Photocatalytic hydrogen(H_(2))evolution using covalent organic frameworks(COFs)is an attractive and promising avenue for exploration,but one of its big challenges is low photo-induced charge separation.In this study,w...Photocatalytic hydrogen(H_(2))evolution using covalent organic frameworks(COFs)is an attractive and promising avenue for exploration,but one of its big challenges is low photo-induced charge separation.In this study,we present a straightforward and facile dipole polarization engineering strategy to enhance charge separation efficiency,achieved through atomic modulation(O,S,and Se)of the COF monomer.Our findings demonstrate that incorporating atoms with varying electronegativities into the COF matrix significantly influences the local dipole moment,thereby affecting charge separation efficiency and photostability,which in turn affects the rates of photocatalytic H_(2) evolution.As a result,the newly developed TMT-BO-COF,which contains highly electronegative O atoms,exhibits the lowest exciton binding energy,the highest efficiency in charge separation and transportation,and the longest lifetime of the active charges.This leads to an impressive average H_(2) production rate of 23.7 mmol g^(−1) h^(−1),which is 2.5 and 24.5 times higher than that of TMT-BS-COF(containing S atoms)and TMT-BSe-COF(containing Se atoms),respectively.A novel photocatalytic hydrogen evolution mechanism based on proton-coupled electron transfer on N in the structure of triazine rings in vinylene-linked COFs is proposed by theoretical calculations.Our findings provide new insights into the design of highly photoactive organic framework materials for H_(2) evolution and beyond.展开更多
A 3D nitrogen⁃doped graphene/multi⁃walled carbon nanotube(CS⁃GO⁃NCNT)crosslinked network mate⁃rial was successfully synthesized utilizing chitosan and melamine as carbon and nitrogen sources,concomitant with the incor...A 3D nitrogen⁃doped graphene/multi⁃walled carbon nanotube(CS⁃GO⁃NCNT)crosslinked network mate⁃rial was successfully synthesized utilizing chitosan and melamine as carbon and nitrogen sources,concomitant with the incorporation of multi⁃wall carbon nanotubes and employing freeze drying technology.The material amalgamates the merits of 1D/2D hybrid carbon materials,wherein 1D carbon nanotubes confer robustness and expedited elec⁃tron transport pathways,while 2D graphene sheets facilitate rapid ion migration.Furthermore,the introduction of nitrogen heteroatoms serves to furnish additional active sites for lithium storage.When served as an anode material for lithium⁃ion batteries,the CS⁃GO⁃NCNT electrode delivered a reversible capacity surpassing 500 mAh·g^(-1),mark⁃edly outperforming commercial graphite anodes.Even after 300 cycles at a high current density of 1 A·g^(-1),it remained a reversible capacity of up to 268 mAh·g^(-1).展开更多
Lithium-ion batteries(LIBs)are used in electric vehicles and portable smart devices,but lithium resources are dwindling and there is an increasing demand which has to be catered for.Sodium ion batteries(SIBs),which ar...Lithium-ion batteries(LIBs)are used in electric vehicles and portable smart devices,but lithium resources are dwindling and there is an increasing demand which has to be catered for.Sodium ion batteries(SIBs),which are less costly,are a promising replacement for LIBs because of the abundant natural reserves of sodium.The anode of a SIB is a necessary component of the battery but is less understood than the cathode.This review outlines the development of various types of anodes,including carbonbased,metallic and organic,which operate using different reaction mechanisms such as intercalation,alloying and conversion,and considers their challenges and prospects.Strategies for modifying their structures by doping and coating,and also modifying the solid electrolyte interface are discussed.In addition,this review also discusses the challenges encountered by the anode of SIBs and the solutions.展开更多
Flower-like CuO and flower-like CuO/graphene composite were prepared successfully by hydrothermal method. They were characterized by X-ray diffraction, scanning electron microscopy, nitrogen adsorption, temperature-pr...Flower-like CuO and flower-like CuO/graphene composite were prepared successfully by hydrothermal method. They were characterized by X-ray diffraction, scanning electron microscopy, nitrogen adsorption, temperature-programmed reduction, and thermogravimetric analysis. It is found that the flower-like CuO microspheres, which are composed of CuO nanosheets, possess an average diameter of 4.2 μm and a Brunauer–Emmett–Teller surface area of 12.6 m2/g. Compared with the flower-like CuO, the obtained flower-like CuO/graphene composite shows an enhanced electrochemical performance with a higher capacity of 603 mA-h/g at 0.1 C rate and 382 mA-h/g at 1 C rate, and exhibits a better cycle stability with a high capacity retention of 95.5 % after 50 cycles even though at 1 C rate.展开更多
Co-P （4.9% P） powders with a chain-like morphology were prepared by a novel chemical reduction method. The Co-P and germanium powders were mixed at various mass ratios to form Co-P composite electrodes. Charge and d...Co-P （4.9% P） powders with a chain-like morphology were prepared by a novel chemical reduction method. The Co-P and germanium powders were mixed at various mass ratios to form Co-P composite electrodes. Charge and discharge test and electrochemical impedance spectroscopy （EIS） were carried out to investigate the electrochemical performance, which can be significantly improved by the addition of germanium. For instance, when the mass ratio of Co-P powders to germanium is 5：1, the sample electrode shows a reversible discharge capacity of 350.3 mA·h/g and a high capacity retention rate of 95.9% after 50 cycles. The results of cyclic voltammmetry （CV） show the reaction mechanism of Co/Co（OH）2 within Co-P composite electrodes and EIS indicates that this electrode shows a low charge-transfer resistance, facilitating the oxidation of Co to Co（OH）2.展开更多
A facile way was used to synthesize Cu2O/reduced graphene oxide （rGO） composites with octahedron-like morphology in aqueous solution without any surfactant. TEM images of the obtained Cu2O/rGOs reveal that the Cu2O ...A facile way was used to synthesize Cu2O/reduced graphene oxide （rGO） composites with octahedron-like morphology in aqueous solution without any surfactant. TEM images of the obtained Cu2O/rGOs reveal that the Cu2O particles and rGO distribute hierarchically and the primary Cu2O particles are encapsulated well in the graphene nanosheets. The electrochemical performance of Cu2O/rGOs is enhanced compared with bare Cu2O when they are employed as anode materials for lithium ion batteries. The Cu2O/rGO composites maintain a reversible capacity of 348.4 mA？h/g after 50 cycles at a current density of 100 mA/g. In addition, the composites retain 305.8 mA？h/g after 60 cycles at various current densities of 50, 100, 200, 400 and 800 mA/g.展开更多
Based on the hexagonal crystallite model of graphite,the electrochemical characteristics of carbon atoms on the edge and basal plane were proposed by analyzing graphite crystal structure and bonds of carbon atoms in d...Based on the hexagonal crystallite model of graphite,the electrochemical characteristics of carbon atoms on the edge and basal plane were proposed by analyzing graphite crystal structure and bonds of carbon atoms in different sites.A spherical close-packed model for graphite particle was developed.The fractions of surface carbon atoms（SCA） and edge carbon atoms（ECA） were derived in the expression of crystallographic parameters and particle size,and the effects of ECA on the initial irreversible capacity and the mechanisms of action were analyzed and verified.The results show that the atoms on the edge are more active for electrochemical reactions,such as electrolyte decomposition and tendency to form stable bond with other atoms and groups.For the practical graphite particle,corresponding modifying factors were introduced to revise the difference in calculating results.The revised expression is suitable for the calculation of the fractions of SCA and ECA for carbon materials such as graphite,disordered carbon and modified graphite.展开更多
A facile ultrasonic method was used to synthesize CoO/graphene nanohybrids by employing Co4（CO）12 as a cobalt precursor. The nanohybrids were characterized by SEM, TEM and XPS, and the results show that CoO nanopart...A facile ultrasonic method was used to synthesize CoO/graphene nanohybrids by employing Co4（CO）12 as a cobalt precursor. The nanohybrids were characterized by SEM, TEM and XPS, and the results show that CoO nanoparticles （3-5 nm） distribute uniformly on the surface of graphene. The CoO/graphene nanohybrids display high performance as an anode material for lithium-ion battery, such as high reversible lithium storage capacity （650 mA-h/g after 50 cycles, almost twice that of commercial graphite anode）, high coulombic efficiency （over 95%） and excellent cycling stability. The extraordinary performance arises from the structure of the nanohybrids： the nanosized CoO particles with high dispersity on conductive graphene substrates are beneficial for lithium-ion insertion/extraction, shortening diffusion length for lithium ions and improving conductivity, thus the lithium storage performance was improved.展开更多
TiO2 nanotube arrays （TNTs） electrode loaded with Zn nanoparticles was prepared by anodization and the size of Zn nanoparticle loaded on TNTs electrode was controlled by chronoamperometry deposition time. Results of...TiO2 nanotube arrays （TNTs） electrode loaded with Zn nanoparticles was prepared by anodization and the size of Zn nanoparticle loaded on TNTs electrode was controlled by chronoamperometry deposition time. Results of SEM and XRD analysis show that Zn nanoparticles had a diameter of about 15-25 nm when the deposition time was 3-5 s. The UV-Vis diffuse reflectance spectra show the Zn loaded harvest light with 480-780 nm more effectively than the unloaded sample. The photocurrent response of Zn loaded TNTs electrodes were studied, the results showed that TNTs electrodes loaded with Zn nanoparti-cles has 50% increased photocurrent response under high-pressure mercury lamp irradiation compared with unloaded TNTs electrode.展开更多
Featuring an assembly of identical pores, through-pore anodic alumina （AAO） makes an ideal monolith-like cat- alyst support for volatile organic compound （VOC） combustion. This work employs the oxidation of toluen...Featuring an assembly of identical pores, through-pore anodic alumina （AAO） makes an ideal monolith-like cat- alyst support for volatile organic compound （VOC） combustion. This work employs the oxidation of toluene as a model reaction to investigate the applicability of AAO supported Pt catalysts in VOC catalytic combustion. In order to modify the microstructure of AAO, some AAO samples were exposed to hot water treatment （HWT） firstly. Re- sults show that the optimum HWT time is 18 h. Pt/HWT18 gives a toluene conversion of95%; at 200 ℃, which is comparable to the initial activity of commercial γ-A1203 particle supported Pt catalyst. Considering its confine- ment effect for the supported metal and its monolith-like compact unit, AAO support offers potential applications in VOC catalytic combustion.展开更多
To improve rate and cycling performance of manganese oxide anode material,a precipitation method was combined with thermal annealing to prepare the Mn O/Mn3O4/Se Ox(x=0,2)hybrid anode by controlling the reaction tempe...To improve rate and cycling performance of manganese oxide anode material,a precipitation method was combined with thermal annealing to prepare the Mn O/Mn3O4/Se Ox(x=0,2)hybrid anode by controlling the reaction temperature of Mn2O3 and Se powders.At 3 A/g,the synthesized Mn O/Mn3O4/Se Ox anode delivers a discharge capacity of 1007 m A·h/g after 560 cycles.A cyclic voltammetry quantitative analysis reveals that 89.5%pseudocapacitive contribution is gained at a scanning rate of 2.0 m V/s,and the test results show that there is a significant synergistic effect between Mn O and Mn3O4 phases.展开更多
We report a γ-ray irradiation reduction method to prepare MnO/reduced graphene oxide （rCO） nanocomposite for the anode of lithium ion batteries. γ-Ray irradiation provides a clean way to generate homogeneously dis...We report a γ-ray irradiation reduction method to prepare MnO/reduced graphene oxide （rCO） nanocomposite for the anode of lithium ion batteries. γ-Ray irradiation provides a clean way to generate homogeneously dispersed MnO nanoparticles with finely tuned size on rGO surface without the use of surfactant. The MnO/rGO composite enables a fully charge/discharge in 2 min to gain a reversible specific capacity of 546 （mA-h）/g which is 45 higher than the theoretical value of commercial graphite anode.展开更多
文摘Photocatalytic hydrogen(H_(2))evolution using covalent organic frameworks(COFs)is an attractive and promising avenue for exploration,but one of its big challenges is low photo-induced charge separation.In this study,we present a straightforward and facile dipole polarization engineering strategy to enhance charge separation efficiency,achieved through atomic modulation(O,S,and Se)of the COF monomer.Our findings demonstrate that incorporating atoms with varying electronegativities into the COF matrix significantly influences the local dipole moment,thereby affecting charge separation efficiency and photostability,which in turn affects the rates of photocatalytic H_(2) evolution.As a result,the newly developed TMT-BO-COF,which contains highly electronegative O atoms,exhibits the lowest exciton binding energy,the highest efficiency in charge separation and transportation,and the longest lifetime of the active charges.This leads to an impressive average H_(2) production rate of 23.7 mmol g^(−1) h^(−1),which is 2.5 and 24.5 times higher than that of TMT-BS-COF(containing S atoms)and TMT-BSe-COF(containing Se atoms),respectively.A novel photocatalytic hydrogen evolution mechanism based on proton-coupled electron transfer on N in the structure of triazine rings in vinylene-linked COFs is proposed by theoretical calculations.Our findings provide new insights into the design of highly photoactive organic framework materials for H_(2) evolution and beyond.
文摘A 3D nitrogen⁃doped graphene/multi⁃walled carbon nanotube(CS⁃GO⁃NCNT)crosslinked network mate⁃rial was successfully synthesized utilizing chitosan and melamine as carbon and nitrogen sources,concomitant with the incorporation of multi⁃wall carbon nanotubes and employing freeze drying technology.The material amalgamates the merits of 1D/2D hybrid carbon materials,wherein 1D carbon nanotubes confer robustness and expedited elec⁃tron transport pathways,while 2D graphene sheets facilitate rapid ion migration.Furthermore,the introduction of nitrogen heteroatoms serves to furnish additional active sites for lithium storage.When served as an anode material for lithium⁃ion batteries,the CS⁃GO⁃NCNT electrode delivered a reversible capacity surpassing 500 mAh·g^(-1),mark⁃edly outperforming commercial graphite anodes.Even after 300 cycles at a high current density of 1 A·g^(-1),it remained a reversible capacity of up to 268 mAh·g^(-1).
文摘Lithium-ion batteries(LIBs)are used in electric vehicles and portable smart devices,but lithium resources are dwindling and there is an increasing demand which has to be catered for.Sodium ion batteries(SIBs),which are less costly,are a promising replacement for LIBs because of the abundant natural reserves of sodium.The anode of a SIB is a necessary component of the battery but is less understood than the cathode.This review outlines the development of various types of anodes,including carbonbased,metallic and organic,which operate using different reaction mechanisms such as intercalation,alloying and conversion,and considers their challenges and prospects.Strategies for modifying their structures by doping and coating,and also modifying the solid electrolyte interface are discussed.In addition,this review also discusses the challenges encountered by the anode of SIBs and the solutions.
基金Project (20110490594) supported by China Postdoctoral Science Foundation
文摘Flower-like CuO and flower-like CuO/graphene composite were prepared successfully by hydrothermal method. They were characterized by X-ray diffraction, scanning electron microscopy, nitrogen adsorption, temperature-programmed reduction, and thermogravimetric analysis. It is found that the flower-like CuO microspheres, which are composed of CuO nanosheets, possess an average diameter of 4.2 μm and a Brunauer–Emmett–Teller surface area of 12.6 m2/g. Compared with the flower-like CuO, the obtained flower-like CuO/graphene composite shows an enhanced electrochemical performance with a higher capacity of 603 mA-h/g at 0.1 C rate and 382 mA-h/g at 1 C rate, and exhibits a better cycle stability with a high capacity retention of 95.5 % after 50 cycles even though at 1 C rate.
基金Project supported by the Priority Academic Program Development of Jiangsu Higher Education Institutions of ChinaProject(CXLX11_0359)supported by Research Innovative Projects for Average College Graduate Students of 2011 in Jiangsu Province,China+2 种基金Project(RERU2011010)supported by Open Subject of State Key Laboratory of Rare Earth Resource Utilization,ChinaProject(51201089)supported by the National Natural Science Foundation of ChinaProject(CPSF2012M521064)supported by China Postdoctoral Science Foundation
文摘Co-P （4.9% P） powders with a chain-like morphology were prepared by a novel chemical reduction method. The Co-P and germanium powders were mixed at various mass ratios to form Co-P composite electrodes. Charge and discharge test and electrochemical impedance spectroscopy （EIS） were carried out to investigate the electrochemical performance, which can be significantly improved by the addition of germanium. For instance, when the mass ratio of Co-P powders to germanium is 5：1, the sample electrode shows a reversible discharge capacity of 350.3 mA·h/g and a high capacity retention rate of 95.9% after 50 cycles. The results of cyclic voltammmetry （CV） show the reaction mechanism of Co/Co（OH）2 within Co-P composite electrodes and EIS indicates that this electrode shows a low charge-transfer resistance, facilitating the oxidation of Co to Co（OH）2.
基金Project (2014CB643406) supported by the National Basic Research Program of ChinaProject (2011FJ1005) supported by Major Special Project of Science and Technology of Hunan Province,China
文摘A facile way was used to synthesize Cu2O/reduced graphene oxide （rGO） composites with octahedron-like morphology in aqueous solution without any surfactant. TEM images of the obtained Cu2O/rGOs reveal that the Cu2O particles and rGO distribute hierarchically and the primary Cu2O particles are encapsulated well in the graphene nanosheets. The electrochemical performance of Cu2O/rGOs is enhanced compared with bare Cu2O when they are employed as anode materials for lithium ion batteries. The Cu2O/rGO composites maintain a reversible capacity of 348.4 mA？h/g after 50 cycles at a current density of 100 mA/g. In addition, the composites retain 305.8 mA？h/g after 60 cycles at various current densities of 50, 100, 200, 400 and 800 mA/g.
基金Project (09001232) supported by the Doctoral Foundation of Henan University of Science and Technology,China
文摘Based on the hexagonal crystallite model of graphite,the electrochemical characteristics of carbon atoms on the edge and basal plane were proposed by analyzing graphite crystal structure and bonds of carbon atoms in different sites.A spherical close-packed model for graphite particle was developed.The fractions of surface carbon atoms（SCA） and edge carbon atoms（ECA） were derived in the expression of crystallographic parameters and particle size,and the effects of ECA on the initial irreversible capacity and the mechanisms of action were analyzed and verified.The results show that the atoms on the edge are more active for electrochemical reactions,such as electrolyte decomposition and tendency to form stable bond with other atoms and groups.For the practical graphite particle,corresponding modifying factors were introduced to revise the difference in calculating results.The revised expression is suitable for the calculation of the fractions of SCA and ECA for carbon materials such as graphite,disordered carbon and modified graphite.
基金Project (4340142501) supported by Start-up Funds of Chair Professor, Tongji University, ChinaProject (51173135) supported by the National Natural Science Foundation of China
文摘A facile ultrasonic method was used to synthesize CoO/graphene nanohybrids by employing Co4（CO）12 as a cobalt precursor. The nanohybrids were characterized by SEM, TEM and XPS, and the results show that CoO nanoparticles （3-5 nm） distribute uniformly on the surface of graphene. The CoO/graphene nanohybrids display high performance as an anode material for lithium-ion battery, such as high reversible lithium storage capacity （650 mA-h/g after 50 cycles, almost twice that of commercial graphite anode）, high coulombic efficiency （over 95%） and excellent cycling stability. The extraordinary performance arises from the structure of the nanohybrids： the nanosized CoO particles with high dispersity on conductive graphene substrates are beneficial for lithium-ion insertion/extraction, shortening diffusion length for lithium ions and improving conductivity, thus the lithium storage performance was improved.
基金ACKNOWLEDGMENTS This work was supported by the Science Foundation of Chongqing Science and Technology Committee （No.CSTS2009BB4047）, and Innovative Talent Training Project, the Third Stage of ＂211 Project＂ of Chongqing University （No.S-09109）.
文摘TiO2 nanotube arrays （TNTs） electrode loaded with Zn nanoparticles was prepared by anodization and the size of Zn nanoparticle loaded on TNTs electrode was controlled by chronoamperometry deposition time. Results of SEM and XRD analysis show that Zn nanoparticles had a diameter of about 15-25 nm when the deposition time was 3-5 s. The UV-Vis diffuse reflectance spectra show the Zn loaded harvest light with 480-780 nm more effectively than the unloaded sample. The photocurrent response of Zn loaded TNTs electrodes were studied, the results showed that TNTs electrodes loaded with Zn nanoparti-cles has 50% increased photocurrent response under high-pressure mercury lamp irradiation compared with unloaded TNTs electrode.
基金Supported by the National Natural Science Foundation of China(21106189,21036009)the Natural Science Foundation(S2011040001767)the Foundation from the Educational Commission(LYM11004)of Guangdong Province
文摘Featuring an assembly of identical pores, through-pore anodic alumina （AAO） makes an ideal monolith-like cat- alyst support for volatile organic compound （VOC） combustion. This work employs the oxidation of toluene as a model reaction to investigate the applicability of AAO supported Pt catalysts in VOC catalytic combustion. In order to modify the microstructure of AAO, some AAO samples were exposed to hot water treatment （HWT） firstly. Re- sults show that the optimum HWT time is 18 h. Pt/HWT18 gives a toluene conversion of95%; at 200 ℃, which is comparable to the initial activity of commercial γ-A1203 particle supported Pt catalyst. Considering its confine- ment effect for the supported metal and its monolith-like compact unit, AAO support offers potential applications in VOC catalytic combustion.
基金Project(2018JJ2513)supported by the Natural Science Foundation of Hunan Province,ChinaProject(18A378)supported by the Education Bureau Research Foundation of Hunan Province,ChinaProject(2019GK4012)supported by the Emerging Strategic Industrial Science and Technology Project of Hunan Province,China。
文摘To improve rate and cycling performance of manganese oxide anode material,a precipitation method was combined with thermal annealing to prepare the Mn O/Mn3O4/Se Ox(x=0,2)hybrid anode by controlling the reaction temperature of Mn2O3 and Se powders.At 3 A/g,the synthesized Mn O/Mn3O4/Se Ox anode delivers a discharge capacity of 1007 m A·h/g after 560 cycles.A cyclic voltammetry quantitative analysis reveals that 89.5%pseudocapacitive contribution is gained at a scanning rate of 2.0 m V/s,and the test results show that there is a significant synergistic effect between Mn O and Mn3O4 phases.
基金This work was supported by the National Natural Science Foundation of China （No.21373197）, the 100 Talents Program of the Chinese Academy of Sciences, USTC Startup and the Fundamental Research Funds for the Central Universities （WK2060140018）.
文摘We report a γ-ray irradiation reduction method to prepare MnO/reduced graphene oxide （rCO） nanocomposite for the anode of lithium ion batteries. γ-Ray irradiation provides a clean way to generate homogeneously dispersed MnO nanoparticles with finely tuned size on rGO surface without the use of surfactant. The MnO/rGO composite enables a fully charge/discharge in 2 min to gain a reversible specific capacity of 546 （mA-h）/g which is 45 higher than the theoretical value of commercial graphite anode.
