Advanced processes for peroxymonosulfate(PMS)-based oxidation are efficient in eliminating toxic and refractory organic pol-lutants from sewage.The activation of electron-withdrawing HSO_(5)^(-)releases reactive speci...Advanced processes for peroxymonosulfate(PMS)-based oxidation are efficient in eliminating toxic and refractory organic pol-lutants from sewage.The activation of electron-withdrawing HSO_(5)^(-)releases reactive species,including sulfate radical(·SO_(4)^(-)),hydroxyl radical(·OH),superoxide radical(·O_(2)^(-)),and singlet oxygen(1O_(2)),which can induce the degradation of organic contaminants.In this work,we synthesized a variety of M-OMS-2 nanorods(M=Co,Ni,Cu,Fe)by doping Co^(2+),Ni^(2+),Cu^(2+),or Fe^(3+)into manganese oxide oc-tahedral molecular sieve(OMS-2)to efficiently remove sulfamethoxazole(SMX)via PMS activation.The catalytic performance of M-OMS-2 in SMX elimination via PMS activation was assessed.The nanorods obtained in decreasing order of SMX removal rate were Cu-OMS-2(96.40%),Co-OMS-2(88.00%),Ni-OMS-2(87.20%),Fe-OMS-2(35.00%),and OMS-2(33.50%).Then,the kinetics and struc-ture-activity relationship of the M-OMS-2 nanorods during the elimination of SMX were investigated.The feasible mechanism underly-ing SMX degradation by the Cu-OMS-2/PMS system was further investigated with a quenching experiment,high-resolution mass spec-troscopy,and electron paramagnetic resonance.Results showed that SMX degradation efficiency was enhanced in seawater and tap water,demonstrating the potential application of Cu-OMS-2/PMS system in sewage treatment.展开更多
The novel Fe-N co-doped ordered mesoporous carbon with high catalytic activity in m-cresol removal was prepared by urea-assisted impregnation and simple pyrolysis method.During the preparation of the Fe-NC catalyst,th...The novel Fe-N co-doped ordered mesoporous carbon with high catalytic activity in m-cresol removal was prepared by urea-assisted impregnation and simple pyrolysis method.During the preparation of the Fe-NC catalyst,the complexation of N elements in urea could anchor Fe,and the formation of C3N4during urea pyrolysis could also prevent migration and aggregation of Fe species,which jointly improve the dispersion and stability of Fe.The FeN4sites and highly dispersed Fe nanoparticles synergistically trigger the dual-site peroxymonosulfate (PMS) activation for highly efficient m-cresol degradation,while the ordered mesoporous structure of the catalyst could improve the mass transfer rate of the catalytic process,which together promote catalytic degradation of m-cresol by PMS activation.Reactive oxygen species (ROS) analytic experiments demonstrate that the system degrades m-cresol by free radical pathway mainly based on SO_(4)^(-)·and·OH,and partially based on·OH as the active components,and a possible PMS activation mechanism by 5Fe-50 for m-cresol degradation was proposed.This study can provide theoretical guidance for the preparation of efficient and stable catalysts for the degradation of organic pollutants by activated PMS.展开更多
As promising catalysts for the degradation of organic pollutants,metal–organic frameworks(MOFs)often face limitations due to the particle agglomeration and challenging recovery in liquid-catalysis application,stemmin...As promising catalysts for the degradation of organic pollutants,metal–organic frameworks(MOFs)often face limitations due to the particle agglomeration and challenging recovery in liquid-catalysis application,stemming from their powdery nature.Engineering macroscopic structures from pulverous MOF is thus of great importance for broadening their practical applications.In this study,three-dimensional porous MOF aerogel catalysts were successfully fabricated for degrading organic dyes by activating peroxymonosulfate(PMS).MOF/gelatin aerogel(MOF/GA)catalysts were prepared by directly integrating bimetallic FeCo-BDC with gelatin solutions,followed by freeze-drying and low-temperature calcination.The FeCo-BDC-0.15/GA/PMS system exhibited remarkable performance in degrading various organic dyes,eliminating 99.2%of rhodamine B within a mere 5 min.Compared to the GA/PMS system,there was over a 300-fold increase in the reaction rate constant.Remarkably,high removal efficiency was maintained across varying conditions,including different solution pH,co-existing inorganic anions,and natural water matrices.Radical trapping experiments and electron paramagnetic resonance analysis revealed that the degradation involved radical(SO_(4)^(-)·)and non-radical routes(^(1)O_(2)),of which ^(1)O_(2) was dominant.Furthermore,even after a continuous 400-min reaction in a fixed-bed reactor at a liquid hourly space velocity of 27 h^(-1),the FeCo-BDC/GA composite sustained a degradation efficiency exceeding 98.7%.This work presents highly active MOF-gelatin aerogels for dye degradation and expands the potential for their large-scale,continuous treatment application in organic dye wastewater management.展开更多
With the continuous deepening of rural revitalization strategy and the increasingly strict sewage discharge standards,rural domestic sewage treatment technology is facing higher challenges and requirements.The combine...With the continuous deepening of rural revitalization strategy and the increasingly strict sewage discharge standards,rural domestic sewage treatment technology is facing higher challenges and requirements.The combined process of micro-electrolysis+micro-nano bubbles coupled with peroxymonosulfate was constructed in this study,and the treatment effect and application value of this technology were explored with the actual rural domestic sewage as the treatment object.The experimental results showed that under the conditions of HRT of 120 min,PMS dosage of 0.15 mmol/L,pH=7,MBs air intake of 15 ml/min,current intensity of 15 A,and Fe/C mass ratio of 1:1,the removal rates of COD,ammonia nitrogen and total phosphorus can reach 88.55%,77.18%and 74.67%,respectively.Under the condition that the pH value of sewage was not adjusted,the non-biochemical simultaneous decarbonization,denitrification and phosphorus removal of rural domestic sewage can be achieved by micro-electrolysis and micro-nano bubbles coupled with peroxymonosulfate.The concentrations of effluent COD,ammonia nitrogen and total phosphorus met the requirements of the first level standard of the Discharge Standard of Water Pollutants for Rural Domestic Sewage Treatment Facilities(DB45T2413-2021).And the comprehensive operating cost was about 1.15 yuan/m 3.展开更多
Among the numerous transition metal catalysts,manganese-based compounds are considered as promising peroxymonosulfate(PMS)catalysts due to their low cost and environmental friendliness,such as cryptomelane manganese o...Among the numerous transition metal catalysts,manganese-based compounds are considered as promising peroxymonosulfate(PMS)catalysts due to their low cost and environmental friendliness,such as cryptomelane manganese oxide(K_(2-x)Mn_(8)O_(16):abbreviation KMnO).However,the limited catalytic performance of KMnO limits its practical application.In this work,iron-doped KMnO(Fe-KMnO)was prepared by one-step hydrothermal method to optimize its catalytic performance.Compared with KMnO/PMS system,Fe-KMnO/PMS system possessed more excellent removal efficiency of tetracycline(TC).Meanwhile,the Fe-KMnO/PMS system also exhibited good practical application potential and excellent stability.The mechanism of Fe-KMnO activation of PMS was further analyzed in detail.It was found that Fe participated in the redox of high-valent Mn,which promoted the activation of PMS.Moreover,The Fe site as an adsorption site enhanced the TC enrichment ability of the catalyst,reducing the mass transfer resistance and further enhancing the TC removal ability of Fe-KMnO/PMS system.This work not only provides an excellent PMS catalyst,but also offers new insights into the mechanism of PMS activation by bimetallic manganese-based catalysts.展开更多
Continuous dynamic experiment was conducted for the treatment of low-concentration organic waste gas with xylene as a representative, using micro-nano bubble and peroxymonosulfate working in synergy. The degradation r...Continuous dynamic experiment was conducted for the treatment of low-concentration organic waste gas with xylene as a representative, using micro-nano bubble and peroxymonosulfate working in synergy. The degradation rule of xylene under different conditions such as the ORP value of the spray liquid, pH value of the spray liquid, liquid-gas ratio of the spray liquid, residence time of xylene, and initial concentration of xylene was investigated. The results showed that at a low concentration, the pH value of the spray liquid had little effect on the degradation rate of xylene. The degradation rate of xylene rose with the increase of the ORP value of the spray liquid, the liquid-gas ratio of the spray liquid, the residence time of xylene, and the initial concentration of xylene.展开更多
Magnetic Cu^0/Fe3O4 submicron composites were prepared using a hydrothermal method and used as heterogeneous catalysts for the activation of peroxymonosulfate（PMS） and the degradation of organic pollutants.The as-pr...Magnetic Cu^0/Fe3O4 submicron composites were prepared using a hydrothermal method and used as heterogeneous catalysts for the activation of peroxymonosulfate（PMS） and the degradation of organic pollutants.The as-prepared magnetic Cu^0/Fe3O4 submicron composites were composed of Cu^0 and Fe3O4 crystals and had an average size of approximately 220 nm.The Cu^0/Fe3O4 composites could efficiently catalyze the activation of PMS to generate singlet oxygen,and thus induced the rapid degradation of rhodamine B,methylene blue,orange Ⅱ,phenol and 4-chlorophenol.The use of0.1 g/L of the Cu^0/Fe3O4 composites induced the complete removal of rhodamine B（20 μmol/L） in15 min,methylene blue（20 μmol/L） in 5 min,orange Ⅱ（20 μmol/L） in 10 min,phenol（0.1mmol/L） in 30 min and 4-chlorophenol（0.1 mmol/L） in 15 min with an initial pH value of 7.0 and a PMS concentration of 0.5 mmol/L.The total organic carbon（TOC） removal higher than 85%for all of these five pollutants was obtained in 30 min when the PMS concentration was 2.5 mmol/L.The rate of degradation was considerably higher than that obtained with Cu^0 or Fe3O4 particles alone.The enhanced catalytic activity of the Cu^0/Fe3O4 composites in the activation of PMS was attributed to the synergistic effect of the Cu^0 and Fe3O4 crystals in the composites.Singlet oxygen was identified as the primary reactive oxygen species responsible for pollutant degradation by electron spin resonance and radical quenching experiments.A possible mechanism for the activation of PMS by Cu^0/Fe3O4 composites is proposed as electron transfer from the organic pollutants to PMS induces the activation of PMS to generate ^1O2,which induces the degradation of the organic pollutants.As a magnetic catalyst,the Cu^0/Fe3O4 composites were easily recovered by magnetic separation,and exhibited excellent stability over five successive degradation cycles.The present study provides a facile and green heterogeneous catalysis method for the oxidative removal of organic pollutants.展开更多
Excitation of metal-free graphitic carbon nitride(g-C3N4) under visible light can successfully achieve efficient activation of peroxymonosulfate(PMS). Synergistic effects and involved mechanism were systematically inv...Excitation of metal-free graphitic carbon nitride(g-C3N4) under visible light can successfully achieve efficient activation of peroxymonosulfate(PMS). Synergistic effects and involved mechanism were systematically investigated using a light-inert endocrine disrupting compound, dimethyl phthalate(DMP), as the target pollutant. Under visible light irradiation, DMP could not be degraded by direct g-C3 N4-mediated photocatalysis, while in the presence of PMS, the dominant radicals were converted from ·O2 to SO4·– and ·OH, resulting in effective DMP degradation and mineralization. Results showed that higher dosage of PMS or g-C3 N4 could increase the activation amount of PMS and corresponding DMP degradation efficiency, but the latter approach was more productive in terms of making the most of PMS. High DMP concentration hindered effective contact between PMS and g-C3 N4, but could provide efficient use of PMS. Higher DMP degradation efficiency was achieved at p H lower than the point of zero charge(5.4). Based on intermediates identification, the DMP degradation was found mainly through radical attack(·OH and SO4·–) of the benzene ring and oxidation of the aliphatic chains.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
Methotrexate(MTX)is one of the most consumed anti-cancer drugs in the pharmaceutical market around the world.The widespread occurrence of MTX in aquatic environment through hospital effluent has attracted increasing c...Methotrexate(MTX)is one of the most consumed anti-cancer drugs in the pharmaceutical market around the world.The widespread occurrence of MTX in aquatic environment through hospital effluent has attracted increasing concern due to its potential to induce water pollution.In the present study,the degradation of MTX in aqueous medium was investigated by UV-activated peroxymonosulfate(PMS).A significant improvement in degradation rate by increasing UV intensity and PMS concentration while the decrease in degradation efficiency with the increase of solution p H and initial concentration of MTX was observed.The proposed UV/PMS process could achieve more than 90%MTX degradation in 30 min with a good mineralization degree(65%).A pseudofirst order kinetic model was employed and successfully predicted the degradation of MTX.The effect of other operational parameters such as the initial concentration of the targeted compound,dosage of oxidant(PMS),solution p H and UV intensity on the degradation rate were investigated.At the last,the main transform intermediates were identified using LC–MS and possible degradation pathways were proposed.The results show that UV/PMS can be used as an efficient technology to treat pharmaceuticals such as methotrexate containing water and wastewater.展开更多
Sulfate radical-advanced oxidation processes(SR-AOPs)are promising technologies for organic pollutants elimination.Heterogeneous metal-based catalysis has been widely studied and applied to activate peroxymonosulfate(...Sulfate radical-advanced oxidation processes(SR-AOPs)are promising technologies for organic pollutants elimination.Heterogeneous metal-based catalysis has been widely studied and applied to activate peroxymonosulfate(PMS)for producing sulfate radicals.Developing highly efficient catalysts is crucial for future extensive use.Importantly,the catalytic activity is mainly determined by mass and electron transfer.This paper aims to overview the recent enhancement strategies for developing heterogeneous metalbased catalysts as effective PMS activators.The main strategies,including surface engineering,structural engineering,electronic modulation,external energy assistance,and membrane filtration enhancement,are summarized.The potential mechanisms for improving catalytic activity are also introduced.Finally,the challenges and future research prospects of heterogenous metal-based catalysis in SR-AOPs are proposed.This work is hoped to guide the rational design of highly efficient heterogenous catalysts in SR-AOPs.展开更多
The MnFe_(2) O_(4)/g-C_(3) N_(4)/diatomite composites(Mn/G/D) were prepared via a facile precipitation-calcination method in this study.The Mn/G/D possessed higher specific surface area,lower electron-hole pairs' ...The MnFe_(2) O_(4)/g-C_(3) N_(4)/diatomite composites(Mn/G/D) were prepared via a facile precipitation-calcination method in this study.The Mn/G/D possessed higher specific surface area,lower electron-hole pairs' recombination rate,as well as wider and stronger visible light absorption capacity.Since the synergistic effect between g-C_(3 )N_(4) and MnFe_(2) O_(4),the photogene rated electron could transfer from g-C3 N4 to MnFe_(2) O_(4),which could promote the migration of electrons as well as enhance the photocatalytic activity and peroxymonosulfate(PMS) activation efficiency.Mn/G/D-5% composite displayed the excellent degradation performance of bisphenol A(BPA) with the removal efficiency of 99.9% under PMS/Vis system,which was approximately 2.47 and 63.8 times as high as that of the Mn/G/D-5%/PMS and Mn/G/D-5%/Vis system,respectively.Moreover,negative electricity derived from diatomite surface also promoted the photogenerated carriers' migration,and the degradation rate constant was around 2.4 times higher than that of MnFe_(2) O_(4)/g-C_(3) N_(4)(Mn/G).In addition,quenching experiments showed that both radical pathway(h^(+),·OH,·O_(2)^(-)and SO_(4)·^(-)) and non-radical pathway(^(1) O_(2)) were responsible for the degradation of BPA.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
β-lactam antibiotics in aquatic environment have severely damaged ecological stability and caused a series of environmental pollution problems to be solved urgently.Herein,a novel composite photocatalyst prepared by ...β-lactam antibiotics in aquatic environment have severely damaged ecological stability and caused a series of environmental pollution problems to be solved urgently.Herein,a novel composite photocatalyst prepared by loading carbon dots(CDs)onto rod-like CoFe_(2)O_(4)(CFO),which can effectively degrade amoxicillin(AMX)by photocata lytic/peroxy mono sulfate(PMS)activation under visible light irradiation.The degradation results exhibits that the optimal degradation efficiency with 97.5%within 80 min is achievd by the CDs-CFO-5 composite.Such enhanced activity is ascribed to the introduction of CDs that effectively improves the separation efficiency of photogenerated electron pairs and creates new active sites as electron bridges that improve the photocata lytic performance.More importantly,a strong synergistic between CDs and photo-induced electrons generated from CFO can further activiate PMS to provide more SO4-·and·OH radicals for boosting the degradation ability towards AMX.The present study aims to elucidate positive role of CDs in photocata lytic/peroxy monosulfate activation during the degradation reaction.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
Switching the reaction routes in peroxymonosulfate(PMS)-based advanced oxidation processes have attracted much attention but remain challenging.Herein,a series of Co-N/C catalysts with different compositions and struc...Switching the reaction routes in peroxymonosulfate(PMS)-based advanced oxidation processes have attracted much attention but remain challenging.Herein,a series of Co-N/C catalysts with different compositions and structures were prepared by using bimetallic zeolitic imidazolate frameworks based on ZIF-8 and ZIF-67(x Zn/Co-ZIFs).Results show that Co doping amount could mediate the transformation of the activation pathway of PMS over CoN/C.When Co doping amount was less than 10%,the constructed x Co-N/C/PMS system(x≤10%)was singlet oxygen-dominated reaction;however further increasing Co doping amount would lead to the generation and coexistence of sulfate radicals and high-valent cobalt,besides singlet oxygen.Furthermore,the nitrogen-coordinated Co(Co-NX)sites could serve as main catalytically active sites to generate singlet oxygen.While excess Co doping amount caused the formation of Co nanoparticles from which leached Co ions were responsible for the generation of sulfate radicals and high-valent cobalt.Compared to undoped N/C,Co doping could significantly enhance the catalytic performance.The 0.5%Co-N/C could achieve the optimum degradation(0.488 min^(-1))and mineralization abilities(78.4%)of sulfamethoxazole among the investigated Co-N/C catalysts,which was superior to most of previously reported catalysts.In addition,the application prospects of the two systems in different environmental scenarios(pH,inorganic anions and natural organic matter)were assessed and showed different degradation behaviors.This study provides a strategy to regulate the reactive species in PMS-based advanced oxidation process.展开更多
Environmental endocrine disruptors,represented by bisphenol A(BPA),have been widely detected in the environment,bringing potential health risks to human beings.Nitrogen-containing biocarbon catalyst can activate perox...Environmental endocrine disruptors,represented by bisphenol A(BPA),have been widely detected in the environment,bringing potential health risks to human beings.Nitrogen-containing biocarbon catalyst can activate peroxymonosulfate(PMS)to degrade BPA in water,but its active sites remain opaque.Herein,in this work,nitrogen-containing biochar,i.e.,C–Nedge,enriched with graphitic-N defects at the edges was prepared by one-pot co-pyrolysis of chitosan and potassium carbonate.The results showed that the C–Nedge/PMS system can effectively degrade 98%of BPA(50 mg/L).The electron transfer based non-radical oxidation mechanism was responsible for BPA degradation.Edge graphitic-N doping endows biochar with strong electron transfer ability.The catalyst had good recovery and reuse performance.This catalytic oxidation was also feasible for other refractory pollutants removal and worked well for treating practical wastewater.This work may provide valuable information in unraveling the N doping configurationactivity relationship during activating PMS by biochar.展开更多
Photocatalytic activation of peroxymonosulfate (PMS) has garnered a lot of interest in the field of wastewater treatment. Herein, a plasmonic Ag nanoparticles decorated MIL-101(Fe) hybrid was synthesized through a pho...Photocatalytic activation of peroxymonosulfate (PMS) has garnered a lot of interest in the field of wastewater treatment. Herein, a plasmonic Ag nanoparticles decorated MIL-101(Fe) hybrid was synthesized through a photodeposition process. Upon light irradiation, the Ag/MIL-101(Fe) exhibit reinforced photocatalytic activities for elimination of bisphenol A (BPA) with PMS. The optimized 2.0% Ag/MIL-101(Fe) composite presented the highest photocatalytic activity with kinetic constant k of 0.102 min-1, which was about 10-fold of the pristine MIL-101(Fe). Loading of plasmonic Ag into MIL-101(Fe) boosts photoinduced carrier separation and accelerates PMS activation to generate strong oxidative radicals. Photoelectrochemical tests and multiple spectroscopic studies confirmed the promoted charge carrier separation and transfer capability of Ag/MIL-101(Fe). Combining the results of radical trapping experiments and electron spin resonance (ESR), the formed SO4·-, ·OH, ·O2- and 1O2 had a significant role in the photocatalytic process. According to intermediate study, the degradation pathway was studied, and the possible mechanism was proposed.展开更多
The monoaminotrinitro iron phthalocyanine(FeMATNPc)is used to connect with isonicotinic acid(INA)for amide bonding and axial coordination to synthetic a unique catalyst FeMATNPc-INA,which is loaded in polyacrylonitril...The monoaminotrinitro iron phthalocyanine(FeMATNPc)is used to connect with isonicotinic acid(INA)for amide bonding and axial coordination to synthetic a unique catalyst FeMATNPc-INA,which is loaded in polyacrylonitrile(PAN)nanofibers by electrospinning.The introduction of INA destroys theπ-πconjugated stack structure in phthalocyanine molecules and exposes more active sites.The FeMATNPc-INA structure is characterized by X-ray photoelectron spectroscopy and UV-visible absorption spectrum,and the FeMATNPcINA/PAN structure is characterized by Fourier transform infrared spectroscopy and X-ray diffraction.The FeMATNPc-INA/PAN can effectively activate peroxymonosulfate(PMS)to eliminate carbamazepine(CBZ)within 40 minutes(PMS 1.5 mmol/L)in the dark.The effects of catalyst dosage,PMS concentration,pH and inorganic anion on the degradation of CBZ are investigated.It has been confirmed by electron paramagnetic resonance,gas chromatography–mass spectroscopy and free radical capture experiments that the catalytic system is degraded by·OH,SO4^(·-)and Fe(IV)=O are the major active species,the singlet oxygen(^(1)O_(2))is the secondary active species.The degradation process of CBZ is analyzed by ultra-high performance liquid chromatography-mass spectrometry and the aromatic compounds have been degraded to small molecular acids.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
基金supported by the National Natural Science Foundation of China(Nos.21972073,22136003,22206188,and 21805166).
文摘Advanced processes for peroxymonosulfate(PMS)-based oxidation are efficient in eliminating toxic and refractory organic pol-lutants from sewage.The activation of electron-withdrawing HSO_(5)^(-)releases reactive species,including sulfate radical(·SO_(4)^(-)),hydroxyl radical(·OH),superoxide radical(·O_(2)^(-)),and singlet oxygen(1O_(2)),which can induce the degradation of organic contaminants.In this work,we synthesized a variety of M-OMS-2 nanorods(M=Co,Ni,Cu,Fe)by doping Co^(2+),Ni^(2+),Cu^(2+),or Fe^(3+)into manganese oxide oc-tahedral molecular sieve(OMS-2)to efficiently remove sulfamethoxazole(SMX)via PMS activation.The catalytic performance of M-OMS-2 in SMX elimination via PMS activation was assessed.The nanorods obtained in decreasing order of SMX removal rate were Cu-OMS-2(96.40%),Co-OMS-2(88.00%),Ni-OMS-2(87.20%),Fe-OMS-2(35.00%),and OMS-2(33.50%).Then,the kinetics and struc-ture-activity relationship of the M-OMS-2 nanorods during the elimination of SMX were investigated.The feasible mechanism underly-ing SMX degradation by the Cu-OMS-2/PMS system was further investigated with a quenching experiment,high-resolution mass spec-troscopy,and electron paramagnetic resonance.Results showed that SMX degradation efficiency was enhanced in seawater and tap water,demonstrating the potential application of Cu-OMS-2/PMS system in sewage treatment.
基金gratefully acknowledge the financial support of the National Natural Science Foundation of China(22108145 and 21978143)the Shandong Province Natural Science Foundation(ZR2020QB189)+1 种基金State Key Laboratory of Heavy Oil Processing(SKLHOP202203008)the Talent Foundation funded by Province and Ministry Co-construction Collaborative Innovation Center of Eco-chemical Engineering(STHGYX2201).
文摘The novel Fe-N co-doped ordered mesoporous carbon with high catalytic activity in m-cresol removal was prepared by urea-assisted impregnation and simple pyrolysis method.During the preparation of the Fe-NC catalyst,the complexation of N elements in urea could anchor Fe,and the formation of C3N4during urea pyrolysis could also prevent migration and aggregation of Fe species,which jointly improve the dispersion and stability of Fe.The FeN4sites and highly dispersed Fe nanoparticles synergistically trigger the dual-site peroxymonosulfate (PMS) activation for highly efficient m-cresol degradation,while the ordered mesoporous structure of the catalyst could improve the mass transfer rate of the catalytic process,which together promote catalytic degradation of m-cresol by PMS activation.Reactive oxygen species (ROS) analytic experiments demonstrate that the system degrades m-cresol by free radical pathway mainly based on SO_(4)^(-)·and·OH,and partially based on·OH as the active components,and a possible PMS activation mechanism by 5Fe-50 for m-cresol degradation was proposed.This study can provide theoretical guidance for the preparation of efficient and stable catalysts for the degradation of organic pollutants by activated PMS.
基金funded by the Natural Science Foundation of Fujian Province(2023J05180)the President's Foundation of Minnan Normal University(KJ2021011).
文摘As promising catalysts for the degradation of organic pollutants,metal–organic frameworks(MOFs)often face limitations due to the particle agglomeration and challenging recovery in liquid-catalysis application,stemming from their powdery nature.Engineering macroscopic structures from pulverous MOF is thus of great importance for broadening their practical applications.In this study,three-dimensional porous MOF aerogel catalysts were successfully fabricated for degrading organic dyes by activating peroxymonosulfate(PMS).MOF/gelatin aerogel(MOF/GA)catalysts were prepared by directly integrating bimetallic FeCo-BDC with gelatin solutions,followed by freeze-drying and low-temperature calcination.The FeCo-BDC-0.15/GA/PMS system exhibited remarkable performance in degrading various organic dyes,eliminating 99.2%of rhodamine B within a mere 5 min.Compared to the GA/PMS system,there was over a 300-fold increase in the reaction rate constant.Remarkably,high removal efficiency was maintained across varying conditions,including different solution pH,co-existing inorganic anions,and natural water matrices.Radical trapping experiments and electron paramagnetic resonance analysis revealed that the degradation involved radical(SO_(4)^(-)·)and non-radical routes(^(1)O_(2)),of which ^(1)O_(2) was dominant.Furthermore,even after a continuous 400-min reaction in a fixed-bed reactor at a liquid hourly space velocity of 27 h^(-1),the FeCo-BDC/GA composite sustained a degradation efficiency exceeding 98.7%.This work presents highly active MOF-gelatin aerogels for dye degradation and expands the potential for their large-scale,continuous treatment application in organic dye wastewater management.
基金Supported by Research Foundation Ability Enhancement Project for Young and Middle-aged Teachers in Guangxi Universities(2023KY2049).
文摘With the continuous deepening of rural revitalization strategy and the increasingly strict sewage discharge standards,rural domestic sewage treatment technology is facing higher challenges and requirements.The combined process of micro-electrolysis+micro-nano bubbles coupled with peroxymonosulfate was constructed in this study,and the treatment effect and application value of this technology were explored with the actual rural domestic sewage as the treatment object.The experimental results showed that under the conditions of HRT of 120 min,PMS dosage of 0.15 mmol/L,pH=7,MBs air intake of 15 ml/min,current intensity of 15 A,and Fe/C mass ratio of 1:1,the removal rates of COD,ammonia nitrogen and total phosphorus can reach 88.55%,77.18%and 74.67%,respectively.Under the condition that the pH value of sewage was not adjusted,the non-biochemical simultaneous decarbonization,denitrification and phosphorus removal of rural domestic sewage can be achieved by micro-electrolysis and micro-nano bubbles coupled with peroxymonosulfate.The concentrations of effluent COD,ammonia nitrogen and total phosphorus met the requirements of the first level standard of the Discharge Standard of Water Pollutants for Rural Domestic Sewage Treatment Facilities(DB45T2413-2021).And the comprehensive operating cost was about 1.15 yuan/m 3.
基金supported by the National Natural Science Foundation of China (21806115)Sichuan Science and Technology Program (2020YJ0149)+1 种基金the Power Construction of China (P42819,DJ-ZDXM-2019-42)the Supported by Sichuan Science and Technology Program (2021ZDZX0012)。
文摘Among the numerous transition metal catalysts,manganese-based compounds are considered as promising peroxymonosulfate(PMS)catalysts due to their low cost and environmental friendliness,such as cryptomelane manganese oxide(K_(2-x)Mn_(8)O_(16):abbreviation KMnO).However,the limited catalytic performance of KMnO limits its practical application.In this work,iron-doped KMnO(Fe-KMnO)was prepared by one-step hydrothermal method to optimize its catalytic performance.Compared with KMnO/PMS system,Fe-KMnO/PMS system possessed more excellent removal efficiency of tetracycline(TC).Meanwhile,the Fe-KMnO/PMS system also exhibited good practical application potential and excellent stability.The mechanism of Fe-KMnO activation of PMS was further analyzed in detail.It was found that Fe participated in the redox of high-valent Mn,which promoted the activation of PMS.Moreover,The Fe site as an adsorption site enhanced the TC enrichment ability of the catalyst,reducing the mass transfer resistance and further enhancing the TC removal ability of Fe-KMnO/PMS system.This work not only provides an excellent PMS catalyst,but also offers new insights into the mechanism of PMS activation by bimetallic manganese-based catalysts.
基金Supported by Guigang City Science Research and Technology Development Plan Project(GUIKEJI2203014).
文摘Continuous dynamic experiment was conducted for the treatment of low-concentration organic waste gas with xylene as a representative, using micro-nano bubble and peroxymonosulfate working in synergy. The degradation rule of xylene under different conditions such as the ORP value of the spray liquid, pH value of the spray liquid, liquid-gas ratio of the spray liquid, residence time of xylene, and initial concentration of xylene was investigated. The results showed that at a low concentration, the pH value of the spray liquid had little effect on the degradation rate of xylene. The degradation rate of xylene rose with the increase of the ORP value of the spray liquid, the liquid-gas ratio of the spray liquid, the residence time of xylene, and the initial concentration of xylene.
基金supported by the National Natural Science Foundation of China (21377169, 21507168)the Fundamental Research Funds for the Central Universities (CZW15078)the Natural Science Foundation of Hubei Province of China (2014CFC1119, 2015CFB505)~~
文摘Magnetic Cu^0/Fe3O4 submicron composites were prepared using a hydrothermal method and used as heterogeneous catalysts for the activation of peroxymonosulfate（PMS） and the degradation of organic pollutants.The as-prepared magnetic Cu^0/Fe3O4 submicron composites were composed of Cu^0 and Fe3O4 crystals and had an average size of approximately 220 nm.The Cu^0/Fe3O4 composites could efficiently catalyze the activation of PMS to generate singlet oxygen,and thus induced the rapid degradation of rhodamine B,methylene blue,orange Ⅱ,phenol and 4-chlorophenol.The use of0.1 g/L of the Cu^0/Fe3O4 composites induced the complete removal of rhodamine B（20 μmol/L） in15 min,methylene blue（20 μmol/L） in 5 min,orange Ⅱ（20 μmol/L） in 10 min,phenol（0.1mmol/L） in 30 min and 4-chlorophenol（0.1 mmol/L） in 15 min with an initial pH value of 7.0 and a PMS concentration of 0.5 mmol/L.The total organic carbon（TOC） removal higher than 85%for all of these five pollutants was obtained in 30 min when the PMS concentration was 2.5 mmol/L.The rate of degradation was considerably higher than that obtained with Cu^0 or Fe3O4 particles alone.The enhanced catalytic activity of the Cu^0/Fe3O4 composites in the activation of PMS was attributed to the synergistic effect of the Cu^0 and Fe3O4 crystals in the composites.Singlet oxygen was identified as the primary reactive oxygen species responsible for pollutant degradation by electron spin resonance and radical quenching experiments.A possible mechanism for the activation of PMS by Cu^0/Fe3O4 composites is proposed as electron transfer from the organic pollutants to PMS induces the activation of PMS to generate ^1O2,which induces the degradation of the organic pollutants.As a magnetic catalyst,the Cu^0/Fe3O4 composites were easily recovered by magnetic separation,and exhibited excellent stability over five successive degradation cycles.The present study provides a facile and green heterogeneous catalysis method for the oxidative removal of organic pollutants.
基金supported by the Natural Science Foundation of Jiangsu Province(BK20160936,BK20160938)the National Natural Science Foundation of China(51708297)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)~~
文摘Excitation of metal-free graphitic carbon nitride(g-C3N4) under visible light can successfully achieve efficient activation of peroxymonosulfate(PMS). Synergistic effects and involved mechanism were systematically investigated using a light-inert endocrine disrupting compound, dimethyl phthalate(DMP), as the target pollutant. Under visible light irradiation, DMP could not be degraded by direct g-C3 N4-mediated photocatalysis, while in the presence of PMS, the dominant radicals were converted from ·O2 to SO4·– and ·OH, resulting in effective DMP degradation and mineralization. Results showed that higher dosage of PMS or g-C3 N4 could increase the activation amount of PMS and corresponding DMP degradation efficiency, but the latter approach was more productive in terms of making the most of PMS. High DMP concentration hindered effective contact between PMS and g-C3 N4, but could provide efficient use of PMS. Higher DMP degradation efficiency was achieved at p H lower than the point of zero charge(5.4). Based on intermediates identification, the DMP degradation was found mainly through radical attack(·OH and SO4·–) of the benzene ring and oxidation of the aliphatic chains.
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the financial support of research grants from the Hong Kong Polytechnic University(Q67H)and Higher Education Commission(HEC),Pakistan for the financial support during IRSIP。
文摘Methotrexate(MTX)is one of the most consumed anti-cancer drugs in the pharmaceutical market around the world.The widespread occurrence of MTX in aquatic environment through hospital effluent has attracted increasing concern due to its potential to induce water pollution.In the present study,the degradation of MTX in aqueous medium was investigated by UV-activated peroxymonosulfate(PMS).A significant improvement in degradation rate by increasing UV intensity and PMS concentration while the decrease in degradation efficiency with the increase of solution p H and initial concentration of MTX was observed.The proposed UV/PMS process could achieve more than 90%MTX degradation in 30 min with a good mineralization degree(65%).A pseudofirst order kinetic model was employed and successfully predicted the degradation of MTX.The effect of other operational parameters such as the initial concentration of the targeted compound,dosage of oxidant(PMS),solution p H and UV intensity on the degradation rate were investigated.At the last,the main transform intermediates were identified using LC–MS and possible degradation pathways were proposed.The results show that UV/PMS can be used as an efficient technology to treat pharmaceuticals such as methotrexate containing water and wastewater.
基金financially supported by the National Natural Science Foundation of China(21938009)。
文摘Sulfate radical-advanced oxidation processes(SR-AOPs)are promising technologies for organic pollutants elimination.Heterogeneous metal-based catalysis has been widely studied and applied to activate peroxymonosulfate(PMS)for producing sulfate radicals.Developing highly efficient catalysts is crucial for future extensive use.Importantly,the catalytic activity is mainly determined by mass and electron transfer.This paper aims to overview the recent enhancement strategies for developing heterogeneous metalbased catalysts as effective PMS activators.The main strategies,including surface engineering,structural engineering,electronic modulation,external energy assistance,and membrane filtration enhancement,are summarized.The potential mechanisms for improving catalytic activity are also introduced.Finally,the challenges and future research prospects of heterogenous metal-based catalysis in SR-AOPs are proposed.This work is hoped to guide the rational design of highly efficient heterogenous catalysts in SR-AOPs.
基金the financial support provided by the Beijing Natural Science Foundation (2202044)the Fok Ying Tung Education Foundation, China (171042)+1 种基金the National Postdoctoral Program for Innovative Talents (BX20190370)the Fundamental Research Funds for the Central Universities (2021JCCXHH04)。
文摘The MnFe_(2) O_(4)/g-C_(3) N_(4)/diatomite composites(Mn/G/D) were prepared via a facile precipitation-calcination method in this study.The Mn/G/D possessed higher specific surface area,lower electron-hole pairs' recombination rate,as well as wider and stronger visible light absorption capacity.Since the synergistic effect between g-C_(3 )N_(4) and MnFe_(2) O_(4),the photogene rated electron could transfer from g-C3 N4 to MnFe_(2) O_(4),which could promote the migration of electrons as well as enhance the photocatalytic activity and peroxymonosulfate(PMS) activation efficiency.Mn/G/D-5% composite displayed the excellent degradation performance of bisphenol A(BPA) with the removal efficiency of 99.9% under PMS/Vis system,which was approximately 2.47 and 63.8 times as high as that of the Mn/G/D-5%/PMS and Mn/G/D-5%/Vis system,respectively.Moreover,negative electricity derived from diatomite surface also promoted the photogenerated carriers' migration,and the degradation rate constant was around 2.4 times higher than that of MnFe_(2) O_(4)/g-C_(3) N_(4)(Mn/G).In addition,quenching experiments showed that both radical pathway(h^(+),·OH,·O_(2)^(-)and SO_(4)·^(-)) and non-radical pathway(^(1) O_(2)) were responsible for the degradation of BPA.
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.
基金founding support from the National Natural Science Foundation of China(Nos.21906072,22006057 and 31971616)the Natural Science Foundation of Jiangsu Province(BK20190982)+4 种基金“Doctor of Mass Entrepreneurship and Innovation”Project in Jiangsu Province,Henan Postdoctoral Foundation(202003013)Doctoral Scientific Research Foundation of Jiangsu University of Science and Technology(China)(1062931806 and 1142931803)the Science and Technology Research Project of the Department of Education of Jilin Province(JJKH20200039KJ)the Science and Technology Research Project of Jilin City(20190104120,201830811)the Project of Jilin Provincial Science and Technology Development Plan(20190201277JC,20200301046RQ,YDZJ202101ZYTS070)。
文摘β-lactam antibiotics in aquatic environment have severely damaged ecological stability and caused a series of environmental pollution problems to be solved urgently.Herein,a novel composite photocatalyst prepared by loading carbon dots(CDs)onto rod-like CoFe_(2)O_(4)(CFO),which can effectively degrade amoxicillin(AMX)by photocata lytic/peroxy mono sulfate(PMS)activation under visible light irradiation.The degradation results exhibits that the optimal degradation efficiency with 97.5%within 80 min is achievd by the CDs-CFO-5 composite.Such enhanced activity is ascribed to the introduction of CDs that effectively improves the separation efficiency of photogenerated electron pairs and creates new active sites as electron bridges that improve the photocata lytic performance.More importantly,a strong synergistic between CDs and photo-induced electrons generated from CFO can further activiate PMS to provide more SO4-·and·OH radicals for boosting the degradation ability towards AMX.The present study aims to elucidate positive role of CDs in photocata lytic/peroxy monosulfate activation during the degradation reaction.
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(Nos.52100081,51978178,and 51521006)the Department of Science and Technology of Guangdong Province of China(Nos.2021A1515011797,2023A1515012062,2019A1515012044,and 2022A1515010226)+4 种基金the Department of Education of Guangdong Province of China(No.2021KTSCX078)the Program for Innovative Research Teams of Guangdong Higher Education Institutes of China(No.2021KCXTD043)Maoming Municipal Department of Science and Technology of Guangdong Province of China(No.2018S0013)the Key Laboratory of Petrochemical Pollution Control of Guangdong Higher Education Institutes(No.2017KSYS004)the Startup Fund of GDUPT(Nos.2018rc63 and 2020rc041)。
文摘Switching the reaction routes in peroxymonosulfate(PMS)-based advanced oxidation processes have attracted much attention but remain challenging.Herein,a series of Co-N/C catalysts with different compositions and structures were prepared by using bimetallic zeolitic imidazolate frameworks based on ZIF-8 and ZIF-67(x Zn/Co-ZIFs).Results show that Co doping amount could mediate the transformation of the activation pathway of PMS over CoN/C.When Co doping amount was less than 10%,the constructed x Co-N/C/PMS system(x≤10%)was singlet oxygen-dominated reaction;however further increasing Co doping amount would lead to the generation and coexistence of sulfate radicals and high-valent cobalt,besides singlet oxygen.Furthermore,the nitrogen-coordinated Co(Co-NX)sites could serve as main catalytically active sites to generate singlet oxygen.While excess Co doping amount caused the formation of Co nanoparticles from which leached Co ions were responsible for the generation of sulfate radicals and high-valent cobalt.Compared to undoped N/C,Co doping could significantly enhance the catalytic performance.The 0.5%Co-N/C could achieve the optimum degradation(0.488 min^(-1))and mineralization abilities(78.4%)of sulfamethoxazole among the investigated Co-N/C catalysts,which was superior to most of previously reported catalysts.In addition,the application prospects of the two systems in different environmental scenarios(pH,inorganic anions and natural organic matter)were assessed and showed different degradation behaviors.This study provides a strategy to regulate the reactive species in PMS-based advanced oxidation process.
基金National Natural Science Foundation of China(No.51908172)“Pioneer”and“Leading Goose”R&D Program of Zhejiang(No.2023C03149)。
文摘Environmental endocrine disruptors,represented by bisphenol A(BPA),have been widely detected in the environment,bringing potential health risks to human beings.Nitrogen-containing biocarbon catalyst can activate peroxymonosulfate(PMS)to degrade BPA in water,but its active sites remain opaque.Herein,in this work,nitrogen-containing biochar,i.e.,C–Nedge,enriched with graphitic-N defects at the edges was prepared by one-pot co-pyrolysis of chitosan and potassium carbonate.The results showed that the C–Nedge/PMS system can effectively degrade 98%of BPA(50 mg/L).The electron transfer based non-radical oxidation mechanism was responsible for BPA degradation.Edge graphitic-N doping endows biochar with strong electron transfer ability.The catalyst had good recovery and reuse performance.This catalytic oxidation was also feasible for other refractory pollutants removal and worked well for treating practical wastewater.This work may provide valuable information in unraveling the N doping configurationactivity relationship during activating PMS by biochar.
基金Natural Science Foundation of Hebei Province, China (No. B2020202044)the Open Foundation of Key Laboratory of Industrial Ecology and Environmental Engineering, MOE, China (No. KLIEEE-21-04).
文摘Photocatalytic activation of peroxymonosulfate (PMS) has garnered a lot of interest in the field of wastewater treatment. Herein, a plasmonic Ag nanoparticles decorated MIL-101(Fe) hybrid was synthesized through a photodeposition process. Upon light irradiation, the Ag/MIL-101(Fe) exhibit reinforced photocatalytic activities for elimination of bisphenol A (BPA) with PMS. The optimized 2.0% Ag/MIL-101(Fe) composite presented the highest photocatalytic activity with kinetic constant k of 0.102 min-1, which was about 10-fold of the pristine MIL-101(Fe). Loading of plasmonic Ag into MIL-101(Fe) boosts photoinduced carrier separation and accelerates PMS activation to generate strong oxidative radicals. Photoelectrochemical tests and multiple spectroscopic studies confirmed the promoted charge carrier separation and transfer capability of Ag/MIL-101(Fe). Combining the results of radical trapping experiments and electron spin resonance (ESR), the formed SO4·-, ·OH, ·O2- and 1O2 had a significant role in the photocatalytic process. According to intermediate study, the degradation pathway was studied, and the possible mechanism was proposed.
基金supported by National Natural Science Foundation of China (No.22006136)。
文摘The monoaminotrinitro iron phthalocyanine(FeMATNPc)is used to connect with isonicotinic acid(INA)for amide bonding and axial coordination to synthetic a unique catalyst FeMATNPc-INA,which is loaded in polyacrylonitrile(PAN)nanofibers by electrospinning.The introduction of INA destroys theπ-πconjugated stack structure in phthalocyanine molecules and exposes more active sites.The FeMATNPc-INA structure is characterized by X-ray photoelectron spectroscopy and UV-visible absorption spectrum,and the FeMATNPcINA/PAN structure is characterized by Fourier transform infrared spectroscopy and X-ray diffraction.The FeMATNPc-INA/PAN can effectively activate peroxymonosulfate(PMS)to eliminate carbamazepine(CBZ)within 40 minutes(PMS 1.5 mmol/L)in the dark.The effects of catalyst dosage,PMS concentration,pH and inorganic anion on the degradation of CBZ are investigated.It has been confirmed by electron paramagnetic resonance,gas chromatography–mass spectroscopy and free radical capture experiments that the catalytic system is degraded by·OH,SO4^(·-)and Fe(IV)=O are the major active species,the singlet oxygen(^(1)O_(2))is the secondary active species.The degradation process of CBZ is analyzed by ultra-high performance liquid chromatography-mass spectrometry and the aromatic compounds have been degraded to small molecular acids.
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.
