Exploration of stable metal single-site supported porous graphitic carbon nitride(PCN)nanostructures and the development of maximum atom utilization for enhanced photocatalytic oxidation of antibiotics remains a chall...Exploration of stable metal single-site supported porous graphitic carbon nitride(PCN)nanostructures and the development of maximum atom utilization for enhanced photocatalytic oxidation of antibiotics remains a challenge in current research.This work proposed a one-step thermal copolymerization to obtain Cu(Ⅰ)doping porous carbon nitride(CUCN)through a spontaneously reducing atmosphere by urea in a covered crucible.The obtained CUCN had crumpled ultrathin nanosheets and mesoporous structures,which possessed higher specific surface areas than PCN.From X-ray absorption near edge structure(XANES)and Fourier transform extended X-ray absorption fine structure(FT-EXAFS)spectra analysis,the Cu doping existed in the oxidation state of Cu(Ⅰ)as single atoms anchored on the 2D layers of CN through two N neighbors,thereby facilitating efficient pathways for the transfer of photoexcited charge carriers.Furthermore,the photoluminescence(PL)spectra,electrochemical impedance spectra(EIS)and transient photocurrent response test proved the improved separation and transfer of photoexcited charge carriers for Cu(Ⅰ)introduction.Consequently,the photocatalytic activity of CUCN was much better than that of PCN for antibiotics norfloxacin(NOR),with 4.7-fold higher degradation reaction rate constants.From species-trapping experiments and density function theory(DFT)calculations,the Cu single atoms in Cu-N_(2)served as catalytic sites that could accelerate charge transfer and facilitate the adsorption of molecular oxygen to produce active species.The stable Cu(Ⅰ)embedded in the layer structure led to the excellent recycling test and remained stable after four runs of degradation and even thermal regenerated treatment.The degradation paths of NOR by CUCN under visible light were also demonstrated.Our work sheds light on a sustainable and practical approach for achieving stable metal single-atom doping and enhancing photocatalytic degradation of aqueous pollutants.展开更多
Based on the microstructure characterization,electrochemical impedance spectroscopy,potentiodynamic polarization,and immersion corrosion,this work comparatively analyzed the differences in the electrochemical corrosio...Based on the microstructure characterization,electrochemical impedance spectroscopy,potentiodynamic polarization,and immersion corrosion,this work comparatively analyzed the differences in the electrochemical corrosion morphology and post-foil formation surface morphology of laser beam welded(LBW)sample and spin-formed sample,and compared the corrosion resistance and Cu foil formation ability of two samples in H_(2)SO_(4)/NaCl solution and CuSO_(4) reducing electrolyte.Results show that in H_(2)SO_(4) and NaCl solutions,LBW sample and spin-formed sample exhibit excellent passivation ability and corrosion resistance.Both samples show uniform corrosion morphologies and similar corrosion resistance in the strong acidic solution containing Cl^(-).Meanwhile,the Cu foil formation ability of the welded joint is similar to that of the spin-formed sample,and both samples obtain intact Cu foils with high-quality surfaces and small differences in properties.展开更多
Background Copper(Cu)is a pervasive environmental pollutant with significant hepatotoxic effects in animals.The endoplasmic reticulum(ER)interacts closely with lysosomes to maintain intracellular homeostasis.However,t...Background Copper(Cu)is a pervasive environmental pollutant with significant hepatotoxic effects in animals.The endoplasmic reticulum(ER)interacts closely with lysosomes to maintain intracellular homeostasis.However,the role and mechanism of ER-lysosome crosstalk in Cu-induced liver injury in ducks remains unclear.To investigate this,we established both an in vivo model of Cu-exposed ducks and an in vitro model of duck hepatocytes,and added baicalin(Ba)to further explore its protective effects.Results The results of this study demonstrated that exposure to Cu resulted in vacuolar degeneration and oxidative stress in duck hepatocytes,while ultrastructural observations revealed ER swelling and an increased number of autophagic lysosomes.Furthermore,Cu exposure significantly upregulated mRNA and protein levels related to ER stress,autophagy,and lysosomal membrane factors.It also markedly increased ER-lysosomal co-localization.Further experiments showed that knockdown of LAPTM4B significantly attenuated Cu-induced ER autophagy and reduced ER-lysosomal co-localization in hepatocytes.Molecular docking and molecular dynamics simulations confirmed that LAPTM4B has a stable binding site to Ba;in vitro experiments demonstrated that Ba could effectively alleviate Cuinduced ER-lysosome crosstalk in duck hepatocytes and reduce hepatocyte injury by targeting LAPTM4B;additionally,in vivo experiments showed that Ba significantly inhibits Cu-induced liver injury in ducks.Conclusions In summary,the present study demonstrates that Cu exposure disrupts ER-lysosomal crosstalk in duck liver,leading to ER-lysosomal damage and subsequent hepatocyte injury.In contrast,Ba alleviates this injury by selectively targeting LAPTM4B,ultimately attenuating Cu-induced hepatotoxicity.展开更多
Herein,the Cu(Ⅲ)synthesized from copper plating effluent was developed for the first time to evaluate the onsite degradation performance of heavy metal complexes in the wastewater,thus achieving the purpose of“treat...Herein,the Cu(Ⅲ)synthesized from copper plating effluent was developed for the first time to evaluate the onsite degradation performance of heavy metal complexes in the wastewater,thus achieving the purpose of“treating waste with waste”.The results indicated that synthetic Cu(Ⅲ)presented the excellent decomplexation performance for Cu(Ⅱ)/Ni(Ⅱ)-organic complexes.The removal efficiency of Cu(Ⅱ)/Ni(Ⅱ)-EDTA significantly increased with increasing Cu(Ⅲ)dosage,and the degradation of Cu(Ⅱ)/Ni(Ⅱ)-EDTA by synthetic Cu(Ⅲ)system displayed highly p H-dependent reactivity.The radical quencher experiments confirmed that Cu(Ⅲ)direct oxidation were mainly involved in the degradation of Cu(Ⅱ)-EDTA.Additionally,the continuous decarboxylation process was proven to be the main degradation pathway of Cu(Ⅱ)-EDTA in Cu(Ⅲ)system.The coexisting substances(SO42-,Cl-and fulvic acids)showed little impacts at low level for the removal of Cu(Ⅱ)/Ni(Ⅱ)-EDTA,while retarded the degradation of Cu(Ⅱ)-EDTA slightly at high level,which features high selective oxidation.Encouragingly,it was also effective to remove Cu(Ⅱ)/Ni(Ⅱ)-EDTA from in treating actual Cu/Ni-containing wastewater through synthetic Cu(Ⅲ)treatment.展开更多
This study was conducted in two sections.Initially,the effects of NaCl,MgCl_(2),and urea were investigated on extracting copper and iron from chalcopyrite.Subsequently,CuFe_(2)O_(4)-based electrodes for supercapacitor...This study was conducted in two sections.Initially,the effects of NaCl,MgCl_(2),and urea were investigated on extracting copper and iron from chalcopyrite.Subsequently,CuFe_(2)O_(4)-based electrodes for supercapacitors were synthesized using the extracted solution.The first phase revealed that 3 mol/L NaCl achieved the highest extraction performance,yielding 60%Cu and 23%Fe.MgCl_(2)at 1.5 mol/L extracted 52%Cu and 27%Fe,while a combination of 0.5 mol/L MgCl_(2)and 1.6 mol/L urea yielded 57%Cu and 20%Fe.Urea effectively reduced iron levels.CuFe_(2)O_(4)-based electrodes were then successfully synthesized via a hydrothermal method using a MgCl_(2)-urea solution.Characterization studies confirmed CuFe_(2)O_(4)formation with a 2D structure and 45−50 nm wall thickness on nickel foam.Electrochemical analysis showed a specific capacitance of 725 mF/cm^(2)at 2 mA/cm^(2)current density,with energy and power densities of 12.3 mW·h/cm^(2)and 175 mW/cm^(2),respectively.These findings suggest that chalcopyrite has the potential for direct use in energy storage.展开更多
The copper-cerium catalysts demonstrate high efficiency in CO_(2)reduction reactions(CO_(2)RR).However,the mechanism governing the formation of C_(2)H_(4)and CH_(4)by regulating Cu bulk phase structure at the copper-c...The copper-cerium catalysts demonstrate high efficiency in CO_(2)reduction reactions(CO_(2)RR).However,the mechanism governing the formation of C_(2)H_(4)and CH_(4)by regulating Cu bulk phase structure at the copper-cerium interface remains unclear due to the instability and dynamic evaluations of copper species.Herein,we synthesized CeO_(2)-CuO containing solely Cu^(2+)species and CeO_(2)-Cu featuring predominantly metallic Cu species at the interface,which exhibit stable structures under various potentials,offering ideal models for in-depth mechanistic studies.The C_(2)H_(4)is the main product over the CeO_(2)-CuO catalyst,exhibiting a Faradaic efficiency(FE)of 42.3%±1.4%,while CH_(4)is the primary product over the CeO_(2)-Cu catalyst,with a FE of 32.4%±1.3%.These results demonstrate that regulating bulk phase Cu structure at the copper-cerium interface influences the selectivity of hydrocarbon products.The operando ATR-SEIRAS finds that CeO_(2)-CuO surfaces with single linear*CO adsorption are advantageous for synthesizing*COCO,whereas bridge-bonded*CO adsorption promoted*CHO formation.Furthermore,DFT simulations demonstrate that the energy barrier of CO-CO coupling(C_(2)H_(4)pathway)at the CeO_(2)-CuO interface decreases as compared to the CeO_(2)-Cu catalyst,thus indicating a facilitated conversion of the CO_(2)to C_(2)H_(4).This research deepens the mechanistic understanding of the copper-cerium system during CO_(2)RR and effectively formulates a strategy for developing high-selectivity catalysts.展开更多
基金supported by the National Natural Science Foundation of China(Nos.52070103 and 22102102)Zhejiang Provincial Natural Science Foundation of China(Nos.LY21E090004 and LQ22B050004)+1 种基金Ningbo Public Welfare Science and Technology Program(No.2021S025)Ningbo Youth Leading Talent Project(No.2024QL038).
文摘Exploration of stable metal single-site supported porous graphitic carbon nitride(PCN)nanostructures and the development of maximum atom utilization for enhanced photocatalytic oxidation of antibiotics remains a challenge in current research.This work proposed a one-step thermal copolymerization to obtain Cu(Ⅰ)doping porous carbon nitride(CUCN)through a spontaneously reducing atmosphere by urea in a covered crucible.The obtained CUCN had crumpled ultrathin nanosheets and mesoporous structures,which possessed higher specific surface areas than PCN.From X-ray absorption near edge structure(XANES)and Fourier transform extended X-ray absorption fine structure(FT-EXAFS)spectra analysis,the Cu doping existed in the oxidation state of Cu(Ⅰ)as single atoms anchored on the 2D layers of CN through two N neighbors,thereby facilitating efficient pathways for the transfer of photoexcited charge carriers.Furthermore,the photoluminescence(PL)spectra,electrochemical impedance spectra(EIS)and transient photocurrent response test proved the improved separation and transfer of photoexcited charge carriers for Cu(Ⅰ)introduction.Consequently,the photocatalytic activity of CUCN was much better than that of PCN for antibiotics norfloxacin(NOR),with 4.7-fold higher degradation reaction rate constants.From species-trapping experiments and density function theory(DFT)calculations,the Cu single atoms in Cu-N_(2)served as catalytic sites that could accelerate charge transfer and facilitate the adsorption of molecular oxygen to produce active species.The stable Cu(Ⅰ)embedded in the layer structure led to the excellent recycling test and remained stable after four runs of degradation and even thermal regenerated treatment.The degradation paths of NOR by CUCN under visible light were also demonstrated.Our work sheds light on a sustainable and practical approach for achieving stable metal single-atom doping and enhancing photocatalytic degradation of aqueous pollutants.
基金Key Research and Development Program of Shaanxi Province(2022GY-410)Funding of Western Titanium Technologies Co.,Ltd(WX2210)。
文摘Based on the microstructure characterization,electrochemical impedance spectroscopy,potentiodynamic polarization,and immersion corrosion,this work comparatively analyzed the differences in the electrochemical corrosion morphology and post-foil formation surface morphology of laser beam welded(LBW)sample and spin-formed sample,and compared the corrosion resistance and Cu foil formation ability of two samples in H_(2)SO_(4)/NaCl solution and CuSO_(4) reducing electrolyte.Results show that in H_(2)SO_(4) and NaCl solutions,LBW sample and spin-formed sample exhibit excellent passivation ability and corrosion resistance.Both samples show uniform corrosion morphologies and similar corrosion resistance in the strong acidic solution containing Cl^(-).Meanwhile,the Cu foil formation ability of the welded joint is similar to that of the spin-formed sample,and both samples obtain intact Cu foils with high-quality surfaces and small differences in properties.
基金supported by the program of Introduce and cultivate high-level innovative and entrepreneurial personnel:Thousand Talents Program of Jiangxi province(jxsg2023201121)the National Natural Science Foundation of China(32460908)Natural Science Foundation of Jiangxi province(20232ACB215004).
文摘Background Copper(Cu)is a pervasive environmental pollutant with significant hepatotoxic effects in animals.The endoplasmic reticulum(ER)interacts closely with lysosomes to maintain intracellular homeostasis.However,the role and mechanism of ER-lysosome crosstalk in Cu-induced liver injury in ducks remains unclear.To investigate this,we established both an in vivo model of Cu-exposed ducks and an in vitro model of duck hepatocytes,and added baicalin(Ba)to further explore its protective effects.Results The results of this study demonstrated that exposure to Cu resulted in vacuolar degeneration and oxidative stress in duck hepatocytes,while ultrastructural observations revealed ER swelling and an increased number of autophagic lysosomes.Furthermore,Cu exposure significantly upregulated mRNA and protein levels related to ER stress,autophagy,and lysosomal membrane factors.It also markedly increased ER-lysosomal co-localization.Further experiments showed that knockdown of LAPTM4B significantly attenuated Cu-induced ER autophagy and reduced ER-lysosomal co-localization in hepatocytes.Molecular docking and molecular dynamics simulations confirmed that LAPTM4B has a stable binding site to Ba;in vitro experiments demonstrated that Ba could effectively alleviate Cuinduced ER-lysosome crosstalk in duck hepatocytes and reduce hepatocyte injury by targeting LAPTM4B;additionally,in vivo experiments showed that Ba significantly inhibits Cu-induced liver injury in ducks.Conclusions In summary,the present study demonstrates that Cu exposure disrupts ER-lysosomal crosstalk in duck liver,leading to ER-lysosomal damage and subsequent hepatocyte injury.In contrast,Ba alleviates this injury by selectively targeting LAPTM4B,ultimately attenuating Cu-induced hepatotoxicity.
基金supported by National Natural Science Foundation of China(Nos.52170092,U22A20403 and 51808406)Hebei Natural Science Foundation(Nos.E2021203140 and B2021203016)。
文摘Herein,the Cu(Ⅲ)synthesized from copper plating effluent was developed for the first time to evaluate the onsite degradation performance of heavy metal complexes in the wastewater,thus achieving the purpose of“treating waste with waste”.The results indicated that synthetic Cu(Ⅲ)presented the excellent decomplexation performance for Cu(Ⅱ)/Ni(Ⅱ)-organic complexes.The removal efficiency of Cu(Ⅱ)/Ni(Ⅱ)-EDTA significantly increased with increasing Cu(Ⅲ)dosage,and the degradation of Cu(Ⅱ)/Ni(Ⅱ)-EDTA by synthetic Cu(Ⅲ)system displayed highly p H-dependent reactivity.The radical quencher experiments confirmed that Cu(Ⅲ)direct oxidation were mainly involved in the degradation of Cu(Ⅱ)-EDTA.Additionally,the continuous decarboxylation process was proven to be the main degradation pathway of Cu(Ⅱ)-EDTA in Cu(Ⅲ)system.The coexisting substances(SO42-,Cl-and fulvic acids)showed little impacts at low level for the removal of Cu(Ⅱ)/Ni(Ⅱ)-EDTA,while retarded the degradation of Cu(Ⅱ)-EDTA slightly at high level,which features high selective oxidation.Encouragingly,it was also effective to remove Cu(Ⅱ)/Ni(Ⅱ)-EDTA from in treating actual Cu/Ni-containing wastewater through synthetic Cu(Ⅲ)treatment.
文摘This study was conducted in two sections.Initially,the effects of NaCl,MgCl_(2),and urea were investigated on extracting copper and iron from chalcopyrite.Subsequently,CuFe_(2)O_(4)-based electrodes for supercapacitors were synthesized using the extracted solution.The first phase revealed that 3 mol/L NaCl achieved the highest extraction performance,yielding 60%Cu and 23%Fe.MgCl_(2)at 1.5 mol/L extracted 52%Cu and 27%Fe,while a combination of 0.5 mol/L MgCl_(2)and 1.6 mol/L urea yielded 57%Cu and 20%Fe.Urea effectively reduced iron levels.CuFe_(2)O_(4)-based electrodes were then successfully synthesized via a hydrothermal method using a MgCl_(2)-urea solution.Characterization studies confirmed CuFe_(2)O_(4)formation with a 2D structure and 45−50 nm wall thickness on nickel foam.Electrochemical analysis showed a specific capacitance of 725 mF/cm^(2)at 2 mA/cm^(2)current density,with energy and power densities of 12.3 mW·h/cm^(2)and 175 mW/cm^(2),respectively.These findings suggest that chalcopyrite has the potential for direct use in energy storage.
基金supported financially by the National Natural Science Foundation of China (22302222, 22072172)the Postdoctoral Science Foundation (2024T170965, 2023M743641)+5 种基金the Youth Innovation Promotion Association CAS (Y2021056)Joint Fund of the Yulin University and the Dalian National Laboratory for Clean Energy (YLU-DNL Fund 2022007)the Major Science and Technology Projects of Shanxi Province (202005D121002)the Special Fund for Science and Technology Innovation Teams of Shanxi Province (202304051001007)the Science and Technology Department of Shanxi Province (202303021222409)the Shanxi Provincial Department of Human and Social Resources Security’s Doctor Introduction Program (2024SHB001)
文摘The copper-cerium catalysts demonstrate high efficiency in CO_(2)reduction reactions(CO_(2)RR).However,the mechanism governing the formation of C_(2)H_(4)and CH_(4)by regulating Cu bulk phase structure at the copper-cerium interface remains unclear due to the instability and dynamic evaluations of copper species.Herein,we synthesized CeO_(2)-CuO containing solely Cu^(2+)species and CeO_(2)-Cu featuring predominantly metallic Cu species at the interface,which exhibit stable structures under various potentials,offering ideal models for in-depth mechanistic studies.The C_(2)H_(4)is the main product over the CeO_(2)-CuO catalyst,exhibiting a Faradaic efficiency(FE)of 42.3%±1.4%,while CH_(4)is the primary product over the CeO_(2)-Cu catalyst,with a FE of 32.4%±1.3%.These results demonstrate that regulating bulk phase Cu structure at the copper-cerium interface influences the selectivity of hydrocarbon products.The operando ATR-SEIRAS finds that CeO_(2)-CuO surfaces with single linear*CO adsorption are advantageous for synthesizing*COCO,whereas bridge-bonded*CO adsorption promoted*CHO formation.Furthermore,DFT simulations demonstrate that the energy barrier of CO-CO coupling(C_(2)H_(4)pathway)at the CeO_(2)-CuO interface decreases as compared to the CeO_(2)-Cu catalyst,thus indicating a facilitated conversion of the CO_(2)to C_(2)H_(4).This research deepens the mechanistic understanding of the copper-cerium system during CO_(2)RR and effectively formulates a strategy for developing high-selectivity catalysts.
