The three-dimensional particle electrode system exhibits significant potential for application in the treatment of wastewater.Nonetheless,the advancement of effective granular electrodes characterized by elevated cata...The three-dimensional particle electrode system exhibits significant potential for application in the treatment of wastewater.Nonetheless,the advancement of effective granular electrodes characterized by elevated catalytic activity and minimal energy consumption continues to pose a significant challenge.In this research,Fluorine-doped copper-carbon(F/Cu-GAC)particle electrodes were effectively synthesized through an impregnationcalcination technique,utilizing granular activated carbon as the carrier and fluorinedoped modified copper oxides as the catalytic agents.The particle electrodes were subsequently utilized to promote the degradation of 2,4,6-trichlorophenol(2,4,6-TCP)in a threedimensional electrocatalytic reactor(3DER).The F/Cu-GAC particle electrodes were polarized under the action of electric field,which promoted the heterogeneous Fenton-like reaction in which H2O2 generated by two-electron oxygen reduction reaction(2e-ORR)of O_(2) was catalytically decomposed to·OH.The 3DER equipped with F/Cu-GAC particle electrodes showed 100%removal of 2,4,6-TCP and 79.24%removal of TOC with a specific energy consumption(EC)of approximately 0.019 kWh/g·COD after 2 h of operation.The F/Cu-GAC particle electrodes exhibited an overpotential of 0.38 V and an electrochemically active surface area(ECSA)of 715 cm^(2),as determined through linear sweep voltammetry(LSV)and cyclic voltammetry(CV)assessments.These findings suggest a high level of electrocatalytic performance.Furthermore,the catalytic mechanism of the 3DER equipped with F/Cu-GAC particle electrodes was elucidated through the application of X-ray photoelectron spectroscopy(XPS),electron spin resonance(ESR),and active species capture experiments.This investigation offers a novel approach for the effective degradation of 2,4,6-TCP.展开更多
Pd modified electrodes possess problems such as easy agglomeration and low electrolytic ability,and the use of manganese dioxide(MnO_(2)) to facilitate Pd reduction of organic pollutants is just started.However,there ...Pd modified electrodes possess problems such as easy agglomeration and low electrolytic ability,and the use of manganese dioxide(MnO_(2)) to facilitate Pd reduction of organic pollutants is just started.However,there is still a limited understanding of how to match the Pd load and MnO_(2) to realize optimal dechlorination efficiency at minimum cost.Here,a Pd/MnO_(2)/Ni foam cathode was successfully fabricated and applied for the efficient electrochemical dechlorination of 2,4,6-trichlorophenol(2,4,6-TCP).The optimal electrocatalytic hydrodechlorination(ECH)performance with 2,4,6-TCP dechlorination efficiency(92.58%in 180 min)was obtained when the concentration of PdCl_(2) precipitation was 1 mmol/L,the deposition time of MnO_(2) was 300 s and cathode potential was-0.8 V.Performance influenced by the exogenous factors(e.g.,initial pH and coexisted ions)were further investigated.It was found that the neutral pH was the most favorable for ECH and a reduction in dechlorination efficiency(6%~47.6%)was observed in presence of 5 mmol/L of NO_(2)^(-),NO_(3)^(-),S^(2-)or SO_(3)^(2-).Cyclic voltammetry(CV)and quenching experiments verified the existence of three hydrogen species on Pd surface,including adsorbed atomic hydrogen(H^(*)_(ads)),absorbed atomic hydrogen(H^(*)_(abs)),and molecular hydrogen(H_(2)).And the introduction of MnO_(2)promoted the generation of atomic H^(*).Only adsorbed atomic hydrogen(H^(*)_(ads)) was confirmed that it truly facilitated the ECH process.Besides H^(*)_(ads) induced reduction,the direct reduction by cathode electrons also participated in the 2,4,6-TCP dechlorination process.Pd/MnO_(2)/Ni foam cathode shows excellent dechlorination performance,fine stability and recyclable potential,which provides strategies for the effective degradation of persistent halogenated organic pollutants in groundwater.展开更多
Adsorption of 2, 4, 6-trichlorophenol（TCP） onto the calcined Mg/Al-CO_3 layered double hydroxide（CLDH） was investigated. The prepared Mg/Al-CO_3 layered double hydroxide（LDH） and CLDH were characterized by powde...Adsorption of 2, 4, 6-trichlorophenol（TCP） onto the calcined Mg/Al-CO_3 layered double hydroxide（CLDH） was investigated. The prepared Mg/Al-CO_3 layered double hydroxide（LDH） and CLDH were characterized by powder X-ray diffraction（XRD） and thermo gravimetric analyzer-differential scanning calorimeters（TG-DSC）. Moreover, 2,4,6-trichlorophenol（TCP） was removed effectively（94.7% of removal percentage in 9h） under the optimized experimental conditions. The adsorption kinetics data fitted the pseudosecond-order model well. The Freundlich, Langmuir, and Tempkin adsorption models were applied to the experimental equilibrium adsorption data at different temperatures of solution. The adsorption data fitted the Freundlieh adsorption isotherm with good values of the correlation coefficient. A mechanism of the adsorption process is proposed according to the intraparticle diffusion model, which indicates that the overall rate of adsorption can be described as three steps.展开更多
Znx</sub>Cd1-x</sub>S solid solutions with controlled morphology have been successfully synthe-sized by a facile solution-phase method. The prepared samples were characterized by X-ray powder diffraction (...Znx</sub>Cd1-x</sub>S solid solutions with controlled morphology have been successfully synthe-sized by a facile solution-phase method. The prepared samples were characterized by X-ray powder diffraction (XRD), UV-vis diffuse reflectance spectra, X-ray photoelec-tron spectroscopy (XPS), scanning electron microscopy (SEM) and transmission elec-tron microscopy (TEM). The photocatalytic activity of Zn<sub>x</sub>Cd<sub>1-x</sub>S was evaluated in the 2,4,6-trichlorophenol (TCP) degradation and mineralization in aqueous solution under direct solar light illumination. The experiment demonstrated that TCP was effectively degraded by more than 95% with 120 min. The results show that ZnS with Cd doping (Znx</sub>Cd1-x</sub>S) exhibits the much stronger visible light adsorption than that of pure ZnS, the light adsorption increasing as the Cd<sup>2+</sup> doping amount. These results indicate that Cd doping into a ZnS crystal lattice can result in the shift of the valence band of ZnS to a positive direction. It may lead to its higher oxidative ability than pure ZnS, which is important for organic pollutant degradation under solar light irradiation. Further-more, the photocatalytic activity studies reveal that the prepared Znx</sub>Cd1-x</sub>S nanostructures exhibit an excellent photocatalytic performance, degrading rapidly the aqueous 2,4,6-trichlorophenol solution under solar light irradiation. These results sug-gest that Znx</sub>Cd1-x</sub>S nanostructure will be a promising candidate of photocatalyst working in solar light range.展开更多
2,4,6-trichlorophenol (TCP) was firstly treated with air ions generated by electric discharge, and high dechlorination (53%) was observed after 60 min treatment, indicating that air ions are an efficient dechlorinatio...2,4,6-trichlorophenol (TCP) was firstly treated with air ions generated by electric discharge, and high dechlorination (53%) was observed after 60 min treatment, indicating that air ions are an efficient dechlorination means and might have a future in the oxidative removal of chlorinated phenols. In addition, a stepwise degradation of TCP, beginning with the formation of a major product 2,6-dichloro-1,4-benzenediol via substitution, is proposed through a detailed analysis of gas chromatography/mass spectrometry.展开更多
Designing efficient and sustainable catalyst for peroxymonosulfate(PMS)activation and refractory 2,4,6-trichlorophenol(2,4,6-TCP)removal is an imminent task.This study synthesized a novelγ-MnO_(2)/NF catalyst,which h...Designing efficient and sustainable catalyst for peroxymonosulfate(PMS)activation and refractory 2,4,6-trichlorophenol(2,4,6-TCP)removal is an imminent task.This study synthesized a novelγ-MnO_(2)/NF catalyst,which has advantages in saving manganese dioxide demand and reducing manganese leaching.Theγ-MnO_(2)/NF+PMS oxidation system achieved a 0.219 min^(−1)2,4,6-TCP apparent rate constant at 20℃,and removed>90%of 2,4,6-TCP at the 5th cycle.Both free radical identification and DFT calculations revealed that•OH and SO_(4)^(•−),rather than 1O_(2),were the dominant reactive species duringγ-MnO_(2)/NF+PMS oxidation.The results indicated that the inner-sphere complexation betweenγ-MnO_(2)/NF and PMS facilitated the formation of•OH and SO_(4)^(•−).To fill the research gap in the molecular-level dissimilarities between•OH and SO_(4)^(•−)in 2,4,6-TCP degradation mechanism,experimental testing and quantum chemical analysis methods were used.The DFT calculation found that the HAA reaction at H13 site and RAF reaction at C1 site were more favorable for both•OH and SO_(4)^(•−).For most reaction sites,SO_(4)^(•−)demonstrates greater energy barriers and substrate selectivity than•OH,attributed to steric constraints.The•OH acted as the predominant oxidative agents responsible for 2,4,6-TCP decomposition.Combining DFT calculation and intermediate identification,potential degradation routes of 2,4,6-TCP were proposed.The ecotoxicity assays verified a substantial reduction in acute toxicity of the treated 2,4,6-TCP solution.This study opens up new avenues for activating PMS withγ-MnO_(2)/NF,and helps to select preferred radical oxidation processes for optimal 2,4,6-TCP removal in practical engineering.展开更多
目的探讨肠道屏障功能、IL-6、血沉(erythrocyte sedimentation rate,ESR)指标在克罗恩病合并贫血患者中的变化及应用价值。方法选取2022年6月至2023年4月至南京市第二医院就诊的克罗恩病患者155例。根据血红蛋白检测结果将患者分为贫血...目的探讨肠道屏障功能、IL-6、血沉(erythrocyte sedimentation rate,ESR)指标在克罗恩病合并贫血患者中的变化及应用价值。方法选取2022年6月至2023年4月至南京市第二医院就诊的克罗恩病患者155例。根据血红蛋白检测结果将患者分为贫血组(55例)及非贫血组(100例),对两组间DAO、D-LA、BT、IL-6及ESR水平进行比较,并进行相关统计学分析。结果与非贫血组相比,贫血组患者D-LA水平明显降低,IL-6及ESR水平显著升高,差异有统计学意义(P<0.05),两组间DAO、BT水平差异无统计学意义(P>0.05);在贫血组中,血清D-LA水平与BT水平呈正相关、与IL-6呈负相关;二元Logistic回归分析结果显示,ESR水平是克罗恩病患者贫血的独立影响因素(OR=1.963,P<0.05);D-LA、IL-6及ESR判断克罗恩病合并贫血的ROC曲线下面积(area under the curve,AUC)分别为0.322、0.714、0.737(P均<0.05),DAO及BT的AUC差异无统计学意义。结论克罗恩病合并贫血患者肠道屏障功能、IL-6及ESR水平发生明显变化,做好其分析对克罗恩病患者的贫血发生机制研究以及临床诊疗具有积极意义。展开更多
基金supported by Guangxi Science and Technology Major Program(No.AA23073008)Hubei Key Laboratory of Water System Science for Sponge City Construction(Wuhan University)(No.2023–05)Nanning Innovation and Entrepreneur Leading Talent Project(No.2021001).
文摘The three-dimensional particle electrode system exhibits significant potential for application in the treatment of wastewater.Nonetheless,the advancement of effective granular electrodes characterized by elevated catalytic activity and minimal energy consumption continues to pose a significant challenge.In this research,Fluorine-doped copper-carbon(F/Cu-GAC)particle electrodes were effectively synthesized through an impregnationcalcination technique,utilizing granular activated carbon as the carrier and fluorinedoped modified copper oxides as the catalytic agents.The particle electrodes were subsequently utilized to promote the degradation of 2,4,6-trichlorophenol(2,4,6-TCP)in a threedimensional electrocatalytic reactor(3DER).The F/Cu-GAC particle electrodes were polarized under the action of electric field,which promoted the heterogeneous Fenton-like reaction in which H2O2 generated by two-electron oxygen reduction reaction(2e-ORR)of O_(2) was catalytically decomposed to·OH.The 3DER equipped with F/Cu-GAC particle electrodes showed 100%removal of 2,4,6-TCP and 79.24%removal of TOC with a specific energy consumption(EC)of approximately 0.019 kWh/g·COD after 2 h of operation.The F/Cu-GAC particle electrodes exhibited an overpotential of 0.38 V and an electrochemically active surface area(ECSA)of 715 cm^(2),as determined through linear sweep voltammetry(LSV)and cyclic voltammetry(CV)assessments.These findings suggest a high level of electrocatalytic performance.Furthermore,the catalytic mechanism of the 3DER equipped with F/Cu-GAC particle electrodes was elucidated through the application of X-ray photoelectron spectroscopy(XPS),electron spin resonance(ESR),and active species capture experiments.This investigation offers a novel approach for the effective degradation of 2,4,6-TCP.
基金supported by the NSFC-JSPS joint research program(No.51961145202)the Natural Science Foundation of Heilongjiang Province,China(No.C2018035)。
文摘Pd modified electrodes possess problems such as easy agglomeration and low electrolytic ability,and the use of manganese dioxide(MnO_(2)) to facilitate Pd reduction of organic pollutants is just started.However,there is still a limited understanding of how to match the Pd load and MnO_(2) to realize optimal dechlorination efficiency at minimum cost.Here,a Pd/MnO_(2)/Ni foam cathode was successfully fabricated and applied for the efficient electrochemical dechlorination of 2,4,6-trichlorophenol(2,4,6-TCP).The optimal electrocatalytic hydrodechlorination(ECH)performance with 2,4,6-TCP dechlorination efficiency(92.58%in 180 min)was obtained when the concentration of PdCl_(2) precipitation was 1 mmol/L,the deposition time of MnO_(2) was 300 s and cathode potential was-0.8 V.Performance influenced by the exogenous factors(e.g.,initial pH and coexisted ions)were further investigated.It was found that the neutral pH was the most favorable for ECH and a reduction in dechlorination efficiency(6%~47.6%)was observed in presence of 5 mmol/L of NO_(2)^(-),NO_(3)^(-),S^(2-)or SO_(3)^(2-).Cyclic voltammetry(CV)and quenching experiments verified the existence of three hydrogen species on Pd surface,including adsorbed atomic hydrogen(H^(*)_(ads)),absorbed atomic hydrogen(H^(*)_(abs)),and molecular hydrogen(H_(2)).And the introduction of MnO_(2)promoted the generation of atomic H^(*).Only adsorbed atomic hydrogen(H^(*)_(ads)) was confirmed that it truly facilitated the ECH process.Besides H^(*)_(ads) induced reduction,the direct reduction by cathode electrons also participated in the 2,4,6-TCP dechlorination process.Pd/MnO_(2)/Ni foam cathode shows excellent dechlorination performance,fine stability and recyclable potential,which provides strategies for the effective degradation of persistent halogenated organic pollutants in groundwater.
基金Funded by the National Natural Science Foundation of China(No.21476269)
文摘Adsorption of 2, 4, 6-trichlorophenol（TCP） onto the calcined Mg/Al-CO_3 layered double hydroxide（CLDH） was investigated. The prepared Mg/Al-CO_3 layered double hydroxide（LDH） and CLDH were characterized by powder X-ray diffraction（XRD） and thermo gravimetric analyzer-differential scanning calorimeters（TG-DSC）. Moreover, 2,4,6-trichlorophenol（TCP） was removed effectively（94.7% of removal percentage in 9h） under the optimized experimental conditions. The adsorption kinetics data fitted the pseudosecond-order model well. The Freundlich, Langmuir, and Tempkin adsorption models were applied to the experimental equilibrium adsorption data at different temperatures of solution. The adsorption data fitted the Freundlieh adsorption isotherm with good values of the correlation coefficient. A mechanism of the adsorption process is proposed according to the intraparticle diffusion model, which indicates that the overall rate of adsorption can be described as three steps.
文摘Znx</sub>Cd1-x</sub>S solid solutions with controlled morphology have been successfully synthe-sized by a facile solution-phase method. The prepared samples were characterized by X-ray powder diffraction (XRD), UV-vis diffuse reflectance spectra, X-ray photoelec-tron spectroscopy (XPS), scanning electron microscopy (SEM) and transmission elec-tron microscopy (TEM). The photocatalytic activity of Zn<sub>x</sub>Cd<sub>1-x</sub>S was evaluated in the 2,4,6-trichlorophenol (TCP) degradation and mineralization in aqueous solution under direct solar light illumination. The experiment demonstrated that TCP was effectively degraded by more than 95% with 120 min. The results show that ZnS with Cd doping (Znx</sub>Cd1-x</sub>S) exhibits the much stronger visible light adsorption than that of pure ZnS, the light adsorption increasing as the Cd<sup>2+</sup> doping amount. These results indicate that Cd doping into a ZnS crystal lattice can result in the shift of the valence band of ZnS to a positive direction. It may lead to its higher oxidative ability than pure ZnS, which is important for organic pollutant degradation under solar light irradiation. Further-more, the photocatalytic activity studies reveal that the prepared Znx</sub>Cd1-x</sub>S nanostructures exhibit an excellent photocatalytic performance, degrading rapidly the aqueous 2,4,6-trichlorophenol solution under solar light irradiation. These results sug-gest that Znx</sub>Cd1-x</sub>S nanostructure will be a promising candidate of photocatalyst working in solar light range.
基金the Alexander von Humboldt Foundation of Germany, and partly by the CAS and the NNSF of China.
文摘2,4,6-trichlorophenol (TCP) was firstly treated with air ions generated by electric discharge, and high dechlorination (53%) was observed after 60 min treatment, indicating that air ions are an efficient dechlorination means and might have a future in the oxidative removal of chlorinated phenols. In addition, a stepwise degradation of TCP, beginning with the formation of a major product 2,6-dichloro-1,4-benzenediol via substitution, is proposed through a detailed analysis of gas chromatography/mass spectrometry.
基金supported by“Pioneer and Leading Goose+X”S&T Program of Zhejiang,China(No.2025C02230)the National Natural Science Foundation of China(Nos.52400110 and 52070111).
文摘Designing efficient and sustainable catalyst for peroxymonosulfate(PMS)activation and refractory 2,4,6-trichlorophenol(2,4,6-TCP)removal is an imminent task.This study synthesized a novelγ-MnO_(2)/NF catalyst,which has advantages in saving manganese dioxide demand and reducing manganese leaching.Theγ-MnO_(2)/NF+PMS oxidation system achieved a 0.219 min^(−1)2,4,6-TCP apparent rate constant at 20℃,and removed>90%of 2,4,6-TCP at the 5th cycle.Both free radical identification and DFT calculations revealed that•OH and SO_(4)^(•−),rather than 1O_(2),were the dominant reactive species duringγ-MnO_(2)/NF+PMS oxidation.The results indicated that the inner-sphere complexation betweenγ-MnO_(2)/NF and PMS facilitated the formation of•OH and SO_(4)^(•−).To fill the research gap in the molecular-level dissimilarities between•OH and SO_(4)^(•−)in 2,4,6-TCP degradation mechanism,experimental testing and quantum chemical analysis methods were used.The DFT calculation found that the HAA reaction at H13 site and RAF reaction at C1 site were more favorable for both•OH and SO_(4)^(•−).For most reaction sites,SO_(4)^(•−)demonstrates greater energy barriers and substrate selectivity than•OH,attributed to steric constraints.The•OH acted as the predominant oxidative agents responsible for 2,4,6-TCP decomposition.Combining DFT calculation and intermediate identification,potential degradation routes of 2,4,6-TCP were proposed.The ecotoxicity assays verified a substantial reduction in acute toxicity of the treated 2,4,6-TCP solution.This study opens up new avenues for activating PMS withγ-MnO_(2)/NF,and helps to select preferred radical oxidation processes for optimal 2,4,6-TCP removal in practical engineering.
文摘目的探讨肠道屏障功能、IL-6、血沉(erythrocyte sedimentation rate,ESR)指标在克罗恩病合并贫血患者中的变化及应用价值。方法选取2022年6月至2023年4月至南京市第二医院就诊的克罗恩病患者155例。根据血红蛋白检测结果将患者分为贫血组(55例)及非贫血组(100例),对两组间DAO、D-LA、BT、IL-6及ESR水平进行比较,并进行相关统计学分析。结果与非贫血组相比,贫血组患者D-LA水平明显降低,IL-6及ESR水平显著升高,差异有统计学意义(P<0.05),两组间DAO、BT水平差异无统计学意义(P>0.05);在贫血组中,血清D-LA水平与BT水平呈正相关、与IL-6呈负相关;二元Logistic回归分析结果显示,ESR水平是克罗恩病患者贫血的独立影响因素(OR=1.963,P<0.05);D-LA、IL-6及ESR判断克罗恩病合并贫血的ROC曲线下面积(area under the curve,AUC)分别为0.322、0.714、0.737(P均<0.05),DAO及BT的AUC差异无统计学意义。结论克罗恩病合并贫血患者肠道屏障功能、IL-6及ESR水平发生明显变化,做好其分析对克罗恩病患者的贫血发生机制研究以及临床诊疗具有积极意义。
