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
The photocatalytic performances in the photocatalytic degradation of tetracycline hydrochloride(TC) of ZnSb2O4 and ZnSb2O6 synthesized by hydrothermal method were explored.The effects of synthesis conditions including...The photocatalytic performances in the photocatalytic degradation of tetracycline hydrochloride(TC) of ZnSb2O4 and ZnSb2O6 synthesized by hydrothermal method were explored.The effects of synthesis conditions including reaction temperature, reaction time, precursor solution pH, and the amount of hydrazine hydrate on the photocatalytic activity were discussed.The ZnSb2O4 and ZnSb2O6 photocatalysts prepared under optimal conditions exhibited similar photocatalytic activities for the degradation of TC. However, the areal photoctalytic activity of ZnSb2O4 was 12 times higher than that of ZnSb2O6 because of their different electronic and geometric structures. The photocatalytic degradation mechanisms of TC over ZnSb2O4 and ZnSb2O6 were proposed. Our work will facilitate the development of composite oxides consisting of p-block metal ions as new semiconductor photocatalysts.展开更多
We tested the utility of chemical marking techniques in the juvenile black rockfish Sebastes schlegelii. Juveniles(30–40 mm total length) were immersed in a range of tetracycline hydrochloride(TC) solutions at concen...We tested the utility of chemical marking techniques in the juvenile black rockfish Sebastes schlegelii. Juveniles(30–40 mm total length) were immersed in a range of tetracycline hydrochloride(TC) solutions at concentrations ranging from 300 to 500 mg/L, and alizarin complexone(ALC) solutions at concentrations ranging from 200 to 400 mg/L in filtered sea water(salinity of 30) for 24 h, respectively. Otoliths(sagittae, asteriscus), scales, fin rays(dorsal, pectoral, ventral, anal, and caudal fin rays), and fin spines(dorsal, ventral, and anal fin spines) were sampled and used to detect fl uorescent marks after a 60-day growth experiment. With the exception of 300 mg/L TC, acceptable marks were produced in the otoliths and fin spines by all concentrations of TC and ALC. In particular, we observed clearly visible marks in the sagittae, asteriscus, and fin spines under normal light at concentrations of 200–400 mg/L, 250–400 mg/L, and 250–400 mg/L ALC, respectively. Scales and fin rays had acceptable marks at much higher concentrations(≥350 mg/L TC, ≥250 mg/L ALC for scales and ≥350 mg/L TC, ≥300 mg/L ALC for fin rays). The best mark quality(i.e., acceptable marks were observed in all sampled structures after immersion marking) were obtained following immersion in TC at between 350–500 mg/L, and ALC between 300–400 mg/L. In addition, there was no significant difference in survival and growth of TC and ALC marked fish compared to their controls up to 60 days post-marking( P > 0.05).展开更多
Porous g-C_3N_4samples were obtained by simply calcining bulk g-C_3N_4in static air in a muffle oven.The photocatalytic performance of these samples was evaluated through the removal of aqueous organic dyes(methylene ...Porous g-C_3N_4samples were obtained by simply calcining bulk g-C_3N_4in static air in a muffle oven.The photocatalytic performance of these samples was evaluated through the removal of aqueous organic dyes(methylene blue and methyl orange)and tetracycline hydrochloride under visible-light irradiation(λ>420 nm).Compared to bulk g-C_3N_4,porous g-C_3N_4exhibited much better capability for removing these contaminants,especially under visible-light irradiation,due to the enlarged specific surface area and more efficient separation of photogenerated charge carries.In particular,porous g-C_3N_4obtained by calcining bulk g-C_3N_4in air at 525°C showed the highest visible-light-driven catalytic activity among these samples.Superoxide radical anions(·O_2^-)were found to be the primary active species responsible for photodegradation.展开更多
A coaxial dielectric barrier discharge (DBD) reactor was used for plasma-catalytic degradation of tetracycline hydrochloride over a series of Mn/γ-Al2O3 catalysts prepared by the incipient wetness impregnation method...A coaxial dielectric barrier discharge (DBD) reactor was used for plasma-catalytic degradation of tetracycline hydrochloride over a series of Mn/γ-Al2O3 catalysts prepared by the incipient wetness impregnation method.The combination of plasma and the Mn/γ-Al2O3 catalysts significantly enhanced the degradation efficiency of tetracycline hydrochloride compared to the plasma process alone,with the 10% Mn/γ-Al2O3 catalyst exhibiting the best tetracycline hydrochloride degradation efficiency.A maximum degradation efficiency of 99.3% can be achieved after 5 min oxidation and a discharge power of 1.3 W,with only 69.7% by a single plasma process.The highest energy yield of the plasma-catalytic process is 91.7 g kWh-1.Probable reaction mechanisms of the plasma-catalytic removal of tetracycline hydrochloride were also proposed.展开更多
The removal of the antibiotic compound tetracycline hydrochloride (TC) was investigated by using goethite/H2O2 as a heterogeneous Fenton reagent. Five principle operational parameters, especially solution pH value, we...The removal of the antibiotic compound tetracycline hydrochloride (TC) was investigated by using goethite/H2O2 as a heterogeneous Fenton reagent. Five principle operational parameters, especially solution pH value, were taken into account to investigate how the heterogeneous Fenton process factors mediated the TC removal. This process was effective but seriously impacted by the pH value and temperature, as well as the dosages of α-FeOOH, TC and H2O2. Very interestingly, the acidic and alkaline aqueous medium conditions were both very favorable due to the occurrence of transformation of Fe(III) to Fe(II) on goethite surfaces reduced by TC at pH 3.0~4.0 even though with a low adsorption capacity of TC because its maximum adsorption of negatively charged form occurred at pH around 8.0[1], thereby greatly promoting the TC Fenton oxidative elimination. However, a rapid initial TC decay was observed at the first 5 min, followed by a much slower retardation stage, which was likely because the reductive transformation of Fe(III) to Fe(II) by TC in the solution was inhibited as the Fenton reaction proceeded. Moreover, the hydroxyl radical scavenger t-butanol addition can decrease the removal rate of TC in the goethite/H2O2 system to a certain extent. This further indicated that the main reactive species in this process were hydroxyl radicals[2]. All the goethite-catalysed heterogeneous Fenton reactions are responsible for the TC removal following the Langmuir-Hinshelwood model, were well fitted to pseudo-first order kinetics (R2】0.99), and their apparent activation energy (E) for this Fenton-like reaction was 31.86 kJ mol 1, a low value that is highly consistent with the ease of TC decay greatly enhanced by the temperature rise, indicated that the interfacial controlling interactions such as a proton induced solubilization and a reductive dissolution of goethite can clearly improve its Fenton catalytic activity[3], and these dissolution processes may not be effective in some cases, while the TC adsorption process may always play an important role to control the TC removal rate during the Fenton reaction.展开更多
In vitro dissolution kinetics of a-tricalcium phosphate （α-TCP） cement and α-TCP cement containing tetracycline Hydrochloride（TTCH） were studied in the present paper. It shows that dissolution process of α-TCP ...In vitro dissolution kinetics of a-tricalcium phosphate （α-TCP） cement and α-TCP cement containing tetracycline Hydrochloride（TTCH） were studied in the present paper. It shows that dissolution process of α-TCP cement and TTCH-loaded α-TCP cement accords with Avrami dissolution kinetics model： x=1-exp（-kt^n）, and Avrami constant n is 0.5 and 0.4 respectively, which means dissolution process is diffusion control. Apparent dissolution activation energy of α-TCP cement and TTCH-loaded α-TCP cement is about 9.87 kJ/moland 7.17 kJ/mol respectively. Comparing with α-TCP cement, activation energy and Avrami constant of TTCH-loaded α-TCP cement decrease slightly, but its [Ca^2＋] solubility decreases from 40 ppm to 11.5 ppm, which could result from the change of interracial property and morphology of hydrated apatite crystal caused by absorption of TTCH on the apatite.展开更多
α- and β-Ga2O3 were prepared via a precipitation method. The as-prepared α- and β-Ga2O3 were characterized by X-ray diffraction （XRD）, N2-sorption BET surface area, UV-vis diffuse reflectance spectra （DRS）, ph...α- and β-Ga2O3 were prepared via a precipitation method. The as-prepared α- and β-Ga2O3 were characterized by X-ray diffraction （XRD）, N2-sorption BET surface area, UV-vis diffuse reflectance spectra （DRS）, photoluminescence spectroscopy （PL） and electron spin resonancespectroscopy （ESR）. The photocatalytic activities of Ga2O3 were evaluated by the photocatalytic degradation of tetracycline sydrochloride solution. The results showed that the photocatalytic activity of β-Ga2O3 was higher than that of α-Ga2O3 and β-Ga2O3 obtained at the calcination temperature of 900℃, which showed the best photocatalytic activity. The reasons for the differences in photocatalytic activity of Ga2O3 are discussed in terms of crystallinity, surface area, crystals and electronic structures.展开更多
The use of biopolymers as bioadhesives for human tissue is becoming a preferred alternative to suturing due to their superior adhesive, biocompatible, and biodegradable properties. In this work, low molecular weight p...The use of biopolymers as bioadhesives for human tissue is becoming a preferred alternative to suturing due to their superior adhesive, biocompatible, and biodegradable properties. In this work, low molecular weight poly(L-lactide-co-ε-caprolactone) (P(LA-co-CL) was synthesized to achieve the glass transition temperature (Tg) of the copolymer at ambient temperature so that during application on the skin, the copolymer when combined with chitosan (CHI) into the CHI/P(LA-co-CL) film could provide the strong support at the injury site. Using alcohols with different numbers of hydroxyl groups as the co-initiator in polymerization provided the distinctive characteristics of copolymers. Among all copolymers synthesized, P(LA-co-CL) copolymer using pentaerythritol as the co-initiator when combined with CHI at the ratio of copolymer/CHI at 70/30 yielded the good film properties in tissue adhesion and tetracycline hydrochloride release.展开更多
The removal of antibiotic pollutants remaining in the environmental media has been a big challenge nowadays.Herein,we report a facile and green approach to fabricate an eco-friendly composite membrane without addition...The removal of antibiotic pollutants remaining in the environmental media has been a big challenge nowadays.Herein,we report a facile and green approach to fabricate an eco-friendly composite membrane without addition of any toxic polymers or chemical cross-linking agents to effectively remove the tetracycline hydrochloride in Water.Firstly,the sulfated cellulose nanocrystalline(CNC) was obtained via hydrolysis of sulfuric acid by using microcrystalline cellulose(MCC) as raw material under ultrasonic condition.The as-prepared CNC has a nanowhisker dimension with 200.2 ± 110.2 nm in length,15.7 ± 9.3 nm in width,and 7.2 ± 3.1 nm in height.The obtained CNC is cellulose type I as determined by X-ray diffraction(XRD),while its crystallinity index(Crl) can reach 82.3%.Then,the composite membrane derived from the obtained CNC and commercial mixed cellulose ester(MCE)membrane was facilely prepared through vacuum dewatering process,which is applied to remove tetracycline hydrochloride(Th) in solution.The results showed that the removal efficiency of Th through the neat MCE was only28 ± 4%,while it could be improved to 58 ± 5% and 89 11%,respectively,by filtering through composite membranes with different contents of CNC deposition.Such effect is derived from the combine factors based on both steric hindrance(sieving) and electrostatic interaction(Donnan) effect of the composite membranes.The development of related CNC materials and composite fabrication processes is in favor of cost-effective and "green"polymer composites for the remediation of increasing antibiotic pollution and the purification of contaminated water nowadays.展开更多
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.
基金supported by the National Natural Science Foundation of China(21307012)Educational Commission of Fujian Province(2014J01035,JA15138)
文摘The photocatalytic performances in the photocatalytic degradation of tetracycline hydrochloride(TC) of ZnSb2O4 and ZnSb2O6 synthesized by hydrothermal method were explored.The effects of synthesis conditions including reaction temperature, reaction time, precursor solution pH, and the amount of hydrazine hydrate on the photocatalytic activity were discussed.The ZnSb2O4 and ZnSb2O6 photocatalysts prepared under optimal conditions exhibited similar photocatalytic activities for the degradation of TC. However, the areal photoctalytic activity of ZnSb2O4 was 12 times higher than that of ZnSb2O6 because of their different electronic and geometric structures. The photocatalytic degradation mechanisms of TC over ZnSb2O4 and ZnSb2O6 were proposed. Our work will facilitate the development of composite oxides consisting of p-block metal ions as new semiconductor photocatalysts.
基金Supported by the Special Fund for Agro-Scientific Research in the Public Interest(No.201003068)the National Natural Science Foundation of China(Nos.31172447,41176117)
文摘We tested the utility of chemical marking techniques in the juvenile black rockfish Sebastes schlegelii. Juveniles(30–40 mm total length) were immersed in a range of tetracycline hydrochloride(TC) solutions at concentrations ranging from 300 to 500 mg/L, and alizarin complexone(ALC) solutions at concentrations ranging from 200 to 400 mg/L in filtered sea water(salinity of 30) for 24 h, respectively. Otoliths(sagittae, asteriscus), scales, fin rays(dorsal, pectoral, ventral, anal, and caudal fin rays), and fin spines(dorsal, ventral, and anal fin spines) were sampled and used to detect fl uorescent marks after a 60-day growth experiment. With the exception of 300 mg/L TC, acceptable marks were produced in the otoliths and fin spines by all concentrations of TC and ALC. In particular, we observed clearly visible marks in the sagittae, asteriscus, and fin spines under normal light at concentrations of 200–400 mg/L, 250–400 mg/L, and 250–400 mg/L ALC, respectively. Scales and fin rays had acceptable marks at much higher concentrations(≥350 mg/L TC, ≥250 mg/L ALC for scales and ≥350 mg/L TC, ≥300 mg/L ALC for fin rays). The best mark quality(i.e., acceptable marks were observed in all sampled structures after immersion marking) were obtained following immersion in TC at between 350–500 mg/L, and ALC between 300–400 mg/L. In addition, there was no significant difference in survival and growth of TC and ALC marked fish compared to their controls up to 60 days post-marking( P > 0.05).
基金Supported by the National Natural Science Foundation of China(Grant No.21477022)
文摘Porous g-C_3N_4samples were obtained by simply calcining bulk g-C_3N_4in static air in a muffle oven.The photocatalytic performance of these samples was evaluated through the removal of aqueous organic dyes(methylene blue and methyl orange)and tetracycline hydrochloride under visible-light irradiation(λ>420 nm).Compared to bulk g-C_3N_4,porous g-C_3N_4exhibited much better capability for removing these contaminants,especially under visible-light irradiation,due to the enlarged specific surface area and more efficient separation of photogenerated charge carries.In particular,porous g-C_3N_4obtained by calcining bulk g-C_3N_4in air at 525°C showed the highest visible-light-driven catalytic activity among these samples.Superoxide radical anions(·O_2^-)were found to be the primary active species responsible for photodegradation.
文摘A coaxial dielectric barrier discharge (DBD) reactor was used for plasma-catalytic degradation of tetracycline hydrochloride over a series of Mn/γ-Al2O3 catalysts prepared by the incipient wetness impregnation method.The combination of plasma and the Mn/γ-Al2O3 catalysts significantly enhanced the degradation efficiency of tetracycline hydrochloride compared to the plasma process alone,with the 10% Mn/γ-Al2O3 catalyst exhibiting the best tetracycline hydrochloride degradation efficiency.A maximum degradation efficiency of 99.3% can be achieved after 5 min oxidation and a discharge power of 1.3 W,with only 69.7% by a single plasma process.The highest energy yield of the plasma-catalytic process is 91.7 g kWh-1.Probable reaction mechanisms of the plasma-catalytic removal of tetracycline hydrochloride were also proposed.
文摘The removal of the antibiotic compound tetracycline hydrochloride (TC) was investigated by using goethite/H2O2 as a heterogeneous Fenton reagent. Five principle operational parameters, especially solution pH value, were taken into account to investigate how the heterogeneous Fenton process factors mediated the TC removal. This process was effective but seriously impacted by the pH value and temperature, as well as the dosages of α-FeOOH, TC and H2O2. Very interestingly, the acidic and alkaline aqueous medium conditions were both very favorable due to the occurrence of transformation of Fe(III) to Fe(II) on goethite surfaces reduced by TC at pH 3.0~4.0 even though with a low adsorption capacity of TC because its maximum adsorption of negatively charged form occurred at pH around 8.0[1], thereby greatly promoting the TC Fenton oxidative elimination. However, a rapid initial TC decay was observed at the first 5 min, followed by a much slower retardation stage, which was likely because the reductive transformation of Fe(III) to Fe(II) by TC in the solution was inhibited as the Fenton reaction proceeded. Moreover, the hydroxyl radical scavenger t-butanol addition can decrease the removal rate of TC in the goethite/H2O2 system to a certain extent. This further indicated that the main reactive species in this process were hydroxyl radicals[2]. All the goethite-catalysed heterogeneous Fenton reactions are responsible for the TC removal following the Langmuir-Hinshelwood model, were well fitted to pseudo-first order kinetics (R2】0.99), and their apparent activation energy (E) for this Fenton-like reaction was 31.86 kJ mol 1, a low value that is highly consistent with the ease of TC decay greatly enhanced by the temperature rise, indicated that the interfacial controlling interactions such as a proton induced solubilization and a reductive dissolution of goethite can clearly improve its Fenton catalytic activity[3], and these dissolution processes may not be effective in some cases, while the TC adsorption process may always play an important role to control the TC removal rate during the Fenton reaction.
基金Supported by the National Natural Science Foundation of China (No.50772045)
文摘In vitro dissolution kinetics of a-tricalcium phosphate （α-TCP） cement and α-TCP cement containing tetracycline Hydrochloride（TTCH） were studied in the present paper. It shows that dissolution process of α-TCP cement and TTCH-loaded α-TCP cement accords with Avrami dissolution kinetics model： x=1-exp（-kt^n）, and Avrami constant n is 0.5 and 0.4 respectively, which means dissolution process is diffusion control. Apparent dissolution activation energy of α-TCP cement and TTCH-loaded α-TCP cement is about 9.87 kJ/moland 7.17 kJ/mol respectively. Comparing with α-TCP cement, activation energy and Avrami constant of TTCH-loaded α-TCP cement decrease slightly, but its [Ca^2＋] solubility decreases from 40 ppm to 11.5 ppm, which could result from the change of interracial property and morphology of hydrated apatite crystal caused by absorption of TTCH on the apatite.
基金supported by the Funds of Department of Education of Fujian province(No.JA14199)
文摘α- and β-Ga2O3 were prepared via a precipitation method. The as-prepared α- and β-Ga2O3 were characterized by X-ray diffraction （XRD）, N2-sorption BET surface area, UV-vis diffuse reflectance spectra （DRS）, photoluminescence spectroscopy （PL） and electron spin resonancespectroscopy （ESR）. The photocatalytic activities of Ga2O3 were evaluated by the photocatalytic degradation of tetracycline sydrochloride solution. The results showed that the photocatalytic activity of β-Ga2O3 was higher than that of α-Ga2O3 and β-Ga2O3 obtained at the calcination temperature of 900℃, which showed the best photocatalytic activity. The reasons for the differences in photocatalytic activity of Ga2O3 are discussed in terms of crystallinity, surface area, crystals and electronic structures.
文摘The use of biopolymers as bioadhesives for human tissue is becoming a preferred alternative to suturing due to their superior adhesive, biocompatible, and biodegradable properties. In this work, low molecular weight poly(L-lactide-co-ε-caprolactone) (P(LA-co-CL) was synthesized to achieve the glass transition temperature (Tg) of the copolymer at ambient temperature so that during application on the skin, the copolymer when combined with chitosan (CHI) into the CHI/P(LA-co-CL) film could provide the strong support at the injury site. Using alcohols with different numbers of hydroxyl groups as the co-initiator in polymerization provided the distinctive characteristics of copolymers. Among all copolymers synthesized, P(LA-co-CL) copolymer using pentaerythritol as the co-initiator when combined with CHI at the ratio of copolymer/CHI at 70/30 yielded the good film properties in tissue adhesion and tetracycline hydrochloride release.
基金financially supported by the Tianjin Science and Technology Committee Major Project Program(18ZXJMTG00070)
文摘The removal of antibiotic pollutants remaining in the environmental media has been a big challenge nowadays.Herein,we report a facile and green approach to fabricate an eco-friendly composite membrane without addition of any toxic polymers or chemical cross-linking agents to effectively remove the tetracycline hydrochloride in Water.Firstly,the sulfated cellulose nanocrystalline(CNC) was obtained via hydrolysis of sulfuric acid by using microcrystalline cellulose(MCC) as raw material under ultrasonic condition.The as-prepared CNC has a nanowhisker dimension with 200.2 ± 110.2 nm in length,15.7 ± 9.3 nm in width,and 7.2 ± 3.1 nm in height.The obtained CNC is cellulose type I as determined by X-ray diffraction(XRD),while its crystallinity index(Crl) can reach 82.3%.Then,the composite membrane derived from the obtained CNC and commercial mixed cellulose ester(MCE)membrane was facilely prepared through vacuum dewatering process,which is applied to remove tetracycline hydrochloride(Th) in solution.The results showed that the removal efficiency of Th through the neat MCE was only28 ± 4%,while it could be improved to 58 ± 5% and 89 11%,respectively,by filtering through composite membranes with different contents of CNC deposition.Such effect is derived from the combine factors based on both steric hindrance(sieving) and electrostatic interaction(Donnan) effect of the composite membranes.The development of related CNC materials and composite fabrication processes is in favor of cost-effective and "green"polymer composites for the remediation of increasing antibiotic pollution and the purification of contaminated water nowadays.
