A series of spinel fe rrites magnetic nanopa rticles NiFe2 O4 we re synthesized as the heterogeneous Fentonlike catalyst by hydrothermal method and then NiFe2 O4@SiO2 catalysts were obtained by the modification of NiF...A series of spinel fe rrites magnetic nanopa rticles NiFe2 O4 we re synthesized as the heterogeneous Fentonlike catalyst by hydrothermal method and then NiFe2 O4@SiO2 catalysts were obtained by the modification of NiFe2 O4 via micro emulsion method.XRD,VSM,FTIR,SEM,TEM,BET and XPS were carried to analyze the difference between the above two catalysts.NiFe2 O4@SiO2 catalyst exhibited the higher catalytic activity than NiFe2 O4 for the degradation of Rhodamine B owe to the outer Si02 layers surface,the more important is both of them showed the better catalytic performance when at neutral pH environment.展开更多
Current research on heterogeneous advanced oxidation processes(HAOPs)predominantly emphasizes catalyst iteration and innovation.Significant efforts have been made to regulate the electron structure and optimize the el...Current research on heterogeneous advanced oxidation processes(HAOPs)predominantly emphasizes catalyst iteration and innovation.Significant efforts have been made to regulate the electron structure and optimize the electron distribution,thereby increasing the catalytic activity.However,this focus often overshadows an equally essential aspect of HAOPs:the adsorption effect.Adsorption is a critical initiator for triggering the interaction of oxidants and contaminants with heterogeneous catalysts.The efficacy of these interactions is influenced by a variety of physicochemical properties,including surface chemistry and pore sizes,which determine the affinities between contaminants and material surfaces.This dispar ity in affinity is pivotal because it underpins the selective removal of contaminants,especially in complex waste streams containing diverse contaminants and competing matrices.Consequently,understanding and mastering these interfacial interactions is fundamentally indispensable not only for improving pro cess efficiency but also for enhancing the selectivity of contaminant removal.Herein,we highlight the importance of adsorption-driven interfacial interactions for fundamentally elucidating the catalytic mechanisms of HAOPs.Such interactions dictate the overall performance of the treatment processes by balancing the adsorption,reaction,and desorption rates on the catalyst surfaces.Elucidating the adsorption effect not only shifts the paradigm in understanding HAOPs but also improves their practical ity in water treatment and wastewater decontamination.Overall,we propose that revisiting adsorption driven interfacial interactions holds great promise for optimizing catalytic processes to develop effective HAOP strategies.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
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
Heterogeneous oxidation by gas-phase oxidants is an important chemical transformation pathway of secondary organic aerosol(SOA)and plays an important role in controlling the abundance,properties,as well as climate and...Heterogeneous oxidation by gas-phase oxidants is an important chemical transformation pathway of secondary organic aerosol(SOA)and plays an important role in controlling the abundance,properties,as well as climate and health impacts of aerosols.However,our knowledge on this heterogeneous chemistry remains inadequate.In this study,the heterogeneous oxidation ofα-pinene ozonolysis SOA by hydroxyl(OH)radicals was investigated under both low and high relative humidity(RH)conditions,with an emphasis on the evolution of molecular composition of SOA and its RH dependence.It is found that the heterogeneous oxidation of SOA at an OH exposure level equivalent to 12 hr of atmospheric aging leads to particle mass loss of 60%at 25%RH and 95%at 90%RH.The heterogeneous oxidation strongly changes the molecular composition of SOA.The dimer-to-monomer signal ratios increase dramatically with rising OH exposure,in particular under high RH conditions,suggesting that aerosol water stimulates the reaction of monomers with OH radicals more than that of dimers.In addition,the typical SOA tracer compounds such as pinic acid,pinonic acid,hydroxy pinonic acid and dimer esters(e.g.,C17H26O8 and C19H28O7)have lifetimes of several hours against heterogeneous OH oxidation under typical atmospheric conditions,which highlights the need for the consideration of their heterogeneous loss in the estimation of monoterpene SOA concentrations using tracer-based methods.Our study sheds lights on the heterogeneous oxidation chemistry ofmonoterpene SOA andwould help to understand their evolution and impacts in the atmosphere.展开更多
A novel iron-glutamate-silicotungstate ternary complex（FeШGluS iW） was synthesized from ferric chloride（FeI II）,glutamic acid（Glu）,and silicotungstic acid（SiW）,and used as a heterogeneous Fenton-like catalyst...A novel iron-glutamate-silicotungstate ternary complex（FeШGluS iW） was synthesized from ferric chloride（FeI II）,glutamic acid（Glu）,and silicotungstic acid（SiW）,and used as a heterogeneous Fenton-like catalyst for 4-chlorophenol（4-CP） degradation at neutral pH value. The prepared FeШGluS iW was characterized using inductively coupled plasma atomic emission spectroscopy,thermogravimetry,Fourier-transform infrared spectroscopy,ultraviolet-visible diffuse reflectance spectroscopy,X-ray diffraction,and field-emission scanning electron microscopy. The results showed that FeШGluS iW has the formula [Fe（C5H8NO4）（H2O）]2SiW 12O40？13H2O,with glutamate moiety and Keggin-structured SiW 12O404- heteropolyanion. The catalyst showed high catalytic activity in 4-CP degradation in the dark and under irradiation. Under the conditions of 4-CP 100 mg/L,FeШGluS iW 1.0 g/L,H2O2 20 mmol/L,and pH = 6.5,4-CP was completely decomposed in 40 min in the dark and in 15 min under irradiation. When the reaction time was prolonged to 2 h,the corresponding total organic carbon removals under dark and irradiated conditions were ca. 27% and 72%,respectively. The high catalytic activity of FeI IIGluS iW is resulted from hydrogen bonding of H2O2 on the FeI IIGluS iW surface. The enhanced degradation of 4-CP under irradiation arises from simultaneous oxidation of 4-CP through Fenton-like and photocatalytic processes respectively catalyzed by ferric iron and the SiW 12O404- hetropolyanion in FeШGluS iW.展开更多
Novel reusable MnOx‐N@C catalyst has been developed for the direct oxidation of N‐heterocycles under solvent‐free conditions using TBHP as benign oxidant to give the corresponding N‐heterocyclic ketones. The catal...Novel reusable MnOx‐N@C catalyst has been developed for the direct oxidation of N‐heterocycles under solvent‐free conditions using TBHP as benign oxidant to give the corresponding N‐heterocyclic ketones. The catalytic system exhibited a broad substrate scope and excellent regi‐oselectivity, as well as being amenable to gram‐scale synthesis. This MnOx‐N@C catalyst also showed good reusability and was successfully recycled six times without any significant loss of activity.展开更多
Sewage sludge from a biological wastewater treatment plant was converted into sewage sludge based activated carbon（SBAC） with Zn Cl2 as activation agent, which was used as a support for ferric oxides to form a catal...Sewage sludge from a biological wastewater treatment plant was converted into sewage sludge based activated carbon（SBAC） with Zn Cl2 as activation agent, which was used as a support for ferric oxides to form a catalyst（Fe Ox/SBAC） by a simple impregnation method.The new material was then used to improve the performance of Fenton oxidation of real biologically pretreated coal gasification wastewater（CGW）. The results indicated that the prepared Fe Ox/SBAC significantly enhanced the pollutant removal performance in the Fenton process, so that the treated wastewater was more biodegradable and less toxic. The best performance was obtained over a wide p H range from 2 to 7, temperature 30°C, 15 mg/L of H2O2 and 1 g/L of catalyst, and the treated effluent concentrations of COD, total phenols,BOD5 and TOC all met the discharge limits in China. Meanwhile, on the basis of significant inhibition by a radical scavenger in the heterogeneous Fenton process as well as the evolution of FT-IR spectra of pollutant-saturated Fe Ox/BAC with and without H2O2, it was deduced that the catalytic activity was responsible for generating hydroxyl radicals, and a possible reaction pathway and interface mechanism were proposed. Moreover, Fe Ox/SBAC showed superior stability over five successive oxidation runs. Thus, heterogeneous Fenton oxidation of biologically pretreated CGW by Fe Ox/SBAC, with the advantages of being economical, efficient and sustainable, holds promise for engineering application.展开更多
MnFe1.4Ru0.45Cu0.15O4 was an effective heterogeneous catalyst for the oxidation of various types of alcohols to the corresponding carbonyl compounds using atmospheric pressure of oxygen under mild conditions. Further...MnFe1.4Ru0.45Cu0.15O4 was an effective heterogeneous catalyst for the oxidation of various types of alcohols to the corresponding carbonyl compounds using atmospheric pressure of oxygen under mild conditions. Furthermore, this catalyst was also effective towards alcohol oxidation using water as solvent instead of toluene.展开更多
The long term exposure of arsenic via drinking water has resulted in wide occurrence of arsenisim globally, and the oxidation of the non-ionic arsenite(As(Ⅲ)) to negatively-charged arsenate(As(Ⅴ)) is of crucial impo...The long term exposure of arsenic via drinking water has resulted in wide occurrence of arsenisim globally, and the oxidation of the non-ionic arsenite(As(Ⅲ)) to negatively-charged arsenate(As(Ⅴ)) is of crucial importance for the promising removal of arsenic. The chemical oxidants of ozone, chlorine, chlorine dioxide, and potassium permanganate may achieve this goal;however, their application in developing countries is sometimes restricted by the complicate operation and high cost. This review paper focuses on the heterogeneous oxidation of As(Ⅲ) by solid oxidants such as manganese oxide, and the adsorption of As(Ⅴ)accordingly. Manganese oxide may be prepared by both chemical and biological methods to achieve good oxidation performance towards As(Ⅲ). Additionally, manganese oxide may be combined with other metal oxides, e.g., iron oxide, to improve the adsorption capability towards As(Ⅴ). Furthermore, manganese oxide may be coated onto porous materials of metal organic frameworks to develop novel adsorbents for arsenic removal. To achieve the application in engineering works, the adsorbents granulation may be achieved by drying and calcination, agglomeration, and the active components may also be in situ coated onto the porous materials to maintain the oxidation and adsorption activities as much as possible. The novel adsorbents with heterogeneous oxidation and adsorption capability may be carefully designed for the removal of arsenic in household purifiers, community-level decentralized small systems, and the large-scale drinking water treatment plants(DWTPs).This review provides insight into the fundamental studies on novel adsorbents, the development of innovative technologies, and the demonstration engineering works involved in the heterogeneous oxidation and adsorption, and may be practically valuable for the arsenic pollution control globally.展开更多
The effect of phosphate on adsorption and oxidation of catechol, 1,2-dihydroxybenzene,in a heterogeneous Fenton system was investigated. In situ attenuated total reflectance infrared spectroscopy（ATR-FTIR） was used ...The effect of phosphate on adsorption and oxidation of catechol, 1,2-dihydroxybenzene,in a heterogeneous Fenton system was investigated. In situ attenuated total reflectance infrared spectroscopy（ATR-FTIR） was used to monitor the surface speciation at the nano-Fe_3O_4 catalyst surface. The presence of phosphate decreased the removal rate of catechol and the abatement of dissolved organic compounds, as well as the decomposition of H2O2. This effect of phosphate was mainly due to its strong reaction with surface sites on the iron oxide catalyst. At neutral and acid pH, phosphate could displace the adsorbed catechol from the surface of catalyst and also could compete for surface sites with H2O2. In situ IR spectra indicated the formation of iron phosphate precipitation at the catalyst surface. The iron phosphate surface species may affect the amount of iron atoms taking part in the catalytic decomposition of H2O2 and formation of hydroxyl radicals,and inhibit the catalytic ability of Fe3O4 catalyst. Therefore, phosphate ions worked as stabilizer and inhibitor in a heterogeneous Fenton reaction at the same time, in effect leading to an increase in oxidation efficiency in this study. However, before use of phosphate as pH buffer or H2O2 stabilizer in a heterogeneous Fenton system, the possible inhibitory effect of phosphate on the actual removal of organic pollutants should be fully considered.展开更多
Pure metal-doped(Cu,Zn)Fe2O4 was synthesized from Zn-containing electric arc furnace dust(EAFD)by solid-state reaction using copper salt as additive.The effects of pretreated EAFD-to-Cu2(OH)2CO3·6H2O mass ratio,c...Pure metal-doped(Cu,Zn)Fe2O4 was synthesized from Zn-containing electric arc furnace dust(EAFD)by solid-state reaction using copper salt as additive.The effects of pretreated EAFD-to-Cu2(OH)2CO3·6H2O mass ratio,calcination time,and calcination temperature on the structure and catalytic ability were systematically studied.Under the optimum conditions,the decolorization efficiency and total organic carbon(TOC)removal efficiency of the as-prepared ferrite for treating a Rhodamine B solution were approximately 90.0%and 45.0%,respectively,and the decolorization efficiency remained 83.0%after five recycles,suggesting that the as-prepared(Cu,Zn)Fe2O4 was an efficient heterogeneous Fenton-like catalyst with high stability.The high catalytic activity mainly depended on the synergistic effect of iron and copper ions occupying octahedral positions.More importantly,the toxicity characteristic leaching procedure(TCLP)analysis illustrated that the toxic Zncontaining EAFD was transformed into harmless(Cu,Zn)Fe2O4 and that the concentrations of toxic ions in the degraded solution were all lower than the national emission standard(GB/31574-2015),further confirming that the as obtained sample is an environment-friendly heterogeneous Fenton-like catalyst.展开更多
Heterogeneous Fenton-like process using fly ash as a catalyst was studied to degrade n-butyl xanthate form aqueous solution. The different reaction parameters on the degradation efficiency of the process were investig...Heterogeneous Fenton-like process using fly ash as a catalyst was studied to degrade n-butyl xanthate form aqueous solution. The different reaction parameters on the degradation efficiency of the process were investigated. The fly ash/H2O2 catalyst possesses a high oxidation activity for n-butyl xanthate degradation in aqueous solution. It is found that both the dosage of catalyst and initial solution pH significantly affect the n-butyl xanthate conversion efficient. The results indicate that by using 1.176 mmol/L H2O2 and 1.0 g/L fly ash catalyst with mass fraction of 4.14% Fe(III) oxide at pH 3.0, almost 96.90% n-butyl xanthate conversion and over 96.66% COD removal can be achieved within 120 min with heterogeneous catalysis by fly ash. CS2 as an intermediate of n-butyl xanthate oxidation. Finally, it is demonstrated that the fly ash/H2O2 catalytic oxidation process can be an efficient method for the treatment of n-butyl xanthate containing wastewater.展开更多
Co-salen functionalized on graphene with an average pore size of 27.7 nm as a heterogeneous catalyst exhibited good catalytic activity and recyclability in cyclohexene oxidation.
Ozone（O3） is an important atmospheric oxidant. Black carbon（BC） particles released into the atmosphere undergo an aging process via O3 oxidation. O3-aged BC particles may change their uptake ability toward trace r...Ozone（O3） is an important atmospheric oxidant. Black carbon（BC） particles released into the atmosphere undergo an aging process via O3 oxidation. O3-aged BC particles may change their uptake ability toward trace reducing gases such as SO2 in the atmosphere,leading to different environmental and health effects. In this paper, the heterogeneous reaction process between O3-aged BC and SO2 was explored via in-situ diffuse reflectance infrared Fourier transform spectroscopy（DRIFTS）. Combined with ion chromatography（IC）,DRIFTS was used to qualitatively and quantitatively analyze the sulfate product. The results showed that O3-aged BC had stronger SO2 oxidation ability than fresh BC, and the reactive species/sites generated on the surface had an important role in the oxidation of SO2.Relative humidity or 254 nm UV（ultraviolet） light illumination enhanced the oxidation uptake of SO2 on O3-aged BC. The oxidation potentials of the BC particles were detected via dithiothreitol（DTT） assay. The DTT activity over BC was decreased in the process of SO2 reduction, with the consumption of oxidative active sites.展开更多
In this study, Fe3O4nanoparticles（Fe3O4NPs） were successfully prepared via oxidation–precipitation method and characterized by scanning electron microscopy（SEM）, X-ray diffraction（XRD） and Fourier transform inf...In this study, Fe3O4nanoparticles（Fe3O4NPs） were successfully prepared via oxidation–precipitation method and characterized by scanning electron microscopy（SEM）, X-ray diffraction（XRD） and Fourier transform infrared spectroscopy（FT-IR）. The characterization results indicated that Fe3O4 NPs with regular crystal structure and a narrow of diameters had been synthesized successfully and had high purity. A series of experiments were carried out to investigate the degradation of Orange II by the obtained heterogeneous Fe3O4 catalysts in the presence of H2O2. The response surface methodology（RSM） based on Box–Behnken design（BBD） was employed to design and optimize individual and interactive effects of the four main independent parameters（catalyst loading, initial p H, reaction temperature and H2O2concentration） on decolorization efficiency of Orange II. A significant quadratic model（p-value 〈0.0001, R2= 0.9369） was derived using analysis of variance（ANOVA）. Optimum conditions were catalyst loading of 1.5 g/L, initial p H of 2.7, reaction temperature of 42 8C and H2O2 concentration of 22 mmol/L, respectively. The predicted decolorization rate under the optimum conditions as determined by the proposed model was 99.55%. Confirmatory tests were carried out and the decolorization rate of 99.49% was observed under the optimum conditions, which agreed well with the model prediction.展开更多
The present study aims to develop effective adsorption and oxidation of synthetic dye in wastewater by using the newly synthesized iron-amended activated carbon. Recently synthetic dye-containing wastewater has gained...The present study aims to develop effective adsorption and oxidation of synthetic dye in wastewater by using the newly synthesized iron-amended activated carbon. Recently synthetic dye-containing wastewater has gained more attention due to its mass discharge, high toxicity and low biodegradation. For enhancing adsorption of dye and oxidative regeneration of dye-exhausted activated carbon, the novel amendment of iron-deposited granular activated carbon (GAC) was developed. It was to amend ferrous ion onto the acid-pretreated GAC when pH of iron solution was higher than the pH at point of zero charge (pH, pzc) of the GAC. Methylene blue (MB) in water was adsorbed onto the acid-treated iron- amended GAC (Fe-GAC) followed by single or multiple applications of H2O2. Batch experiments were carried out to study the adsorption isotherm and kinetics indicating adsorption of MB onto the Fe-GAC followed Langmuir isotherm and the pseudo-second order kinetics. The Fe-GACshowed the maximum adsorption capacity (qm) of 238.1 ± 0.78 mg/g which was higher than the virgin GAC with qm of 175.4 ± 13.6 mg/g at 20?C, pH 6 and the initial concentration of 20 - 200 mg/L. The heterogeneous Fenton oxidation of MB in the Fe-GAC revealedthat increasing the H2O2 loading from 7 to 140 mmol H2O2/mmol MB led to enhancing the oxidation efficiency of MB in the GAC from 62.6% to 100% due to the increased generation of hydroxyl radicals. Further enhancement of oxidation of MB in the Fe-GAC was made by the multiple application of H2O2 while minimizing OH radical scavenging often occurring at high concentration of H2O2. Therefore, the acid-treated iron-amended GAC would provide excellent adsorption capacity for MB and high oxidation efficiency of MB in the GAC with multiple applications of H2O2 and optimum iron loading.展开更多
Magnetically modified Fe-Al pillared bentonite（Fe3O4/ Fe-Al-Bent） was prepared via chemical co-precipitation method and characterized by powder X-ray diffraction（XRD）, Brunauer-EmmettTeller（BET）, Fourier transfo...Magnetically modified Fe-Al pillared bentonite（Fe3O4/ Fe-Al-Bent） was prepared via chemical co-precipitation method and characterized by powder X-ray diffraction（XRD）, Brunauer-EmmettTeller（BET）, Fourier transform infrared spectroscopy（FTIR） and scanning electron microscopy（SEM）. A series of experiments were carried out to investigate the degradation of Orange II by the obtained heterogeneous catalysts in the presence of H2O2. The experimental result indicated that the synthetic materials had a high catalytic activity and good reusability.展开更多
The elimination of neonicotinoids(NEOs)from water has been a research priority due to their threats to human health and ecosystems.In this study,we established the heterogeneous peroxymonosulfate(PMS)activation system...The elimination of neonicotinoids(NEOs)from water has been a research priority due to their threats to human health and ecosystems.In this study,we established the heterogeneous peroxymonosulfate(PMS)activation system using manganese catalyst(Mn NC)and cobalt catalyst(Co NC)to trigger the nonradical oxidation and synergistic oxidation pathway,respectively to remove NEOs.The results showed that the nonradical oxidation system exhibited superior NEOs degradation capability.The composition of organic pollutants in wastewater significantly impacted subsequent degradation processes.The charge distribution and reaction sites of various NEOs were analyzed using density functional theory(DFT)calculations,and it demonstrated the electron distribution and activity of NEOs were significantly influenced by the type and number of substituents.Nitro group(–NO_(2))and cyanide group(–C≡N)were identified as strong electron-withdrawing groups and prone to be attacked by negatively charged radicals.The transformation of NEOs was analyzed,and result showed that the C and N sites adjacent to the nitro group and cyanide group were more susceptible to oxidation attacks.S and N atoms,which possess strong electronegativity and high electron cloud density,were identified as key active sites in the degradation pathway.The outcomes of this study provide valuable guidance for the oriented regulation of oxidation pathways towards efficient removal of NEOs in water.展开更多
Nano-Fe2O3/goldmine complex was obtained by chemical coprecipitation reaction on the surface of goldmine waste-solid. Being used as the heterogeneous catalyst in Fenton-like advanced oxidation processes (AOPs), its tr...Nano-Fe2O3/goldmine complex was obtained by chemical coprecipitation reaction on the surface of goldmine waste-solid. Being used as the heterogeneous catalyst in Fenton-like advanced oxidation processes (AOPs), its treatment effect was studied in the removal performance of industrial dyes effluent. Although the maximal COD removal efficiency would reach 35.4% when 5 mL NaClO was added in 100 mL industrial dyes effluent, it is found that by using nano-Fe2O3/goldmine system, the COD removal efficiency of 13,000 mg/L dyes wastewater could reach up to 75.5% in the presence of 30 g/L nano-Fe2O3/goldmine complex and 50 mL/L NaClO at 50。C.展开更多
基金the financial support from the Fundamental Research Funds for the Central Universities(No. xjj2016045)
文摘A series of spinel fe rrites magnetic nanopa rticles NiFe2 O4 we re synthesized as the heterogeneous Fentonlike catalyst by hydrothermal method and then NiFe2 O4@SiO2 catalysts were obtained by the modification of NiFe2 O4 via micro emulsion method.XRD,VSM,FTIR,SEM,TEM,BET and XPS were carried to analyze the difference between the above two catalysts.NiFe2 O4@SiO2 catalyst exhibited the higher catalytic activity than NiFe2 O4 for the degradation of Rhodamine B owe to the outer Si02 layers surface,the more important is both of them showed the better catalytic performance when at neutral pH environment.
基金supported by the National Key Research and Development Program of China(2022YFC3205300)the National Natural Science Foundation of China(22176124).
文摘Current research on heterogeneous advanced oxidation processes(HAOPs)predominantly emphasizes catalyst iteration and innovation.Significant efforts have been made to regulate the electron structure and optimize the electron distribution,thereby increasing the catalytic activity.However,this focus often overshadows an equally essential aspect of HAOPs:the adsorption effect.Adsorption is a critical initiator for triggering the interaction of oxidants and contaminants with heterogeneous catalysts.The efficacy of these interactions is influenced by a variety of physicochemical properties,including surface chemistry and pore sizes,which determine the affinities between contaminants and material surfaces.This dispar ity in affinity is pivotal because it underpins the selective removal of contaminants,especially in complex waste streams containing diverse contaminants and competing matrices.Consequently,understanding and mastering these interfacial interactions is fundamentally indispensable not only for improving pro cess efficiency but also for enhancing the selectivity of contaminant removal.Herein,we highlight the importance of adsorption-driven interfacial interactions for fundamentally elucidating the catalytic mechanisms of HAOPs.Such interactions dictate the overall performance of the treatment processes by balancing the adsorption,reaction,and desorption rates on the catalyst surfaces.Elucidating the adsorption effect not only shifts the paradigm in understanding HAOPs but also improves their practical ity in water treatment and wastewater decontamination.Overall,we propose that revisiting adsorption driven interfacial interactions holds great promise for optimizing catalytic processes to develop effective HAOP strategies.
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 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.
基金supported by the National Natural Science Foundation of China (Nos.22022607 and 42005090)the Shanghai Pujiang Program (No.20PJ1407600)。
文摘Heterogeneous oxidation by gas-phase oxidants is an important chemical transformation pathway of secondary organic aerosol(SOA)and plays an important role in controlling the abundance,properties,as well as climate and health impacts of aerosols.However,our knowledge on this heterogeneous chemistry remains inadequate.In this study,the heterogeneous oxidation ofα-pinene ozonolysis SOA by hydroxyl(OH)radicals was investigated under both low and high relative humidity(RH)conditions,with an emphasis on the evolution of molecular composition of SOA and its RH dependence.It is found that the heterogeneous oxidation of SOA at an OH exposure level equivalent to 12 hr of atmospheric aging leads to particle mass loss of 60%at 25%RH and 95%at 90%RH.The heterogeneous oxidation strongly changes the molecular composition of SOA.The dimer-to-monomer signal ratios increase dramatically with rising OH exposure,in particular under high RH conditions,suggesting that aerosol water stimulates the reaction of monomers with OH radicals more than that of dimers.In addition,the typical SOA tracer compounds such as pinic acid,pinonic acid,hydroxy pinonic acid and dimer esters(e.g.,C17H26O8 and C19H28O7)have lifetimes of several hours against heterogeneous OH oxidation under typical atmospheric conditions,which highlights the need for the consideration of their heterogeneous loss in the estimation of monoterpene SOA concentrations using tracer-based methods.Our study sheds lights on the heterogeneous oxidation chemistry ofmonoterpene SOA andwould help to understand their evolution and impacts in the atmosphere.
基金supported by the National Natural Science Foundation of China(51268001)~~
文摘A novel iron-glutamate-silicotungstate ternary complex（FeШGluS iW） was synthesized from ferric chloride（FeI II）,glutamic acid（Glu）,and silicotungstic acid（SiW）,and used as a heterogeneous Fenton-like catalyst for 4-chlorophenol（4-CP） degradation at neutral pH value. The prepared FeШGluS iW was characterized using inductively coupled plasma atomic emission spectroscopy,thermogravimetry,Fourier-transform infrared spectroscopy,ultraviolet-visible diffuse reflectance spectroscopy,X-ray diffraction,and field-emission scanning electron microscopy. The results showed that FeШGluS iW has the formula [Fe（C5H8NO4）（H2O）]2SiW 12O40？13H2O,with glutamate moiety and Keggin-structured SiW 12O404- heteropolyanion. The catalyst showed high catalytic activity in 4-CP degradation in the dark and under irradiation. Under the conditions of 4-CP 100 mg/L,FeШGluS iW 1.0 g/L,H2O2 20 mmol/L,and pH = 6.5,4-CP was completely decomposed in 40 min in the dark and in 15 min under irradiation. When the reaction time was prolonged to 2 h,the corresponding total organic carbon removals under dark and irradiated conditions were ca. 27% and 72%,respectively. The high catalytic activity of FeI IIGluS iW is resulted from hydrogen bonding of H2O2 on the FeI IIGluS iW surface. The enhanced degradation of 4-CP under irradiation arises from simultaneous oxidation of 4-CP through Fenton-like and photocatalytic processes respectively catalyzed by ferric iron and the SiW 12O404- hetropolyanion in FeШGluS iW.
基金supported by the National Basic research Program of China (973 Program,2009CB623505)the National Natural Science Foundation of China (21273225)~~
文摘Novel reusable MnOx‐N@C catalyst has been developed for the direct oxidation of N‐heterocycles under solvent‐free conditions using TBHP as benign oxidant to give the corresponding N‐heterocyclic ketones. The catalytic system exhibited a broad substrate scope and excellent regi‐oselectivity, as well as being amenable to gram‐scale synthesis. This MnOx‐N@C catalyst also showed good reusability and was successfully recycled six times without any significant loss of activity.
基金supported by the State Key Laboratory of Urban Water Resource and Environment (Harbin Institute of Technology) (No.2015DX02)
文摘Sewage sludge from a biological wastewater treatment plant was converted into sewage sludge based activated carbon（SBAC） with Zn Cl2 as activation agent, which was used as a support for ferric oxides to form a catalyst（Fe Ox/SBAC） by a simple impregnation method.The new material was then used to improve the performance of Fenton oxidation of real biologically pretreated coal gasification wastewater（CGW）. The results indicated that the prepared Fe Ox/SBAC significantly enhanced the pollutant removal performance in the Fenton process, so that the treated wastewater was more biodegradable and less toxic. The best performance was obtained over a wide p H range from 2 to 7, temperature 30°C, 15 mg/L of H2O2 and 1 g/L of catalyst, and the treated effluent concentrations of COD, total phenols,BOD5 and TOC all met the discharge limits in China. Meanwhile, on the basis of significant inhibition by a radical scavenger in the heterogeneous Fenton process as well as the evolution of FT-IR spectra of pollutant-saturated Fe Ox/BAC with and without H2O2, it was deduced that the catalytic activity was responsible for generating hydroxyl radicals, and a possible reaction pathway and interface mechanism were proposed. Moreover, Fe Ox/SBAC showed superior stability over five successive oxidation runs. Thus, heterogeneous Fenton oxidation of biologically pretreated CGW by Fe Ox/SBAC, with the advantages of being economical, efficient and sustainable, holds promise for engineering application.
文摘MnFe1.4Ru0.45Cu0.15O4 was an effective heterogeneous catalyst for the oxidation of various types of alcohols to the corresponding carbonyl compounds using atmospheric pressure of oxygen under mild conditions. Furthermore, this catalyst was also effective towards alcohol oxidation using water as solvent instead of toluene.
基金supported by the National Natural Science Foundation of China (No. 51925807)。
文摘The long term exposure of arsenic via drinking water has resulted in wide occurrence of arsenisim globally, and the oxidation of the non-ionic arsenite(As(Ⅲ)) to negatively-charged arsenate(As(Ⅴ)) is of crucial importance for the promising removal of arsenic. The chemical oxidants of ozone, chlorine, chlorine dioxide, and potassium permanganate may achieve this goal;however, their application in developing countries is sometimes restricted by the complicate operation and high cost. This review paper focuses on the heterogeneous oxidation of As(Ⅲ) by solid oxidants such as manganese oxide, and the adsorption of As(Ⅴ)accordingly. Manganese oxide may be prepared by both chemical and biological methods to achieve good oxidation performance towards As(Ⅲ). Additionally, manganese oxide may be combined with other metal oxides, e.g., iron oxide, to improve the adsorption capability towards As(Ⅴ). Furthermore, manganese oxide may be coated onto porous materials of metal organic frameworks to develop novel adsorbents for arsenic removal. To achieve the application in engineering works, the adsorbents granulation may be achieved by drying and calcination, agglomeration, and the active components may also be in situ coated onto the porous materials to maintain the oxidation and adsorption activities as much as possible. The novel adsorbents with heterogeneous oxidation and adsorption capability may be carefully designed for the removal of arsenic in household purifiers, community-level decentralized small systems, and the large-scale drinking water treatment plants(DWTPs).This review provides insight into the fundamental studies on novel adsorbents, the development of innovative technologies, and the demonstration engineering works involved in the heterogeneous oxidation and adsorption, and may be practically valuable for the arsenic pollution control globally.
基金supported by the National Natural Science Foundation of China(Nos.21107125,21577160,51290282,51221892)the National Basic Research Program(973s)of China(No.2011CB933704)the Hjalmar Lundbom Research Center at Lulea niversity of Technology
文摘The effect of phosphate on adsorption and oxidation of catechol, 1,2-dihydroxybenzene,in a heterogeneous Fenton system was investigated. In situ attenuated total reflectance infrared spectroscopy（ATR-FTIR） was used to monitor the surface speciation at the nano-Fe_3O_4 catalyst surface. The presence of phosphate decreased the removal rate of catechol and the abatement of dissolved organic compounds, as well as the decomposition of H2O2. This effect of phosphate was mainly due to its strong reaction with surface sites on the iron oxide catalyst. At neutral and acid pH, phosphate could displace the adsorbed catechol from the surface of catalyst and also could compete for surface sites with H2O2. In situ IR spectra indicated the formation of iron phosphate precipitation at the catalyst surface. The iron phosphate surface species may affect the amount of iron atoms taking part in the catalytic decomposition of H2O2 and formation of hydroxyl radicals,and inhibit the catalytic ability of Fe3O4 catalyst. Therefore, phosphate ions worked as stabilizer and inhibitor in a heterogeneous Fenton reaction at the same time, in effect leading to an increase in oxidation efficiency in this study. However, before use of phosphate as pH buffer or H2O2 stabilizer in a heterogeneous Fenton system, the possible inhibitory effect of phosphate on the actual removal of organic pollutants should be fully considered.
基金financially supported by the National Natural Science Foundation of China(No.U1810205)the National Basic Research Program of China(No.2014CB 643401)Shanxi Collaborative Innovation Center of High Value-added Utilization of Coal-related Wastes。
文摘Pure metal-doped(Cu,Zn)Fe2O4 was synthesized from Zn-containing electric arc furnace dust(EAFD)by solid-state reaction using copper salt as additive.The effects of pretreated EAFD-to-Cu2(OH)2CO3·6H2O mass ratio,calcination time,and calcination temperature on the structure and catalytic ability were systematically studied.Under the optimum conditions,the decolorization efficiency and total organic carbon(TOC)removal efficiency of the as-prepared ferrite for treating a Rhodamine B solution were approximately 90.0%and 45.0%,respectively,and the decolorization efficiency remained 83.0%after five recycles,suggesting that the as-prepared(Cu,Zn)Fe2O4 was an efficient heterogeneous Fenton-like catalyst with high stability.The high catalytic activity mainly depended on the synergistic effect of iron and copper ions occupying octahedral positions.More importantly,the toxicity characteristic leaching procedure(TCLP)analysis illustrated that the toxic Zncontaining EAFD was transformed into harmless(Cu,Zn)Fe2O4 and that the concentrations of toxic ions in the degraded solution were all lower than the national emission standard(GB/31574-2015),further confirming that the as obtained sample is an environment-friendly heterogeneous Fenton-like catalyst.
基金Project(CZQ13002)supported by the Special Fund for Basic Scientific Research of Central Universities,China
文摘Heterogeneous Fenton-like process using fly ash as a catalyst was studied to degrade n-butyl xanthate form aqueous solution. The different reaction parameters on the degradation efficiency of the process were investigated. The fly ash/H2O2 catalyst possesses a high oxidation activity for n-butyl xanthate degradation in aqueous solution. It is found that both the dosage of catalyst and initial solution pH significantly affect the n-butyl xanthate conversion efficient. The results indicate that by using 1.176 mmol/L H2O2 and 1.0 g/L fly ash catalyst with mass fraction of 4.14% Fe(III) oxide at pH 3.0, almost 96.90% n-butyl xanthate conversion and over 96.66% COD removal can be achieved within 120 min with heterogeneous catalysis by fly ash. CS2 as an intermediate of n-butyl xanthate oxidation. Finally, it is demonstrated that the fly ash/H2O2 catalytic oxidation process can be an efficient method for the treatment of n-butyl xanthate containing wastewater.
基金the National Natural Science Foundation of China(20973079 and U1162201)Graduate Innovation Fund of Jilin University(20121051)
文摘Co-salen functionalized on graphene with an average pore size of 27.7 nm as a heterogeneous catalyst exhibited good catalytic activity and recyclability in cyclohexene oxidation.
基金the financial support provided by the National Natural Science Foundation of China(Nos.21277004,21190051,41121004)the Beijing Natural Science Foundation(No.8132035)+1 种基金the Fujitsu Laboratories Limited Foundation(No.k120400)the Special Fund of State Key Joint Laboratory of Environmental Simulation and Pollution Control(2015)
文摘Ozone（O3） is an important atmospheric oxidant. Black carbon（BC） particles released into the atmosphere undergo an aging process via O3 oxidation. O3-aged BC particles may change their uptake ability toward trace reducing gases such as SO2 in the atmosphere,leading to different environmental and health effects. In this paper, the heterogeneous reaction process between O3-aged BC and SO2 was explored via in-situ diffuse reflectance infrared Fourier transform spectroscopy（DRIFTS）. Combined with ion chromatography（IC）,DRIFTS was used to qualitatively and quantitatively analyze the sulfate product. The results showed that O3-aged BC had stronger SO2 oxidation ability than fresh BC, and the reactive species/sites generated on the surface had an important role in the oxidation of SO2.Relative humidity or 254 nm UV（ultraviolet） light illumination enhanced the oxidation uptake of SO2 on O3-aged BC. The oxidation potentials of the BC particles were detected via dithiothreitol（DTT） assay. The DTT activity over BC was decreased in the process of SO2 reduction, with the consumption of oxidative active sites.
基金financially supported by the Specialized Research Fund for the Doctoral Program of Higher Education of China(No.20114219110002)Fund from Coal Conversion and New Carbon Materials Hubei Key Laboratory(Wuhan University of Science and Technology)(No.WKDM201107)Educational Commission of Hubei Province of China(No.D20131107)
文摘In this study, Fe3O4nanoparticles（Fe3O4NPs） were successfully prepared via oxidation–precipitation method and characterized by scanning electron microscopy（SEM）, X-ray diffraction（XRD） and Fourier transform infrared spectroscopy（FT-IR）. The characterization results indicated that Fe3O4 NPs with regular crystal structure and a narrow of diameters had been synthesized successfully and had high purity. A series of experiments were carried out to investigate the degradation of Orange II by the obtained heterogeneous Fe3O4 catalysts in the presence of H2O2. The response surface methodology（RSM） based on Box–Behnken design（BBD） was employed to design and optimize individual and interactive effects of the four main independent parameters（catalyst loading, initial p H, reaction temperature and H2O2concentration） on decolorization efficiency of Orange II. A significant quadratic model（p-value 〈0.0001, R2= 0.9369） was derived using analysis of variance（ANOVA）. Optimum conditions were catalyst loading of 1.5 g/L, initial p H of 2.7, reaction temperature of 42 8C and H2O2 concentration of 22 mmol/L, respectively. The predicted decolorization rate under the optimum conditions as determined by the proposed model was 99.55%. Confirmatory tests were carried out and the decolorization rate of 99.49% was observed under the optimum conditions, which agreed well with the model prediction.
文摘The present study aims to develop effective adsorption and oxidation of synthetic dye in wastewater by using the newly synthesized iron-amended activated carbon. Recently synthetic dye-containing wastewater has gained more attention due to its mass discharge, high toxicity and low biodegradation. For enhancing adsorption of dye and oxidative regeneration of dye-exhausted activated carbon, the novel amendment of iron-deposited granular activated carbon (GAC) was developed. It was to amend ferrous ion onto the acid-pretreated GAC when pH of iron solution was higher than the pH at point of zero charge (pH, pzc) of the GAC. Methylene blue (MB) in water was adsorbed onto the acid-treated iron- amended GAC (Fe-GAC) followed by single or multiple applications of H2O2. Batch experiments were carried out to study the adsorption isotherm and kinetics indicating adsorption of MB onto the Fe-GAC followed Langmuir isotherm and the pseudo-second order kinetics. The Fe-GACshowed the maximum adsorption capacity (qm) of 238.1 ± 0.78 mg/g which was higher than the virgin GAC with qm of 175.4 ± 13.6 mg/g at 20?C, pH 6 and the initial concentration of 20 - 200 mg/L. The heterogeneous Fenton oxidation of MB in the Fe-GAC revealedthat increasing the H2O2 loading from 7 to 140 mmol H2O2/mmol MB led to enhancing the oxidation efficiency of MB in the GAC from 62.6% to 100% due to the increased generation of hydroxyl radicals. Further enhancement of oxidation of MB in the Fe-GAC was made by the multiple application of H2O2 while minimizing OH radical scavenging often occurring at high concentration of H2O2. Therefore, the acid-treated iron-amended GAC would provide excellent adsorption capacity for MB and high oxidation efficiency of MB in the GAC with multiple applications of H2O2 and optimum iron loading.
基金Funded by the Specialized Research Fund for the Doctoral Program of Higher Education of China(20114219110002)the Natural Science Foundation of Hubei Province(Nos.2014CFB810&2014CFB812)
文摘Magnetically modified Fe-Al pillared bentonite（Fe3O4/ Fe-Al-Bent） was prepared via chemical co-precipitation method and characterized by powder X-ray diffraction（XRD）, Brunauer-EmmettTeller（BET）, Fourier transform infrared spectroscopy（FTIR） and scanning electron microscopy（SEM）. A series of experiments were carried out to investigate the degradation of Orange II by the obtained heterogeneous catalysts in the presence of H2O2. The experimental result indicated that the synthetic materials had a high catalytic activity and good reusability.
基金funded by National Natural Science Foundation of China(No.42177382)。
文摘The elimination of neonicotinoids(NEOs)from water has been a research priority due to their threats to human health and ecosystems.In this study,we established the heterogeneous peroxymonosulfate(PMS)activation system using manganese catalyst(Mn NC)and cobalt catalyst(Co NC)to trigger the nonradical oxidation and synergistic oxidation pathway,respectively to remove NEOs.The results showed that the nonradical oxidation system exhibited superior NEOs degradation capability.The composition of organic pollutants in wastewater significantly impacted subsequent degradation processes.The charge distribution and reaction sites of various NEOs were analyzed using density functional theory(DFT)calculations,and it demonstrated the electron distribution and activity of NEOs were significantly influenced by the type and number of substituents.Nitro group(–NO_(2))and cyanide group(–C≡N)were identified as strong electron-withdrawing groups and prone to be attacked by negatively charged radicals.The transformation of NEOs was analyzed,and result showed that the C and N sites adjacent to the nitro group and cyanide group were more susceptible to oxidation attacks.S and N atoms,which possess strong electronegativity and high electron cloud density,were identified as key active sites in the degradation pathway.The outcomes of this study provide valuable guidance for the oriented regulation of oxidation pathways towards efficient removal of NEOs in water.
文摘Nano-Fe2O3/goldmine complex was obtained by chemical coprecipitation reaction on the surface of goldmine waste-solid. Being used as the heterogeneous catalyst in Fenton-like advanced oxidation processes (AOPs), its treatment effect was studied in the removal performance of industrial dyes effluent. Although the maximal COD removal efficiency would reach 35.4% when 5 mL NaClO was added in 100 mL industrial dyes effluent, it is found that by using nano-Fe2O3/goldmine system, the COD removal efficiency of 13,000 mg/L dyes wastewater could reach up to 75.5% in the presence of 30 g/L nano-Fe2O3/goldmine complex and 50 mL/L NaClO at 50。C.
