There is a relatively low efficiency of Fe(Ⅲ)/Fe(Ⅱ) conversion cycle and H2 O2 decomposition(<30%) in conventional Fenton process,which further results in a low production efficiency of ·OH and seriously res...There is a relatively low efficiency of Fe(Ⅲ)/Fe(Ⅱ) conversion cycle and H2 O2 decomposition(<30%) in conventional Fenton process,which further results in a low production efficiency of ·OH and seriously restricts the application of Fenton.Herein,we report that the commercial MoO2 can be used as the cocatalyst in Fenton process to dramatically accelerate the oxidation of Lissamine rhodamine B(L-RhB),where the efficiency of Fe(Ⅲ)/Fe(Ⅱ) cycling is greatly enhanced in the Fenton reaction meanwhile.And the L-RhB solution could be degraded nearly 100% in 1 min in the MoO2 cocatalytic Fenton system under the optimal reaction condition,which is apparently better than that of the conventional Fenton system(~50%).Different from the conventional Fenton reaction where the ’OH plays an important role in the oxidation process,it shows that 1 O2 contributes most in the MoO2 cocatalytic Fenton reaction.However,it is found that the exposed Mo^4+ active sites on the surface of MoO2 powders can greatly promote the rate-limiting step of Fe^3+/Fe^2+ cycle conversion,thus minimizing the dosage of H2 O2(0.400 mmol/L) and Fe^2+(0.105 mmol/L).Interestingly,the MoO2 cocatalytic Fenton system also exhibits a good ability for reducing Cr(Ⅵ) ions,where the reduction ability for Cr(Ⅵ) reaches almost 100% within 2 h.In short,this work shows a new discovery for M002 cocatalytic advanced oxidation processes(AOPs),which devotes a lot to the practical water remediation application.展开更多
The heterogeneous Fenton reaction can generate highly reactive hydroxyl radicals（·OH）from reactions between recyclable solid catalysts and H2O2 at acidic or even circumneutral pH.Hence,it can effectively oxidiz...The heterogeneous Fenton reaction can generate highly reactive hydroxyl radicals（·OH）from reactions between recyclable solid catalysts and H2O2 at acidic or even circumneutral pH.Hence,it can effectively oxidize refractory organics in water or soils and has become a promising environmentally friendly treatment technology.Due to the complex reaction system,the mechanism behind heterogeneous Fenton reactions remains unresolved but fascinating,and is crucial for understanding Fenton chemistry and the development and application of efficient heterogeneous Fenton technologies.Iron-based materials usually possess high catalytic activity,low cost,negligible toxicity and easy recovery,and are a superior type of heterogeneous Fenton catalysts.Therefore,this article reviews the fundamental but important interfacial mechanisms of heterogeneous Fenton reactions catalyzed by iron-based materials..OH,hydroperoxyl radicals/superoxide anions（HO2./O2^-.）and high-valent iron are the three main types of reactive oxygen species（ROS）,with different oxidation reactivity and selectivity.Based on the mechanisms of ROS generation,the interfacial mechanisms of heterogeneous Fenton systems can be classified as the homogeneous Fenton mechanism induced by surface-leached iron,the heterogeneous catalysis mechanism,and the heterogeneous reaction-induced homogeneous mechanism.Different heterogeneous Fenton systems catalyzed by characteristic iron-based materials are comprehensively reviewed.Finally,related future research directions are also suggested.展开更多
Magnetic field was tentatively introduced into Fenton reactions system for the degradation and discoloration of methyl blue as the represent of organic chemical dye, which was a bio-refractory organic pollutant in ind...Magnetic field was tentatively introduced into Fenton reactions system for the degradation and discoloration of methyl blue as the represent of organic chemical dye, which was a bio-refractory organic pollutant in industry wastewater. It was found that under optimal Fenton reaction conditions, with the assistant of magnetic field in Fenton reactions, the degradation rate of methyl blue, the decomposition rate of H2O2 and the conversion rate of Fe^2＋ were accelerated, the extent of them would be improved by the increase of magnetic field intensity. Meanwhile, the mineralization of methyl blue （CODer） was improved by over 10% with magnetic field.展开更多
The effect of heterogeneous Fenton reaction was studied on methylene blue（MB） and Nitrosomonas europaea（N. europaea） cells. Four Fenton systems were prepared and compared with each other, including Nickel Foam（NF...The effect of heterogeneous Fenton reaction was studied on methylene blue（MB） and Nitrosomonas europaea（N. europaea） cells. Four Fenton systems were prepared and compared with each other, including Nickel Foam（NF）/TiO2, NF/Bi2WO6, Ceramic foam（CM）/TiO2, and CM/Bi2WO6. The order of effect of fenton reaction ranked as NF/TiO2〉CM/TiO2〉NF/Bi2WO6〉CM/Bi2WO6. In acid or alkaline solution, the removal efficiency also decreased compared with neutral solution. With lower p H values, the nanoparticles were easier to break off from NF skeleton. Thus the synergetic effect of photocatalysis and fenton reaction can not take action. As for CM skeleton, the bond –Si-O-can bind with TiO2 or Bi2WO6. The membrane fluidity was used as an indicating parameter. After being treated by Fenton reaction, N. europaea surface was rougher than the native bacterium and the bulges on cell surface became irregular, which is attributed to change of lipopolysaccharide patches. Polarization of N. europaea cell membrane in acid medium increased more obvious than alkaline medium.展开更多
The photo-Fenton reaction is a key source of the highly reactive hydroxyl radical（HOU） that is produced by the reaction of simultaneous photo-induced generation of Fe^（2＋）-dissolved organic matter（DOM） with H_2...The photo-Fenton reaction is a key source of the highly reactive hydroxyl radical（HOU） that is produced by the reaction of simultaneous photo-induced generation of Fe^（2＋）-dissolved organic matter（DOM） with H_2O_2 in sunlit surface waters as well as in the treatment of organic pollutants in the advanced oxidation processes（AOPs）.Concentrations of both H_2O_2 and Fe^（2＋）-DOM were dependent on time and total solar intensity flux,and their levels were highest in the diurnal samples collected at noon compared with the samples collected during the period before sunrise and after sunset.H_2O_2 and Fe^（2＋）-DOM concentrations during monthly readings were also found higher in comparison with the diurnal samples,shortly before sunrise or after sunset.A π-electron bonding system is formed between Fe and the functional groups in DOM（Fe-DOM）,through electron donation from the functional groups of DOM to an empty d-orbital of Fe.The π-electron is loosely bound and is highly susceptible to a rapid excitation upon light exposure that will provide better understanding of the formation of aqueous electrons,superoxide radical anions,H_2O_2 and finally,photo-Fenton reactions,too.Our results imply that simultaneous generation of H_2O_2 and Fe^（2＋）-DOM upon sunlight exposure during the daytime is most likely to be the key photo-Fenton reaction pathway,taking place in surface waters.展开更多
A novel, simple and convenient method for the determination of hydroxyl radicals isestablished. Hydroxyl radicals produced by Fenton reaction is trapped by spin trap reagent phenyl-t-butyl nitrone (PBN), and the free ...A novel, simple and convenient method for the determination of hydroxyl radicals isestablished. Hydroxyl radicals produced by Fenton reaction is trapped by spin trap reagent phenyl-t-butyl nitrone (PBN), and the free radical adduct of PBN can be detected by single sweeposcillopolarography, with its second order derivative cathodic wave at -0.52V vs SCE. Theoptimum experimental conditions for the detemination is discussed, and the scavenging effects ofsome compounds on OH was also studied.展开更多
Bacterial infection is a major issue after artificial bone transplantation due to the absence of antibacterial function of bone scaffold,which seriously causes the transplant failure and even amputation in severe case...Bacterial infection is a major issue after artificial bone transplantation due to the absence of antibacterial function of bone scaffold,which seriously causes the transplant failure and even amputation in severe cases.In this study,oxygen vacancy(OV)defects Fe-doped Ti O2(OV-FeTiO2)nanoparticles were synthesized by nano TiO2and Fe3O4via high-energy ball milling,which was then incorporated into polycaprolactone/polyglycolic acid(PCLGA)biodegradable polymer matrix to construct composite bone scaffold with good antibacterial activities by selective laser sintering.The results indicated that OV defects were introduced into the core/shell-structured OV-FeTiO2nanoparticles through multiple welding and breaking during the high-energy ball milling,which facilitated the adsorption of hydrogen peroxide(H2O2)in the bacterial infection microenvironment at the bone transplant site.The accumulated H2O2could amplify the Fenton reaction efficiency to induce more hydroxyl radicals(·OH),thereby resulting in more bacterial deaths through·OH-mediated oxidative damage.This antibacterial strategy had more effective broad-spectrum antibacterial properties against Gram-negative Escherichia coli(E.coli)and Gram-positive Staphylococcus aureus(S.aureus).In addition,the PCLGA/OV-FeTiO2scaffold possessed mechanical properties that match those of human cancellous bone and good biocompatibility including cell attachment,proliferation and osteogenic differentiation.展开更多
Photocatalytic Fenton reactions combined the advantages from both photocatalysis and Fenton reaction in mineralizing organic pollutants. The key problems are the efficiency and recycling stability. Herein, we reported...Photocatalytic Fenton reactions combined the advantages from both photocatalysis and Fenton reaction in mineralizing organic pollutants. The key problems are the efficiency and recycling stability. Herein, we reported a novel Fe_(2)O_(3)/TiO_(2)/reduced graphene oxide(FTG) nanocomposite synthesized by a facile solvothermal method. The TiO_(2)in FTG degraded organic pollutants and mineralized intermediates via photocatalysis under visible light irradiation, which could also promote Fenton reaction by accelerating Fe^(3+)-Fe^(2+)recycle. Meanwhile, the Fe_(2)O_(3)rapidly degraded organic pollutants via Fenton reactions, which also promoted photocatalysis by enhancing visible light absorbance and diminishing photoelectronhole recombination. The high distribution of TiO_(2)and Fe_(2)O_(3)on rGO, together with their strong interaction resulted in enhanced synergetic cooperation between photocatalysis and Fenton reactions, leading to the high mineralization efficiency of organic pollutants. More importantly, it could also inhibit the leaching of Fe species, leading to the long lifetime of FTG during photocatalytic Fenton reactions in a wide pH range from 3.4 to 9.2.展开更多
Fe-based solid catalysts in promoting Fenton reaction to generate ·OH radical has drawn much attention,and interestingly,FeOCl was reported to have superior activity compared with the traditional Fe2 O3 catalysts...Fe-based solid catalysts in promoting Fenton reaction to generate ·OH radical has drawn much attention,and interestingly,FeOCl was reported to have superior activity compared with the traditional Fe2 O3 catalysts.However,the mechanism of Fenton reaction on FeOCl and the origin of high activity remain unclear.Herein,by virtue of DFT+ U calculations,the H2 O2 decomposition and conversion mechanism on FeOCl(100)surface were systematically investigated.It is found that on clean FeOCl(100)surface,the exposed[Fe^3+-Fe^3+]sites can hardly break O-O bond of H2 O2 into OH groups,but instead H2 O2 tends to dehydrogenate by the surface lattice O,resulting in a series of side reactions and final conversion into O2,while the left H atoms gradually saturate the surface lattice O and reduce Fe^3+ into Fe^2+.On fully H-covered FeOCl(100),H2O2 can efficiently dissociate at[Fe^2+-Fe^2+]sites into two OH,but OH binds with Fe^2+ so strongly that it cannot desorb as OH radical as easily as that on Fe^3+.Interestingly,FeOCl(100)tends to be partially protonated in the real acid solution,which,along with H2 O2 dehydrogenation,results in the formation of active unit [Fe^2+-Fe^3+].On[Fe^2+-Fe^3+]unit,H2 O2 can easily break its O-O bond and OH at Fe3+ can desorb as OH radical,while the other OH at Fe^2+ couples with the surface H into H2O and finish the catalytic cycle.By comparison,Fe2 O3(012)cannot provide enough [Fe^2+-Fe^3+] active units due to the relative difficulty in H2 O2 dehydrogenation,which accounts for its inferior catalytic efficiency for Fenton reaction.展开更多
This work studied the structural effects of hematite(α-Fe2 O3), 2-line ferrihydrite(HFO) and goethite(α-FeOOH) on diethyl phthalate ester(DEP) degradation. The results showed that the degradation of DEP was faster u...This work studied the structural effects of hematite(α-Fe2 O3), 2-line ferrihydrite(HFO) and goethite(α-FeOOH) on diethyl phthalate ester(DEP) degradation. The results showed that the degradation of DEP was faster under 365 nm light irradiation than in the dark in the presence of iron(hydr)oxides. The apparent kinetic rates of DEP degradation followed the order HFO > goethite ≈ hematite in the dark and HFO > hematite > goethite under 365 nm light irradiation. Two pathways governed H2 O2 decomposition efficiency on iron(hydr)oxide surfaces:(1) forming UOH on inherent surface hydroxyl groups(Fe-OH) and(2) producing O2 and H2 O on the surface oxygen vacancies. X-ray photoelectron spectroscopy(XPS) analyses indicated that HFO not only has high Fe-OH content but also has high Vo content, resulting in its low H2 O2 utilization efficiency(η). DEP was degraded through hydrogen abstraction and deesterification, and the major products were(OH)2-DEP, mono-ethyl phthalate(MEP), OH-MEP,and phthalate acid(PA). The study is important in understanding the transformation of phthalate esters in top surface soils and surface waters under ultraviolet light.展开更多
Hydroxyl radical is one of the most reactive oxygen species (ROS) in biological systems, which can react with proteins and result in protein oxidation and damage. Oxidative
A scheme of the processes in Fenton solution with various substances is offered, and the channels of light formation registered by the luminometer are analyzed. Under the proposed scheme we discuss the possibilities o...A scheme of the processes in Fenton solution with various substances is offered, and the channels of light formation registered by the luminometer are analyzed. Under the proposed scheme we discuss the possibilities of studying the properties of antioxidants and prooxidants. Oxidation of alanine, albumin and sodium oxalate have been taken as an example. The properties of ascorbic acid and the mechanism of display of its oxidant and prooxidant properties are analyzed herewith. Methodical questions of the chemiluminescence research in Fenton solution such as the selection of reagents concentration, water preparation and the effect of the background radiation have been considered in this study as well.展开更多
To develop more efficient chemical methods for the demineralization of organic pollutants from water bodies, which one was also mimic to the nature, a degradation of methylene blue by Fe(Ⅲ) and H 2O 2 in the absenc...To develop more efficient chemical methods for the demineralization of organic pollutants from water bodies, which one was also mimic to the nature, a degradation of methylene blue by Fe(Ⅲ) and H 2O 2 in the absence of light instead of Fe(Ⅱ) and H 2O 2 was studied. Results showed that use of Fe (Ⅲ) is more promising than Fe(Ⅱ). The present study reflects that Fenton reaction is more efficient, in the presence of a small amount of salicylic acid is added which is a one of the priority pollutant.展开更多
We present a computational study of tissue transcriptomic data of 14 cancer types to address： what may drive cancer cell division？ Our analyses point to that persistent disruption of the intraceUular pH by Fenton re...We present a computational study of tissue transcriptomic data of 14 cancer types to address： what may drive cancer cell division？ Our analyses point to that persistent disruption of the intraceUular pH by Fenton reactions may be at the root of cancer development. Specifically, we have statistically demonstrated that Fenton reactions take place in cancer cytosoi and mitochondria across all the 14 cancer types, based on cancer tissue gene-expression data integrated via the Michaelis-Menten equation. In addition, we have shown that （i） Fenton reactions in cytosol of the disease cells will continuously increase their pH, to which the cells respond by generating net protons to keep the pH stable through a combination of synthesizing glycolytic ATPs and consuming them by nucleotide syntheses, which may drive cell division to rid of the continuously synthesized nucleotides; and （ii） Fenton reactions in mitochondria give rise to novel ways for ATP synthesis with electrons ultimately coming from H2O2, largely originated from immune cells. A model is developed to link these to cancer development, where some mutations may be selected to facilitate cell division at rates dictated by Fenton reactions.展开更多
Environmental deterioration,especially water pollution,is widely dispersed and could affect the quality of people's life at large.Though the sewage treatment plants are constructed to meet the demands of cities,di...Environmental deterioration,especially water pollution,is widely dispersed and could affect the quality of people's life at large.Though the sewage treatment plants are constructed to meet the demands of cities,distributed treatment units are still in request for the supplementary of centralized purification beyond the range of plants.Electrochemical degradation can reduce organic pollution to some degree,but it has to be powered.Triboelectric nanogenerator(TENG)is a newly-invented technology for low-frequency mechanical energy harvesting.Here,by integrating a rotary TENG(R-TENG)as electric power source with an electrochemical cell containing a modified graphite felt cathode for hydrogen peroxide(H2O2)along with hydroxyl radical(·OH)generation by Fenton reaction and a platinum sheet anode for active chlorine generation,a self-powered electrochemical system(SPECS)was constructed.Under the driven of mechanical energy or wind flow,such SPECS can efficiently degrade dyes after power management in neutral condition without any O2 aeration.This work not only provides a guideline for optimizing self-powered electrochemical reaction,but also displays a strategy based on the conversion from distributed mechanical energy to chemical energy for environmental remediation.展开更多
To better understand the mechanisms of hydrogen peroxide(H_(2)O_(2))’s decomposition and reactive oxygen species(ROS)’s formation on the catalyst’s surface is always a critical issue for the environmental applicati...To better understand the mechanisms of hydrogen peroxide(H_(2)O_(2))’s decomposition and reactive oxygen species(ROS)’s formation on the catalyst’s surface is always a critical issue for the environmental application of Fenton/Fenton-like reaction.We here report a new approach to activate H_(2)O_(2) in a co-catalytic Fenton system with oxygen incorporated MoS2,namely MoS_(2−x) O_(x) nanosheets.The MoS_(2−x) O_(x) nanosheets assisted co-catalytic Fenton system exhibited superior degradation activity of emerging antibiotic contaminants(e.g.,sulfamethoxazole).Combining density functional theory(DFT)calculation and experimental investigation,we demonstrated that oxygen incorporation could improve the intrinsic conductivity of MoS_(2−x) O_(x) nanosheets and accelerate surface/interfacial charge transfer,which further leads to the efficacious activation of H_(2)O_(2).Moreover,by tuning the oxygen proportion in MoS_(2−x) O_(x) nanosheets,we are able to modulate the generation of ROS and further direct the oriented-conversion of H_(2)O_(2) to surface-bounded superoxide radical(·O_(2−surface)).It sheds light on the generation and transformation of ROS in the engineered system(e.g.,Fenton,Fenton-like reaction)for efficient degradation of persistent pollutants.展开更多
Unexpected benefits to the catalytic performance of materials often originate from the presence of surface defects.Here,novel Dpenicillamine modified molybdenum oxide nanodots,with abundant oxygen vacancy defects,were...Unexpected benefits to the catalytic performance of materials often originate from the presence of surface defects.Here,novel Dpenicillamine modified molybdenum oxide nanodots,with abundant oxygen vacancy defects,were fabrication by a mild,simple,and cost-effective method.Ultraviolet–visible(UV–Vis)absorption spectra analysis showed that the nanodots had peroxidaselike and catalase-like activities.The reactive oxygen species were probed by electronic paramagnetic resonance technique and spectroscopic methods,demonstrating that the nanodots also had oxidase-like activity.Interestingly,the peroxidase-like activity of nanodots was synergistically enhanced in the presence of ferrous ions or ferric ions.Remarkably,less than nanomolar levels of ferrous ions were required to display this phenomenon,meaning Fenton reagent acted as leverage.Based on this,a sensitive colorimetric and fluorescent dual-mode sensor for alendronate sodium was developed.The linear ranges for colorimetric and fluorescence analysis were 0.2–2.5 and 0.2–2.0μM,with detection limits of 31.21 and 71.84 nM,correspondingly.The method has a simple large-scale material preparation process with higher sensitivity and shorter reaction time,which can inspire and enlighten the design of nanozyme sensors.展开更多
Acetaminophen(APAP), a classic nonsteroidal anti-inflammatory drug(NSAID), has attracted much attention due to the overdose-induced hepatotoxicity in the past several decades. N-Acetyl-p-benzoquinone imine(NAPQI), the...Acetaminophen(APAP), a classic nonsteroidal anti-inflammatory drug(NSAID), has attracted much attention due to the overdose-induced hepatotoxicity in the past several decades. N-Acetyl-p-benzoquinone imine(NAPQI), the P450-dependent metabolism of APAP, leads to GSH depletion, protein binding, mitochondrial oxidative stress, and eventually the liver injury. Herein, we develop a Fe-based metal-organic framework(MOF) to deliver and transform acetaminophen into toxic “chemo” drug through the cascade reaction for enhanced cancer therapy. In the acidic tumor microenvironment, the Fe-based MOF collapses and releases abundant Fe ions to generate hydroxyl radicals(·OH) via Fenton reaction, subsequently catalyzing nontoxic APAP into toxic NAPQI. Meanwhile, NAPQI depletes intracellular glutathione(GSH) rapidly, leading to alleviating the antioxidant ability of cancer cells and amplifying Fenton activity. The intracellular oxidative stress and the toxic metabolite of APAP can provide a synergistic effect on antitumor activity.展开更多
基金supported by the State Key Research Development Program of China (No.2016YFA0204200)National Natural Science Foundation of China (Nos.21822603,21811540394,5171101651,21677048,21773062,21577036)+3 种基金Shanghai Pujiang Program (No.17PJD011)the Fundamental Research Funds for the Central Universities (No.22A201514021)Project supported by Shanghai Municipal Science and Technology Major Project (No. 2018SHZDZX03)the Program of Introducing Talents of Discipline to Universities (No.B16017)
文摘There is a relatively low efficiency of Fe(Ⅲ)/Fe(Ⅱ) conversion cycle and H2 O2 decomposition(<30%) in conventional Fenton process,which further results in a low production efficiency of ·OH and seriously restricts the application of Fenton.Herein,we report that the commercial MoO2 can be used as the cocatalyst in Fenton process to dramatically accelerate the oxidation of Lissamine rhodamine B(L-RhB),where the efficiency of Fe(Ⅲ)/Fe(Ⅱ) cycling is greatly enhanced in the Fenton reaction meanwhile.And the L-RhB solution could be degraded nearly 100% in 1 min in the MoO2 cocatalytic Fenton system under the optimal reaction condition,which is apparently better than that of the conventional Fenton system(~50%).Different from the conventional Fenton reaction where the ’OH plays an important role in the oxidation process,it shows that 1 O2 contributes most in the MoO2 cocatalytic Fenton reaction.However,it is found that the exposed Mo^4+ active sites on the surface of MoO2 powders can greatly promote the rate-limiting step of Fe^3+/Fe^2+ cycle conversion,thus minimizing the dosage of H2 O2(0.400 mmol/L) and Fe^2+(0.105 mmol/L).Interestingly,the MoO2 cocatalytic Fenton system also exhibits a good ability for reducing Cr(Ⅵ) ions,where the reduction ability for Cr(Ⅵ) reaches almost 100% within 2 h.In short,this work shows a new discovery for M002 cocatalytic advanced oxidation processes(AOPs),which devotes a lot to the practical water remediation application.
基金supported by the National Natural Science Foundation of China (Nos. 21107125, 21577160, 51221892, 51290282 and 41201498)
文摘The heterogeneous Fenton reaction can generate highly reactive hydroxyl radicals（·OH）from reactions between recyclable solid catalysts and H2O2 at acidic or even circumneutral pH.Hence,it can effectively oxidize refractory organics in water or soils and has become a promising environmentally friendly treatment technology.Due to the complex reaction system,the mechanism behind heterogeneous Fenton reactions remains unresolved but fascinating,and is crucial for understanding Fenton chemistry and the development and application of efficient heterogeneous Fenton technologies.Iron-based materials usually possess high catalytic activity,low cost,negligible toxicity and easy recovery,and are a superior type of heterogeneous Fenton catalysts.Therefore,this article reviews the fundamental but important interfacial mechanisms of heterogeneous Fenton reactions catalyzed by iron-based materials..OH,hydroperoxyl radicals/superoxide anions（HO2./O2^-.）and high-valent iron are the three main types of reactive oxygen species（ROS）,with different oxidation reactivity and selectivity.Based on the mechanisms of ROS generation,the interfacial mechanisms of heterogeneous Fenton systems can be classified as the homogeneous Fenton mechanism induced by surface-leached iron,the heterogeneous catalysis mechanism,and the heterogeneous reaction-induced homogeneous mechanism.Different heterogeneous Fenton systems catalyzed by characteristic iron-based materials are comprehensively reviewed.Finally,related future research directions are also suggested.
基金support by the Natural Science Research Foundation of Jiangnan University(No.005796).
文摘Magnetic field was tentatively introduced into Fenton reactions system for the degradation and discoloration of methyl blue as the represent of organic chemical dye, which was a bio-refractory organic pollutant in industry wastewater. It was found that under optimal Fenton reaction conditions, with the assistant of magnetic field in Fenton reactions, the degradation rate of methyl blue, the decomposition rate of H2O2 and the conversion rate of Fe^2＋ were accelerated, the extent of them would be improved by the increase of magnetic field intensity. Meanwhile, the mineralization of methyl blue （CODer） was improved by over 10% with magnetic field.
基金Funded by National Natural Science Foundation of Chinathe State Key Laboratory of Urban Water Resource and Environment(No.51208141)the National Key Research and Development Program of China(No.2016YFC0401102)
文摘The effect of heterogeneous Fenton reaction was studied on methylene blue（MB） and Nitrosomonas europaea（N. europaea） cells. Four Fenton systems were prepared and compared with each other, including Nickel Foam（NF）/TiO2, NF/Bi2WO6, Ceramic foam（CM）/TiO2, and CM/Bi2WO6. The order of effect of fenton reaction ranked as NF/TiO2〉CM/TiO2〉NF/Bi2WO6〉CM/Bi2WO6. In acid or alkaline solution, the removal efficiency also decreased compared with neutral solution. With lower p H values, the nanoparticles were easier to break off from NF skeleton. Thus the synergetic effect of photocatalysis and fenton reaction can not take action. As for CM skeleton, the bond –Si-O-can bind with TiO2 or Bi2WO6. The membrane fluidity was used as an indicating parameter. After being treated by Fenton reaction, N. europaea surface was rougher than the native bacterium and the bulges on cell surface became irregular, which is attributed to change of lipopolysaccharide patches. Polarization of N. europaea cell membrane in acid medium increased more obvious than alkaline medium.
基金the Japan Society for the Promotion of Science for the financial support through a Grant-in-Aid for Scientific Research (B) (No.18310010)partly supported by the Key Construction Program of the National "985" Project,Tianjin University,China
文摘The photo-Fenton reaction is a key source of the highly reactive hydroxyl radical（HOU） that is produced by the reaction of simultaneous photo-induced generation of Fe^（2＋）-dissolved organic matter（DOM） with H_2O_2 in sunlit surface waters as well as in the treatment of organic pollutants in the advanced oxidation processes（AOPs）.Concentrations of both H_2O_2 and Fe^（2＋）-DOM were dependent on time and total solar intensity flux,and their levels were highest in the diurnal samples collected at noon compared with the samples collected during the period before sunrise and after sunset.H_2O_2 and Fe^（2＋）-DOM concentrations during monthly readings were also found higher in comparison with the diurnal samples,shortly before sunrise or after sunset.A π-electron bonding system is formed between Fe and the functional groups in DOM（Fe-DOM）,through electron donation from the functional groups of DOM to an empty d-orbital of Fe.The π-electron is loosely bound and is highly susceptible to a rapid excitation upon light exposure that will provide better understanding of the formation of aqueous electrons,superoxide radical anions,H_2O_2 and finally,photo-Fenton reactions,too.Our results imply that simultaneous generation of H_2O_2 and Fe^（2＋）-DOM upon sunlight exposure during the daytime is most likely to be the key photo-Fenton reaction pathway,taking place in surface waters.
文摘A novel, simple and convenient method for the determination of hydroxyl radicals isestablished. Hydroxyl radicals produced by Fenton reaction is trapped by spin trap reagent phenyl-t-butyl nitrone (PBN), and the free radical adduct of PBN can be detected by single sweeposcillopolarography, with its second order derivative cathodic wave at -0.52V vs SCE. Theoptimum experimental conditions for the detemination is discussed, and the scavenging effects ofsome compounds on OH was also studied.
基金supported by the following funds:The Natural Science Foundation of China(52275393,51935014,82072084)Hunan Provincial Natural Science Foundation of China(2021JJ20061)+4 种基金Jiangxi Provincial Natural Science Foundation of China(20224ACB204013)The Project of State Key Laboratory of Precision Manufacturing for Extreme Service PerformanceTechnology Innovation Platform Project of Shenzhen Institute of Information Technology 2020(PT2020E002)Guangdong Province Precision Manufacturing and Intelligent production education Integration Innovation Platform(2022CJPT019)Independent Exploration and Innovation Project of Central South University(1053320220553)。
文摘Bacterial infection is a major issue after artificial bone transplantation due to the absence of antibacterial function of bone scaffold,which seriously causes the transplant failure and even amputation in severe cases.In this study,oxygen vacancy(OV)defects Fe-doped Ti O2(OV-FeTiO2)nanoparticles were synthesized by nano TiO2and Fe3O4via high-energy ball milling,which was then incorporated into polycaprolactone/polyglycolic acid(PCLGA)biodegradable polymer matrix to construct composite bone scaffold with good antibacterial activities by selective laser sintering.The results indicated that OV defects were introduced into the core/shell-structured OV-FeTiO2nanoparticles through multiple welding and breaking during the high-energy ball milling,which facilitated the adsorption of hydrogen peroxide(H2O2)in the bacterial infection microenvironment at the bone transplant site.The accumulated H2O2could amplify the Fenton reaction efficiency to induce more hydroxyl radicals(·OH),thereby resulting in more bacterial deaths through·OH-mediated oxidative damage.This antibacterial strategy had more effective broad-spectrum antibacterial properties against Gram-negative Escherichia coli(E.coli)and Gram-positive Staphylococcus aureus(S.aureus).In addition,the PCLGA/OV-FeTiO2scaffold possessed mechanical properties that match those of human cancellous bone and good biocompatibility including cell attachment,proliferation and osteogenic differentiation.
基金supported by the National Key Research and Development Program of China (No.2020YFA0211004)the National Natural Science Foundation of China (Nos.22176128 and 21876114)+4 种基金the Program of Shanghai Academic Research Leader (No. 21XD1422800)Shanghai Government (Nos. 19DZ1205102 and 19160712900)Chinese Education Ministry Key Laboratory and International Joint Laboratory on Resource Chemistry, and Shanghai Eastern Scholar Program, “111 Innovation and Talent Recruitment Base on Photochemical and Energy Materials” (No. D18020)Shanghai Engineering Research Center of Green Energy Chemical Engineering (No. 18DZ2254200)Shanghai Frontiers Science Center of Biomimetic Catalysis。
文摘Photocatalytic Fenton reactions combined the advantages from both photocatalysis and Fenton reaction in mineralizing organic pollutants. The key problems are the efficiency and recycling stability. Herein, we reported a novel Fe_(2)O_(3)/TiO_(2)/reduced graphene oxide(FTG) nanocomposite synthesized by a facile solvothermal method. The TiO_(2)in FTG degraded organic pollutants and mineralized intermediates via photocatalysis under visible light irradiation, which could also promote Fenton reaction by accelerating Fe^(3+)-Fe^(2+)recycle. Meanwhile, the Fe_(2)O_(3)rapidly degraded organic pollutants via Fenton reactions, which also promoted photocatalysis by enhancing visible light absorbance and diminishing photoelectronhole recombination. The high distribution of TiO_(2)and Fe_(2)O_(3)on rGO, together with their strong interaction resulted in enhanced synergetic cooperation between photocatalysis and Fenton reactions, leading to the high mineralization efficiency of organic pollutants. More importantly, it could also inhibit the leaching of Fe species, leading to the long lifetime of FTG during photocatalytic Fenton reactions in a wide pH range from 3.4 to 9.2.
基金financially supported by the National Natural Science Foundation of China(Nos.21622305 and21333003)the Young Elite Scientist Sponsorship Program by China Association for Science and Technology(No.YESS20150131)+1 种基金"Shu Guang"Project supported by Shanghai Municipal Education Commission and Shanghai Education Development Foundation(No.17SG30)the Fundamental Research Funds for the Central Universities(No.WJ1616007)
文摘Fe-based solid catalysts in promoting Fenton reaction to generate ·OH radical has drawn much attention,and interestingly,FeOCl was reported to have superior activity compared with the traditional Fe2 O3 catalysts.However,the mechanism of Fenton reaction on FeOCl and the origin of high activity remain unclear.Herein,by virtue of DFT+ U calculations,the H2 O2 decomposition and conversion mechanism on FeOCl(100)surface were systematically investigated.It is found that on clean FeOCl(100)surface,the exposed[Fe^3+-Fe^3+]sites can hardly break O-O bond of H2 O2 into OH groups,but instead H2 O2 tends to dehydrogenate by the surface lattice O,resulting in a series of side reactions and final conversion into O2,while the left H atoms gradually saturate the surface lattice O and reduce Fe^3+ into Fe^2+.On fully H-covered FeOCl(100),H2O2 can efficiently dissociate at[Fe^2+-Fe^2+]sites into two OH,but OH binds with Fe^2+ so strongly that it cannot desorb as OH radical as easily as that on Fe^3+.Interestingly,FeOCl(100)tends to be partially protonated in the real acid solution,which,along with H2 O2 dehydrogenation,results in the formation of active unit [Fe^2+-Fe^3+].On[Fe^2+-Fe^3+]unit,H2 O2 can easily break its O-O bond and OH at Fe3+ can desorb as OH radical,while the other OH at Fe^2+ couples with the surface H into H2O and finish the catalytic cycle.By comparison,Fe2 O3(012)cannot provide enough [Fe^2+-Fe^3+] active units due to the relative difficulty in H2 O2 dehydrogenation,which accounts for its inferior catalytic efficiency for Fenton reaction.
基金funded by the National Natural Science Foundation of China (No. 41773125)the Research Instrument Development Program of Chinese Academy of Sciences (No. YZ201638)the 135 Research Program of the Chinese Academy of Sciences (No. ISSASIP1620)
文摘This work studied the structural effects of hematite(α-Fe2 O3), 2-line ferrihydrite(HFO) and goethite(α-FeOOH) on diethyl phthalate ester(DEP) degradation. The results showed that the degradation of DEP was faster under 365 nm light irradiation than in the dark in the presence of iron(hydr)oxides. The apparent kinetic rates of DEP degradation followed the order HFO > goethite ≈ hematite in the dark and HFO > hematite > goethite under 365 nm light irradiation. Two pathways governed H2 O2 decomposition efficiency on iron(hydr)oxide surfaces:(1) forming UOH on inherent surface hydroxyl groups(Fe-OH) and(2) producing O2 and H2 O on the surface oxygen vacancies. X-ray photoelectron spectroscopy(XPS) analyses indicated that HFO not only has high Fe-OH content but also has high Vo content, resulting in its low H2 O2 utilization efficiency(η). DEP was degraded through hydrogen abstraction and deesterification, and the major products were(OH)2-DEP, mono-ethyl phthalate(MEP), OH-MEP,and phthalate acid(PA). The study is important in understanding the transformation of phthalate esters in top surface soils and surface waters under ultraviolet light.
文摘Hydroxyl radical is one of the most reactive oxygen species (ROS) in biological systems, which can react with proteins and result in protein oxidation and damage. Oxidative
文摘A scheme of the processes in Fenton solution with various substances is offered, and the channels of light formation registered by the luminometer are analyzed. Under the proposed scheme we discuss the possibilities of studying the properties of antioxidants and prooxidants. Oxidation of alanine, albumin and sodium oxalate have been taken as an example. The properties of ascorbic acid and the mechanism of display of its oxidant and prooxidant properties are analyzed herewith. Methodical questions of the chemiluminescence research in Fenton solution such as the selection of reagents concentration, water preparation and the effect of the background radiation have been considered in this study as well.
文摘To develop more efficient chemical methods for the demineralization of organic pollutants from water bodies, which one was also mimic to the nature, a degradation of methylene blue by Fe(Ⅲ) and H 2O 2 in the absence of light instead of Fe(Ⅱ) and H 2O 2 was studied. Results showed that use of Fe (Ⅲ) is more promising than Fe(Ⅱ). The present study reflects that Fenton reaction is more efficient, in the presence of a small amount of salicylic acid is added which is a one of the priority pollutant.
基金This work was supported by grants from Georgia Research Alliance, the National Natural Science Foundation of China （61572227）, Projects of international Cooperation and Exchanges of the National Natural Science Foundation of China （81320108025）, and Jilin University.
文摘We present a computational study of tissue transcriptomic data of 14 cancer types to address： what may drive cancer cell division？ Our analyses point to that persistent disruption of the intraceUular pH by Fenton reactions may be at the root of cancer development. Specifically, we have statistically demonstrated that Fenton reactions take place in cancer cytosoi and mitochondria across all the 14 cancer types, based on cancer tissue gene-expression data integrated via the Michaelis-Menten equation. In addition, we have shown that （i） Fenton reactions in cytosol of the disease cells will continuously increase their pH, to which the cells respond by generating net protons to keep the pH stable through a combination of synthesizing glycolytic ATPs and consuming them by nucleotide syntheses, which may drive cell division to rid of the continuously synthesized nucleotides; and （ii） Fenton reactions in mitochondria give rise to novel ways for ATP synthesis with electrons ultimately coming from H2O2, largely originated from immune cells. A model is developed to link these to cancer development, where some mutations may be selected to facilitate cell division at rates dictated by Fenton reactions.
基金the National Key Technology R&D Program of China(No.2016YFA0202704)Beijing Municipal Science 8c Technology Commission(Nos.Z171100000317001,Z171100002017017,and Y3993113DF)the National Natural Science Foundation of China(Nos.51432005,5151101243,51561145021,and 21761142011).
文摘Environmental deterioration,especially water pollution,is widely dispersed and could affect the quality of people's life at large.Though the sewage treatment plants are constructed to meet the demands of cities,distributed treatment units are still in request for the supplementary of centralized purification beyond the range of plants.Electrochemical degradation can reduce organic pollution to some degree,but it has to be powered.Triboelectric nanogenerator(TENG)is a newly-invented technology for low-frequency mechanical energy harvesting.Here,by integrating a rotary TENG(R-TENG)as electric power source with an electrochemical cell containing a modified graphite felt cathode for hydrogen peroxide(H2O2)along with hydroxyl radical(·OH)generation by Fenton reaction and a platinum sheet anode for active chlorine generation,a self-powered electrochemical system(SPECS)was constructed.Under the driven of mechanical energy or wind flow,such SPECS can efficiently degrade dyes after power management in neutral condition without any O2 aeration.This work not only provides a guideline for optimizing self-powered electrochemical reaction,but also displays a strategy based on the conversion from distributed mechanical energy to chemical energy for environmental remediation.
基金the National Natural Science Foundation of China(Nos.42077293 and 22006088)Natural Science Foundation of Guangdong Province(Nos.2019A1515011692 and 2019QN01L797)+2 种基金Shenzhen Municipal Science and Technology Innovation Committee(Nos.JCYJ20190809181413713 and WDZC20200817103015002)Y.X.H.also thanks the financial support from Overseas Cooperation Research Fund of Tsinghua Shenzhen International Graduate School(Nos.HW2020002 and QD2021010N)This work was also supported by the China Postdoctoral Science Foundation(No.2019M66067).
文摘To better understand the mechanisms of hydrogen peroxide(H_(2)O_(2))’s decomposition and reactive oxygen species(ROS)’s formation on the catalyst’s surface is always a critical issue for the environmental application of Fenton/Fenton-like reaction.We here report a new approach to activate H_(2)O_(2) in a co-catalytic Fenton system with oxygen incorporated MoS2,namely MoS_(2−x) O_(x) nanosheets.The MoS_(2−x) O_(x) nanosheets assisted co-catalytic Fenton system exhibited superior degradation activity of emerging antibiotic contaminants(e.g.,sulfamethoxazole).Combining density functional theory(DFT)calculation and experimental investigation,we demonstrated that oxygen incorporation could improve the intrinsic conductivity of MoS_(2−x) O_(x) nanosheets and accelerate surface/interfacial charge transfer,which further leads to the efficacious activation of H_(2)O_(2).Moreover,by tuning the oxygen proportion in MoS_(2−x) O_(x) nanosheets,we are able to modulate the generation of ROS and further direct the oriented-conversion of H_(2)O_(2) to surface-bounded superoxide radical(·O_(2−surface)).It sheds light on the generation and transformation of ROS in the engineered system(e.g.,Fenton,Fenton-like reaction)for efficient degradation of persistent pollutants.
基金National Natural Science Foundation of China(No.21603276)Fundamental Research Funds for the Central Universities(Nos.19CX02060A and 22CX03024A)the Natural Science Foundation of Shandong Province(No.ZR2022MB148).
文摘Unexpected benefits to the catalytic performance of materials often originate from the presence of surface defects.Here,novel Dpenicillamine modified molybdenum oxide nanodots,with abundant oxygen vacancy defects,were fabrication by a mild,simple,and cost-effective method.Ultraviolet–visible(UV–Vis)absorption spectra analysis showed that the nanodots had peroxidaselike and catalase-like activities.The reactive oxygen species were probed by electronic paramagnetic resonance technique and spectroscopic methods,demonstrating that the nanodots also had oxidase-like activity.Interestingly,the peroxidase-like activity of nanodots was synergistically enhanced in the presence of ferrous ions or ferric ions.Remarkably,less than nanomolar levels of ferrous ions were required to display this phenomenon,meaning Fenton reagent acted as leverage.Based on this,a sensitive colorimetric and fluorescent dual-mode sensor for alendronate sodium was developed.The linear ranges for colorimetric and fluorescence analysis were 0.2–2.5 and 0.2–2.0μM,with detection limits of 31.21 and 71.84 nM,correspondingly.The method has a simple large-scale material preparation process with higher sensitivity and shorter reaction time,which can inspire and enlighten the design of nanozyme sensors.
基金financial support of this work by the National Natural Science Foundation of China (No. 81872813)the Outstanding Youth Fund of Jiangsu Province of China (No. BK20190029)+1 种基金the China Postdoctoral Science Foundation (No. 2021M703597)the Program of State Key Laboratory of Natural Medicines-China Pharmaceutical University (No. SKLNMZZ202031)。
文摘Acetaminophen(APAP), a classic nonsteroidal anti-inflammatory drug(NSAID), has attracted much attention due to the overdose-induced hepatotoxicity in the past several decades. N-Acetyl-p-benzoquinone imine(NAPQI), the P450-dependent metabolism of APAP, leads to GSH depletion, protein binding, mitochondrial oxidative stress, and eventually the liver injury. Herein, we develop a Fe-based metal-organic framework(MOF) to deliver and transform acetaminophen into toxic “chemo” drug through the cascade reaction for enhanced cancer therapy. In the acidic tumor microenvironment, the Fe-based MOF collapses and releases abundant Fe ions to generate hydroxyl radicals(·OH) via Fenton reaction, subsequently catalyzing nontoxic APAP into toxic NAPQI. Meanwhile, NAPQI depletes intracellular glutathione(GSH) rapidly, leading to alleviating the antioxidant ability of cancer cells and amplifying Fenton activity. The intracellular oxidative stress and the toxic metabolite of APAP can provide a synergistic effect on antitumor activity.
