Synergistic regulation of hierarchical nanostructures and defect engineering is effective in accelerating electron and ion transport for metal oxide electrodes.Herein,carbon nanofiber-supported V_(2)O_(3) with enriche...Synergistic regulation of hierarchical nanostructures and defect engineering is effective in accelerating electron and ion transport for metal oxide electrodes.Herein,carbon nanofiber-supported V_(2)O_(3) with enriched oxygen vacancies(OV-V_(2)O_(3)@CNF)was fabricated using the facile electrospinning method,followed by thermal reduction.Differing from the traditional particles embedded within carbon nanofibers or irregularly distributed between carbon nanofibers,the free-standing OV-V_(2)O_(3)@CNF allows for V_(2)O_(3) nanosheets to grow vertically on one-dimensional(1D)carbon nanofibers,enabling abundant active sites,shortened ion diffusion pathway,continuous electron transport,and robust structural stability.Meanwhile,density functional theory calculations confirmed that the oxygen vacancies can promote intrinsic electron conductivity and reduce ion diffusion energy barrier.Consequently,the OV-V_(2)O_(3)@CNF anode delivers a large reversible capacity of 812 mAh g^(-1) at 0.1 A g^(-1),superior rate capability(405 mAh g^(-1) at 5 A g^(-1)),and long cycle life(378 mAh g^(-1) at 5 A g^(-1) after 1000 cycles).Moreover,an all-vanadium full battery(V2O5//OV-V_(2)O_(3)@CNF)was assembled using an OV-V_(2)O_(3)@CNF anode and a V2O5 cathode,which outputs a working voltage of 2.5 V with high energy density and power density,suggesting promising practical application.This work offers fresh perspectives on constructing hierarchical 1D nanofiber electrodes by combining defect engineering and electrospinning technology.展开更多
The corrosion inhibition efficacy of titanate(CaTiO_(3))for carbon anodes in molten salts was investigated through various analytical techniques,including linear sweep voltammetry,X-ray diffraction,scanning electron m...The corrosion inhibition efficacy of titanate(CaTiO_(3))for carbon anodes in molten salts was investigated through various analytical techniques,including linear sweep voltammetry,X-ray diffraction,scanning electron microscopy,and energy dispersion spectroscopy.The results demonstrate that the addition of CaTiO_(3)corrosion inhibitor efficiently passivates the carbon anode and leads to the formation of a dense CaTiO_(3)layer during the electrolysis process in molten CaCl_(2)-CaO.Subsequently,the passivated carbon anode effectively undergoes the oxygen evolution reaction,with an optimal current density for passivation identified at 400 m A/cm~2.Comprehensive investigations,including CaTiO_(3)solubility tests in molten CaCl_(2)-CaO and numerical modeling of the stability of complex ionic structures,provide compelling evidence supporting“complexation-precipitation”passivation mechanism.This mechanism involves the initial formation of a complex containing TiO_(2)·nCaO by CaTiO_(3)and CaO,which subsequently decomposes to yield CaTiO_(3),firmly coating the surface of the carbon anode.In practical applications,the integration of CaTiO_(3)corrosion inhibitor with the carbon anode leads to the successful preparation of the FeCoNiCrMn high-entropy alloy without carbon contamination in the molten CaCl_(2)-Ca O.展开更多
Metal-free defective carbon materials with abundant active sites have been widely studied as low-cost and efficient oxygen reduction reaction(ORR)electrocatalysts in metal-air batteries.However,the active sites in def...Metal-free defective carbon materials with abundant active sites have been widely studied as low-cost and efficient oxygen reduction reaction(ORR)electrocatalysts in metal-air batteries.However,the active sites in defective carbon are easily subjected to serious oxidation or hydroxylation during ORR or storage,leading to rapid degradation of activity.Herein,we design a van der Waals heterostructure comprised of vitamin C(VC)and defective carbon(DC)to not only boost the activity but also enhance the durability and storage stability of the DC-VC electrocatalyst.The formation of VC van der Waals between DC and VC is demonstrated to be an effective strategy to protect the defect active sites from oxidation and hydroxylation degradation,thus significantly enhancing the electrochemical durability and storage anti-aging performance.Moreover,the DC-VC van der Waals can reduce the reaction energy barrier to facilitate the ORR.These findings are also confirmed by operando Fourier transform infrared spectroscopy and density functional theory calculations.It is necessary to mention that the preparation of this DC-VC electrocatalyst can be scaled up,and the ORR performance of the largely produced electrocatalyst is demonstrated to be very consistent.Furthermore,the DC-VC-based aluminum-air batteries display very competitive power density with good performance maintenance.展开更多
Enhancing both the number of active sites available and the intrinsic activity of Co-based electrocatalysts simultaneously is a desirable goal.Herein,a ZIF-67-derived hierarchical porous cobalt sulfide decorated by Au...Enhancing both the number of active sites available and the intrinsic activity of Co-based electrocatalysts simultaneously is a desirable goal.Herein,a ZIF-67-derived hierarchical porous cobalt sulfide decorated by Au nanoparticles(NPs)(denoted as HP-Au@CoxSy@ZIF-67)hybrid is synthesized by low-temperature sulfuration treatment.The well-defined macroporous-mesoporous-microporous structure is obtained based on the combination of polystyrene spheres,as-formed CoxSy nanosheets,and ZIF-67 frameworks.This novel three-dimensional hierarchical structure significantly enlarges the three-phase interfaces,accelerating the mass transfer and exposing the active centers for oxygen evolution reaction.The electronic structure of Co is modulated by Au through charge transfer,and a series of experiments,together with theoretical analysis,is performed to ascertain the electronic modulation of Co by Au.Meanwhile,HP-Au@CoxSy@ZIF-67 catalysts with different amounts of Au were synthesized,wherein Au and NaBH4 reductant result in an interesting“competition effect”to regulate the relative ratio of Co^(2+)/Co^(3+),and moderate Au assists the electrochemical performance to reach the highest value.Consequently,the optimized HP-Au@CoxSy@ZIF-67 exhibits a low overpotential of 340 mV at 10 mA cm^(-2)and a Tafel slope of 42 mV dec-1 for OER in 0.1 M aqueous KOH,enabling efficient water splitting and Zn-air battery performance.The work here highlights the pivotal roles of both microstructural and electronic modulation in enhancing electrocatalytic activity and presents a feasible strategy for designing and optimizing advanced electrocatalysts.展开更多
Ni^(2+)/Cu^(2+)/SO_(4)^(2-)/polyvinyl alcohol precursor fibers with uniform diameters were prepared through electrospinning.Nickel-based composite nanoalloys containing Ni,Cu,and S were prepared through heat treatment...Ni^(2+)/Cu^(2+)/SO_(4)^(2-)/polyvinyl alcohol precursor fibers with uniform diameters were prepared through electrospinning.Nickel-based composite nanoalloys containing Ni,Cu,and S were prepared through heat treatment in an Ar atmosphere.The experimental results show that the main components of the prepared nanoalloys are NiCu,Ni_(3)S_(2),Ni,and C.The nanoalloys exhibit fine grain sizes about 200-500 nm,which can increase with increasing heat treatment temperature.Electrochemical test results show that the nickel sulfidemodified NiCu nanoalloy composites exhibit excellent oxygen evolution reaction properties,and the oxygen evolution reaction properties gradually improve with the increasing heat treatment temperature.The sample prepared at 1 000℃ for 40 min show a low overpotential of 423 mV and a small Tafel slope of 134 mV·dec^(-1) at a current density of 10 mA·cm^(-2).展开更多
Reactive oxygen species(ROS)plays important roles in living organisms.While ROS is a double-edged sword,which can eliminate drug-resistant bacteria,but excessive levels can cause oxidative damage to cells.A core–shel...Reactive oxygen species(ROS)plays important roles in living organisms.While ROS is a double-edged sword,which can eliminate drug-resistant bacteria,but excessive levels can cause oxidative damage to cells.A core–shell nanozyme,Ce O_(2)@ZIF-8/Au,has been crafted,spontaneously activating both ROS generating and scavenging functions,achieving the multifaceted functions of eliminating bacteria,reducing inflammation,and promoting wound healing.The Au Nanoparticles(NPs)on the shell exhibit high-efficiency peroxidase-like activity,producing ROS to kill bacteria.Meanwhile,the encapsulation of Ce O_(2) core within ZIF-8 provides a seal for temporarily limiting the superoxide dismutase and catalase-like activities of Ce O_(2) nanoparticles.Subsequently,as the ZIF-8 structure decomposes in the acidic microenvironment,the Ce O_(2) core is gradually released,exerting its ROS scavenging activity to eliminate excess ROS produced by the Au NPs.These two functions automatically and continuously regulate the balance of ROS levels,ultimately achieving the function of killing bacteria,reducing inflammation,and promoting wound healing.Such innovative ROS spontaneous regulators hold immense potential for revolutionizing the field of antibacterial agents and therapies.展开更多
Oxygen reduction reaction(ORR)has been disclosed in recent studies as a significant secondary cathodic process during magnesium corrosion.This work elaborates on the contribution of ORR to the total corrosion process ...Oxygen reduction reaction(ORR)has been disclosed in recent studies as a significant secondary cathodic process during magnesium corrosion.This work elaborates on the contribution of ORR to the total corrosion process of pure Mg at different impurity levels in NaCl electrolyte with the assistance of local techniques.A finite element based numerical model taking into account the contribution of ORR during the corrosion of the Mg test materials has been designed in this study considering the local oxygen concentration.Respective computational simulations were calibrated based on the experimental data and evaluated accordingly.Finally,the simultaneous monitoring of local concentration of H_(2) and O_(2),and the combined modeling study reveal the relation between ORR and hydrogen evolution reaction.展开更多
基金This work was financially supported by the National Natural Science Foundation of China(Grant Nos.52173091,51973235)the Hubei Provincial Natural Science Foundation of China(Grant No.2021CFA022)Fundamental Research Funds for Central Universities(Grant No.CPT22023).
文摘Synergistic regulation of hierarchical nanostructures and defect engineering is effective in accelerating electron and ion transport for metal oxide electrodes.Herein,carbon nanofiber-supported V_(2)O_(3) with enriched oxygen vacancies(OV-V_(2)O_(3)@CNF)was fabricated using the facile electrospinning method,followed by thermal reduction.Differing from the traditional particles embedded within carbon nanofibers or irregularly distributed between carbon nanofibers,the free-standing OV-V_(2)O_(3)@CNF allows for V_(2)O_(3) nanosheets to grow vertically on one-dimensional(1D)carbon nanofibers,enabling abundant active sites,shortened ion diffusion pathway,continuous electron transport,and robust structural stability.Meanwhile,density functional theory calculations confirmed that the oxygen vacancies can promote intrinsic electron conductivity and reduce ion diffusion energy barrier.Consequently,the OV-V_(2)O_(3)@CNF anode delivers a large reversible capacity of 812 mAh g^(-1) at 0.1 A g^(-1),superior rate capability(405 mAh g^(-1) at 5 A g^(-1)),and long cycle life(378 mAh g^(-1) at 5 A g^(-1) after 1000 cycles).Moreover,an all-vanadium full battery(V2O5//OV-V_(2)O_(3)@CNF)was assembled using an OV-V_(2)O_(3)@CNF anode and a V2O5 cathode,which outputs a working voltage of 2.5 V with high energy density and power density,suggesting promising practical application.This work offers fresh perspectives on constructing hierarchical 1D nanofiber electrodes by combining defect engineering and electrospinning technology.
基金supported by the National Natural Science Foundation of China(Nos.52031008,51874211,21673162,51325102,U22B2071)the International Science and Technology Cooperation Program of China(No.2015DFA90750)the China Postdoctoral Science Foundation(No.2020M682468)。
文摘The corrosion inhibition efficacy of titanate(CaTiO_(3))for carbon anodes in molten salts was investigated through various analytical techniques,including linear sweep voltammetry,X-ray diffraction,scanning electron microscopy,and energy dispersion spectroscopy.The results demonstrate that the addition of CaTiO_(3)corrosion inhibitor efficiently passivates the carbon anode and leads to the formation of a dense CaTiO_(3)layer during the electrolysis process in molten CaCl_(2)-CaO.Subsequently,the passivated carbon anode effectively undergoes the oxygen evolution reaction,with an optimal current density for passivation identified at 400 m A/cm~2.Comprehensive investigations,including CaTiO_(3)solubility tests in molten CaCl_(2)-CaO and numerical modeling of the stability of complex ionic structures,provide compelling evidence supporting“complexation-precipitation”passivation mechanism.This mechanism involves the initial formation of a complex containing TiO_(2)·nCaO by CaTiO_(3)and CaO,which subsequently decomposes to yield CaTiO_(3),firmly coating the surface of the carbon anode.In practical applications,the integration of CaTiO_(3)corrosion inhibitor with the carbon anode leads to the successful preparation of the FeCoNiCrMn high-entropy alloy without carbon contamination in the molten CaCl_(2)-Ca O.
基金financially supported by the National Natural Science Foundation of China (51874197)the Natural Science Foundation of Shanghai (21ZR1429400,22ZR1429700)。
文摘Metal-free defective carbon materials with abundant active sites have been widely studied as low-cost and efficient oxygen reduction reaction(ORR)electrocatalysts in metal-air batteries.However,the active sites in defective carbon are easily subjected to serious oxidation or hydroxylation during ORR or storage,leading to rapid degradation of activity.Herein,we design a van der Waals heterostructure comprised of vitamin C(VC)and defective carbon(DC)to not only boost the activity but also enhance the durability and storage stability of the DC-VC electrocatalyst.The formation of VC van der Waals between DC and VC is demonstrated to be an effective strategy to protect the defect active sites from oxidation and hydroxylation degradation,thus significantly enhancing the electrochemical durability and storage anti-aging performance.Moreover,the DC-VC van der Waals can reduce the reaction energy barrier to facilitate the ORR.These findings are also confirmed by operando Fourier transform infrared spectroscopy and density functional theory calculations.It is necessary to mention that the preparation of this DC-VC electrocatalyst can be scaled up,and the ORR performance of the largely produced electrocatalyst is demonstrated to be very consistent.Furthermore,the DC-VC-based aluminum-air batteries display very competitive power density with good performance maintenance.
基金National Natural Science Foundation of China,Grant/Award Numbers:52102260,52171211,51972220,61903235,U22A20145Shandong Provincial Natural Science Foundation,Grant/Award Numbers:ZR2020QB069,ZR2022ME051+4 种基金National Key Research and Development Program of China,Grant/Award Number:2022YFB4002004Scientific and Technological Innovation Ability Improvement Project of Minor Enterprises in Shandong Province,Grant/Award Number:2022TSGC1021Announce the List and Take Charge Project in Jinan,Grant/Award Number:202214012Major innovation project for integrating science,education and industry of Qilu University of Technology (Shandong Academy of Sciences),Grant/Award Numbers:2022JBZ01-07,2022PY044China Postdoctoral Science Foundation,Grant/Award Number:2022M711545。
文摘Enhancing both the number of active sites available and the intrinsic activity of Co-based electrocatalysts simultaneously is a desirable goal.Herein,a ZIF-67-derived hierarchical porous cobalt sulfide decorated by Au nanoparticles(NPs)(denoted as HP-Au@CoxSy@ZIF-67)hybrid is synthesized by low-temperature sulfuration treatment.The well-defined macroporous-mesoporous-microporous structure is obtained based on the combination of polystyrene spheres,as-formed CoxSy nanosheets,and ZIF-67 frameworks.This novel three-dimensional hierarchical structure significantly enlarges the three-phase interfaces,accelerating the mass transfer and exposing the active centers for oxygen evolution reaction.The electronic structure of Co is modulated by Au through charge transfer,and a series of experiments,together with theoretical analysis,is performed to ascertain the electronic modulation of Co by Au.Meanwhile,HP-Au@CoxSy@ZIF-67 catalysts with different amounts of Au were synthesized,wherein Au and NaBH4 reductant result in an interesting“competition effect”to regulate the relative ratio of Co^(2+)/Co^(3+),and moderate Au assists the electrochemical performance to reach the highest value.Consequently,the optimized HP-Au@CoxSy@ZIF-67 exhibits a low overpotential of 340 mV at 10 mA cm^(-2)and a Tafel slope of 42 mV dec-1 for OER in 0.1 M aqueous KOH,enabling efficient water splitting and Zn-air battery performance.The work here highlights the pivotal roles of both microstructural and electronic modulation in enhancing electrocatalytic activity and presents a feasible strategy for designing and optimizing advanced electrocatalysts.
基金Funded by the Doctoral Fund of Chengdu University(No.2081919131)the Sichuan Science and Technology Program(No.2023YFG0229)。
文摘Ni^(2+)/Cu^(2+)/SO_(4)^(2-)/polyvinyl alcohol precursor fibers with uniform diameters were prepared through electrospinning.Nickel-based composite nanoalloys containing Ni,Cu,and S were prepared through heat treatment in an Ar atmosphere.The experimental results show that the main components of the prepared nanoalloys are NiCu,Ni_(3)S_(2),Ni,and C.The nanoalloys exhibit fine grain sizes about 200-500 nm,which can increase with increasing heat treatment temperature.Electrochemical test results show that the nickel sulfidemodified NiCu nanoalloy composites exhibit excellent oxygen evolution reaction properties,and the oxygen evolution reaction properties gradually improve with the increasing heat treatment temperature.The sample prepared at 1 000℃ for 40 min show a low overpotential of 423 mV and a small Tafel slope of 134 mV·dec^(-1) at a current density of 10 mA·cm^(-2).
基金supported by the Natural Science Foundation of Fujian Province of China(No.2022J01043)China Scholarship Council(201806315005 and 201703170071).
文摘Reactive oxygen species(ROS)plays important roles in living organisms.While ROS is a double-edged sword,which can eliminate drug-resistant bacteria,but excessive levels can cause oxidative damage to cells.A core–shell nanozyme,Ce O_(2)@ZIF-8/Au,has been crafted,spontaneously activating both ROS generating and scavenging functions,achieving the multifaceted functions of eliminating bacteria,reducing inflammation,and promoting wound healing.The Au Nanoparticles(NPs)on the shell exhibit high-efficiency peroxidase-like activity,producing ROS to kill bacteria.Meanwhile,the encapsulation of Ce O_(2) core within ZIF-8 provides a seal for temporarily limiting the superoxide dismutase and catalase-like activities of Ce O_(2) nanoparticles.Subsequently,as the ZIF-8 structure decomposes in the acidic microenvironment,the Ce O_(2) core is gradually released,exerting its ROS scavenging activity to eliminate excess ROS produced by the Au NPs.These two functions automatically and continuously regulate the balance of ROS levels,ultimately achieving the function of killing bacteria,reducing inflammation,and promoting wound healing.Such innovative ROS spontaneous regulators hold immense potential for revolutionizing the field of antibacterial agents and therapies.
基金the China Scholarship Council for the award of fellowship and funding(No.201806310128,201908510177)。
文摘Oxygen reduction reaction(ORR)has been disclosed in recent studies as a significant secondary cathodic process during magnesium corrosion.This work elaborates on the contribution of ORR to the total corrosion process of pure Mg at different impurity levels in NaCl electrolyte with the assistance of local techniques.A finite element based numerical model taking into account the contribution of ORR during the corrosion of the Mg test materials has been designed in this study considering the local oxygen concentration.Respective computational simulations were calibrated based on the experimental data and evaluated accordingly.Finally,the simultaneous monitoring of local concentration of H_(2) and O_(2),and the combined modeling study reveal the relation between ORR and hydrogen evolution reaction.
