In this work,the TiO_(2)/Sb_(2)S_(3) nanorod arrays(NRAs)were synthesized through a two-stage hydrothermal route for photoelectrochemical(PEC)water splitting.The effect of annealing treatment in Ar ambience on the PEC...In this work,the TiO_(2)/Sb_(2)S_(3) nanorod arrays(NRAs)were synthesized through a two-stage hydrothermal route for photoelectrochemical(PEC)water splitting.The effect of annealing treatment in Ar ambience on the PEC activity of TiO_(2)/Sb_(2)S_(3) composite sample was investigated by electrochemical impedance analysis,including Nyquist and Mott-Schottky(M-S)plots.It was demonstrated that vacuum annealing could crystallize Sb_(2)S_(3) component and change its color from red to black,leading to an increment of photocurrent density from 1.9 A/m^(2) to 4.25 A/m^(2) at 0 V versus saturated calomel electrode(VSCE).The enhanced PEC performance was mainly attributed to the improved visible light absorption.Moreover,annealing treatment facilitated retarding the electron-hole recombination occurred at the solid/liquid interfaces.Our work might provide a novel strategy for enhancing the PEC performance of a semiconductor electrode.展开更多
The structural phase transition of MnO_(2) nanorods was investigated using in situ high pressure synchrotron x-ray diffraction(XRD) and transmission electron microscopy(TEM). At pressures exceeding 10.9 GPa, a second-...The structural phase transition of MnO_(2) nanorods was investigated using in situ high pressure synchrotron x-ray diffraction(XRD) and transmission electron microscopy(TEM). At pressures exceeding 10.9 GPa, a second-order structural phase transition from tetragonal to orthogonal, which was accompanied by fine-scale crystal twinning phenomena, was observed in MnO_(2) nanorods. On account of the significant contribution of surface energy, the phase transition pressure exhibited appreciable hysteresis compared with the bulk counterparts, suggesting the enhanced structural stability of nanorod morphology. These findings reveal that the size and morphology exhibit a manifest correlation with the high pressure behavior of MnO_(2) nanomaterials, providing useful insights into the intricate interplay between structure and properties.展开更多
Elemental doping is an effective strategy to enhance photocatalytic activity and extend the light absorption range of single-component photocatalysts.In this work,a series of La-doped CeO_(2) nanorods(La-CeO_(2)-x) wi...Elemental doping is an effective strategy to enhance photocatalytic activity and extend the light absorption range of single-component photocatalysts.In this work,a series of La-doped CeO_(2) nanorods(La-CeO_(2)-x) with La content of 1 wt%-15 wt% are synthesized by a simple hydrothermal method and further used as photocatalyst for sulfamerazine(SMR) degradation.The prepared La-CeO_(2)-x nanorods exhibit a great improvement in electron-hole pair migration and visible-light response due to the synergistic effect of abundant oxygen vacancies and heterogeneous elements(La).Consequently,La-CeO_(2)-x exhibited excellent visible-light photocatalytic performances and chemical stability for SMR degradation,the La-CeO_(2)-5 sample achieved the highest SMR degradation rate of 81%,which was 3.4 times higher than that of the original CeO_(2).Furthermore,three possible degradation pathways of SMR in La-CeO_(2) photocatalytic reactions were proposed by liquid chromatography-mass spectrometry technique.Finally,density functional theory calculations were carried out to provide an in-depth understanding of the structure-performance relationships.Considering its excellent properties and better photocatalytic performance,this study demonstrates that La doping in CeO_(2) is an effective way to increase oxygen vacancy and improve the photochemical properties of photocatalysts.展开更多
The research of poly(ethylene oxide)(PEO)-based solid composite electrolyte with high ionic conductivity and excellent interfacial stability is the key to the development of all-solid-state lithium-ion batteries(ASSLI...The research of poly(ethylene oxide)(PEO)-based solid composite electrolyte with high ionic conductivity and excellent interfacial stability is the key to the development of all-solid-state lithium-ion batteries(ASSLIBs). Herein, uniform nanorod structured CeO_(2) fillers were controllably synthesized by electrospinning, which were subsequently filled into PEO polymer to prepare CeO_(2)/PEO solid composite electrolyte. The addition of CeO_(2) nanorods can reduce both the glass transition temperature and the melting point of PEO polymer, and also interact with PEO and lithium bis(trifluoromethanesulphonyl)imide(LITFSI) by Lewis acid—base reaction. Therefore, the solid composite electrolyte exhibits a high ionic conductivity of 4.52 × 10^(-4)S/cm, a wide electrochemical stability window of about 4.8 V, and a good interfacial stability with Li at 55℃. Moreover, the LiFePO_4/Li ASSLIB divulges the discharging specific capacity of 165, 162, 156 and 146 mA,h/g at 0.2, 0.5, 1 and 2 C, respectively, and achieves the capacity retention of 90.3% after 150 cycles at 0.5 C. Consequently, one dimensional CeO_(2) nanorods can be considered as an alternative filler for polymeric solid electrolyte.展开更多
Aqueous Zn//MnO2 batteries are emerging as promising large-scale energy storage devices owing to their cost-effectiveness,high safety,high output voltage,and energy density.However,the MnO2 cathode suffers from intrin...Aqueous Zn//MnO2 batteries are emerging as promising large-scale energy storage devices owing to their cost-effectiveness,high safety,high output voltage,and energy density.However,the MnO2 cathode suffers from intrinsically poor rate performance and rapid capacity deterioration.Here,we remove the roadblock by compositing MnO2 nanorods with highly conductive graphene,which remarkably enhances the electrochemical properties of the MnO2 cathode.Benefiting from the boosted electric conductivity and ion diffusion rate as well as the structural protection of graphene,the Zn//MnO2-graphene battery presents an admirable capacity of 301 mAh g^-1 at 0.5 A g^-1,corresponding to a high energy density of 411.6 Wh kg^-1.Even at a high current density of 10 A g^-1,a decent capacity of 95.8 mAh g^-1 is still obtained,manifesting its excellent rate property.Furthermore,an impressive power density of 15 kW kg^-1 is achieved by the Zn//MnO2-graphene battery.展开更多
γ-MnO2 nanorod-assembled hierarchical micro-spheres with abundant oxygen defects are synthesized by a simple thermal treatment approach as oxygen reduction electrocatalysts for Al(aluminum)-air batteries. The rich ox...γ-MnO2 nanorod-assembled hierarchical micro-spheres with abundant oxygen defects are synthesized by a simple thermal treatment approach as oxygen reduction electrocatalysts for Al(aluminum)-air batteries. The rich oxygen vacancies on the surface of γ-MnO2 are verified by morphology, structure,electron paramagnetic resonance(EPR) and X-ray photoelectron spectroscopy(XPS) results. The oxygen reduction reaction(ORR) electrocatalytic activity of γ-MnO2 is significantly improved by the incoming oxygen vacancies. The γ-MnO2 nanorod-assembled hierarchical micro-spheres calcined under 300 °C in Ar atmosphere show the best ORR performance. The primary Al-air batteries using γ-MnO2 catalysts as the cathode, which demonstrates excellent peal power density of 318 m W cm^(-2) when applying theγ-MnO2 catalysts with optimal amount of oxygen vacancies.展开更多
In this study,a series of CuCl_(2)-modified MnO_(x)-CeO_(x)nanorods were synthesized for the oxidation of Hg^(0).The addition of CuCl_(2)resulted in an enhancement in the catalyst’s Hg^(0)oxidation ability,and Hg^(0)...In this study,a series of CuCl_(2)-modified MnO_(x)-CeO_(x)nanorods were synthesized for the oxidation of Hg^(0).The addition of CuCl_(2)resulted in an enhancement in the catalyst’s Hg^(0)oxidation ability,and Hg^(0)oxidation efficiency reached>97%from 150 to 250°C.In the MnO_(x)-CeO_(x)catalysts,Mn^(4+)played the role of the active species for Hg^(0)oxidization,but in the CuCl_(2)-doped catalysts Cl−also contributed to Hg^(0)oxidation,conferring the superior performance of these samples.The introduction of SO_(2) led to a decrease in the availability of Mn^(4+),and the Hg^(0)oxidation efficiency of MnO_(x)-CeO_(x)decreased from about 100%to about 78%.By contrast,CuCl_(2)-promoted samples maintained a Hg^(0)oxidation efficiency of about 100%during the SO_(2) deactivation cycle due to the high reactivity of Cl−.展开更多
Heterogeneous structure and carbon coating are important ways to enhance the reaction kinetics and cycling stability of metal phosphides as anode materials for sodium-ion batteries.Therefore,nitrogen-doped carbon-capp...Heterogeneous structure and carbon coating are important ways to enhance the reaction kinetics and cycling stability of metal phosphides as anode materials for sodium-ion batteries.Therefore,nitrogen-doped carbon-capped triphasic heterostructure Cu_(3)P/Co_(2)P/CoP@NC stands for nitrogen doped carbon nanorods were designed and synthesized through a combination of phosphide and carbonization.Kinetic analyses(cyclic voltammetry,electrochemical impedance spectroscopy,and galvanostatic intermittent titration technique)and density functional theory calculations show that the three-phase heterostructure and carbon layer effectively improve Na adsorption and migration as well as the electrochemical reactivity of the electrode.Based on this,Cu_(3)P/Co_(2)P/CoP@NC demonstrated excellent rate performance(305.9 mAh g^(-1)at 0.3 A g^(-1)and 202.8 mAh g^(-1)even at 10 A g^(-1))and cycling stability(the capacity decay rate is only 0.12%from the 5th to 300th cycle)when it is used for sodium-ion battery anodes.The in situ X-ray diffraction,ex situ X-ray photoelectron spectroscopy,and high-resolution transmission electron microscopy tests showed that Cu_(3)P/Co_(2)P/CoP@NC is based on a conversion reaction mechanism for sodium-ion storage.In addition,the NVP@reduced graphene oxide(rGO)//Cu_(3)P/Co_(2)P/CoP@NC full-cell delivers a high capacity of 210.2 mAh g^(-1)after 50 cycles at 0.3 A g^(-1).This work can provide a reference for the design of high-performance sodium electrode anode materials.展开更多
基金supported by the Fundamental Research Funds for the Central Universities(No.2019ZDPY04).
文摘In this work,the TiO_(2)/Sb_(2)S_(3) nanorod arrays(NRAs)were synthesized through a two-stage hydrothermal route for photoelectrochemical(PEC)water splitting.The effect of annealing treatment in Ar ambience on the PEC activity of TiO_(2)/Sb_(2)S_(3) composite sample was investigated by electrochemical impedance analysis,including Nyquist and Mott-Schottky(M-S)plots.It was demonstrated that vacuum annealing could crystallize Sb_(2)S_(3) component and change its color from red to black,leading to an increment of photocurrent density from 1.9 A/m^(2) to 4.25 A/m^(2) at 0 V versus saturated calomel electrode(VSCE).The enhanced PEC performance was mainly attributed to the improved visible light absorption.Moreover,annealing treatment facilitated retarding the electron-hole recombination occurred at the solid/liquid interfaces.Our work might provide a novel strategy for enhancing the PEC performance of a semiconductor electrode.
基金Project supported by China Postdoctoral Science Foundation (Grant No. 2023M742049)Guangdong Basic and Applied Basic Research Foundation (Grant No. 2023A1515110844)the Innovative Training Program for College Students (Grant No. 20249076)。
文摘The structural phase transition of MnO_(2) nanorods was investigated using in situ high pressure synchrotron x-ray diffraction(XRD) and transmission electron microscopy(TEM). At pressures exceeding 10.9 GPa, a second-order structural phase transition from tetragonal to orthogonal, which was accompanied by fine-scale crystal twinning phenomena, was observed in MnO_(2) nanorods. On account of the significant contribution of surface energy, the phase transition pressure exhibited appreciable hysteresis compared with the bulk counterparts, suggesting the enhanced structural stability of nanorod morphology. These findings reveal that the size and morphology exhibit a manifest correlation with the high pressure behavior of MnO_(2) nanomaterials, providing useful insights into the intricate interplay between structure and properties.
基金financially supported by the National Natural Science Foundation of China (No.52300206)the Natural Science Foundation of Jiangsu Province (No.BK20230705)+3 种基金the Industry-University Research Cooperation Project of Jiangsu Province,China (No.BY20221227)Natural Science Foundation of Jiangsu Higher Education Institutions of China (No.22KJB610014)the Talent-Recruiting Program of Nanjing Institute of Technology (No.YKJ202124)the Open Fund of Advanced Industrial Technology Research Institute,Nanjing Institute of Technology (No. XJY202110)。
文摘Elemental doping is an effective strategy to enhance photocatalytic activity and extend the light absorption range of single-component photocatalysts.In this work,a series of La-doped CeO_(2) nanorods(La-CeO_(2)-x) with La content of 1 wt%-15 wt% are synthesized by a simple hydrothermal method and further used as photocatalyst for sulfamerazine(SMR) degradation.The prepared La-CeO_(2)-x nanorods exhibit a great improvement in electron-hole pair migration and visible-light response due to the synergistic effect of abundant oxygen vacancies and heterogeneous elements(La).Consequently,La-CeO_(2)-x exhibited excellent visible-light photocatalytic performances and chemical stability for SMR degradation,the La-CeO_(2)-5 sample achieved the highest SMR degradation rate of 81%,which was 3.4 times higher than that of the original CeO_(2).Furthermore,three possible degradation pathways of SMR in La-CeO_(2) photocatalytic reactions were proposed by liquid chromatography-mass spectrometry technique.Finally,density functional theory calculations were carried out to provide an in-depth understanding of the structure-performance relationships.Considering its excellent properties and better photocatalytic performance,this study demonstrates that La doping in CeO_(2) is an effective way to increase oxygen vacancy and improve the photochemical properties of photocatalysts.
基金Project supported by the Education Department of Henan Province(22A170017)the Science and Technology Department of Henan Province(232102240011)+1 种基金Henan Institute of Science and Technology(2016034)National College Students'Innovation and Entrepreneurship Training Program(202211071012)。
文摘The research of poly(ethylene oxide)(PEO)-based solid composite electrolyte with high ionic conductivity and excellent interfacial stability is the key to the development of all-solid-state lithium-ion batteries(ASSLIBs). Herein, uniform nanorod structured CeO_(2) fillers were controllably synthesized by electrospinning, which were subsequently filled into PEO polymer to prepare CeO_(2)/PEO solid composite electrolyte. The addition of CeO_(2) nanorods can reduce both the glass transition temperature and the melting point of PEO polymer, and also interact with PEO and lithium bis(trifluoromethanesulphonyl)imide(LITFSI) by Lewis acid—base reaction. Therefore, the solid composite electrolyte exhibits a high ionic conductivity of 4.52 × 10^(-4)S/cm, a wide electrochemical stability window of about 4.8 V, and a good interfacial stability with Li at 55℃. Moreover, the LiFePO_4/Li ASSLIB divulges the discharging specific capacity of 165, 162, 156 and 146 mA,h/g at 0.2, 0.5, 1 and 2 C, respectively, and achieves the capacity retention of 90.3% after 150 cycles at 0.5 C. Consequently, one dimensional CeO_(2) nanorods can be considered as an alternative filler for polymeric solid electrolyte.
基金financially supported by the Guangdong Power Grid Co.,Ltd.(Grant No.GDKJXM20160000)。
文摘Aqueous Zn//MnO2 batteries are emerging as promising large-scale energy storage devices owing to their cost-effectiveness,high safety,high output voltage,and energy density.However,the MnO2 cathode suffers from intrinsically poor rate performance and rapid capacity deterioration.Here,we remove the roadblock by compositing MnO2 nanorods with highly conductive graphene,which remarkably enhances the electrochemical properties of the MnO2 cathode.Benefiting from the boosted electric conductivity and ion diffusion rate as well as the structural protection of graphene,the Zn//MnO2-graphene battery presents an admirable capacity of 301 mAh g^-1 at 0.5 A g^-1,corresponding to a high energy density of 411.6 Wh kg^-1.Even at a high current density of 10 A g^-1,a decent capacity of 95.8 mAh g^-1 is still obtained,manifesting its excellent rate property.Furthermore,an impressive power density of 15 kW kg^-1 is achieved by the Zn//MnO2-graphene battery.
基金supported by the National Natural Science Foundation of China (21975163, 51902204)。
文摘γ-MnO2 nanorod-assembled hierarchical micro-spheres with abundant oxygen defects are synthesized by a simple thermal treatment approach as oxygen reduction electrocatalysts for Al(aluminum)-air batteries. The rich oxygen vacancies on the surface of γ-MnO2 are verified by morphology, structure,electron paramagnetic resonance(EPR) and X-ray photoelectron spectroscopy(XPS) results. The oxygen reduction reaction(ORR) electrocatalytic activity of γ-MnO2 is significantly improved by the incoming oxygen vacancies. The γ-MnO2 nanorod-assembled hierarchical micro-spheres calcined under 300 °C in Ar atmosphere show the best ORR performance. The primary Al-air batteries using γ-MnO2 catalysts as the cathode, which demonstrates excellent peal power density of 318 m W cm^(-2) when applying theγ-MnO2 catalysts with optimal amount of oxygen vacancies.
基金supported by the Zhejiang Provincial Natural Science Foundation of China(No.LQ22E060003)the General Research Projects of Zhejiang Provincial Department of Education in 2023(No.Y202353660)the Public Welfare Science and Technology Project of Ningbo City(No.202002N3105),China.
文摘In this study,a series of CuCl_(2)-modified MnO_(x)-CeO_(x)nanorods were synthesized for the oxidation of Hg^(0).The addition of CuCl_(2)resulted in an enhancement in the catalyst’s Hg^(0)oxidation ability,and Hg^(0)oxidation efficiency reached>97%from 150 to 250°C.In the MnO_(x)-CeO_(x)catalysts,Mn^(4+)played the role of the active species for Hg^(0)oxidization,but in the CuCl_(2)-doped catalysts Cl−also contributed to Hg^(0)oxidation,conferring the superior performance of these samples.The introduction of SO_(2) led to a decrease in the availability of Mn^(4+),and the Hg^(0)oxidation efficiency of MnO_(x)-CeO_(x)decreased from about 100%to about 78%.By contrast,CuCl_(2)-promoted samples maintained a Hg^(0)oxidation efficiency of about 100%during the SO_(2) deactivation cycle due to the high reactivity of Cl−.
基金supported by the National Natural Science Foundation of China (No. 22305210, 52371238 to C. D.)the Shandong Provincial Natural Science Foundation (No. ZR2020QB108)+1 种基金the Graduate Innovation Foundation of Yantai University (GIFYTU)the Shandong Laboratory of Advanced Materials and Green Manufacturing (Yantai, AMGM2024A01)
文摘Heterogeneous structure and carbon coating are important ways to enhance the reaction kinetics and cycling stability of metal phosphides as anode materials for sodium-ion batteries.Therefore,nitrogen-doped carbon-capped triphasic heterostructure Cu_(3)P/Co_(2)P/CoP@NC stands for nitrogen doped carbon nanorods were designed and synthesized through a combination of phosphide and carbonization.Kinetic analyses(cyclic voltammetry,electrochemical impedance spectroscopy,and galvanostatic intermittent titration technique)and density functional theory calculations show that the three-phase heterostructure and carbon layer effectively improve Na adsorption and migration as well as the electrochemical reactivity of the electrode.Based on this,Cu_(3)P/Co_(2)P/CoP@NC demonstrated excellent rate performance(305.9 mAh g^(-1)at 0.3 A g^(-1)and 202.8 mAh g^(-1)even at 10 A g^(-1))and cycling stability(the capacity decay rate is only 0.12%from the 5th to 300th cycle)when it is used for sodium-ion battery anodes.The in situ X-ray diffraction,ex situ X-ray photoelectron spectroscopy,and high-resolution transmission electron microscopy tests showed that Cu_(3)P/Co_(2)P/CoP@NC is based on a conversion reaction mechanism for sodium-ion storage.In addition,the NVP@reduced graphene oxide(rGO)//Cu_(3)P/Co_(2)P/CoP@NC full-cell delivers a high capacity of 210.2 mAh g^(-1)after 50 cycles at 0.3 A g^(-1).This work can provide a reference for the design of high-performance sodium electrode anode materials.
