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
Herein,a diatomite biomorphic Si-O doped carbon-based catalyst(DB-SiOC)was prepared using natura mineral diatomite as the silicon source and porous template.The results showed that the metal-free DB SiOC catalyst exhi...Herein,a diatomite biomorphic Si-O doped carbon-based catalyst(DB-SiOC)was prepared using natura mineral diatomite as the silicon source and porous template.The results showed that the metal-free DB SiOC catalyst exhibited ultrafast oxidation towards chlorophenol(CP)via peroxymonosulfate(PMS)activa tion,which was almost one order of magnitudes than most of carbon-based catalysts.The DB-SiOC/PMS system also showed the high ability to resist the interference of environmental matrix.The radicals(^(·)OH and SO_(4)^(·–))exhibited a very small contribution to the CP oxidation while the electron transfer processe(ETP)played the major role in the DB-SiOC/PMS system.The electron shuttles from the electron-donating CP molecules to the adjacent DB-SiOC/PMS^(*)could be efficiently triggered via Si-O bonds as bridges,mak ing it possible for ultrafast oxidation of CP.In addition,the hollow-disc shaped DB-Si OC provided the biomorphic DE structures with abundant pores for enriching the PMS and pollutants,thus further ac celerating the oxidation reaction.This work provided a new routine for the fabrication of Si-O doped carbon-based catalysts with excellent Fenton-like catalytic activity,which would greatly promote thei application prospects in Fenton-like systems.展开更多
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
The UV photooxidation with Fe（Ⅲ） and H2O2 was employed to treat a naval derusting wastewater, which contains the high COD （chemical oxygen demand） and various metal concentrations exceptionally with high concentr...The UV photooxidation with Fe（Ⅲ） and H2O2 was employed to treat a naval derusting wastewater, which contains the high COD （chemical oxygen demand） and various metal concentrations exceptionally with high concentrations of citric acid and iron. Because of its iron containment, the Fenton-like reaction automatically took place with the added amount of H2O2. The decomposition rate was found in a sequence of： UV/HEOE/Fe（Ⅲ） 〉 UV/H2O2 〉 Fe（Ⅱ）/H2O2. Two H2O2 injection methods, single and multiple points, were evaluated. The multiple-point H2O2 injection was more efficient to decompose the citric acid. The decomposition of the synthetic citric acid and the real derusting citric acid wastewater was also compared. The 93% COD reduction of the derusting wastewater was achieved using the UV/HEOE/Fe（Ⅲ） treatment.展开更多
The sluggish kinetics of Fe(Ⅱ)recovery in Fenton/Fenton-like reactions significantly limits the oxidation efficiency.In this study,we for the first time use boron carbide(BC)as a green and stable promotor to enhance ...The sluggish kinetics of Fe(Ⅱ)recovery in Fenton/Fenton-like reactions significantly limits the oxidation efficiency.In this study,we for the first time use boron carbide(BC)as a green and stable promotor to enhance the reaction of Fe(Ⅲ)/H_(2)O_(2) for degradation of diverse organic pollutants.Electron paramagnetic resonance analysis and chemical quenching/capturing experiments demonstrate that hydroxyl radicals(·OH)are the primary reactive species in the BC/Fe(Ⅲ)/H_(2)O_(2) system.In situ electrochemical analysis indicates that BC remarkably boosts the Fe(Ⅲ)/Fe(Ⅱ)redox cycles,where the adsorbed Fe(Ⅲ)cations were transformed to more active Fe(Ⅲ)species with a higher oxidative potential to react with H_(2)O_(2) to produce Fe(Ⅱ).Thus,the recovery of Fe(Ⅱ)from Fe(Ⅲ)is facilitated over BC surface,which enhancesOH generation via Fenton reactions.Moreover,BC exhibits outstanding reusability and stability in successive cycles and avoids the secondary pollution caused by conventional organic and metalliferous promotors.Therefore,metal-free BC boosting Fe(Ⅲ)/H_(2)O_(2) oxidation of organics provides a green and advanced strategy for water decontamination.展开更多
During the oxidative degradation of nonbiodegradable Malachite green (MG) by means of H2O2 /FeIIIR (iron supported on ion-exchage resin) in a dynamic column,the binding energy of the Fe(2p3/2) region for XPS spectra w...During the oxidative degradation of nonbiodegradable Malachite green (MG) by means of H2O2 /FeIIIR (iron supported on ion-exchage resin) in a dynamic column,the binding energy of the Fe(2p3/2) region for XPS spectra was found to be different between the top layer and the bottom layer in this column. Based on the data from XPS spectra and DMPO-OH·signal by EPR spectra,it is shown that the formation of ferryl (IV) is the key step for the oxidation of MG. The ferryl (IV) species can oxidize MG,and its redox potential is about 0. 739 - 0. 803 V measured by cyclic voltammograms (CV) . The catalytic capability of ferryl (IV) species was also evaluated,and it is found that it can promote the decomposition of H2O2 more efficiently than ferric iron. The removal rate of MG mainly depends on the adsorption of catalyst. Both ferryl (IV) and HO·radicals are the reactive species in the system. The oxidation of HO·is only a small part of the overall removal rate. Based on the obtained results,a possible mechanism for a resin-supported Fenton-like oxidation reaction is proposed.展开更多
Oxidation by Fenton like reactions (Fe3+/H2O2) is economically process for destructive hazardous pollutants in waste water. The effects of different parameters such as, amaranth red dye, ferric chloride, hydrogen pero...Oxidation by Fenton like reactions (Fe3+/H2O2) is economically process for destructive hazardous pollutants in waste water. The effects of different parameters such as, amaranth red dye, ferric chloride, hydrogen peroxide concentrations, pH value of solution, temperature and the presence of inorganic ions (carbonate, nitrate, chloride) on oxidative decolorization of amaranth were investigated. Amaranth degradation by (Fe3+/H2O2) reagent was found to follow first order kinetic model. Under optimum condition, pH = 2.6 and [FeCl3] = 3.75 × 10-4 mol·dm-3, the amaranth in aqueous solution with an initial concentration of 5 × 10-5 mol·dm-3 was degraded by 95% within 6 minutes. Increasing temperature in the range of 298 - 308 K increases the rate of dye degradation. Thermodynamic constants, ΔH*, ΔS* and ΔG* were evaluated. The results implied that the oxidation process was favorable and endothermic.展开更多
Pitch produced by the lique-faction of coal was divided into two frac-tions:soluble in toluene(TS)and insol-uble in toluene but soluble in pyridine(TI-PS),and their differences in molecu-lar structure and oxidation ac...Pitch produced by the lique-faction of coal was divided into two frac-tions:soluble in toluene(TS)and insol-uble in toluene but soluble in pyridine(TI-PS),and their differences in molecu-lar structure and oxidation activity were studied.Several different carbon materi-als were produced from them by oxida-tion in air(350℃,300 mL/min)fol-lowed by carbonization(1000℃ in Ar),and the effect of the cross-linked structure on their structure and sodium storage properties was investigated.The results showed that the two pitch fractions were obviously different after the air oxidation.The TS fraction with a low degree of condensation and abundant side chains had a stronger oxidation activity and thus introduced more cross-linked oxygen-containing functional groups C(O)―O which prevented carbon layer rearrangement during the carbonization.As a result,a disordered hard carbon with more defects was formed,which improved the electrochemical performance.Therefore,the carbon materials derived from TS(O-TS-1000)had an obvious disordered structure and a larger layer spacing,giving them better sodium storage perform-ance than those derived from the TI-PS fraction(O-TI-PS-1000).The specific capacity of O-TS-1000 was about 250 mAh/g at 20 mA/g,which was 1.67 times higher than that of O-TI-PS-1000(150 mAh/g).展开更多
Up-and-coming high-temperature materials,refractory high entropy alloys,are suffering from lower oxidation resistance,restricting their applications in the aerospace field.In this study,two novel treatments of Al-depo...Up-and-coming high-temperature materials,refractory high entropy alloys,are suffering from lower oxidation resistance,restricting their applications in the aerospace field.In this study,two novel treatments of Al-deposited and remelted were developed to refine the microstructure and enhance the oxidation resistance of refractory high entropy alloy using electron beam freeform fabrication(EBF3).Finer and short-range ordering structures were observed in the remelted sample,whereas the Al-deposited sample showcased the formation of silicide and intermetallic phases.High-temperature cyclic and isothermal oxidation tests at 1000℃ were carried out.The total weight gain after 60 h of cyclic oxidation decreased by 17.49%and 30.46%for the remelted and deposited samples,respectively,compared to the as-cast state.Oxidation kinetics reveal an evident lower mass gain and oxidation rate in the treated samples.A multilayer oxide consisting of TiO_(2)+Al_(2)O_(3)+SiO_(2)+AlNbO_(4) was studied for its excellent oxidation resistance.The oxidation behavior of rutile,corundum and other oxides was analyzed using first principles calculations and chemical defect analysis.Overall,this research,which introduces novel treatments,offers promising insights for enhancing the inherent oxidation resistance of refractory high entropy alloys.展开更多
The novel Co-based superalloys are extensively used in gas-powered and jet engine turbines due to their excellent high-temperature performance, achieved by strengthening the L12-γ′ ordered phase. This review present...The novel Co-based superalloys are extensively used in gas-powered and jet engine turbines due to their excellent high-temperature performance, achieved by strengthening the L12-γ′ ordered phase. This review presents an overview of the research progress on oxidation behavior of Co-based superalloys, including oxidation kinetics, oxides morphology, the formation and spallation of oxide layers, and importantly, the synergistic effects of alloying elements on oxidation resistance—a critical area considering the complex interactions with multiple alloying elements. Additionally, this review compares the oxidation resistance of single crystal versus polycrystalline alloys. The effect of phase interface and dislocations on oxidation behavior is also discussed. While significant progress has been achieved, areas necessitating further investigation include optimizing alloy compositions for enhanced oxidation resistance and understanding the long-term stability of oxide layers. The future prospects for Co-based superalloys are promising as ongoing research aims to address the existing challenges and unlock new applications at even higher operating temperatures.展开更多
Traumatic brain injury involves complex pathophysiological mechanisms,among which oxidative stress significantly contributes to the occurrence of secondary injury.In this study,we evaluated hypidone hydrochloride(YL-0...Traumatic brain injury involves complex pathophysiological mechanisms,among which oxidative stress significantly contributes to the occurrence of secondary injury.In this study,we evaluated hypidone hydrochloride(YL-0919),a self-developed antidepressant with selective sigma-1 receptor agonist properties,and its associated mechanisms and targets in traumatic brain injury.Behavioral experiments to assess functional deficits were followed by assessment of neuronal damage through histological analyses and examination of blood-brain barrier permeability and brain edema.Next,we investigated the antioxidative effects of YL-0919 by assessing the levels of traditional markers of oxidative stress in vivo in mice and in vitro in HT22 cells.Finally,the targeted action of YL-0919 was verified by employing a sigma-1 receptor antagonist(BD-1047).Our findings demonstrated that YL-0919 markedly improved deficits in motor function and spatial cognition on day 3 post traumatic brain injury,while also decreasing neuronal mortality and reversing blood-brain barrier disruption and brain edema.Furthermore,YL-0919 effectively combated oxidative stress both in vivo and in vitro.The protective effects of YL-0919 were partially inhibited by BD-1047.These results indicated that YL-0919 relieved impairments in motor and spatial cognition by restraining oxidative stress,a neuroprotective effect that was partially reversed by the sigma-1 receptor antagonist BD-1047.YL-0919 may have potential as a new treatment for traumatic brain injury.展开更多
Magnesium matrix composites with both high strength and ductility have been achieved by introducing pure Ti particles.However,the properties of the surfaces of the composites need to be improved by surface technology,...Magnesium matrix composites with both high strength and ductility have been achieved by introducing pure Ti particles.However,the properties of the surfaces of the composites need to be improved by surface technology,such as micro-arc oxidation(MAO).In this study,we investigated the influence of the Ti-reinforcement phase on coating growth and evolution by subjecting both AZ91 alloy and AZ91/Ti composite to MAO treatment using silicate-based and phosphate-based electrolytes.Results revealed that the Ti-reinforcement phase influenced the MAO process,altering discharge behavior,and leading to a decreased cell voltage.The vigorous discharge of the Ti-reinforcement phase induced the formation of coating discharge channels,concurrently dissolving and oxidizing Ti-reinforcement to produce a composite ceramic coating with TiO2.The MAO coating on the AZ91/Ti composite exhibited a dark blue macromorphology and distinctive local micromorphological anomalies.In silicate electrolyte,a“volcano-like”localized morphology centered on the discharge channel emerged.In contrast,treatment in phosphate-based electrolyte resulted in a coating morphology similar to typical porous ceramic coatings,with visible radial discharge micropores at the reinforcement phase location.Compared to the AZ91 alloy,the coating on the AZ91/Ti composite exhibited lower thickness and higher porosity.MAO treatment reduced the self-corrosion current density of the AZ91/Ti surface by two orders of magnitude.The silicate coating demonstrated better corrosion resistance than the phosphate coating,attributed to its lower porosity.The formation mechanism of MAO coatings on AZ91/Ti composites in phosphate-based and silicate-based electrolytes was proposed.展开更多
Nano-zinc oxides(ZnO)demonstrate remarkable antibacterial properties.To further enhance the corrosion resistance and antibacterial efficiency of magnesium alloy micro-arc oxidation(MAO)coatings,this study investigates...Nano-zinc oxides(ZnO)demonstrate remarkable antibacterial properties.To further enhance the corrosion resistance and antibacterial efficiency of magnesium alloy micro-arc oxidation(MAO)coatings,this study investigates the preparation of ZnO-containing micro-arc oxidation coatings with dual functionality by incorporating nano-ZnO into MAO electrolyte.The influence of varying ZnO concentrations on the microstructure,corrosion resistance,and antibacterial properties of the coating was examined through microstructure analysis,immersion tests,electrochemical experiments,and antibacterial assays.The findings revealed that the addition of nano-ZnO significantly enhanced the corrosion resistance of the MAO-coated alloy.Specifically,when the ZnO concentration in the electrolyte was 5 g/L,the corrosion rate was more than ten times lower compared to the MAO coatings without ZnO.Moreover,the antibacterial efficacy of ZnO+MAO coating,prepared with a ZnO concentration of 5 g/L,surpassed 95%after 24 h of co-culturing with Staphylococcus aureus(S.aureus).The nano-ZnO+MAO-coated alloy exhibited exceptional degradation resistance,corrosion resistance,and antibacterial effectiveness.展开更多
A Cr/CoNiCrAlTaY bilayer coating was prepared on the Ti-45Al-8.5Nb alloy by plasma surface metallurgy technique.The as-prepared coating with a grain size of~2μm exhibited a dense microstructure and strong adhesion du...A Cr/CoNiCrAlTaY bilayer coating was prepared on the Ti-45Al-8.5Nb alloy by plasma surface metallurgy technique.The as-prepared coating with a grain size of~2μm exhibited a dense microstructure and strong adhesion due to metallurgical bonding,consisting of outermost Cr layer and CoNiCrAlTaY transition layer.The typical power-law relationship between mass gain and time was obtained for the coated specimens with a rate exponent of 3.18 following oxidation at 1173 K.The top Cr_(2)O_(3)film and spinel oxides(i.e.,NiCr_(2)O_(4)and CoCr_(2)O_(4))exhibited a protective effect with a low oxidation reaction rate.Interfacial analysis identified Ta precipitates(Cr_(2)Ta and TaAl_(3))and Ta oxides(Ta_(2)O_(5)and Ta_(2)O_(3)),which played an essential role in retarding rapid diffusion and enhancing adhesion and oxidation resistance.展开更多
Enhancing the corrosion resistance of carriers within Fenton-like systems and inhibiting the migration and aggregation of single atoms in reaction environments are essential for maintaining both high activity and stab...Enhancing the corrosion resistance of carriers within Fenton-like systems and inhibiting the migration and aggregation of single atoms in reaction environments are essential for maintaining both high activity and stability at catalytic sites,thus meeting fundamental requirements for practical application.The Fenton-like process of activating various strong oxidants by silicon-based single atom catalysts(SACs)prepared based on silicon-based materials(mesoporous silica,silicon-based minerals,and organosilicon materials)has unique advantages such as structural stability(especially important under strong oxidation conditions)and environmental protection.In this paper,the preparation strategies for the silicon-based SACs were assessed first,and the structural characteristics of various silicon-based SACs are systematically discussed,their application process and mechanism in Fenton-like process to achieve water purification are investigated,and the progress of Fenton-like process in density functional theory(DFT)of siliconbased derived single atom catalysts is summarized.In this paper,the preparation strategies and applications of silicon-based derived SACs are analyzed in depth,and their oxidation activities and pathways to different pollutants in water are reviewed.In addition,this paper also summarizes the device design and application of silicon-based derived SACs,and prospects the future development of silicon-based SACs in Fenton-like applications.展开更多
This study presents a novel approach to improving the anticorrosive performance of AZ31 Mg alloy by exploiting the role of the hydration reaction to induce interactions between Quinolin-8-ol(8HQ)molecules and the poro...This study presents a novel approach to improving the anticorrosive performance of AZ31 Mg alloy by exploiting the role of the hydration reaction to induce interactions between Quinolin-8-ol(8HQ)molecules and the porous MgO layer formed via plasma electrolytic oxidation(PEO).The AZ31 Mg alloy,initially coated with a PEO layer,underwent a dipping treatment in an ethanolic solution of 0.05 M 8HQ at 50℃ for 3 h.The results were compared with those from a different procedure where the PEO layer was subjected to a hydration reaction for 2 h at 90℃ before immersion in the 8HQ solution under the same conditions.The hydration treatment played a crucial role by converting MgO to Mg(OH)_(2),significantly enhancing the surface reactivity.This transformation introduced hydroxyl groups(−OH)on the surface,which facilitated donor-acceptor interactions with the electron-accepting sites on 8HQ molecules.The calculated binding energy(Ebinding)from DFT indicated that the interaction energy of 8HQ with Mg(OH)_(2) was lower compared to 8HQ with MgO,suggesting easier adsorption of 8HQ molecules on the hydrated surface.This,combined with the increased number of active sites and enhanced surface area,allowed for extensive surface coverage by 8HQ,leading to the formation of a stable,flake-like protective layer that sealed the majority of pores on the PEO layer.DFT calculations further suggested that the hydration treatment provided multiple active sites,enabling effective contact with 8HQ and rapid electron transfer,creating ideal conditions for charge-transfer-induced physical and chemical bonding.This study shows that hydration and 8HQ treatments significantly enhance the corrosion resistance of Mg alloys,highlighting their potential for advanced anticorrosive coatings.展开更多
Silicide coatings have proven to be promising for improving the high-temperature oxidation resistance of niobium alloy.However,the long-term protective property of single silicide coating remains a long-time endeavor ...Silicide coatings have proven to be promising for improving the high-temperature oxidation resistance of niobium alloy.However,the long-term protective property of single silicide coating remains a long-time endeavor due to the deficiency of oxygen-consuming phases,as well as the self-healing ability of the protective layer.Herein,a silicide-based composite coating is constructed on niobium alloy by incor-poration of nano-SiC particles for enhancing the high-temperature oxidation resistance.Isothermal oxi-dation results at 1250℃ for 50 h indicate that NbSi_(2)/Nb_(2)O_(5)-SiO_(2)/SiC multilayer coated sample with a low mass gain of 2.49 mg/cm^(2) shows an improved oxidation resistance compared with NbSi_(2) coating(6.49 mg/cm^(2)).The enhanced high-temperature antioxidant performance of NbSi_(2)/Nb_(2)O_(5)-SiO_(2)/SiC multi-layer coating is mainly attributed to the formation of the protective SiO_(2) self-healing film and the high-temperature diffusion behavior of NbSi_(2)/substrate.展开更多
In this study,different types of small molecular carbon sources such as melamine,dicyandiamine,pyrocatechol,and o-phenylenediamine were used to regulate the surface structures of iron/nitrogen/carbonbased composites(F...In this study,different types of small molecular carbon sources such as melamine,dicyandiamine,pyrocatechol,and o-phenylenediamine were used to regulate the surface structures of iron/nitrogen/carbonbased composites(Fe-N/C),which were used to activate peroxymonosulfate(PMS).The relationship between different small molecular carbon sources and the electronic structure was investigated.The characteristics of metal-carrier interaction in the Fe-N/C were clarified.As a result,there were significant differences in the degradation efficiency of catalysts prepared with different small molecular carbon sources,which was related to the types of active sites.Density functional theory(DFT)and experiments results showed that the catalyst rich in C-O-C and FeN_(x)exhibited better catalytic activity,which may be attributed to the higher adsorption energy for PMS.The main active species for catalytic degradation of ofloxacin were identified as sulfate radical(SO_(4)^(·-))and hydroxyl radical(^(·)OH)by electron paramagnetic resonance(EPR)spectra.The introduction of different small molecular carbon sources can significantly affect the distribution and electronic structure of active sites on the catalyst surface,thereby regulating the generation and migration of radicals.展开更多
Precise manipulation of the catalytic spin configuration and delineation of the relationship between spin related properties and oxidation pathways remain significant challenges in Fenton-like processes.Herein,encapsu...Precise manipulation of the catalytic spin configuration and delineation of the relationship between spin related properties and oxidation pathways remain significant challenges in Fenton-like processes.Herein,encapsulated cobalt nanoparticles and cobalt-nitrogen-doped carbon moieties,endowed with confinement effects and variations in shell curvature were constructed via straightforward pyrolysis strategies,inducing alterations in magnetic anisotropy,electronic energy levels and spin polarization.The enhanced spin polarization at cobalt sites leads to a reduction in crystal field splitting energy and an increase in electronic spin density.This phenomenon facilitated electron transfer from cobalt orbitals to pz orbitals of oxygen species within peroxymonosulfate molecules,thereby promoting the formation of high-valent cobalt species.The encapsulation effectively stabilized cobalt nanoparticles,mitigating their dissolution or deactivation during reactions,which in turn enhances stability and durability in continuous flow processes.The high-valent cobalt species within the shell exhibit increased exposure and generate localized high concentrations,thereby intensifying interactions with migrating pollutants and enabling efficient and selective oxidation of emerging compounds with elevated redox potentials.This work underscores the profound impact of confined encapsulation curvature and spin polarization characteristics of metal sites on catalytic oxidation pathways and performance,opening novel avenues for spin engineering in practical environmental catalysis.展开更多
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 National Natural Science Foundation of China(No.52170086)Shandong Provincial Excellent Youth(No.ZR2022YQ47)。
文摘Herein,a diatomite biomorphic Si-O doped carbon-based catalyst(DB-SiOC)was prepared using natura mineral diatomite as the silicon source and porous template.The results showed that the metal-free DB SiOC catalyst exhibited ultrafast oxidation towards chlorophenol(CP)via peroxymonosulfate(PMS)activa tion,which was almost one order of magnitudes than most of carbon-based catalysts.The DB-SiOC/PMS system also showed the high ability to resist the interference of environmental matrix.The radicals(^(·)OH and SO_(4)^(·–))exhibited a very small contribution to the CP oxidation while the electron transfer processe(ETP)played the major role in the DB-SiOC/PMS system.The electron shuttles from the electron-donating CP molecules to the adjacent DB-SiOC/PMS^(*)could be efficiently triggered via Si-O bonds as bridges,mak ing it possible for ultrafast oxidation of CP.In addition,the hollow-disc shaped DB-Si OC provided the biomorphic DE structures with abundant pores for enriching the PMS and pollutants,thus further ac celerating the oxidation reaction.This work provided a new routine for the fabrication of Si-O doped carbon-based catalysts with excellent Fenton-like catalytic activity,which would greatly promote thei application prospects in Fenton-like systems.
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.
文摘The UV photooxidation with Fe（Ⅲ） and H2O2 was employed to treat a naval derusting wastewater, which contains the high COD （chemical oxygen demand） and various metal concentrations exceptionally with high concentrations of citric acid and iron. Because of its iron containment, the Fenton-like reaction automatically took place with the added amount of H2O2. The decomposition rate was found in a sequence of： UV/HEOE/Fe（Ⅲ） 〉 UV/H2O2 〉 Fe（Ⅱ）/H2O2. Two H2O2 injection methods, single and multiple points, were evaluated. The multiple-point H2O2 injection was more efficient to decompose the citric acid. The decomposition of the synthetic citric acid and the real derusting citric acid wastewater was also compared. The 93% COD reduction of the derusting wastewater was achieved using the UV/HEOE/Fe（Ⅲ） treatment.
基金support to visit The University of Adelaide from the China Scholarship Council(No.201906240037).
文摘The sluggish kinetics of Fe(Ⅱ)recovery in Fenton/Fenton-like reactions significantly limits the oxidation efficiency.In this study,we for the first time use boron carbide(BC)as a green and stable promotor to enhance the reaction of Fe(Ⅲ)/H_(2)O_(2) for degradation of diverse organic pollutants.Electron paramagnetic resonance analysis and chemical quenching/capturing experiments demonstrate that hydroxyl radicals(·OH)are the primary reactive species in the BC/Fe(Ⅲ)/H_(2)O_(2) system.In situ electrochemical analysis indicates that BC remarkably boosts the Fe(Ⅲ)/Fe(Ⅱ)redox cycles,where the adsorbed Fe(Ⅲ)cations were transformed to more active Fe(Ⅲ)species with a higher oxidative potential to react with H_(2)O_(2) to produce Fe(Ⅱ).Thus,the recovery of Fe(Ⅱ)from Fe(Ⅲ)is facilitated over BC surface,which enhancesOH generation via Fenton reactions.Moreover,BC exhibits outstanding reusability and stability in successive cycles and avoids the secondary pollution caused by conventional organic and metalliferous promotors.Therefore,metal-free BC boosting Fe(Ⅲ)/H_(2)O_(2) oxidation of organics provides a green and advanced strategy for water decontamination.
基金Sponsored by the National High Technology Research and Development Program of China(863 Program) (Grant No.2006AA06Z306)the Natural Science Foundation of China under the Scheme of Innovation Group Fund
文摘During the oxidative degradation of nonbiodegradable Malachite green (MG) by means of H2O2 /FeIIIR (iron supported on ion-exchage resin) in a dynamic column,the binding energy of the Fe(2p3/2) region for XPS spectra was found to be different between the top layer and the bottom layer in this column. Based on the data from XPS spectra and DMPO-OH·signal by EPR spectra,it is shown that the formation of ferryl (IV) is the key step for the oxidation of MG. The ferryl (IV) species can oxidize MG,and its redox potential is about 0. 739 - 0. 803 V measured by cyclic voltammograms (CV) . The catalytic capability of ferryl (IV) species was also evaluated,and it is found that it can promote the decomposition of H2O2 more efficiently than ferric iron. The removal rate of MG mainly depends on the adsorption of catalyst. Both ferryl (IV) and HO·radicals are the reactive species in the system. The oxidation of HO·is only a small part of the overall removal rate. Based on the obtained results,a possible mechanism for a resin-supported Fenton-like oxidation reaction is proposed.
文摘Oxidation by Fenton like reactions (Fe3+/H2O2) is economically process for destructive hazardous pollutants in waste water. The effects of different parameters such as, amaranth red dye, ferric chloride, hydrogen peroxide concentrations, pH value of solution, temperature and the presence of inorganic ions (carbonate, nitrate, chloride) on oxidative decolorization of amaranth were investigated. Amaranth degradation by (Fe3+/H2O2) reagent was found to follow first order kinetic model. Under optimum condition, pH = 2.6 and [FeCl3] = 3.75 × 10-4 mol·dm-3, the amaranth in aqueous solution with an initial concentration of 5 × 10-5 mol·dm-3 was degraded by 95% within 6 minutes. Increasing temperature in the range of 298 - 308 K increases the rate of dye degradation. Thermodynamic constants, ΔH*, ΔS* and ΔG* were evaluated. The results implied that the oxidation process was favorable and endothermic.
文摘Pitch produced by the lique-faction of coal was divided into two frac-tions:soluble in toluene(TS)and insol-uble in toluene but soluble in pyridine(TI-PS),and their differences in molecu-lar structure and oxidation activity were studied.Several different carbon materi-als were produced from them by oxida-tion in air(350℃,300 mL/min)fol-lowed by carbonization(1000℃ in Ar),and the effect of the cross-linked structure on their structure and sodium storage properties was investigated.The results showed that the two pitch fractions were obviously different after the air oxidation.The TS fraction with a low degree of condensation and abundant side chains had a stronger oxidation activity and thus introduced more cross-linked oxygen-containing functional groups C(O)―O which prevented carbon layer rearrangement during the carbonization.As a result,a disordered hard carbon with more defects was formed,which improved the electrochemical performance.Therefore,the carbon materials derived from TS(O-TS-1000)had an obvious disordered structure and a larger layer spacing,giving them better sodium storage perform-ance than those derived from the TI-PS fraction(O-TI-PS-1000).The specific capacity of O-TS-1000 was about 250 mAh/g at 20 mA/g,which was 1.67 times higher than that of O-TI-PS-1000(150 mAh/g).
基金supported by the National Key Research and Development Program of China(Grant No.2022YFF0609000)National Natural Science Foundation of China(Grant Nos.52171034 and 52101037)Postdoctoral Fellowship Program of CPSFara(No.GZB20230944).
文摘Up-and-coming high-temperature materials,refractory high entropy alloys,are suffering from lower oxidation resistance,restricting their applications in the aerospace field.In this study,two novel treatments of Al-deposited and remelted were developed to refine the microstructure and enhance the oxidation resistance of refractory high entropy alloy using electron beam freeform fabrication(EBF3).Finer and short-range ordering structures were observed in the remelted sample,whereas the Al-deposited sample showcased the formation of silicide and intermetallic phases.High-temperature cyclic and isothermal oxidation tests at 1000℃ were carried out.The total weight gain after 60 h of cyclic oxidation decreased by 17.49%and 30.46%for the remelted and deposited samples,respectively,compared to the as-cast state.Oxidation kinetics reveal an evident lower mass gain and oxidation rate in the treated samples.A multilayer oxide consisting of TiO_(2)+Al_(2)O_(3)+SiO_(2)+AlNbO_(4) was studied for its excellent oxidation resistance.The oxidation behavior of rutile,corundum and other oxides was analyzed using first principles calculations and chemical defect analysis.Overall,this research,which introduces novel treatments,offers promising insights for enhancing the inherent oxidation resistance of refractory high entropy alloys.
基金support from the National Natural Science Foundation of China(Nos.52171107,52201203)the Hebei Provincial Natural Science Foundation,China(No.E2021501026)the National Natural Science Foundation of China-Joint Fund of Iron and Steel Research(No.U1960204).
文摘The novel Co-based superalloys are extensively used in gas-powered and jet engine turbines due to their excellent high-temperature performance, achieved by strengthening the L12-γ′ ordered phase. This review presents an overview of the research progress on oxidation behavior of Co-based superalloys, including oxidation kinetics, oxides morphology, the formation and spallation of oxide layers, and importantly, the synergistic effects of alloying elements on oxidation resistance—a critical area considering the complex interactions with multiple alloying elements. Additionally, this review compares the oxidation resistance of single crystal versus polycrystalline alloys. The effect of phase interface and dislocations on oxidation behavior is also discussed. While significant progress has been achieved, areas necessitating further investigation include optimizing alloy compositions for enhanced oxidation resistance and understanding the long-term stability of oxide layers. The future prospects for Co-based superalloys are promising as ongoing research aims to address the existing challenges and unlock new applications at even higher operating temperatures.
基金supported by the National Natural Science Foundation of China,Nos.82204360(to HM)and 82270411(to GW)National Science and Technology Innovation 2030 Major Program,No.2021ZD0200900(to YL)。
文摘Traumatic brain injury involves complex pathophysiological mechanisms,among which oxidative stress significantly contributes to the occurrence of secondary injury.In this study,we evaluated hypidone hydrochloride(YL-0919),a self-developed antidepressant with selective sigma-1 receptor agonist properties,and its associated mechanisms and targets in traumatic brain injury.Behavioral experiments to assess functional deficits were followed by assessment of neuronal damage through histological analyses and examination of blood-brain barrier permeability and brain edema.Next,we investigated the antioxidative effects of YL-0919 by assessing the levels of traditional markers of oxidative stress in vivo in mice and in vitro in HT22 cells.Finally,the targeted action of YL-0919 was verified by employing a sigma-1 receptor antagonist(BD-1047).Our findings demonstrated that YL-0919 markedly improved deficits in motor function and spatial cognition on day 3 post traumatic brain injury,while also decreasing neuronal mortality and reversing blood-brain barrier disruption and brain edema.Furthermore,YL-0919 effectively combated oxidative stress both in vivo and in vitro.The protective effects of YL-0919 were partially inhibited by BD-1047.These results indicated that YL-0919 relieved impairments in motor and spatial cognition by restraining oxidative stress,a neuroprotective effect that was partially reversed by the sigma-1 receptor antagonist BD-1047.YL-0919 may have potential as a new treatment for traumatic brain injury.
基金supported by the Guangdong Major Project of Basic and Applied Basic Research(Grant No.2020B0301030006).
文摘Magnesium matrix composites with both high strength and ductility have been achieved by introducing pure Ti particles.However,the properties of the surfaces of the composites need to be improved by surface technology,such as micro-arc oxidation(MAO).In this study,we investigated the influence of the Ti-reinforcement phase on coating growth and evolution by subjecting both AZ91 alloy and AZ91/Ti composite to MAO treatment using silicate-based and phosphate-based electrolytes.Results revealed that the Ti-reinforcement phase influenced the MAO process,altering discharge behavior,and leading to a decreased cell voltage.The vigorous discharge of the Ti-reinforcement phase induced the formation of coating discharge channels,concurrently dissolving and oxidizing Ti-reinforcement to produce a composite ceramic coating with TiO2.The MAO coating on the AZ91/Ti composite exhibited a dark blue macromorphology and distinctive local micromorphological anomalies.In silicate electrolyte,a“volcano-like”localized morphology centered on the discharge channel emerged.In contrast,treatment in phosphate-based electrolyte resulted in a coating morphology similar to typical porous ceramic coatings,with visible radial discharge micropores at the reinforcement phase location.Compared to the AZ91 alloy,the coating on the AZ91/Ti composite exhibited lower thickness and higher porosity.MAO treatment reduced the self-corrosion current density of the AZ91/Ti surface by two orders of magnitude.The silicate coating demonstrated better corrosion resistance than the phosphate coating,attributed to its lower porosity.The formation mechanism of MAO coatings on AZ91/Ti composites in phosphate-based and silicate-based electrolytes was proposed.
基金supported by the National Natural Science Foundation of China(No.52001034)the China Postdoctoral Science Foundation(No.2023M731677)the Postgraduate Research&Practice Innovation Program of Jiangsu Province(No.KYCX23_3032).
文摘Nano-zinc oxides(ZnO)demonstrate remarkable antibacterial properties.To further enhance the corrosion resistance and antibacterial efficiency of magnesium alloy micro-arc oxidation(MAO)coatings,this study investigates the preparation of ZnO-containing micro-arc oxidation coatings with dual functionality by incorporating nano-ZnO into MAO electrolyte.The influence of varying ZnO concentrations on the microstructure,corrosion resistance,and antibacterial properties of the coating was examined through microstructure analysis,immersion tests,electrochemical experiments,and antibacterial assays.The findings revealed that the addition of nano-ZnO significantly enhanced the corrosion resistance of the MAO-coated alloy.Specifically,when the ZnO concentration in the electrolyte was 5 g/L,the corrosion rate was more than ten times lower compared to the MAO coatings without ZnO.Moreover,the antibacterial efficacy of ZnO+MAO coating,prepared with a ZnO concentration of 5 g/L,surpassed 95%after 24 h of co-culturing with Staphylococcus aureus(S.aureus).The nano-ZnO+MAO-coated alloy exhibited exceptional degradation resistance,corrosion resistance,and antibacterial effectiveness.
基金financial supports from Shanxi Provincial Natural Science Foundation,China(No.20210302123162)Shanxi Scholarship Council of China(No.2024-057)+2 种基金State Key Laboratory of Advanced Metal Materials,China(No.2019-ZD02)Science and Technology Achievement Transformation and Cultivation Project of Shanxi,China(No.2020CG011)Shanxi“1331 Project”Quality Improvement and Efficiency Project,China。
文摘A Cr/CoNiCrAlTaY bilayer coating was prepared on the Ti-45Al-8.5Nb alloy by plasma surface metallurgy technique.The as-prepared coating with a grain size of~2μm exhibited a dense microstructure and strong adhesion due to metallurgical bonding,consisting of outermost Cr layer and CoNiCrAlTaY transition layer.The typical power-law relationship between mass gain and time was obtained for the coated specimens with a rate exponent of 3.18 following oxidation at 1173 K.The top Cr_(2)O_(3)film and spinel oxides(i.e.,NiCr_(2)O_(4)and CoCr_(2)O_(4))exhibited a protective effect with a low oxidation reaction rate.Interfacial analysis identified Ta precipitates(Cr_(2)Ta and TaAl_(3))and Ta oxides(Ta_(2)O_(5)and Ta_(2)O_(3)),which played an essential role in retarding rapid diffusion and enhancing adhesion and oxidation resistance.
基金supported by National Natural Science Foundation of China(No.52170086)Natural Science Foundation of Shandong Province(No.ZR2021ME013)+1 种基金Natural science Foundation of Shaanxi province(No.2024JC-YBQN-0252)Special Scientific Research Project of Hanzhong City-Shaanxi University of Technology Co-construction State Key Laboratory(No.SXJ2106)。
文摘Enhancing the corrosion resistance of carriers within Fenton-like systems and inhibiting the migration and aggregation of single atoms in reaction environments are essential for maintaining both high activity and stability at catalytic sites,thus meeting fundamental requirements for practical application.The Fenton-like process of activating various strong oxidants by silicon-based single atom catalysts(SACs)prepared based on silicon-based materials(mesoporous silica,silicon-based minerals,and organosilicon materials)has unique advantages such as structural stability(especially important under strong oxidation conditions)and environmental protection.In this paper,the preparation strategies for the silicon-based SACs were assessed first,and the structural characteristics of various silicon-based SACs are systematically discussed,their application process and mechanism in Fenton-like process to achieve water purification are investigated,and the progress of Fenton-like process in density functional theory(DFT)of siliconbased derived single atom catalysts is summarized.In this paper,the preparation strategies and applications of silicon-based derived SACs are analyzed in depth,and their oxidation activities and pathways to different pollutants in water are reviewed.In addition,this paper also summarizes the device design and application of silicon-based derived SACs,and prospects the future development of silicon-based SACs in Fenton-like applications.
基金supported by the National Research Foundation of Korea(NRF)funded by the Korean government(MSIT)(No.2022R1A2C1006743).
文摘This study presents a novel approach to improving the anticorrosive performance of AZ31 Mg alloy by exploiting the role of the hydration reaction to induce interactions between Quinolin-8-ol(8HQ)molecules and the porous MgO layer formed via plasma electrolytic oxidation(PEO).The AZ31 Mg alloy,initially coated with a PEO layer,underwent a dipping treatment in an ethanolic solution of 0.05 M 8HQ at 50℃ for 3 h.The results were compared with those from a different procedure where the PEO layer was subjected to a hydration reaction for 2 h at 90℃ before immersion in the 8HQ solution under the same conditions.The hydration treatment played a crucial role by converting MgO to Mg(OH)_(2),significantly enhancing the surface reactivity.This transformation introduced hydroxyl groups(−OH)on the surface,which facilitated donor-acceptor interactions with the electron-accepting sites on 8HQ molecules.The calculated binding energy(Ebinding)from DFT indicated that the interaction energy of 8HQ with Mg(OH)_(2) was lower compared to 8HQ with MgO,suggesting easier adsorption of 8HQ molecules on the hydrated surface.This,combined with the increased number of active sites and enhanced surface area,allowed for extensive surface coverage by 8HQ,leading to the formation of a stable,flake-like protective layer that sealed the majority of pores on the PEO layer.DFT calculations further suggested that the hydration treatment provided multiple active sites,enabling effective contact with 8HQ and rapid electron transfer,creating ideal conditions for charge-transfer-induced physical and chemical bonding.This study shows that hydration and 8HQ treatments significantly enhance the corrosion resistance of Mg alloys,highlighting their potential for advanced anticorrosive coatings.
基金supported by the National Natural Science Foundation of China(Nos.U21B2053,52071114,52001100,and 523B2010)Outstanding Youth Project of Natural Science Foundation of Heilongjiang Province(No.YQ2023E008)+1 种基金Young Elite Scientists Sponsorship Program by CAST(NO.2021QNRC001)Heilongjiang Touyan Team Program.
文摘Silicide coatings have proven to be promising for improving the high-temperature oxidation resistance of niobium alloy.However,the long-term protective property of single silicide coating remains a long-time endeavor due to the deficiency of oxygen-consuming phases,as well as the self-healing ability of the protective layer.Herein,a silicide-based composite coating is constructed on niobium alloy by incor-poration of nano-SiC particles for enhancing the high-temperature oxidation resistance.Isothermal oxi-dation results at 1250℃ for 50 h indicate that NbSi_(2)/Nb_(2)O_(5)-SiO_(2)/SiC multilayer coated sample with a low mass gain of 2.49 mg/cm^(2) shows an improved oxidation resistance compared with NbSi_(2) coating(6.49 mg/cm^(2)).The enhanced high-temperature antioxidant performance of NbSi_(2)/Nb_(2)O_(5)-SiO_(2)/SiC multi-layer coating is mainly attributed to the formation of the protective SiO_(2) self-healing film and the high-temperature diffusion behavior of NbSi_(2)/substrate.
基金supported by National Natural Science Foundation of China(Nos.52170086,52300056)Natural Science Foundation of Shandong Province(Nos.ZR2021ME013,ZR202211280298)。
文摘In this study,different types of small molecular carbon sources such as melamine,dicyandiamine,pyrocatechol,and o-phenylenediamine were used to regulate the surface structures of iron/nitrogen/carbonbased composites(Fe-N/C),which were used to activate peroxymonosulfate(PMS).The relationship between different small molecular carbon sources and the electronic structure was investigated.The characteristics of metal-carrier interaction in the Fe-N/C were clarified.As a result,there were significant differences in the degradation efficiency of catalysts prepared with different small molecular carbon sources,which was related to the types of active sites.Density functional theory(DFT)and experiments results showed that the catalyst rich in C-O-C and FeN_(x)exhibited better catalytic activity,which may be attributed to the higher adsorption energy for PMS.The main active species for catalytic degradation of ofloxacin were identified as sulfate radical(SO_(4)^(·-))and hydroxyl radical(^(·)OH)by electron paramagnetic resonance(EPR)spectra.The introduction of different small molecular carbon sources can significantly affect the distribution and electronic structure of active sites on the catalyst surface,thereby regulating the generation and migration of radicals.
文摘Precise manipulation of the catalytic spin configuration and delineation of the relationship between spin related properties and oxidation pathways remain significant challenges in Fenton-like processes.Herein,encapsulated cobalt nanoparticles and cobalt-nitrogen-doped carbon moieties,endowed with confinement effects and variations in shell curvature were constructed via straightforward pyrolysis strategies,inducing alterations in magnetic anisotropy,electronic energy levels and spin polarization.The enhanced spin polarization at cobalt sites leads to a reduction in crystal field splitting energy and an increase in electronic spin density.This phenomenon facilitated electron transfer from cobalt orbitals to pz orbitals of oxygen species within peroxymonosulfate molecules,thereby promoting the formation of high-valent cobalt species.The encapsulation effectively stabilized cobalt nanoparticles,mitigating their dissolution or deactivation during reactions,which in turn enhances stability and durability in continuous flow processes.The high-valent cobalt species within the shell exhibit increased exposure and generate localized high concentrations,thereby intensifying interactions with migrating pollutants and enabling efficient and selective oxidation of emerging compounds with elevated redox potentials.This work underscores the profound impact of confined encapsulation curvature and spin polarization characteristics of metal sites on catalytic oxidation pathways and performance,opening novel avenues for spin engineering in practical environmental catalysis.
