AgVO_(3)/ZIF-8 composites with enhanced photocatalytic effect were prepared by the combination of AgVO_(3)and ZIF-8.X-ray diffraction(XRD),scanning electron microscopy(SEM),high-power transmission electron microscopy(...AgVO_(3)/ZIF-8 composites with enhanced photocatalytic effect were prepared by the combination of AgVO_(3)and ZIF-8.X-ray diffraction(XRD),scanning electron microscopy(SEM),high-power transmission electron microscopy(HRTEM),X-ray photoelectron spectroscopy(XPS),ultraviolet-visible diffuse reflectance spectroscopy(UV-Vis DRS),photoluminescence(PL)spectroscopy,electron spin resonance(ESR)spectroscopy,transient photocurrent and electrochemical impedance spectroscopy(EIS)were used to characterize binary composites.Tetracycline(TC)was used as a substrate to study the performance efficiency of the degradation of photocatalysts under light conditions,and the degradation effect of TC was also evaluated under different mass concentrations and ionic contents.In addition,we further investigated the photocatalytic mechanism of the binary composite material AgVO_(3)/ZIF-8 and identified the key active components responsible for the catalytic degradation of this new photocatalyst.The experimental results show that the degradation efficiency of 10%-AZ,prepared with a molar ratio of 10%AgVO_(3)and ZIF-8 to TC,was 75.0%.This indicates that the photocatalytic activity can be maintained even under a certain ionic content,making it a suitable photocatalyst for optimal use.In addition,the photocatalytic mechanism of binary composites was further studied by the active species trapping experiment.展开更多
Metal-organic frameworks(MOFs)and their derivatives have gained significant attention in recent years for their ability to catalyze the advanced oxidation of persulfates.Cerium-doped MOFs,in particular,have shown prom...Metal-organic frameworks(MOFs)and their derivatives have gained significant attention in recent years for their ability to catalyze the advanced oxidation of persulfates.Cerium-doped MOFs,in particular,have shown promise due to their high catalytic efficiency,practical applicability,and cost-effectiveness.However,their structure,catalytic properties,and mechanisms are not yet fully understood.ZIF-8 was chosen as the raw material to prepare cerium-doped hollow carbon nano fibers(Ce-HCNFs)using the electrostatic spinning-calcination method.The objective is to investigate the structure,catalytic performance,and catalytic mechanism of Ce-HCNFs.The results show that Ce-HCNFs catalyzed the degradation of tetracycline(TC)by persulfate up to 76.9%,Quenching experiments and electron paramagnetic resonance experiments indicate the dominant role of single-linear oxygen.Furthermore,the experiments on the influence factor and cycling demonstrate the exceptional stability and recycling capability of Ce-HCNFs in real-world water environments.展开更多
Tetracycline(TC)is a broad-spectrum antibiotic,and its residues in the environment and food are harmful to human health.Therefore,it is essential to rapidly,sensitively,and conveniently detect TC.In this work,we devel...Tetracycline(TC)is a broad-spectrum antibiotic,and its residues in the environment and food are harmful to human health.Therefore,it is essential to rapidly,sensitively,and conveniently detect TC.In this work,we developed a portable silicon nanoparticles chelated Europium(Ⅲ)-based polyacrylonitrile(Eu-SiNPs/PAN)nanofiber membrane for rapid,sensitive,and convenient detection of TC.The Eu-SiNPs were synthesized with a facile one-pot method.The Eu-SiNPs/PAN nanofiber membrane was fabricated by electrospinning,combining Eu-SiNPs and PAN with three-dimensional porous membrane structures and UV resistance.Both the Eu-SiNPs and the Eu-SiNPs/PAN nanofiber membranes have good selectivity and anti-interference ability towards TC.The combined merits of rapid response,long storage life,easy portability,and naked-eye recognition of TC make the Eu-SiNPs/PAN nanofiber membrane a promising material for convenient TC detection applications.The practicability of these nanofiber membranes was further verified by detecting TC in real samples,such as lake water,drinking water and honey,and achieved quantitative detection.展开更多
A series of CeO_(2)@MnO_(2)composites was prepared by deposition-precipitation methods.These materials were used to activate sodium persulfate(PDS)for the oxidation of tetracycline.It is found that the composites,espe...A series of CeO_(2)@MnO_(2)composites was prepared by deposition-precipitation methods.These materials were used to activate sodium persulfate(PDS)for the oxidation of tetracycline.It is found that the composites,especially the CeO_(2)@MnO_(2)-1:4 composites,exhibit better tetracycline removal rates than the pure components.X-ray diffraction(XRD),Raman and scanning electron microscopy(SEM)analyses all indicate that the composite has been successfully prepared with high purity and high crystalline.The XPS analysis shows that the strong interaction between the components promotes the electron transfer.Additionally,the kinetic rate constants of CeO_(2)@MnO_(2)-1:4 after 60 min are 3.8 and 12.7 times higher than pure CeO_(2)and MnO_(2),respectively.CeO_(2)@MnO_(2-)1:4 composite also exhibits excellent catalytic activity for individual and hybrid pollutants.The effects of wastewater matrix,pH,circulation and ion stre ngth on the degradation of tetracycline were investigated.It is found that CeO_(2)@MnO_(2)-1:4 composite has good practical application prospects.CeO_(2)@MnO_(2)composites with synergistic adsorption catalysis can activate PDS and peroxymo no sulfate(PMS)for efficient organic catalytic oxidation.This paper provides the theoretical basis and data support for the practical application of the CeO_(2)@MnO_(2)composite materials.展开更多
Herein,a luminescent europium-based metal-organic framework(Eu-MOF,[Eu_(3)(L)(HL)(NO_(3))_(2)(DMF)_(2)]·4DMF·5H_(2)O,H_(4)L=5,5′-(pyrazine-2,6-diyl)diisophthalic acid,DMF=N,N-dimethylformamide)was developed...Herein,a luminescent europium-based metal-organic framework(Eu-MOF,[Eu_(3)(L)(HL)(NO_(3))_(2)(DMF)_(2)]·4DMF·5H_(2)O,H_(4)L=5,5′-(pyrazine-2,6-diyl)diisophthalic acid,DMF=N,N-dimethylformamide)was developed for the dual-functional detection of environmental pollutants.This fluorescence-quenching-based sensor exhibited excep-tional sensitivity for both 2,4,6-trinitrophenol(TNP)and tetracycline(TC),achieving remarkably low detection lim-its of 1.96×10^(-6)and 1.71×10^(-7)mol·L^(-1),respectively.Notably,the system exhibited 99%fluorescence quenching ef-ficiency for TC,indicating ultra-efficient analyte recognition.The detection performance surpasses most reported lu-minescent MOF sensors,attributed to synergistic mechanisms of fluorescence resonance energy transfer(FRET)and photoinduced electron transfer(PET).CCDC:2446483.展开更多
The synergetic technology of hydrodynamic cavitation(HC)and peroxydisulfate(PDS)has been adopted for the treatment of organic pollutants,while the rationale behind the thermal-activation of PDS in this process remains...The synergetic technology of hydrodynamic cavitation(HC)and peroxydisulfate(PDS)has been adopted for the treatment of organic pollutants,while the rationale behind the thermal-activation of PDS in this process remains lacking.This paper presented investigation on the degradation of tetracycline under two types of operating conditions,including“internal reaction conditions”(pH value and TC/PDS molar ratio)and“external physical conditions”(hole shape,solution temperature and inlet pressure).Special emphasis was paid on the analysis of thermal effects through a robust modeling approach.The results showed that a synergy index of 6.26 and a degradation rate of 56.71%could be obtained by the HC-PDS process,respectively,when the reaction conditions were optimized.Quenching experiment revealed that·OH and·SO_(4)^(-)were the predominant free radicals and their contribution to the degradation was 75.4%and 24.6%respectively,since a part of·SO_(4)^(-)was transformed into·OH in the solution.The thermal activation of PDS mainly occurred near the hole where the fitting temperature was around 340 K,while·OH was generated in the bubble collapse region downstream the hole,where the temperature was much higher and favorable for the cleavage of water molecular.The average temperature under different external physical conditions was in good consistence with the degradation rates.This research developed a useful method to effectively evaluate the activation extent of PDS by HC and could provide reliable guidance for further development of cavitational reactors to treat organic pollutants based on this hybrid approach.展开更多
Tetracyclines (TCs) are the second most commonly used antibiotics worldwide, utilized in medical treatments and animal husbandry. Although effective against various infectious diseases, TC residues persist in the envi...Tetracyclines (TCs) are the second most commonly used antibiotics worldwide, utilized in medical treatments and animal husbandry. Although effective against various infectious diseases, TC residues persist in the environment and contribute to the emergence of antibiotic-resistant pathogens, posing significant risks to human health. This study employed the heterogeneous Fenton process to degrade TC using soybean residue-derived magnetic biochar (Fe-SoyB) as the catalyst. The Fe-SoyB sample was characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), and superconducting quantum interference device (SQUID) techniques. The effects of key parameters, including pH, H2O2 concentration, catalyst dosage, and initial TC concentration, on TC degradation were investigated. The results indicated that the TC removal efficiency decreased with increasing initial TC concentration, while it was improved with higher H2O2 concentrations and greater catalyst dosages. The optimal conditions for the Fenton-like process were determined: a pH of 3, a H2O2 concentration of 245 mmol/L, an initial TC concentration of 800 mg/L, and a catalyst dosage of 0.75 g/L, achieving a removal efficiency of 90.0% after 150 min. Additionally, the TC removal efficiency of the Fe-SoyB system varied significantly across different water matrices, with 87.1% for deionized water, 78.5% for tap water, and 72.5% for river water. The catalyst demonstrated notable stability, maintaining a TC removal efficiency of 79.7% after three cycles of use. Overall, Fe-SoyB shows promise as a cost-effective catalyst for the elimination of organic pollutants in aqueous solutions.展开更多
Eliminating highly concentrated antibiotic wastewater by transition metal catalyst-assisted AOPs is challenging.Herein,by varying the metal precursor composition(Co/Fe ratios of 1/1,1.5/2/3),alloyed Co_(7)Fe_(3)nanocr...Eliminating highly concentrated antibiotic wastewater by transition metal catalyst-assisted AOPs is challenging.Herein,by varying the metal precursor composition(Co/Fe ratios of 1/1,1.5/2/3),alloyed Co_(7)Fe_(3)nanocrystals or spinel-like CoFe_(2)O_(4)can be switched and both confined within the porous N-doped graphitic carbon fibers by electrospinning and controlled graphitization.Impressively,iron precursors played a dual role in working as reactive centers and main activators for the creation of porous carbon networks affording improved accessibility to catalytic sites and easy tetracycline(TC)diffusion effect.The catalytic activity of the resulting materials was closely related to surface metal valence and composition.Notably,the CoFe_(2)O_(4)exhibited a significant improvement in peroxymonosulfate(PMS)adsorption and activation,explained by the present electron-deficient Co and Fe synergetic sites together with the interesting Jahn-Teller effect.Fe_(1)Co_(2)/CNF demonstrated the highest efficiency in degrading TC,achieving a reaction rate constant of 0.4647 min^(-1)with a low activation energy of 9.3 kJ·mol^(-1),nearly a 7.5-fold enhancement compared to Fe_(1)Co_(3)/CNF(0.062 min^(-1)).The reaction mechanism and the role of reactive oxidative species revealed a synergy of·SO_(4)^(-),·OH,·O_(2)^(-)and^(1)O_(2).Wherein,·O_(2)^(-)plays a more dominant role in the degradation of TC than other reactive species.Additionally,a reinforced electron-transfer pathway in the Fe_(1)Co_(2)/CNF system during PMS interaction was demonstrated.Furthermore,the degradation routes of TC were unraveled,and the toxicity of various intermediate by-products was assessed.Importantly,our continuous flow-type TC degradation process and light-driven photothermal strengthened reaction process demonstrated consistent performance,thereby offering a promising approach for tackling highly concentrated antibiotic wastewater.展开更多
This study introduced a microwave-assisted pyrolysis method for the rapid and efficientpreparation of boron-doped porous biochar. The resulting biochar exhibited a large specificsurface area (933.39 m^(2)/g), a rich p...This study introduced a microwave-assisted pyrolysis method for the rapid and efficientpreparation of boron-doped porous biochar. The resulting biochar exhibited a large specificsurface area (933.39 m^(2)/g), a rich porous structure (1.044 cm3/g), and abundant active sites.Consequently, the prepared boron-doped porous biochar exhibited higher efficiency in adsorbingtetracycline with a maximum adsorption capacity of 413.223 mg/g, which significantlyexceeded that of unmodified biochar andmost commercial and reported adsorbents.The correlation analysis between the adsorption capacity and adsorbent characteristics revealedthat the formation of the –BCO_(2) group enhanced π–π electron donor–acceptor interactionsbetween boron-doped porous biochar and tetracycline. This mechanism mainlycontributed to the enhanced adsorption of tetracycline by boron-doped porous biochar. Additionally,the as-prepared boron-doped porous biochar exhibited broad applications in removingantibiotics (tetracycline), phenolics (bisphenol A), and dyes (methylene blue andrhodamine B). Moreover, the boron-doped porous biochar exhibited satisfactory stability,and its adsorption capacity can be nearly completely regenerated through simple heat treatment.This study provides new insights into the effectiveness of boron-doped carbonaceousmaterials in removing antibiotic contaminants.展开更多
Harnessing the redox potential of biochar to activate airborne O_(2)for contaminant removal is challenging.In this study,ferrihydrite(Fh)modified the boron(B),nitrogen(N)co-doped biochars(BCs)composites(Fh/B(n)NC)were...Harnessing the redox potential of biochar to activate airborne O_(2)for contaminant removal is challenging.In this study,ferrihydrite(Fh)modified the boron(B),nitrogen(N)co-doped biochars(BCs)composites(Fh/B(n)NC)were developed for enhancing the degradation of a model pollutant,tetracycline(TC),merely by airborne O_(2).Fh/B(3)NC showed excellent O_(2)activation activity for efficient TC degradation with a apparent TC degradation rate of 5.54,6.88,and 22.15 times that of B(3)NC,Fh,and raw BCs,respectively,where 1O_(2)and H_(2)O_(2)were identified as the dominant ROS for TC degradation.The B incorporation into the carbon lattice of Fh/B(3)NC promoted the generation of electron donors,sp2 C and the reductive B species,hence boosting Fe(III)reduction and 1O_(2)generation.O_(2)adsorption was enhanced due to the positively charged adsorption sites(C-B+and N-C+).And 1O_(2)was generated via Fe(II)catalyzed low-efficient successive one-electron transfer(O_(2)→O_(2)·−→1O_(2),H_(2)O_(2)),as well as biochar catalyzed high-efficient two-electron transfer(O_(2)→H_(2)O_(2)→1O_(2))that does not involve.O_(2)−as the intermediate.Moreover,Fh/B,N co-doped biochar showed a wide pH range,remarkable anti-interference capabilities,and effective detoxification.These findings shed new light on the development of environmentally benign BCs materials capable of degradading organic pollutants.展开更多
Mariculture tailwater typically contains a certain concentration of antibiotics;however,conventional biological treatment methods struggle to effectively remove these antibiotics.Therefore,in this study,we modified th...Mariculture tailwater typically contains a certain concentration of antibiotics;however,conventional biological treatment methods struggle to effectively remove these antibiotics.Therefore,in this study,we modified the carbon felt(CF)anode in sediment microbial fuel cells(SMFCs)to enhance tetracycline(TC)removal in mariculture systems.We fabricated a novel composite material by integrating instant freeze-drying technology with the solvothermal reaction method to combine graphene oxide(GO)and nanoscale SiO_(2).Subsequently,the composite material was incorporated into CF for anodic modification,resulting in improved performance of SMFCs in TC removal and electricity generation.The maximum power density achieved was 63.72 mW/m^(2),nearly 2.9 times higher than that of the unmodified anode.Modified SMFCs exhibited a twofold increase in the degradation rate of tetracycline compared to natural degradation alone and showed significant improvements compared to both the control group and conditions with only GO addition.Furthermore,the modified anode effectively enriched populations of Leisingera,Oceanimonas,and Halomonas,thereby significantly enhancing the electrochemical performance of the SMFCs.This study successfully demonstrates the application of a modified-anode SMFC using a composite material consisting of GO and SiO_(2)for on-site removal of TC from mariculture environments.展开更多
The arbitrary discharge of tetracycline(TC)residuals has seriously influenced the ecosystem and human health.Laccase(Lac)-based biodegradation technology is considered a more effective way to remove TC due to its high...The arbitrary discharge of tetracycline(TC)residuals has seriously influenced the ecosystem and human health.Laccase(Lac)-based biodegradation technology is considered a more effective way to remove TC due to its high catalytic efficiency and less by-product.Nevertheless,free Lac suffers from poor stability,easy inactivation and difficult recovery,restricting its application.Immobilization of Lac is considered an efficient strategy for addressing these obstacles.In this study,a magnetic metal-organic framework of Fe_(3)O_(4)@SiO_(2)@UiO-66-NH_(2)(MMOF)was prepared and used as a carrier to immobilize Lac(Lac@MMOF)for TC degradation.Benefiting from the multiple binding sites,adsorption,and protection effect of MMOF,Lac@MMOF displayed a wider pH application range(2–7)and better thermal(15–85℃),repeatability,and storage stability than free Lac.Furthermore,owing to the synergism of MOF adsorption and Lac biocatalysis,the removal rate of Lac@MMOF for TC could be up to 98%at pH=7 within 1 hr,which was 1.29 and 1.24 times that of free Lac and MMOF,respectively.More importantly,Lac@MMOF could easily be separated from aqueous solution under a magnetic field and maintained good removal performance(80%)after five cycles.The degradation products were identified by applying LC-MS/MS,and possible degradation mechanisms and pathways were proposed.Finally,the antibacterial activity of intermediate products was evaluated using Escherichia coli,which revealed that the toxicity of TC was reduced effectively by the degradation of Lac@MMOF.Overall,Lac@MMOF is a green alternative for residual antibiotic removal in water.展开更多
The high band gap of zinc oxide(ZnO)has significantly limited its potential application for organic contaminant removal in photocatalysis.In this study,ZnO/halloysites(HNTs)composites(ZnO/HNTs)were prepared using a hi...The high band gap of zinc oxide(ZnO)has significantly limited its potential application for organic contaminant removal in photocatalysis.In this study,ZnO/halloysites(HNTs)composites(ZnO/HNTs)were prepared using a high-temperature calcination method to enhance the removal of tetracycline hydrochloride(TCH).The experimental results demonstrated that the band gap of ZnO/HNTs decreased to 3.12 eV,compared to 3.21 eV for pure ZnO.The observed removal rate(k_(obs))of TCH in the ZnO/HNTs/vis system was 1.90×10^(-2) min^(-1),significantly higher than the rates in the HNTs/vis(1.25×10^(-3)min^(-1))and ZnO/vis(1.13×10^(-2) min^(-1))systems.Additionally,ZnO/HNTs exhibited strong resistance to coexisting natural organic and inorganic matter,maintaining high pollutant removal efficiency in natural water samples.The ZnO/HNTs/vis system also effectively removed other common organic pollutants,such as ciprofloxacin and methylene blue.Cycle tests indicated that the ZnO/HNTs/vis system retained 65.57%of its original efficiency,demonstrating good reusability and versatility.Scavenging and electron paramagnetic resonance experiments identified that h+was the primary species in the ZnO/HNTs/vis system,with other species playing auxiliary roles in TCH degradation.This study provides valuable insights into the design of novel ZnO-based photocatalysts for the degradation of organic pollutants in water.展开更多
Rational design of composite catalysts with efficient charge separation and transfer is of great significance to achieve efficient degradation of pollutants.Herein,CuInS_(2)nanoparticles are skillfully deposited on Ti...Rational design of composite catalysts with efficient charge separation and transfer is of great significance to achieve efficient degradation of pollutants.Herein,CuInS_(2)nanoparticles are skillfully deposited on TiO_(2)nanofibers through a hydrothermal method.The formation of S-scheme heterojunction is confirmed through free radical trapping experiments,in‐situ irradiated X-ray photoelectron spectroscopy(ISI-XPS)measurements,density functional theory(DFT)calculations and femtosecond transient absorption spectroscopy(fs-TAS)results.These results reveal that the built-in electric field within the S-scheme heterojunction significantly enhances charge separation and transfer,boosting the catalyst's redox capabilities.The TiO_(2)/CuInS_(2)photocatalyst exhibits superior photocatalytic performance,achieving a degradation rate of 89%within 21 min of light irradiation,which is almost 2.2 times higher than that of TiO_(2).Additionally,the degradation products of TCH are investigated using in-situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)and liquid chromatography–mass spectrometry(LC-MS),offering insights into the degradation pathway.This study highlights the potential advantage of ultrafast charge carrier transfer in S-scheme heterojunction,providing a promising strategy for designing high-efficiency photocatalytic systems for environmental remediation.The findings offer new directions for improving the degradation of persistent pollutants like tetracyclines.展开更多
Given their unique structure-dependent properties,strategically designing semiconductor-based photocatalysts,which expose highly reactive crystalline facets,is widely used to tune their performance.Herein,AgBr/Ag/TiO_...Given their unique structure-dependent properties,strategically designing semiconductor-based photocatalysts,which expose highly reactive crystalline facets,is widely used to tune their performance.Herein,AgBr/Ag/TiO_(2){100}nanorods Z-scheme heterojunction composites were prepared via hydrothermal and in situ facet-induced reduction.Transmission electron microscopy,X-ray diffraction,X-ray photoelectron spectroscopy,electron paramagnetic resonance spectroscopy,and density functional theory calculations reveal that the selective exposure of TiO_(2){100}facets with abundant oxygen vacancies(OV)promotes the formation of metallic silver on the interfaces between AgBr and TiO_(2){100}.Metallic silver can mediate interfacial charge transfer by facilitating the photogenerated carrier recombination of the conduction band of TiO_(2){100}and the valence band of AgBr.As a result,a Z-scheme heterojunction is formed in AgBr/Ag/TiO_(2){100}.The AgBr/Ag/TiO_(2){100}exhibits faster degradation of tetracycline in aqueous solution compared to pristine AgBr,TiO_(2){101},TiO_(2){100}and AgBr/TiO_(2){101}p-n heterojunctions.This is attributed to the effect of the Z-scheme heterojunction on prolonging the lifetime of photogenerated carriers,which is confirmed by femtosecond transient absorption spectroscopy.The photocatalytic mechanism and degradation pathways are discussed along with a toxicity assessment of the intermediates.Overall,this work develops a new approach for designing Z-scheme heterojunction photocatalysts via selective facet control of anatase TiO_(2).展开更多
With the burgeoning growth of aquaculture industry,high concentration of NH_(4)^(+)-N,phosphorus and tetracycline are the prevalent pollutants in aquaculturewastewater posing a significant health risk to aquatic organ...With the burgeoning growth of aquaculture industry,high concentration of NH_(4)^(+)-N,phosphorus and tetracycline are the prevalent pollutants in aquaculturewastewater posing a significant health risk to aquatic organisms.Therefore,an effective method for treating aquaculture wastewater should be urgently explored.Simultaneous removal of NH_(4)^(+)-N,phosphorus,tetracycline,and chemical oxygen demand(COD)in aquaculture wastewater was developed bymoving bed biofilm reactor(MBBR)under co-metabolic substances.The result showed that co-metabolism substances had different effects on MBBR performance,and 79.4%of tetracycline,68.2%of NH_(4)^(+)-N,61.3%of total nitrogen,88.3%of COD,and 38.1%of total phosphorus(TP)were synchronously removed with sodium acetate as a co-metabolic carbon source.Protein(PN),polysaccharide(PS),and electron transfer system activity were used to evaluate the MBBR performances,suggesting that PN/PS ratio was 1.48,0.91,1.07,3.58,and 0.79 at phases Ⅰ-Ⅴ.Additionally,a mode of tetracycline degradation and TP removal was explored,and the cell apoptosis was evaluated by flow cytometry.The result suggested that 74%,83%,and 83%of tetracycline were degraded by extracellular extracts,intracellular extracts,and cell debris,and there was no difference between extracts and non-enzyme in TP removal.The ratio of viable and dead cells from biofilm reached 33.3%and 7.68%with sodium acetate as a co-metabolic carbon source.Furthermore,Proteobacteria and Bacteroidetes in biofilm were identified as the dominant phyla for tetracycline and nutrients removal.This study provides a new strategy for tetracycline and nutrients removal from aquaculture wastewater through co-metabolism.展开更多
Quantitative determination of tetracycline(TC)in environment and foods is of great importance,as excessive residues might have negative effects on human health and environmental risks.Herein,a selfpowered molecularly ...Quantitative determination of tetracycline(TC)in environment and foods is of great importance,as excessive residues might have negative effects on human health and environmental risks.Herein,a selfpowered molecularly imprinted photoelectrochemical(PEC)sensor based on the Zn O/C photoanode and the Fe-doped CuBi_(2)O_(4)(CBFO)photocathode is developed for the sensitive detection of TC.The photocathodic current can be amplified by the efficient electron transfer caused by the Fermi energy level gap between the photoanode and photocathode.Furthermore,molecularly imprinted polymers(MIPs)at photocathode can selectivity identify the TC templates and thus improve the specificity.Under the optimal conditions,the sensor has a linear range of 10^(-2)-1.0×10^(5) nmol/L,and a limit of detection(LOD)of 0.007 nmol/L(S/N=3).More crucially,the milk sample detection is carried out using the as-prepared sensor,and the outcome is satisfactory.The research gives us a novel sensing platform for quick and accurate antibiotic(like TC)in environment and food monitoring.展开更多
The synergistic reaction of photocatalysis and advanced oxidation is a valid strategy for the degradation of harmful antibiotic wastewater.Herein,carbon dots(CDs)modified MIL-101(Fe)octahedrons to form CDs/MIL-101(Fe)...The synergistic reaction of photocatalysis and advanced oxidation is a valid strategy for the degradation of harmful antibiotic wastewater.Herein,carbon dots(CDs)modified MIL-101(Fe)octahedrons to form CDs/MIL-101(Fe)composite photocatalyst was synthesized for visible light-driven photocatalytic/persulfate(PS)-activated tetracycline(TC)degradation.The electron spin resonance(ESR)spectra,scavenging experiment and electrochemical analysis were carried out to reveal that the high visible light-driven photocatalytic degradation activity of TC over CDs/MIL-101(Fe)photocatalysts is not only ascribed to the production of free active radicals in the CDs/MIL-101(Fe)/PS system(·OH,·SO_(4-),^(1)O_(2),h^(+)and·O_(2)^(-))but also attributed to the consumption of electrons caused by the PS,which can suppress the recombination of photo-generated carriers as well as strong light scattering and electron trapping effects of CDs.Finally,the possible degradation pathways were proposed by analyzing intermediates via liquid chromatography-mass spectrometry technique.This research presents a rational design conception to construct a CDs/PS-based photocatalysis/advanced oxidation technology with high-efficient degradation activity for the remediation of organic antibiotic pollutant wastewater and for the improvement of carrier transport kinetics of photocatalysts.展开更多
Environmental photocatalysis is a promising technology for treating antibiotics in wastewater.In this study,a supercritical carbonization method was developed to synthesize a single-atom photocatalyst with a high load...Environmental photocatalysis is a promising technology for treating antibiotics in wastewater.In this study,a supercritical carbonization method was developed to synthesize a single-atom photocatalyst with a high loading of Ni(above 5 wt.%)anchored on a carbonnitrogen-silicate substrate for the efficient photodegradation of a ubiquitous environmental contaminant of tetracycline(TC).The photocatalyst was prepared from an easily obtained metal-biopolymer-inorganic supramolecular hydrogel,followed by supercritical drying and carbonization treatment.The low-temperature(300℃)supercritical ethanol treatment prevents the excessive structural degradation of hydrogel and greatly reduces the metal clustering and aggregation,which contributed to the high Ni loading.Atomic characterizations confirmed that Ni was present at isolated sites and stabilized by Ni-N and Ni-O bonds in a Ni-(N/O)_(6)-C/SiC configuration.A 5%Ni-C-Si catalyst,which performed the best among the studied catalysts,exhibited a wide visible light response with a narrow bandgap of 1.45 eV that could efficiently and repeatedly catalyze the oxidation of TC with a conversion rate of almost 100% within 40 min.The reactive species trapping experiments and electron spin resonance(ESR)tests demonstrated that the h+,and·O_(2)-were mainly responsible for TC degradation.The TC degradation mechanism and possible reaction pathways were provided also.Overall,this study proposed a novel strategy to synthesize a high metal loading singleatom photocatalyst that can efficiently remove TC with high concentrations,and this strategy might be extended for synthesis of other carbon-based single-atom catalysts with valuable properties.展开更多
Carbon-doped copper ferrite(C–CuFe_(2)O_(4))was synthesized by a simple two-step hydrothermal method,which showed enhanced tetracycline hydrochloride(TCH)removal efficiency as compared to the pure CuFe_(2)O_(4) in Fe...Carbon-doped copper ferrite(C–CuFe_(2)O_(4))was synthesized by a simple two-step hydrothermal method,which showed enhanced tetracycline hydrochloride(TCH)removal efficiency as compared to the pure CuFe_(2)O_(4) in Fenton-like reaction.A removal efficiency of 94%was achieved with 0.2 g L^(-1) catalyst and 20 mmol L^(-1) H_(2)O_(2) within 90 min.We demonstrated that 5%C–CuFe_(2)O_(4) catalyst in the presence of H_(2)O_(2) was significantly efficient for TCH degradation under the near-neutral pH(5–9)without buffer.Multiple techniques,including SEM,TEM,XRD,FTIR,Raman,XPS M€ossbauer and so on,were conducted to investigate the structures,morphologies and electronic properties of as-prepared samples.The introduction of carbon can effectively accelerate electron transfer by cooperating with Cu and Fe to activate H_(2)O_(2) to generate·OH and·O_(2)^(-).Particularly,theoretical calculations display that the p,p,d orbital hybridization of C,O,Cu and Fe can form C–O–Cu and C–O–Fe bonds,and the electrons on carbon can transfer to metal Cu and Fe along the C–O–Fe and C–O–Cu channels,thus forming electron-rich reactive centers around Fe and Cu.This work provides lightful reference for the modification of spinel ferrites in Fenton-like application.展开更多
文摘AgVO_(3)/ZIF-8 composites with enhanced photocatalytic effect were prepared by the combination of AgVO_(3)and ZIF-8.X-ray diffraction(XRD),scanning electron microscopy(SEM),high-power transmission electron microscopy(HRTEM),X-ray photoelectron spectroscopy(XPS),ultraviolet-visible diffuse reflectance spectroscopy(UV-Vis DRS),photoluminescence(PL)spectroscopy,electron spin resonance(ESR)spectroscopy,transient photocurrent and electrochemical impedance spectroscopy(EIS)were used to characterize binary composites.Tetracycline(TC)was used as a substrate to study the performance efficiency of the degradation of photocatalysts under light conditions,and the degradation effect of TC was also evaluated under different mass concentrations and ionic contents.In addition,we further investigated the photocatalytic mechanism of the binary composite material AgVO_(3)/ZIF-8 and identified the key active components responsible for the catalytic degradation of this new photocatalyst.The experimental results show that the degradation efficiency of 10%-AZ,prepared with a molar ratio of 10%AgVO_(3)and ZIF-8 to TC,was 75.0%.This indicates that the photocatalytic activity can be maintained even under a certain ionic content,making it a suitable photocatalyst for optimal use.In addition,the photocatalytic mechanism of binary composites was further studied by the active species trapping experiment.
基金Project supported by the National Natural Science Foundation of China(22206080)the Natural Science Foundation of Jiangsu(SBK2022041070)+1 种基金the Science and Technology Project of Henan Province(232102321050,232102321035)the International Science,Innovators,Technology Cooperation Projects of Henan Province(232102521009)。
文摘Metal-organic frameworks(MOFs)and their derivatives have gained significant attention in recent years for their ability to catalyze the advanced oxidation of persulfates.Cerium-doped MOFs,in particular,have shown promise due to their high catalytic efficiency,practical applicability,and cost-effectiveness.However,their structure,catalytic properties,and mechanisms are not yet fully understood.ZIF-8 was chosen as the raw material to prepare cerium-doped hollow carbon nano fibers(Ce-HCNFs)using the electrostatic spinning-calcination method.The objective is to investigate the structure,catalytic performance,and catalytic mechanism of Ce-HCNFs.The results show that Ce-HCNFs catalyzed the degradation of tetracycline(TC)by persulfate up to 76.9%,Quenching experiments and electron paramagnetic resonance experiments indicate the dominant role of single-linear oxygen.Furthermore,the experiments on the influence factor and cycling demonstrate the exceptional stability and recycling capability of Ce-HCNFs in real-world water environments.
基金supported by the Natural Science Foundation of Tianjin(Nos.18JCQNJC72400 and 22JCQNJC01510).
文摘Tetracycline(TC)is a broad-spectrum antibiotic,and its residues in the environment and food are harmful to human health.Therefore,it is essential to rapidly,sensitively,and conveniently detect TC.In this work,we developed a portable silicon nanoparticles chelated Europium(Ⅲ)-based polyacrylonitrile(Eu-SiNPs/PAN)nanofiber membrane for rapid,sensitive,and convenient detection of TC.The Eu-SiNPs were synthesized with a facile one-pot method.The Eu-SiNPs/PAN nanofiber membrane was fabricated by electrospinning,combining Eu-SiNPs and PAN with three-dimensional porous membrane structures and UV resistance.Both the Eu-SiNPs and the Eu-SiNPs/PAN nanofiber membranes have good selectivity and anti-interference ability towards TC.The combined merits of rapid response,long storage life,easy portability,and naked-eye recognition of TC make the Eu-SiNPs/PAN nanofiber membrane a promising material for convenient TC detection applications.The practicability of these nanofiber membranes was further verified by detecting TC in real samples,such as lake water,drinking water and honey,and achieved quantitative detection.
基金Project supported by the Science and Technology Project of Henan Province(242102321048,242102321045,232102320211)National Natural Science Foundation of China(22206080)+2 种基金Natural Science Foundation of Jiangsu(SBK2022041070)International Science and Technology Cooperation Projects of Henan Province(232102521009)Natural Science Youth Foundation of Henan Province(232300420336)。
文摘A series of CeO_(2)@MnO_(2)composites was prepared by deposition-precipitation methods.These materials were used to activate sodium persulfate(PDS)for the oxidation of tetracycline.It is found that the composites,especially the CeO_(2)@MnO_(2)-1:4 composites,exhibit better tetracycline removal rates than the pure components.X-ray diffraction(XRD),Raman and scanning electron microscopy(SEM)analyses all indicate that the composite has been successfully prepared with high purity and high crystalline.The XPS analysis shows that the strong interaction between the components promotes the electron transfer.Additionally,the kinetic rate constants of CeO_(2)@MnO_(2)-1:4 after 60 min are 3.8 and 12.7 times higher than pure CeO_(2)and MnO_(2),respectively.CeO_(2)@MnO_(2-)1:4 composite also exhibits excellent catalytic activity for individual and hybrid pollutants.The effects of wastewater matrix,pH,circulation and ion stre ngth on the degradation of tetracycline were investigated.It is found that CeO_(2)@MnO_(2)-1:4 composite has good practical application prospects.CeO_(2)@MnO_(2)composites with synergistic adsorption catalysis can activate PDS and peroxymo no sulfate(PMS)for efficient organic catalytic oxidation.This paper provides the theoretical basis and data support for the practical application of the CeO_(2)@MnO_(2)composite materials.
文摘Herein,a luminescent europium-based metal-organic framework(Eu-MOF,[Eu_(3)(L)(HL)(NO_(3))_(2)(DMF)_(2)]·4DMF·5H_(2)O,H_(4)L=5,5′-(pyrazine-2,6-diyl)diisophthalic acid,DMF=N,N-dimethylformamide)was developed for the dual-functional detection of environmental pollutants.This fluorescence-quenching-based sensor exhibited excep-tional sensitivity for both 2,4,6-trinitrophenol(TNP)and tetracycline(TC),achieving remarkably low detection lim-its of 1.96×10^(-6)and 1.71×10^(-7)mol·L^(-1),respectively.Notably,the system exhibited 99%fluorescence quenching ef-ficiency for TC,indicating ultra-efficient analyte recognition.The detection performance surpasses most reported lu-minescent MOF sensors,attributed to synergistic mechanisms of fluorescence resonance energy transfer(FRET)and photoinduced electron transfer(PET).CCDC:2446483.
基金supported by the National Natural Science Foundation of China(Nos.22136003 and 21972073)the Opening foundation of the Engineering Research Center of Ecoenvironment in Three Gorges Reservoir Region,Ministry of Education(No.KF2023-01)the Natural Science Foundation of Yichang City(No.A22-3-005)。
文摘The synergetic technology of hydrodynamic cavitation(HC)and peroxydisulfate(PDS)has been adopted for the treatment of organic pollutants,while the rationale behind the thermal-activation of PDS in this process remains lacking.This paper presented investigation on the degradation of tetracycline under two types of operating conditions,including“internal reaction conditions”(pH value and TC/PDS molar ratio)and“external physical conditions”(hole shape,solution temperature and inlet pressure).Special emphasis was paid on the analysis of thermal effects through a robust modeling approach.The results showed that a synergy index of 6.26 and a degradation rate of 56.71%could be obtained by the HC-PDS process,respectively,when the reaction conditions were optimized.Quenching experiment revealed that·OH and·SO_(4)^(-)were the predominant free radicals and their contribution to the degradation was 75.4%and 24.6%respectively,since a part of·SO_(4)^(-)was transformed into·OH in the solution.The thermal activation of PDS mainly occurred near the hole where the fitting temperature was around 340 K,while·OH was generated in the bubble collapse region downstream the hole,where the temperature was much higher and favorable for the cleavage of water molecular.The average temperature under different external physical conditions was in good consistence with the degradation rates.This research developed a useful method to effectively evaluate the activation extent of PDS by HC and could provide reliable guidance for further development of cavitational reactors to treat organic pollutants based on this hybrid approach.
文摘Tetracyclines (TCs) are the second most commonly used antibiotics worldwide, utilized in medical treatments and animal husbandry. Although effective against various infectious diseases, TC residues persist in the environment and contribute to the emergence of antibiotic-resistant pathogens, posing significant risks to human health. This study employed the heterogeneous Fenton process to degrade TC using soybean residue-derived magnetic biochar (Fe-SoyB) as the catalyst. The Fe-SoyB sample was characterized using X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR), and superconducting quantum interference device (SQUID) techniques. The effects of key parameters, including pH, H2O2 concentration, catalyst dosage, and initial TC concentration, on TC degradation were investigated. The results indicated that the TC removal efficiency decreased with increasing initial TC concentration, while it was improved with higher H2O2 concentrations and greater catalyst dosages. The optimal conditions for the Fenton-like process were determined: a pH of 3, a H2O2 concentration of 245 mmol/L, an initial TC concentration of 800 mg/L, and a catalyst dosage of 0.75 g/L, achieving a removal efficiency of 90.0% after 150 min. Additionally, the TC removal efficiency of the Fe-SoyB system varied significantly across different water matrices, with 87.1% for deionized water, 78.5% for tap water, and 72.5% for river water. The catalyst demonstrated notable stability, maintaining a TC removal efficiency of 79.7% after three cycles of use. Overall, Fe-SoyB shows promise as a cost-effective catalyst for the elimination of organic pollutants in aqueous solutions.
基金supported by the National Natural Science Foundation of China(No.21908085).
文摘Eliminating highly concentrated antibiotic wastewater by transition metal catalyst-assisted AOPs is challenging.Herein,by varying the metal precursor composition(Co/Fe ratios of 1/1,1.5/2/3),alloyed Co_(7)Fe_(3)nanocrystals or spinel-like CoFe_(2)O_(4)can be switched and both confined within the porous N-doped graphitic carbon fibers by electrospinning and controlled graphitization.Impressively,iron precursors played a dual role in working as reactive centers and main activators for the creation of porous carbon networks affording improved accessibility to catalytic sites and easy tetracycline(TC)diffusion effect.The catalytic activity of the resulting materials was closely related to surface metal valence and composition.Notably,the CoFe_(2)O_(4)exhibited a significant improvement in peroxymonosulfate(PMS)adsorption and activation,explained by the present electron-deficient Co and Fe synergetic sites together with the interesting Jahn-Teller effect.Fe_(1)Co_(2)/CNF demonstrated the highest efficiency in degrading TC,achieving a reaction rate constant of 0.4647 min^(-1)with a low activation energy of 9.3 kJ·mol^(-1),nearly a 7.5-fold enhancement compared to Fe_(1)Co_(3)/CNF(0.062 min^(-1)).The reaction mechanism and the role of reactive oxidative species revealed a synergy of·SO_(4)^(-),·OH,·O_(2)^(-)and^(1)O_(2).Wherein,·O_(2)^(-)plays a more dominant role in the degradation of TC than other reactive species.Additionally,a reinforced electron-transfer pathway in the Fe_(1)Co_(2)/CNF system during PMS interaction was demonstrated.Furthermore,the degradation routes of TC were unraveled,and the toxicity of various intermediate by-products was assessed.Importantly,our continuous flow-type TC degradation process and light-driven photothermal strengthened reaction process demonstrated consistent performance,thereby offering a promising approach for tackling highly concentrated antibiotic wastewater.
基金supported by the National Natural Science Foundation of China(Nos.52100062,and 52230001)China Postdoctoral Science Foundation(No.2023M732785).
文摘This study introduced a microwave-assisted pyrolysis method for the rapid and efficientpreparation of boron-doped porous biochar. The resulting biochar exhibited a large specificsurface area (933.39 m^(2)/g), a rich porous structure (1.044 cm3/g), and abundant active sites.Consequently, the prepared boron-doped porous biochar exhibited higher efficiency in adsorbingtetracycline with a maximum adsorption capacity of 413.223 mg/g, which significantlyexceeded that of unmodified biochar andmost commercial and reported adsorbents.The correlation analysis between the adsorption capacity and adsorbent characteristics revealedthat the formation of the –BCO_(2) group enhanced π–π electron donor–acceptor interactionsbetween boron-doped porous biochar and tetracycline. This mechanism mainlycontributed to the enhanced adsorption of tetracycline by boron-doped porous biochar. Additionally,the as-prepared boron-doped porous biochar exhibited broad applications in removingantibiotics (tetracycline), phenolics (bisphenol A), and dyes (methylene blue andrhodamine B). Moreover, the boron-doped porous biochar exhibited satisfactory stability,and its adsorption capacity can be nearly completely regenerated through simple heat treatment.This study provides new insights into the effectiveness of boron-doped carbonaceousmaterials in removing antibiotic contaminants.
基金supported by the National Natural Science Foundation of China(No.U21A20293).
文摘Harnessing the redox potential of biochar to activate airborne O_(2)for contaminant removal is challenging.In this study,ferrihydrite(Fh)modified the boron(B),nitrogen(N)co-doped biochars(BCs)composites(Fh/B(n)NC)were developed for enhancing the degradation of a model pollutant,tetracycline(TC),merely by airborne O_(2).Fh/B(3)NC showed excellent O_(2)activation activity for efficient TC degradation with a apparent TC degradation rate of 5.54,6.88,and 22.15 times that of B(3)NC,Fh,and raw BCs,respectively,where 1O_(2)and H_(2)O_(2)were identified as the dominant ROS for TC degradation.The B incorporation into the carbon lattice of Fh/B(3)NC promoted the generation of electron donors,sp2 C and the reductive B species,hence boosting Fe(III)reduction and 1O_(2)generation.O_(2)adsorption was enhanced due to the positively charged adsorption sites(C-B+and N-C+).And 1O_(2)was generated via Fe(II)catalyzed low-efficient successive one-electron transfer(O_(2)→O_(2)·−→1O_(2),H_(2)O_(2)),as well as biochar catalyzed high-efficient two-electron transfer(O_(2)→H_(2)O_(2)→1O_(2))that does not involve.O_(2)−as the intermediate.Moreover,Fh/B,N co-doped biochar showed a wide pH range,remarkable anti-interference capabilities,and effective detoxification.These findings shed new light on the development of environmentally benign BCs materials capable of degradading organic pollutants.
基金supported by the National Natural Science Foundation of China(No.41977315)the Fundamental Research Funds for the Central Universities of China(No.201964004).
文摘Mariculture tailwater typically contains a certain concentration of antibiotics;however,conventional biological treatment methods struggle to effectively remove these antibiotics.Therefore,in this study,we modified the carbon felt(CF)anode in sediment microbial fuel cells(SMFCs)to enhance tetracycline(TC)removal in mariculture systems.We fabricated a novel composite material by integrating instant freeze-drying technology with the solvothermal reaction method to combine graphene oxide(GO)and nanoscale SiO_(2).Subsequently,the composite material was incorporated into CF for anodic modification,resulting in improved performance of SMFCs in TC removal and electricity generation.The maximum power density achieved was 63.72 mW/m^(2),nearly 2.9 times higher than that of the unmodified anode.Modified SMFCs exhibited a twofold increase in the degradation rate of tetracycline compared to natural degradation alone and showed significant improvements compared to both the control group and conditions with only GO addition.Furthermore,the modified anode effectively enriched populations of Leisingera,Oceanimonas,and Halomonas,thereby significantly enhancing the electrochemical performance of the SMFCs.This study successfully demonstrates the application of a modified-anode SMFC using a composite material consisting of GO and SiO_(2)for on-site removal of TC from mariculture environments.
基金supported by the National Natural Science Foundation of China(No.U20A20133)the National Key Research and Development Program of China(No.2022YFF0606703).
文摘The arbitrary discharge of tetracycline(TC)residuals has seriously influenced the ecosystem and human health.Laccase(Lac)-based biodegradation technology is considered a more effective way to remove TC due to its high catalytic efficiency and less by-product.Nevertheless,free Lac suffers from poor stability,easy inactivation and difficult recovery,restricting its application.Immobilization of Lac is considered an efficient strategy for addressing these obstacles.In this study,a magnetic metal-organic framework of Fe_(3)O_(4)@SiO_(2)@UiO-66-NH_(2)(MMOF)was prepared and used as a carrier to immobilize Lac(Lac@MMOF)for TC degradation.Benefiting from the multiple binding sites,adsorption,and protection effect of MMOF,Lac@MMOF displayed a wider pH application range(2–7)and better thermal(15–85℃),repeatability,and storage stability than free Lac.Furthermore,owing to the synergism of MOF adsorption and Lac biocatalysis,the removal rate of Lac@MMOF for TC could be up to 98%at pH=7 within 1 hr,which was 1.29 and 1.24 times that of free Lac and MMOF,respectively.More importantly,Lac@MMOF could easily be separated from aqueous solution under a magnetic field and maintained good removal performance(80%)after five cycles.The degradation products were identified by applying LC-MS/MS,and possible degradation mechanisms and pathways were proposed.Finally,the antibacterial activity of intermediate products was evaluated using Escherichia coli,which revealed that the toxicity of TC was reduced effectively by the degradation of Lac@MMOF.Overall,Lac@MMOF is a green alternative for residual antibiotic removal in water.
基金financially supported by the National Natural Science Foundation of China(Nos.52270149,51908528,2200013)Natural Science Foundation of Henan Province,China(No.242300421443)+1 种基金The Science and Technology Key Project of Henan Province,China(No.242102321073)Doctoral Fund Project of Henan University of Technology,China(Nos.2020BS005,2023BS004).
文摘The high band gap of zinc oxide(ZnO)has significantly limited its potential application for organic contaminant removal in photocatalysis.In this study,ZnO/halloysites(HNTs)composites(ZnO/HNTs)were prepared using a high-temperature calcination method to enhance the removal of tetracycline hydrochloride(TCH).The experimental results demonstrated that the band gap of ZnO/HNTs decreased to 3.12 eV,compared to 3.21 eV for pure ZnO.The observed removal rate(k_(obs))of TCH in the ZnO/HNTs/vis system was 1.90×10^(-2) min^(-1),significantly higher than the rates in the HNTs/vis(1.25×10^(-3)min^(-1))and ZnO/vis(1.13×10^(-2) min^(-1))systems.Additionally,ZnO/HNTs exhibited strong resistance to coexisting natural organic and inorganic matter,maintaining high pollutant removal efficiency in natural water samples.The ZnO/HNTs/vis system also effectively removed other common organic pollutants,such as ciprofloxacin and methylene blue.Cycle tests indicated that the ZnO/HNTs/vis system retained 65.57%of its original efficiency,demonstrating good reusability and versatility.Scavenging and electron paramagnetic resonance experiments identified that h+was the primary species in the ZnO/HNTs/vis system,with other species playing auxiliary roles in TCH degradation.This study provides valuable insights into the design of novel ZnO-based photocatalysts for the degradation of organic pollutants in water.
基金financially supported by the National Natural Science Foundation of China(Nos.42207386,22378103,52372294,and 22262025)the Middle-aged and Young Teachers’Basic Ability Promotion Project of Guangxi(No.2021KY0390).
文摘Rational design of composite catalysts with efficient charge separation and transfer is of great significance to achieve efficient degradation of pollutants.Herein,CuInS_(2)nanoparticles are skillfully deposited on TiO_(2)nanofibers through a hydrothermal method.The formation of S-scheme heterojunction is confirmed through free radical trapping experiments,in‐situ irradiated X-ray photoelectron spectroscopy(ISI-XPS)measurements,density functional theory(DFT)calculations and femtosecond transient absorption spectroscopy(fs-TAS)results.These results reveal that the built-in electric field within the S-scheme heterojunction significantly enhances charge separation and transfer,boosting the catalyst's redox capabilities.The TiO_(2)/CuInS_(2)photocatalyst exhibits superior photocatalytic performance,achieving a degradation rate of 89%within 21 min of light irradiation,which is almost 2.2 times higher than that of TiO_(2).Additionally,the degradation products of TCH are investigated using in-situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS)and liquid chromatography–mass spectrometry(LC-MS),offering insights into the degradation pathway.This study highlights the potential advantage of ultrafast charge carrier transfer in S-scheme heterojunction,providing a promising strategy for designing high-efficiency photocatalytic systems for environmental remediation.The findings offer new directions for improving the degradation of persistent pollutants like tetracyclines.
文摘Given their unique structure-dependent properties,strategically designing semiconductor-based photocatalysts,which expose highly reactive crystalline facets,is widely used to tune their performance.Herein,AgBr/Ag/TiO_(2){100}nanorods Z-scheme heterojunction composites were prepared via hydrothermal and in situ facet-induced reduction.Transmission electron microscopy,X-ray diffraction,X-ray photoelectron spectroscopy,electron paramagnetic resonance spectroscopy,and density functional theory calculations reveal that the selective exposure of TiO_(2){100}facets with abundant oxygen vacancies(OV)promotes the formation of metallic silver on the interfaces between AgBr and TiO_(2){100}.Metallic silver can mediate interfacial charge transfer by facilitating the photogenerated carrier recombination of the conduction band of TiO_(2){100}and the valence band of AgBr.As a result,a Z-scheme heterojunction is formed in AgBr/Ag/TiO_(2){100}.The AgBr/Ag/TiO_(2){100}exhibits faster degradation of tetracycline in aqueous solution compared to pristine AgBr,TiO_(2){101},TiO_(2){100}and AgBr/TiO_(2){101}p-n heterojunctions.This is attributed to the effect of the Z-scheme heterojunction on prolonging the lifetime of photogenerated carriers,which is confirmed by femtosecond transient absorption spectroscopy.The photocatalytic mechanism and degradation pathways are discussed along with a toxicity assessment of the intermediates.Overall,this work develops a new approach for designing Z-scheme heterojunction photocatalysts via selective facet control of anatase TiO_(2).
基金supported by the Research Support Project for Stabilizing and Introducing Talents of Anhui Agricultural University(No.rc522010).
文摘With the burgeoning growth of aquaculture industry,high concentration of NH_(4)^(+)-N,phosphorus and tetracycline are the prevalent pollutants in aquaculturewastewater posing a significant health risk to aquatic organisms.Therefore,an effective method for treating aquaculture wastewater should be urgently explored.Simultaneous removal of NH_(4)^(+)-N,phosphorus,tetracycline,and chemical oxygen demand(COD)in aquaculture wastewater was developed bymoving bed biofilm reactor(MBBR)under co-metabolic substances.The result showed that co-metabolism substances had different effects on MBBR performance,and 79.4%of tetracycline,68.2%of NH_(4)^(+)-N,61.3%of total nitrogen,88.3%of COD,and 38.1%of total phosphorus(TP)were synchronously removed with sodium acetate as a co-metabolic carbon source.Protein(PN),polysaccharide(PS),and electron transfer system activity were used to evaluate the MBBR performances,suggesting that PN/PS ratio was 1.48,0.91,1.07,3.58,and 0.79 at phases Ⅰ-Ⅴ.Additionally,a mode of tetracycline degradation and TP removal was explored,and the cell apoptosis was evaluated by flow cytometry.The result suggested that 74%,83%,and 83%of tetracycline were degraded by extracellular extracts,intracellular extracts,and cell debris,and there was no difference between extracts and non-enzyme in TP removal.The ratio of viable and dead cells from biofilm reached 33.3%and 7.68%with sodium acetate as a co-metabolic carbon source.Furthermore,Proteobacteria and Bacteroidetes in biofilm were identified as the dominant phyla for tetracycline and nutrients removal.This study provides a new strategy for tetracycline and nutrients removal from aquaculture wastewater through co-metabolism.
基金supported by the Fuxiaquan Collaborative Innovation Platform(No.K30001)Major Scientific Research Program for Young and Middle-aged Health Professionals of Fujian Province,China(No.2022ZQNZD007)Youth Innovation Technology Project of Higher School in Shandong Province(Food Nanotechnology Innovation Team)。
文摘Quantitative determination of tetracycline(TC)in environment and foods is of great importance,as excessive residues might have negative effects on human health and environmental risks.Herein,a selfpowered molecularly imprinted photoelectrochemical(PEC)sensor based on the Zn O/C photoanode and the Fe-doped CuBi_(2)O_(4)(CBFO)photocathode is developed for the sensitive detection of TC.The photocathodic current can be amplified by the efficient electron transfer caused by the Fermi energy level gap between the photoanode and photocathode.Furthermore,molecularly imprinted polymers(MIPs)at photocathode can selectivity identify the TC templates and thus improve the specificity.Under the optimal conditions,the sensor has a linear range of 10^(-2)-1.0×10^(5) nmol/L,and a limit of detection(LOD)of 0.007 nmol/L(S/N=3).More crucially,the milk sample detection is carried out using the as-prepared sensor,and the outcome is satisfactory.The research gives us a novel sensing platform for quick and accurate antibiotic(like TC)in environment and food monitoring.
基金the funding support from the National Natural Science Foundation of China(21906072,22006057)the Natural Science Foundation of Jiangsu Province(BK20190982)“Doctor of Mass entrepreneurship and innovation”Project in Jiangsu Province。
文摘The synergistic reaction of photocatalysis and advanced oxidation is a valid strategy for the degradation of harmful antibiotic wastewater.Herein,carbon dots(CDs)modified MIL-101(Fe)octahedrons to form CDs/MIL-101(Fe)composite photocatalyst was synthesized for visible light-driven photocatalytic/persulfate(PS)-activated tetracycline(TC)degradation.The electron spin resonance(ESR)spectra,scavenging experiment and electrochemical analysis were carried out to reveal that the high visible light-driven photocatalytic degradation activity of TC over CDs/MIL-101(Fe)photocatalysts is not only ascribed to the production of free active radicals in the CDs/MIL-101(Fe)/PS system(·OH,·SO_(4-),^(1)O_(2),h^(+)and·O_(2)^(-))but also attributed to the consumption of electrons caused by the PS,which can suppress the recombination of photo-generated carriers as well as strong light scattering and electron trapping effects of CDs.Finally,the possible degradation pathways were proposed by analyzing intermediates via liquid chromatography-mass spectrometry technique.This research presents a rational design conception to construct a CDs/PS-based photocatalysis/advanced oxidation technology with high-efficient degradation activity for the remediation of organic antibiotic pollutant wastewater and for the improvement of carrier transport kinetics of photocatalysts.
基金supported by the National Key Research and Development Program(No.2019YFC1803903)the Program for Guangdong Introducing Innovative and Entrepreneurial Teams(No.2017ZT07Z479)+1 种基金China Postdoctoral Science Foundation(No.2021M701561)the National Natural Science Foundation of China(No.42007318)。
文摘Environmental photocatalysis is a promising technology for treating antibiotics in wastewater.In this study,a supercritical carbonization method was developed to synthesize a single-atom photocatalyst with a high loading of Ni(above 5 wt.%)anchored on a carbonnitrogen-silicate substrate for the efficient photodegradation of a ubiquitous environmental contaminant of tetracycline(TC).The photocatalyst was prepared from an easily obtained metal-biopolymer-inorganic supramolecular hydrogel,followed by supercritical drying and carbonization treatment.The low-temperature(300℃)supercritical ethanol treatment prevents the excessive structural degradation of hydrogel and greatly reduces the metal clustering and aggregation,which contributed to the high Ni loading.Atomic characterizations confirmed that Ni was present at isolated sites and stabilized by Ni-N and Ni-O bonds in a Ni-(N/O)_(6)-C/SiC configuration.A 5%Ni-C-Si catalyst,which performed the best among the studied catalysts,exhibited a wide visible light response with a narrow bandgap of 1.45 eV that could efficiently and repeatedly catalyze the oxidation of TC with a conversion rate of almost 100% within 40 min.The reactive species trapping experiments and electron spin resonance(ESR)tests demonstrated that the h+,and·O_(2)-were mainly responsible for TC degradation.The TC degradation mechanism and possible reaction pathways were provided also.Overall,this study proposed a novel strategy to synthesize a high metal loading singleatom photocatalyst that can efficiently remove TC with high concentrations,and this strategy might be extended for synthesis of other carbon-based single-atom catalysts with valuable properties.
基金supported by the Program for the National Natural Science Foundation of China(52070077,51879101,51779090)the National Program for Support of Top-Notch Young Professionals of China(2014)+1 种基金the Program for Changjiang Scholars and Innovative Research Team in University(IRT-13R17)Natural Science Foundation of Hunan Province(2022JJ20013,2021JJ40098).
文摘Carbon-doped copper ferrite(C–CuFe_(2)O_(4))was synthesized by a simple two-step hydrothermal method,which showed enhanced tetracycline hydrochloride(TCH)removal efficiency as compared to the pure CuFe_(2)O_(4) in Fenton-like reaction.A removal efficiency of 94%was achieved with 0.2 g L^(-1) catalyst and 20 mmol L^(-1) H_(2)O_(2) within 90 min.We demonstrated that 5%C–CuFe_(2)O_(4) catalyst in the presence of H_(2)O_(2) was significantly efficient for TCH degradation under the near-neutral pH(5–9)without buffer.Multiple techniques,including SEM,TEM,XRD,FTIR,Raman,XPS M€ossbauer and so on,were conducted to investigate the structures,morphologies and electronic properties of as-prepared samples.The introduction of carbon can effectively accelerate electron transfer by cooperating with Cu and Fe to activate H_(2)O_(2) to generate·OH and·O_(2)^(-).Particularly,theoretical calculations display that the p,p,d orbital hybridization of C,O,Cu and Fe can form C–O–Cu and C–O–Fe bonds,and the electrons on carbon can transfer to metal Cu and Fe along the C–O–Fe and C–O–Cu channels,thus forming electron-rich reactive centers around Fe and Cu.This work provides lightful reference for the modification of spinel ferrites in Fenton-like application.
