,a novel strategy is reported for the rational design of highly loaded Co ASACs(CoN_(1)C_(2)/C_(2)N)immobilized on three-dimensional flower-like C_(2)N using an in situ-generated carbon defect method.In particular,the asymmetrically tricoordinated CoN_(1)C_(2)/C_(2)N exhibited excellent catalytic activity for sulfachloropyridazine degradation,with a turnover frequency of 36.8 min^(–1).Experimental results and theoretical calculations revealed that the electron spin state of the Co-active sites was transferred from the low-spin configuration(t_(2g)^(6)e_(g)^(1))to the high-spin configuration(t_(2g)^(5)e_(g)^(2))owing to asymmetric coordination.The high-spin Co 3d orbital in CoN_(1)C_(2)/C_(2)N possessed more unpaired electrons and therefore,had a strong ability to gain electrons from the O 2p orbitals of HSO_(5)^(–),boosting d-p orbital hybridization.More importantly,the spin-electron filling in theσ^(*)orbital of high-spin Co 3d−O 2p accelerated the desorption of^(*)SO_(5)•^(−),which acted as a rate-limiting step in the reaction,thus facilitating more^(1)O_(2)generation.This study provides an innovative synthetic route for practical ASACs and clarifies the critical relationship between structure and spin state,paving the way for advancements in environmental remediation and energy conversion applications.展开更多
Assembling MnO_(2)nanowires into macroscopic membrane is a promising engineered technology for catalyst separation and enhancement of Fenton-like reaction activity,yet its development is limited by the deficiencies in...Assembling MnO_(2)nanowires into macroscopic membrane is a promising engineered technology for catalyst separation and enhancement of Fenton-like reaction activity,yet its development is limited by the deficiencies in preparation and property modulation of the MnO_(2)nanowires.In this work,we developed a facile method using C_(2)H_5OH and CH_(3)COOK as reductive and vital control reagents to react with KMnO_(4)by hydrothermal reaction at 140℃for 12 h,to prepare the ultralongα-MnO_(2)nanowires up to tens of micrometers with high purity and aspect ratio.Such strategy not only had the advantages of being mild,easily controlled and environmental pollution-free,but also endowedα-MnO_(2)nanowires with excellent ability as a Fenton catalyst when assembled into free-standing membrane for degrading phenolic compounds(k_(obs)=0.0738~0.1695 min^(-1))in a continuous flow reaction.The reactive oxygen species(i.e.,~·OH)from Fenton-like reaction were enriched within thisα-MnO_(2)nanowire membrane via nanoconfinement effect,which further enhanced the mass transportation of~·OH available for phenolic contaminants.MnO_(2)nanowire membrane using our method possessed the high practical potential for water purify due to its easy-preparation and enhanced catalytic performances.展开更多
The use of Fenton's reagent (Fe^2+/H2O2) and Fenton-like reagents containing transition metals of Cu(Ⅱ), Zn(Ⅱ), Co(Ⅱ), and Mn(Ⅱ) for an alum sludge conditioning to improve its dewaterability was invest...The use of Fenton's reagent (Fe^2+/H2O2) and Fenton-like reagents containing transition metals of Cu(Ⅱ), Zn(Ⅱ), Co(Ⅱ), and Mn(Ⅱ) for an alum sludge conditioning to improve its dewaterability was investigated. The results obtained were compared with those obtained from conditioning the same alum sludge using cationic and anionic polymers. Experimental results show that Fenton's reagent was the best among the Fenton and Fenton-like reagents for the alum sludge conditioning. A considerable effectiveness of capillary suction time (CST) reduction efficiency of 47% can be achieved under test conditions of Fe^2+/H2O2 = 20/125 mg/g DS (dry solid) and pH 6.0. The observation of floc-like particles after Fenton's reagent conditioning of alum sludge suggested that the mechanism of Fenton's reagent conditioning was different from that of polymer conditioning. In spite of the lower efficiency in the CST reduction of Fenton's reagent in alum sludge conditioning compared to that of polymer conditioning, Fenton's reagent offers a more environmentally safe option. Tiffs study provided an example of proactive treatment engineering, which is aimed at seeking a safe alternative to the use of polymers in sludge conditioning towards achieving a more sustainable sludge management strategy.展开更多
A novel composite electrode was constructed by pressing together Co3O4 and graphite and it was used as the cathode in an electro-Fenton-like (EFL) system. The poor electron transport characteristic of Co3O4 was overco...A novel composite electrode was constructed by pressing together Co3O4 and graphite and it was used as the cathode in an electro-Fenton-like (EFL) system. The poor electron transport characteristic of Co3O4 was overcome by incorporating graphite. In situ electro-catalytic generation of hydroxyl radicals (·OH) occurred at high current efficiencies from pH 2-10, extending the traditional Fenton reaction pH range. Cyclic voltammetry and AC impedance spectrometry were used to characterize the composite electrode. The ability of the EFL system to degrade organic compounds was investigated using sulforhodamine B (SRB) and 2,4-dichlorophenol (2,4-DCP) as probes. Decoloration of SRB (1.0×10-5 mol/L) was complete (100%) in 150 min and SRB was effectively degraded from pH 2-10. The decomposition of SRB was studied using Fourier transform infrared spectroscopy (FT-IR) and total organic carbon (TOC) analysis and results indicated that the final degradation products were carbon dioxide, carboxylic acids and amines. The EFL system also decomposed 2,4-DCP and the degradation was 98.6% in 240 min. Electro-catalytic degradation of SRB occurs by a ·OH mechanism. After 5 times reused, the degradation rate of SRB did not significantly slow down. The electrode shows excellent potential for use in advanced oxidation processes (AOPs) used to treat persistent organic pollutants (POPs) in wastewater.展开更多
A novel coupled system using Co–Ti O2 was successfully designed which combined two different heterogeneous advanced oxidation processes, sulfate radical based Fenton-like reaction(SR-Fenton) and visible light photo...A novel coupled system using Co–Ti O2 was successfully designed which combined two different heterogeneous advanced oxidation processes, sulfate radical based Fenton-like reaction(SR-Fenton) and visible light photocatalysis(Vis-Photo), for degradation of organic contaminants. The synergistic effect of SR-Fenton and Vis-Photo was observed through comparative tests of 50 mg/L Rhodamine B(Rh B) degradation and TOC removal. The Rhodamine B degradation rate and TOC removal were 100% and 68.1% using the SR-Fenton/Vis-Photo combined process under ambient conditions, respectively. Moreover, based on XRD, XPS and UV-DRS characterization, it can be deduced that tricobalt tetroxide located on the surface of the catalyst is the SR-Fenton active site, and cobalt ion implanted in the Ti O2 lattice is the reason for the visible light photocatalytic activity of Co–Ti O2. Finally, the effects of the calcination temperature and cobalt concentration on the synergistic performance were also investigated and a possible mechanism for the synergistic system was proposed. This coupled system exhibited excellent catalytic stability and reusability,and almost no dissolution of Co2+was found.展开更多
Phosphate residue is regarded as a hazardous waste, which could potentially create significant environmental and health problems if it is not properly treated and disposed of. In this study, nitrogen-doped carbon nano...Phosphate residue is regarded as a hazardous waste, which could potentially create significant environmental and health problems if it is not properly treated and disposed of. In this study, nitrogen-doped carbon nanotubes-FePO_4(NCNTs-FePO_4) composite was successfully synthesized from phosphate residue, and its application as an effective catalyst was explored. Firstly, an effective method was developed to recover FePO_4 from phosphate residue, achieving an impressive FePO_4 mass recovery rate of 98.14%. Then, the NCNTsFePO_4 catalyst was synthesized from the recovered FePO_4 by two main reactions, including surface modification and chemical vapor deposition. Finally, the synthesized NCNTs-FePO_4 was applied to photo-degrade 15 mg/L Rhodamine B(RhB) in a Fenton-like system. The results showed that 98.9% of RhB could be degraded in 60 min, closely following the pseudofirst-order kinetics model. It was found that even after six consecutive cycles, NCNTs-FePO_4 still retained a high catalytic capacity(>50%). Moreover, ·OH radicals participating in the RhB degradation process were evidenced using quenching experiments and electron paramagnetic resonance analysis, and a rational mechanism was proposed. It was demonstrated that the materials synthesized from hazardous phosphate residue can be used as an effective catalyst for dye removal.展开更多
Photocatalysis and Fenton process are two primary and promising advanced oxidation processes to degrade organic pollutants.However,the practical applications of single photocatalysis and Fenton process are still limit...Photocatalysis and Fenton process are two primary and promising advanced oxidation processes to degrade organic pollutants.However,the practical applications of single photocatalysis and Fenton process are still limited.Introducing one of them into another to form a combined photocatalytic Fentonlike system has shown great potential but still faces challenges in designing a well-tailored catalyst.Herein,a confined photocatalytic Fenton-like micro-reactor catalyst with a movable Fe_(3) O_(4) core and a mesoporous TiO_(2) shell has been constructed via a successive Stober coating strategy,followed by an ultrasound assisted etching method.The resulting micro-reactor possesses well-defined yolk-shell structures with unifo rm mesopores(~4 nm),a large Brunauer-Emmett-Teller(BET) surface area(~166.7 m^(2)/g),a high pore volume(~0.56 cm^(3)/g) and a strong magnetization(~51 emu/g),as well as tunable reactor sizes(20-90 nm).When evaluated for degrading bisphenol A under solar light in the presence of peroxymo no sulfate,the micro-reactor exhibits a superior catalytic degradation perfo rmance with a high magnetic separation efficiency and an excellent recycle ability.The outstanding performance can be attributed to its unique textual structure,which leads to a great syne rgistic effect from the photocatalytic and Fenton-like process.This study gives an important insight into the design and synthesis of an advanced micro-reactor for a combined advanced oxidation processes(AOPs).展开更多
A versatile wet impregnation method was employed to conveniently and controllably deposit Fe_2O_3 nanoparticles on zeolites including commercial Y, mordenite and ZSM-5 with the similar framework Si/Al ratios and cryst...A versatile wet impregnation method was employed to conveniently and controllably deposit Fe_2O_3 nanoparticles on zeolites including commercial Y, mordenite and ZSM-5 with the similar framework Si/Al ratios and crystal sizes, respectively. The ultrafine Fe_2O_3 nanoparticles in size of 5 nm can be highly dispersed on zeolite Y matrix due to its much better wettability than ZSM-5 and mordenite. By using the obtained Fe_2O_3/zeolite composite as the heterogeneous Fenton-like catalysts, the degradation of phenol as a model reaction was systematically investigated, including the zeolite supports, particle size and dispersion of Fe_2O_3, and reaction conditions of H_2O_2 concentration, temperature, and pH value. The catalyst based on zeolite Y with Fe loading of 9% exhibited the best phenol degradation efficiency (> 90%)in neutral pH within 2 h. Its high catalytic activity in Fenton reaction can be attributed to the bifunctional properties of strong surface BrФnsted acidity and high reactivity of octahedral Fe^(3+) in the highlydispersed ultrafine Fe_2O_3 nanoparticles in size of 5 nm, which were the primary active centers to quickly decompose H_2O_2 into hydroxyl radicals. Since phenol degradation can be performed under mild conditions of ambient temperature (283-323 K) and a wide pH range (4.0-7.0), the catalysts can be easily recovered for recyclable use with stable degradation activity, which own the immense potential in deep treatment of organic pollutants in industrial wastewater.展开更多
基金supported by National Natural Science Foundation of China (No. 52170086)
文摘Metal-based catalysts with different site sizes(e.g.,metal nanoparticles(NPs)and single atom catalysts(SACs))demonstrated outstanding catalytic activities in versatile Fenton-like reactions.However,the surface/structural instability is a critical issue,which will result in rapid passivation in Fenton-like reaction and fail in long-term operation.The catalytic stability of the catalysts with different metal sizes considering versatile peroxides(H_(2)O_(2),peroxymonosulfate(PMS),and peroxodisulfate(PDS))should be analyzed.In addition,strategies for catalyst regeneration and recyclability improvement are also important to realize the metal-based catalysts for practical applications.In this review,catalytic stability of catalysts with different metal sizes in the backgrounds of versatile peroxides and water matrixes in Fenton-like reactions were first evaluated.Regeneration of metal catalytic sites with different methods were also reviewed.Finally,major challenges and development of methods concerning the stability and regeneration of metal catalytic sites with different sizes were discussed to understand the future researches of metal catalytic sites in Fenton-like reactions.
基金supported by National Natural Science Foundation of China (No. 52070047)Guangzhou City Science and Technology Project (Nos. 201904010217, 202002010007)+3 种基金Guangdong Natural Science Foundation (No. 2021A1515011898)Featured Innovation Project of Guangdong Education Department (No.2019KTSCX135)State Key Laboratory of Pollution Control and Resource Reuse Foundation (No. PCRRF19010)the Scientific Project of Guangzhou University (No. YG2020020)。
文摘The leaching and non-recoverability of mental ions have always limited the practical application of Fenton-like processes. For the first time, we synthesized molybdenum phosphide (MoP) with dual active sites for the degradation of diclofenac (DCF) in the Fenton-like process. The DCF degradation rate constant (k) of MoP + H_(2)O_(2) process was calculated to be 0.13 min^(-1) within 40 min, indicating a highly efficient catalytic ability of MoP. In addition, this catalyst exhibits a stable structure and good activity, which could apply in a broad pH range, different ions solution and real wastewater condition. Accordingly, this efficient catalytic capability may be attributed to the presence of the metal sites Mo^(δ+) and the electron-rich sites P^(δ-) in MoP, which could induce the generation of hydroxyl radical (^(·)OH) and superoxide radical (^(·)O_(2)^(-)) through electron transfer, resulting in the effective removal of DCF. This study provides an idea for the optimization of Fenton-like technologies and environmental remediation.
基金supported by the National Natural Science Foundation of China(Nos.52300120 and 52070144)the Fundamental Research Funds for the Central Universities(No.22120240465).
文摘Regulating the photo-response region of iron metal-organic frameworks(Fe-MOFs)is a viable strategy for enhancing their practical application in the visible-light driven photo-Fenton-like process.This study developed a novel pyrazine-based Fe-MOFs(MIL-101(Fe)-Pz)by substituting the 1,4-dicarboxybenzene acid ligands in typical MIL-101(Fe)with 2,5-pyrazinedicarboxylic acid(PzDC),in which sodium acetate was used as coordinative modulator to control the crystal size(2–3μm).The incorporation of Fe-pyridine N coordination structures originated from PzDC ligands gave MIL-101(Fe)-Pz narrowed band gap(1.45 eV)than MIL-101(Fe)(2.54 eV)resulting in improved visible-light adsorption capacity(λ>420 nm),and also increased the proportion of Fe(Ⅱ)in the Fe-clusters.Thus MIL-101(Fe)-Pz exhibited a synergistic enhanced photo-Fenton-like catalytic performance under visible-light irradiation.The MIL-101(Fe)-Pz/H_(2)O_(2)/Vis system could degrade 99%of sulfamethoxazolewithin 30min,whichwas 10-fold faster than that of the pristine MIL-101(Fe),it also effectively removed other organic micropollutants with high durability and stability.Mechanistic analysis revealed that the PzDC ligands substitution decreased the band gap of MIL-101(Fe),giving MIL-101(Fe)-Pz appropriate band structure(-0.40∼1.05 V vs.NHE)which can cover several light-driven process for the generation of reactive oxygen species,including Fe(Ⅲ)reduction and H_(2)O_(2) activation for accelerating•OH generation,as well as oxygen reduction reaction for generating H_(2)O_(2),O_(2)^(•−) and ^(1)O_(2).This study highlights the role of pyridine-N containing ligands in regulating the band structure of Fe-MOFs,providing valuable guidance for the design of Fe-MOFs photocatalysts.
基金supported by Gansu Cuihua Technology Co.,Ltd.(H2020292)Science and Technology Planning of Baiyin City,Fundamental Research Funds for the Central Universities (buctrc202208)+2 种基金Engineering Research Center of Non-metallic Minerals of Zhejiang Province and the Beijing Engineering Center for Hierarchical Catalysts. Central Government Guiding Funds for Local Science and Technology Development (2022ZY015)Nanjiang Technology Project(2023AB028)Open Laboratory of State Key Laboratory of Organic and Inorganic Composites (oic-202301006)。
文摘Coupling adsorption and in-situ Fenton-like oxidation process was developed for Methylene blue(MB) using refined iron-containing lowgrade attapulgite(ATP) clay, and the removal mechanism was investigated. The MB was initially adsorbed on the porous ATPs, and then the enriched MB was removed by the H2O2-assisted Fenton-like oxidation with the iron-containing ATP catalyst. Under optimal conditions, the ATP powder exhibits the maximum removal efficiency of 100% with negligible iron leaching(1.5 mg L^(-1)) and no sludge formation. Furthermore,polysulfone/ATP(PSF/ATP) pellets were fabricated through a water-induced phase separation process to construct a fixed-bed reactor(FBR) for continuous contaminant removal. For the first cycle, the maximum adsorption capacity was 15.5 L with an outlet MB concentration of1.973 mg L-1(< 2 mg L^(-1), GB4287-2012) using the PSF/ATP pellets containing 50.0 g of ATP powders, and the maximum Fenton-like oxidation capacity was 35.5 L with the outlet concentration of 0.831 mg L^(-1). After five cycles, the total treated volume of the MB solution was ca. 255 L, and the efficiency remained above 99%. After 10 h of continuous treatment towards practical resin industrial wastewater, the chemical oxygen demand(COD) removal efficiency was still measured at 83.05%, costing 0.398 $ m^(-3). These results demonstrate the practical applicability of iron-containing low-grade ATP clay for textile water treatment.
基金supported by National Natural Science Foundation of China(Nos.52170086,52300056)Natural Science Foundation of Shandong Province(Nos.ZR2021ME013,ZR202211280298)。
文摘In this study,different types of small molecular carbon sources such as melamine,dicyandiamine,pyrocatechol,and o-phenylenediamine were used to regulate the surface structures of iron/nitrogen/carbonbased composites(Fe-N/C),which were used to activate peroxymonosulfate(PMS).The relationship between different small molecular carbon sources and the electronic structure was investigated.The characteristics of metal-carrier interaction in the Fe-N/C were clarified.As a result,there were significant differences in the degradation efficiency of catalysts prepared with different small molecular carbon sources,which was related to the types of active sites.Density functional theory(DFT)and experiments results showed that the catalyst rich in C-O-C and FeN_(x)exhibited better catalytic activity,which may be attributed to the higher adsorption energy for PMS.The main active species for catalytic degradation of ofloxacin were identified as sulfate radical(SO_(4)^(·-))and hydroxyl radical(^(·)OH)by electron paramagnetic resonance(EPR)spectra.The introduction of different small molecular carbon sources can significantly affect the distribution and electronic structure of active sites on the catalyst surface,thereby regulating the generation and migration of radicals.
基金supported by National Natural Science Foundation of China(Nos.52170086,22308194,U22A20423)Natural Science Foundation of Shandong Province(No.ZR2021ME013)+4 种基金Shandong Provincial Excellent Youth(No.ZR2022YQ47)the doctor research start Foundation of Shaanxi University of Technology(No.SLGRCQD004)Science and Technology Innovation Team Project of Shaanxi Province(No.2025RS-CXTD-040)the General Special Scientific Research Program of the Shaanxi Provincial Department of Education(No.24JK0366)supported by funding from Shandong Provincial Key Laboratory of Monocrystalline Silicon Semiconductor Materials and Technology。
文摘Most carbon-based catalysts utilized in Fenton-like systems face challenges such as structural instability,susceptibility to deactivation,and a tendency to disperse during operation.Wood-derived catalysts have garnered considerable attention due to their well-defined structures,extensive pipeline networks,superior mechanical strength,and adaptability for device customization.However,there remains a paucity of research that systematically summarizes Fenton-like systems based on wood-derived catalysts.In this review,we first summarize the structural designs of wood-derived catalysts based on nano-metal sites and single-atom sites,while also outlining their advantages and limitations applied in Fenton-like systems.Furthermore,we evaluate catalytic modules of wood-derived catalysts for scale-up and continuous Fenton-like systems.Additionally,wood-inspired catalytic materials utilizing commercial textures and their applications in Fenton-like processes are also discussed.This paper aims to comprehensively explore the fundamental mechanisms(e.g.,characteristics of catalytic sites,catalytic performance,and mechanisms)of wood-based catalysts in Fenton-like chemistry,as well as their equipment designs and application scenarios,as well as providing the insights into future developments.
基金supported by National Natural Science Fundation of China(Nos.52170086,22308194,U22A20423)Natural Science Foundation of Shandong Province(No.ZR2021ME013)+1 种基金Taishan Scholars Program of Shandong Province(No.tsqn202211012)Shandong Provincial Excellent Youth(No.ZR2022YQ47)。
文摘Although the powder Fenton-like catalysts have exhibited high catalytic performances towards pollutant degradation,they cannot be directly used for Fenton-like industrialization considering the problems of loss and recovery.Therefore,the membrane fixation of catalyst is an important step to realize the actual application of Fenton-like catalysts.In this work,an efficient catalyst was developed with Co-N_(x)configuration facilely reconstructed on the surface of Co_(3)O_(4)(Co-N_(x)/Co_(3)O_(4)),which exhibited superior catalytic activity.We further fixed the highly efficient Co-N_(x)/Co_(3)O_(4)onto three kinds of organic membranes and one kind of inorganic ceramic membrane installing with the residual PMS treatment device to investigate its catalytic stability and sustainability.Results indicated that the inorganic ceramic membrane(CM)can achieve high water flux of 710 L m-2h-1,and the similar water flux can be achieved by Co-N_(x)/Co_(3)O_(4)/CM even without the pressure extraction.We also employed the Co-N_(x)/Co_(3)O_(4)/CM system to the wastewater secondary effluent,and the pollutant in complicated secondary effluent could be highly removed by the Co-N_(x)/Co_(3)O_(4)/CM system.This paper provides a new point of view for the application of metal-based catalysts with M-N_(x)coordination in catalytic reaction device.
文摘The Fenton-like reaction between Cu^(2+)and H_(2)O_(2)was employed in chemical mechanical polishing to achieve efficient and high-quality processing of tungsten.The microstructure evolution and material removal rate of tungsten during polishing process were investigated via scanning electron microscopy,X-ray photoelectron spectroscopy,ultraviolet−visible spectrophotometry,and electrochemical experiments.The passivation behavior and material removal mechanism were discussed.Results show that the use of mixed H_(2)O_(2)+Cu(NO_(3))_(2)oxidant can achieve higher polishing efficiency and surface quality compared with the single oxidant Cu(NO_(3))_(2)or H_(2)O_(2).The increase in material removal rate is attributed to the rapid oxidation of W into WO_(3)via the chemical reaction between the substrate and hydroxyl radicals produced by the Fenton-like reaction.In addition,material removal rate and static etch rate exhibit significantly different dependencies on the concentration of Cu(NO_(3))_(2),while the superior oxidant for achieving the balance between polishing efficiency and surface quality is 0.5 wt.%H_(2)O_(2)+1.0 wt.%Cu(NO_(3))_(2).
基金the support of Natural Science Foundation of China(No.22276123)the Shanghai Engineering Research Center of Water Environment Simulation and Ecological Restoration(No.WESER-202201)the Postdoctoral Fellowship Program of CPSF(No.GZB20240456)。
文摘Carbon dot(CD)is an edge-bound,nanometer-sized carbon material possessing unique optical and electronic properties,making it promising metal-free,environmentally benign.In this study,we identified a highly hydrophilic CD complexed with Fe(Ⅲ)via carboxyl groups to form CD-COOFeⅢ,which exhibited remarkably enhanced Fenton-like reaction performance boosted by visible light irradiation.CD-COOFeⅢenabled high activity in the visible region beyondλ>420 nm,and maintained stable oxidation efficiency in the presence of H_(2)O_(2)over at least ten cycles.The capacity of electrons transferred from photo-excited CD to reduce Fe(Ⅲ)was calculated to be 1.1 mmol/g of CD.Furthermore,the quantum yield(QY)of solarto-Fe(Ⅱ)conversion reached an impressive 87.7%.These findings not only suggest a viable strategy for efficient conversion of solar-to-chemical using a CD-COOFeⅢcomplex in visible light boosted Fenton-like oxidation reaction,but also provide insight for understanding the effect of nanosized artificial and/or natural carbon materials in iron recycling in a natural surface environment.
文摘Asymmetric single-atom catalysts(ASACs)have attracted much attention owing to their excellent catalytic properties.However,the relationship between asymmetric coordination and the spin states of metal sites remains unclear.Additionally,the modulation of reactive oxygen species in Fenton-like reactions remains challenging.Herein,a novel strategy is reported for the rational design of highly loaded Co ASACs(CoN_(1)C_(2)/C_(2)N)immobilized on three-dimensional flower-like C_(2)N using an in situ-generated carbon defect method.In particular,the asymmetrically tricoordinated CoN_(1)C_(2)/C_(2)N exhibited excellent catalytic activity for sulfachloropyridazine degradation,with a turnover frequency of 36.8 min^(–1).Experimental results and theoretical calculations revealed that the electron spin state of the Co-active sites was transferred from the low-spin configuration(t_(2g)^(6)e_(g)^(1))to the high-spin configuration(t_(2g)^(5)e_(g)^(2))owing to asymmetric coordination.The high-spin Co 3d orbital in CoN_(1)C_(2)/C_(2)N possessed more unpaired electrons and therefore,had a strong ability to gain electrons from the O 2p orbitals of HSO_(5)^(–),boosting d-p orbital hybridization.More importantly,the spin-electron filling in theσ^(*)orbital of high-spin Co 3d−O 2p accelerated the desorption of^(*)SO_(5)•^(−),which acted as a rate-limiting step in the reaction,thus facilitating more^(1)O_(2)generation.This study provides an innovative synthetic route for practical ASACs and clarifies the critical relationship between structure and spin state,paving the way for advancements in environmental remediation and energy conversion applications.
基金The support from National Natural Science Foundation of China(Nos.52000050,52100024 and 42007115)Postdoctoral Science Foundation of China(Nos.2019M663245 and 2020M670913)+1 种基金Heilongjiang Postdoctoral Fund(No.LBH-Z20063)State Key Laboratory of Urban Water Resource and Environment(Harbin Institute of Technology)(Nos.2021TS22 and QAK202111)。
文摘Assembling MnO_(2)nanowires into macroscopic membrane is a promising engineered technology for catalyst separation and enhancement of Fenton-like reaction activity,yet its development is limited by the deficiencies in preparation and property modulation of the MnO_(2)nanowires.In this work,we developed a facile method using C_(2)H_5OH and CH_(3)COOK as reductive and vital control reagents to react with KMnO_(4)by hydrothermal reaction at 140℃for 12 h,to prepare the ultralongα-MnO_(2)nanowires up to tens of micrometers with high purity and aspect ratio.Such strategy not only had the advantages of being mild,easily controlled and environmental pollution-free,but also endowedα-MnO_(2)nanowires with excellent ability as a Fenton catalyst when assembled into free-standing membrane for degrading phenolic compounds(k_(obs)=0.0738~0.1695 min^(-1))in a continuous flow reaction.The reactive oxygen species(i.e.,~·OH)from Fenton-like reaction were enriched within thisα-MnO_(2)nanowire membrane via nanoconfinement effect,which further enhanced the mass transportation of~·OH available for phenolic contaminants.MnO_(2)nanowire membrane using our method possessed the high practical potential for water purify due to its easy-preparation and enhanced catalytic performances.
基金The first author would like to appreciate Ministry of Higher Education, Missions Department, Egypt for the fi- nancial support granted through Channel Scheme Mission.
文摘The use of Fenton's reagent (Fe^2+/H2O2) and Fenton-like reagents containing transition metals of Cu(Ⅱ), Zn(Ⅱ), Co(Ⅱ), and Mn(Ⅱ) for an alum sludge conditioning to improve its dewaterability was investigated. The results obtained were compared with those obtained from conditioning the same alum sludge using cationic and anionic polymers. Experimental results show that Fenton's reagent was the best among the Fenton and Fenton-like reagents for the alum sludge conditioning. A considerable effectiveness of capillary suction time (CST) reduction efficiency of 47% can be achieved under test conditions of Fe^2+/H2O2 = 20/125 mg/g DS (dry solid) and pH 6.0. The observation of floc-like particles after Fenton's reagent conditioning of alum sludge suggested that the mechanism of Fenton's reagent conditioning was different from that of polymer conditioning. In spite of the lower efficiency in the CST reduction of Fenton's reagent in alum sludge conditioning compared to that of polymer conditioning, Fenton's reagent offers a more environmentally safe option. Tiffs study provided an example of proactive treatment engineering, which is aimed at seeking a safe alternative to the use of polymers in sludge conditioning towards achieving a more sustainable sludge management strategy.
基金supported by the National Natural Science Foundation of China (21177072, 21207079)the Educational Commission for Distinguished Group of Hubei Province, China (T200703)the Natural Science Foundation for Innovation Group of Hubei Province, China(2009CDA020)
文摘A novel composite electrode was constructed by pressing together Co3O4 and graphite and it was used as the cathode in an electro-Fenton-like (EFL) system. The poor electron transport characteristic of Co3O4 was overcome by incorporating graphite. In situ electro-catalytic generation of hydroxyl radicals (·OH) occurred at high current efficiencies from pH 2-10, extending the traditional Fenton reaction pH range. Cyclic voltammetry and AC impedance spectrometry were used to characterize the composite electrode. The ability of the EFL system to degrade organic compounds was investigated using sulforhodamine B (SRB) and 2,4-dichlorophenol (2,4-DCP) as probes. Decoloration of SRB (1.0×10-5 mol/L) was complete (100%) in 150 min and SRB was effectively degraded from pH 2-10. The decomposition of SRB was studied using Fourier transform infrared spectroscopy (FT-IR) and total organic carbon (TOC) analysis and results indicated that the final degradation products were carbon dioxide, carboxylic acids and amines. The EFL system also decomposed 2,4-DCP and the degradation was 98.6% in 240 min. Electro-catalytic degradation of SRB occurs by a ·OH mechanism. After 5 times reused, the degradation rate of SRB did not significantly slow down. The electrode shows excellent potential for use in advanced oxidation processes (AOPs) used to treat persistent organic pollutants (POPs) in wastewater.
基金supported by the Fundamental Research Funds for the Central Universities(No.CDJXS12210002)the Major Project Foundation of Science and Technology Innovation in Minister of Education(No.708071)+2 种基金the Financial Supports of the National Natural Science Foundation of China(No.51108483)Natural Science Foundation Project of CQ CSTC(No.cstcjjA 20002)the 111 Project(No.B13041)
文摘A novel coupled system using Co–Ti O2 was successfully designed which combined two different heterogeneous advanced oxidation processes, sulfate radical based Fenton-like reaction(SR-Fenton) and visible light photocatalysis(Vis-Photo), for degradation of organic contaminants. The synergistic effect of SR-Fenton and Vis-Photo was observed through comparative tests of 50 mg/L Rhodamine B(Rh B) degradation and TOC removal. The Rhodamine B degradation rate and TOC removal were 100% and 68.1% using the SR-Fenton/Vis-Photo combined process under ambient conditions, respectively. Moreover, based on XRD, XPS and UV-DRS characterization, it can be deduced that tricobalt tetroxide located on the surface of the catalyst is the SR-Fenton active site, and cobalt ion implanted in the Ti O2 lattice is the reason for the visible light photocatalytic activity of Co–Ti O2. Finally, the effects of the calcination temperature and cobalt concentration on the synergistic performance were also investigated and a possible mechanism for the synergistic system was proposed. This coupled system exhibited excellent catalytic stability and reusability,and almost no dissolution of Co2+was found.
基金supported by the Science and Technology Development Foundation of Pudong New Area (No.PKJ2014Z03)Dawn Program of Shanghai (No.09SG54)+1 种基金Material Science and Engineering Key Subject of Shanghai Polytechnic University (No.XXKZD1601)Gaoyuan Discipline of Shanghai-Environmental Science and Engineering (Resource Recycling Science and Engineering)
文摘Phosphate residue is regarded as a hazardous waste, which could potentially create significant environmental and health problems if it is not properly treated and disposed of. In this study, nitrogen-doped carbon nanotubes-FePO_4(NCNTs-FePO_4) composite was successfully synthesized from phosphate residue, and its application as an effective catalyst was explored. Firstly, an effective method was developed to recover FePO_4 from phosphate residue, achieving an impressive FePO_4 mass recovery rate of 98.14%. Then, the NCNTsFePO_4 catalyst was synthesized from the recovered FePO_4 by two main reactions, including surface modification and chemical vapor deposition. Finally, the synthesized NCNTs-FePO_4 was applied to photo-degrade 15 mg/L Rhodamine B(RhB) in a Fenton-like system. The results showed that 98.9% of RhB could be degraded in 60 min, closely following the pseudofirst-order kinetics model. It was found that even after six consecutive cycles, NCNTs-FePO_4 still retained a high catalytic capacity(>50%). Moreover, ·OH radicals participating in the RhB degradation process were evidenced using quenching experiments and electron paramagnetic resonance analysis, and a rational mechanism was proposed. It was demonstrated that the materials synthesized from hazardous phosphate residue can be used as an effective catalyst for dye removal.
基金supported by the National Natural Science Foundation of China (Nos.5182220221972163 and 51772050)the Fundamental Research Funds for the Central Universities (No. 2232020D-02)+7 种基金Shanghai Sailing Program (No.20YF1400500)Shanghai Natural Science Foundation (No.20ZR1401500)Shanghai Rising-Star Program (No.18QA1400100)Youth Top-notch Talent Support Program of Shanghai,Science and Technology Commission of Shanghai Municipality (No.19520713200)Shanghai Scientific and Technological Innovation Project (No. 19JC1410400)Key Basic Research Program of Science and Technology Commission of Shanghai Municipality (No. 20JC1415300)DHU Distinguished Young Professor ProgramFundamental Research Funds for the Central Universities。
文摘Photocatalysis and Fenton process are two primary and promising advanced oxidation processes to degrade organic pollutants.However,the practical applications of single photocatalysis and Fenton process are still limited.Introducing one of them into another to form a combined photocatalytic Fentonlike system has shown great potential but still faces challenges in designing a well-tailored catalyst.Herein,a confined photocatalytic Fenton-like micro-reactor catalyst with a movable Fe_(3) O_(4) core and a mesoporous TiO_(2) shell has been constructed via a successive Stober coating strategy,followed by an ultrasound assisted etching method.The resulting micro-reactor possesses well-defined yolk-shell structures with unifo rm mesopores(~4 nm),a large Brunauer-Emmett-Teller(BET) surface area(~166.7 m^(2)/g),a high pore volume(~0.56 cm^(3)/g) and a strong magnetization(~51 emu/g),as well as tunable reactor sizes(20-90 nm).When evaluated for degrading bisphenol A under solar light in the presence of peroxymo no sulfate,the micro-reactor exhibits a superior catalytic degradation perfo rmance with a high magnetic separation efficiency and an excellent recycle ability.The outstanding performance can be attributed to its unique textual structure,which leads to a great syne rgistic effect from the photocatalytic and Fenton-like process.This study gives an important insight into the design and synthesis of an advanced micro-reactor for a combined advanced oxidation processes(AOPs).
基金sponsored by Shanghai Pujiang Program, China (No. 16PJ1401100)the Shanghai Committee of Science and Technology, China (No.15ZR1402000)+3 种基金Key Basic Research Program of Science and Technology Commission of Shanghai Municipality (No. 17JC1400100)the NSF of China(No. 21673048)National Youth Top Talent Support Program of National High-Level Personnel of Special Support Program (Youth Top-notch Talent Support Program)the State Key Laboratory of Transducer Technology of China (No. SKT1503)
文摘A versatile wet impregnation method was employed to conveniently and controllably deposit Fe_2O_3 nanoparticles on zeolites including commercial Y, mordenite and ZSM-5 with the similar framework Si/Al ratios and crystal sizes, respectively. The ultrafine Fe_2O_3 nanoparticles in size of 5 nm can be highly dispersed on zeolite Y matrix due to its much better wettability than ZSM-5 and mordenite. By using the obtained Fe_2O_3/zeolite composite as the heterogeneous Fenton-like catalysts, the degradation of phenol as a model reaction was systematically investigated, including the zeolite supports, particle size and dispersion of Fe_2O_3, and reaction conditions of H_2O_2 concentration, temperature, and pH value. The catalyst based on zeolite Y with Fe loading of 9% exhibited the best phenol degradation efficiency (> 90%)in neutral pH within 2 h. Its high catalytic activity in Fenton reaction can be attributed to the bifunctional properties of strong surface BrФnsted acidity and high reactivity of octahedral Fe^(3+) in the highlydispersed ultrafine Fe_2O_3 nanoparticles in size of 5 nm, which were the primary active centers to quickly decompose H_2O_2 into hydroxyl radicals. Since phenol degradation can be performed under mild conditions of ambient temperature (283-323 K) and a wide pH range (4.0-7.0), the catalysts can be easily recovered for recyclable use with stable degradation activity, which own the immense potential in deep treatment of organic pollutants in industrial wastewater.