Carbon materials have shown remarkable usefulness in facilitating the performance of insulating sulfur cathode for lithium–sulfur batteries owing to their excellent conductivity and porous structure. However,the anxi...Carbon materials have shown remarkable usefulness in facilitating the performance of insulating sulfur cathode for lithium–sulfur batteries owing to their excellent conductivity and porous structure. However,the anxiety is the poor affinity toward polar polysulfides due to the intrinsic nonpolar surface of carbon.Herein, we report a direct pyrolysis of the mixture urea and boric acid to synthesize B/N–codoped hierarchically porous carbon nanosheets(B–N–CSs) as efficient sulfur host for lithium–sulfur battery. The graphene–like B–N–CSs provides high specific surface area and porous structure with abundant micropores(1.1 nm) and low–range mesopores(2.3 nm), thereby constraining the sulfur active materials within the pores. More importantly, the codoped B/N elements can further enhance the polysulfide confinement through strong Li–N and B–S interaction based on the Lewis acid–base theory. These structural superiorities significantly suppress the shuttle effect by both physical confinement and chemical interaction, and promote the redox kinetics of polysulfide conversion. When evaluated as the cathode host, the S/B–N–CSs composite displays the excellent performance with a high reversible capacity up to 772 m A h g–1 at 0.5 C and a low fading rate of ^0.09% per cycle averaged upon 500 cycles. In particular, remarkable stability with a high capacity retention of 87.1% can be realized when augmenting the sulfur loading in the cathode up to 4.6 mg cm^(-2).展开更多
Pore size and distribution in carbon-based materials are regarded to be a key factor to affect the electrochemical capacitive performances of the resultant electrodes.In this study,nitrogen and oxygen codoped porous c...Pore size and distribution in carbon-based materials are regarded to be a key factor to affect the electrochemical capacitive performances of the resultant electrodes.In this study,nitrogen and oxygen codoped porous carbons(NOPCs) are fabricated based on a simple Schiff-base reaction between m-phenylenediamine and terephthalaldehyde.The NOPCs have tunable morphologies,high surface areas,abundant heteroatom doping.More importantly,the carbons show a dominant micropores of 0.5-0.8 nm,comparable to the ionic sizes of LiTFSI(Li^+0.069 nm;TFSI-0.79 nm) water-in-salt electrolyte with a high potential window of 2.2 V.Consequently,the fabricated symmetric supercapacitor gives a high energy output of 30.5 Wh/kg at 1 kW/kg,and high stability after successive 10,000 cycles with ^96.8% retention.This study provides promising potential to develop high-energy supercapacitors.展开更多
N-F-codoped TiO2 （NFTO） photocatalysts were synthesized by a simple sol-gel process with tetrabutyl titanate （Ti（OBu）4 ） as the precursor of TiO 2 and ammonium fluoride （NH4 F） as the source of N and F.The syn...N-F-codoped TiO2 （NFTO） photocatalysts were synthesized by a simple sol-gel process with tetrabutyl titanate （Ti（OBu）4 ） as the precursor of TiO 2 and ammonium fluoride （NH4 F） as the source of N and F.The synthesized photocatalysts were investigated by X- ray diffraction （XRD）,X-ray photoelectron spectroscopy （XPS）,ultraviolet-visible diffuse reflectance spectroscopy （UV-Vis DRS） and photodegradation reaction tests of 4-chlorophenol under visible light irradiation to understand the relationship between the structure of NFTO catalyst and corresponding photocatalytic activity.The crystal phase and particle size of catalysts were found to be largely affected by the calcination temperature.In addition,N-F-codoping could inhibit phase transition of TiO2 from anatase to rutile.The presence of N and F atoms in the lattice of TiO2 is responsible for the visible light catalytic activity.In UV-Vis DRS tests,the spectrum of NFTO exhibited red shift compared with Degussa P25 and the band gap was reduced to around 2.92 eV.Under optimal calcination temperature and dopant concentration conditions,the NFTO photocatalyst exhibited the highest activity in the photodegradation reaction tests of 4-chlorophenol under visible light irradiation with a degradation rate of 75.84%.Besides,the 5-recycle test showed that NFTO photocatalyst could be reused and its activity kept stable under visible light irradiation.展开更多
Currently, the oxygen reduction reaction(ORR) mainly depends on precious metal platinum(Pt) catalysts. However, Pt-based catalysts have several shortcomings, such as high cost, scarcity, and poor long-term stability. ...Currently, the oxygen reduction reaction(ORR) mainly depends on precious metal platinum(Pt) catalysts. However, Pt-based catalysts have several shortcomings, such as high cost, scarcity, and poor long-term stability. Therefore, development of e cient metal-free electrocatalysts to replace Pt-based electrocatalysts is important. In this study, we successfully prepared nitrogen-and fluorinecodoped microporous carbon nanofibers(N, F-MCFs) via electrospinning polyacrylonitrile/polyvinylidene fluoride/polyvinylpyrrolidone(PAN/PVDF/PVP) tricomponent polymers followed by a hydrothermal process and thermal treatment, which was achieved for the first time in the literature. The results indicated that N, F-MCFs exhibit a high catalytic activity(E_(onset): 0.94 V vs. RHE, E_(1/2): 0.81 V vs. RHE, and electron transfer number: 4.0) and considerably better stability and methanol tolerance for ORR in alkaline solutions as compared to commercial Pt/carbon(Pt/C, 20 wt%) catalysts. Furthermore, in acidic media, N, F-MCFs showed a four-electron transfer pathway for ORR. This study provides a new strategy for in situ synthesis of N, F-MCFs as highly e cient metal-free electrocatalysts for ORR in fuel cells.展开更多
The desire for practical utilization of rechargeable lithium batteries with high energy density has motivated attempts to develop new electrode materials and battery systems. Here, without additional binders we presen...The desire for practical utilization of rechargeable lithium batteries with high energy density has motivated attempts to develop new electrode materials and battery systems. Here, without additional binders we present a simple vacuum filtration method to synthesize nitrogen and sulfur codoped graphene(N,S-G) blocking layer, which is ultra-lightweight, conductive, and free standing. When the N,S-G membrane was inserted between the catholyte and separator, the lithium–selenium(Li–Se)batteries exhibited a high reversible discharge capacity of 330.7 mAh g^(-1) at 1 C(1 C = 675 mA g^(-1)) after 500 cycles and high rate performance(over 310 mAh g^(-1) at 4 C) even at an active material loading as high as ～5 mg cm^(-2). This excellent performance can be ascribed to homogenous dispersion of the liquid active material in the electrode, good Li^+-ion conductivity, fast electronic transport in the conductive graphene framework, andstrong chemical confinement of polyselenides by nitrogen and sulfur atoms. More importantly, it is a promising strategy for enhancing the energy density of Li–Se batteries by using the catholyte with a lightweight heteroatom doping carbon matrix.展开更多
（N, F）-codoped anatase TiO2 nanocrystals with active visible light response were prepared by using a simple sol-gel approach. X-ray photoelectron spectroscopy measurements suggested that the substitutional N and F s...（N, F）-codoped anatase TiO2 nanocrystals with active visible light response were prepared by using a simple sol-gel approach. X-ray photoelectron spectroscopy measurements suggested that the substitutional N and F species replaced the lattice oxygen atoms in TiO2 nanocrystals. Such nanocrystals showed strong absorption from 400 to 550 nm, which was mainly induced by nitrogen doping. The phase transformation from anatase to rutile was hindered by fluorine doping at high calcination temperatures, which was verified by XRD patterns. The N2 adsorption-desorption isotherms revealed the absence of mesopores in these nanocrystals. The （N, F）- codoped TiO2 nanocrystals showed satisfying photocatalytic activity on the photo-degradation of methylene blue under visible light.展开更多
A facile fabrication strategy is reported to obtain N/O codoped porous carbon nanosheets for pur-pose of ameliorating the charge transfer and accumulation in the concentrated LiTFSI(lithium bis(trifluoromethane sulfon...A facile fabrication strategy is reported to obtain N/O codoped porous carbon nanosheets for pur-pose of ameliorating the charge transfer and accumulation in the concentrated LiTFSI(lithium bis(trifluoromethane sulfonyl)imide)electrolyte.By tunning the feed ratio of comonomers,the porous nanosheet structure is endowed with a significant ion-adsorption surface area(1630 m^(2)/g)and intercon-nected hierarchical porosity;meanwhile,high-level N/O dopants(N:3.58 at%,O:12.91 at%)increase the effective contact area for electrolyte ions,and further facilitate rapid ion/electron transfer.Benefiting from the advantageous features,carbon nanosheets electrode reveal an enhanced specific capacitance(375 F/g)in three-electrode configuration and the H_(2)SO_(4)-based device yields a high gravimetric energy density of 11.4 Wh/kg.Particularly,the ion-diffusion highways in porous carbon nanosheets contribute to the 2.25 V LiTFSI-based symmetric device with a high energy delivery up to 33.1 Wh/kg.This work offers an in-spiring strategy for facile fabrication of carbon nanosheets,and demonstrates their promising application in“water-in-salt”electrolyte-based supercapacitor systems.展开更多
C,N-codoped TiO 2 films have been deposited onto stainless steel substrates using plasma surface alloying and thermal oxidation duplex process.Composition analysis shows that the films shield the substrates entirely.T...C,N-codoped TiO 2 films have been deposited onto stainless steel substrates using plasma surface alloying and thermal oxidation duplex process.Composition analysis shows that the films shield the substrates entirely.The TiO 2 films are anatase in structure as characterized by X-ray diffraction.The electrochemical measurements show that the equilibrium corrosion potential positively shifts from-0.275 eV for bare stainless steel to-0.267 eV for C,N-codoped TiO 2 coated stainless steel,and the corrosion current density decreases from 1.3×10-5 A/cm2 to 4.1×10-6 A/cm2.The corrosion resistance obtained by electrochemistry noise also reveals that the C,N-codoped TiO 2 films provide good protection for stainless steel against corrosion in stimulated body fluid.The above results indicate that C,N-codoped TiO 2 films deposited by plasma surface alloying and thermal oxidation duplex process are effective in protecting stainless steel from corrosion.展开更多
基金financial support of the National Natural Science Foundation of China (Grant No. 21263016, 21363015, 51662029, 21863006)the Youth Science Foundation of Jiangxi Province (Grant No. 20192BAB216001)the Key Laboratory of Jiangxi Province for Environment and Energy Catalysis (20181BCD40004)。
文摘Carbon materials have shown remarkable usefulness in facilitating the performance of insulating sulfur cathode for lithium–sulfur batteries owing to their excellent conductivity and porous structure. However,the anxiety is the poor affinity toward polar polysulfides due to the intrinsic nonpolar surface of carbon.Herein, we report a direct pyrolysis of the mixture urea and boric acid to synthesize B/N–codoped hierarchically porous carbon nanosheets(B–N–CSs) as efficient sulfur host for lithium–sulfur battery. The graphene–like B–N–CSs provides high specific surface area and porous structure with abundant micropores(1.1 nm) and low–range mesopores(2.3 nm), thereby constraining the sulfur active materials within the pores. More importantly, the codoped B/N elements can further enhance the polysulfide confinement through strong Li–N and B–S interaction based on the Lewis acid–base theory. These structural superiorities significantly suppress the shuttle effect by both physical confinement and chemical interaction, and promote the redox kinetics of polysulfide conversion. When evaluated as the cathode host, the S/B–N–CSs composite displays the excellent performance with a high reversible capacity up to 772 m A h g–1 at 0.5 C and a low fading rate of ^0.09% per cycle averaged upon 500 cycles. In particular, remarkable stability with a high capacity retention of 87.1% can be realized when augmenting the sulfur loading in the cathode up to 4.6 mg cm^(-2).
基金financially supported by the National Natural Science Foundation of China(Nos.21875165,51772216 and 21703161)the Science and Technology Commission of Shanghai Municipality,China(No.14DZ2261100)the Fundamental Research Funds for the Central Universities。
文摘Pore size and distribution in carbon-based materials are regarded to be a key factor to affect the electrochemical capacitive performances of the resultant electrodes.In this study,nitrogen and oxygen codoped porous carbons(NOPCs) are fabricated based on a simple Schiff-base reaction between m-phenylenediamine and terephthalaldehyde.The NOPCs have tunable morphologies,high surface areas,abundant heteroatom doping.More importantly,the carbons show a dominant micropores of 0.5-0.8 nm,comparable to the ionic sizes of LiTFSI(Li^+0.069 nm;TFSI-0.79 nm) water-in-salt electrolyte with a high potential window of 2.2 V.Consequently,the fabricated symmetric supercapacitor gives a high energy output of 30.5 Wh/kg at 1 kW/kg,and high stability after successive 10,000 cycles with ^96.8% retention.This study provides promising potential to develop high-energy supercapacitors.
基金supported by the Scienceand Technology Project of Education Commission of Chongqing of China(No.KJ110709)the Key Science Project of Ministry of Education of China(No.2008119)+1 种基金the Colleges and Universities Innovation Team Project of Chongqing of China(No.KJTD201020)the Scienceand Technology Project of Engineering Research Centre for Waste Oil,Ministry of Education of China(No.FYKJ2009012)
文摘N-F-codoped TiO2 （NFTO） photocatalysts were synthesized by a simple sol-gel process with tetrabutyl titanate （Ti（OBu）4 ） as the precursor of TiO 2 and ammonium fluoride （NH4 F） as the source of N and F.The synthesized photocatalysts were investigated by X- ray diffraction （XRD）,X-ray photoelectron spectroscopy （XPS）,ultraviolet-visible diffuse reflectance spectroscopy （UV-Vis DRS） and photodegradation reaction tests of 4-chlorophenol under visible light irradiation to understand the relationship between the structure of NFTO catalyst and corresponding photocatalytic activity.The crystal phase and particle size of catalysts were found to be largely affected by the calcination temperature.In addition,N-F-codoping could inhibit phase transition of TiO2 from anatase to rutile.The presence of N and F atoms in the lattice of TiO2 is responsible for the visible light catalytic activity.In UV-Vis DRS tests,the spectrum of NFTO exhibited red shift compared with Degussa P25 and the band gap was reduced to around 2.92 eV.Under optimal calcination temperature and dopant concentration conditions,the NFTO photocatalyst exhibited the highest activity in the photodegradation reaction tests of 4-chlorophenol under visible light irradiation with a degradation rate of 75.84%.Besides,the 5-recycle test showed that NFTO photocatalyst could be reused and its activity kept stable under visible light irradiation.
基金funding for this work provided by the National Nature Science Foundation of China (51573090)National Key R&D Program of China (2016YFB0302000)Open Foundation from State Key Laboratory of Fluorinated Functional Membrane Material
文摘Currently, the oxygen reduction reaction(ORR) mainly depends on precious metal platinum(Pt) catalysts. However, Pt-based catalysts have several shortcomings, such as high cost, scarcity, and poor long-term stability. Therefore, development of e cient metal-free electrocatalysts to replace Pt-based electrocatalysts is important. In this study, we successfully prepared nitrogen-and fluorinecodoped microporous carbon nanofibers(N, F-MCFs) via electrospinning polyacrylonitrile/polyvinylidene fluoride/polyvinylpyrrolidone(PAN/PVDF/PVP) tricomponent polymers followed by a hydrothermal process and thermal treatment, which was achieved for the first time in the literature. The results indicated that N, F-MCFs exhibit a high catalytic activity(E_(onset): 0.94 V vs. RHE, E_(1/2): 0.81 V vs. RHE, and electron transfer number: 4.0) and considerably better stability and methanol tolerance for ORR in alkaline solutions as compared to commercial Pt/carbon(Pt/C, 20 wt%) catalysts. Furthermore, in acidic media, N, F-MCFs showed a four-electron transfer pathway for ORR. This study provides a new strategy for in situ synthesis of N, F-MCFs as highly e cient metal-free electrocatalysts for ORR in fuel cells.
基金supported by the National Natural Science Foundation of China (51125001,51172005)the NSFCRGC Joint Research Scheme (51361165201)the Start-up Foundation of High-level Talents in Chongqing Technology and Business University (1856008)
文摘The desire for practical utilization of rechargeable lithium batteries with high energy density has motivated attempts to develop new electrode materials and battery systems. Here, without additional binders we present a simple vacuum filtration method to synthesize nitrogen and sulfur codoped graphene(N,S-G) blocking layer, which is ultra-lightweight, conductive, and free standing. When the N,S-G membrane was inserted between the catholyte and separator, the lithium–selenium(Li–Se)batteries exhibited a high reversible discharge capacity of 330.7 mAh g^(-1) at 1 C(1 C = 675 mA g^(-1)) after 500 cycles and high rate performance(over 310 mAh g^(-1) at 4 C) even at an active material loading as high as ～5 mg cm^(-2). This excellent performance can be ascribed to homogenous dispersion of the liquid active material in the electrode, good Li^+-ion conductivity, fast electronic transport in the conductive graphene framework, andstrong chemical confinement of polyselenides by nitrogen and sulfur atoms. More importantly, it is a promising strategy for enhancing the energy density of Li–Se batteries by using the catholyte with a lightweight heteroatom doping carbon matrix.
基金supported by the Excellent Young Teachers Program of MOEKey Project of Shanghai Science and Technology Committee (No. 06DZ05025),China
文摘（N, F）-codoped anatase TiO2 nanocrystals with active visible light response were prepared by using a simple sol-gel approach. X-ray photoelectron spectroscopy measurements suggested that the substitutional N and F species replaced the lattice oxygen atoms in TiO2 nanocrystals. Such nanocrystals showed strong absorption from 400 to 550 nm, which was mainly induced by nitrogen doping. The phase transformation from anatase to rutile was hindered by fluorine doping at high calcination temperatures, which was verified by XRD patterns. The N2 adsorption-desorption isotherms revealed the absence of mesopores in these nanocrystals. The （N, F）- codoped TiO2 nanocrystals showed satisfying photocatalytic activity on the photo-degradation of methylene blue under visible light.
基金financially supported by the National Natural Science Foundation of China (Nos. 21875165, 51772216, 22172111 and 21905207)the Science and Technology Commission of Shanghai Municipality, China (Nos. 20ZR1460300, 14DZ2261100)+2 种基金Anhui University of Science and Technology Introduced Talent Research Startup Fund (No. 13210572)Zhejiang Provincial Natural Science Foundation of China (No. LY19B010003)the Fundamental Research Funds for the Central Universities and the Large Equipment Test Foundation of Tongji University
文摘A facile fabrication strategy is reported to obtain N/O codoped porous carbon nanosheets for pur-pose of ameliorating the charge transfer and accumulation in the concentrated LiTFSI(lithium bis(trifluoromethane sulfonyl)imide)electrolyte.By tunning the feed ratio of comonomers,the porous nanosheet structure is endowed with a significant ion-adsorption surface area(1630 m^(2)/g)and intercon-nected hierarchical porosity;meanwhile,high-level N/O dopants(N:3.58 at%,O:12.91 at%)increase the effective contact area for electrolyte ions,and further facilitate rapid ion/electron transfer.Benefiting from the advantageous features,carbon nanosheets electrode reveal an enhanced specific capacitance(375 F/g)in three-electrode configuration and the H_(2)SO_(4)-based device yields a high gravimetric energy density of 11.4 Wh/kg.Particularly,the ion-diffusion highways in porous carbon nanosheets contribute to the 2.25 V LiTFSI-based symmetric device with a high energy delivery up to 33.1 Wh/kg.This work offers an in-spiring strategy for facile fabrication of carbon nanosheets,and demonstrates their promising application in“water-in-salt”electrolyte-based supercapacitor systems.
基金Funded by the National Natural Science Foundation of China (No.50771070)Project Innovation of the Graduate Students of Shanxi Province(No.20093038)
文摘C,N-codoped TiO 2 films have been deposited onto stainless steel substrates using plasma surface alloying and thermal oxidation duplex process.Composition analysis shows that the films shield the substrates entirely.The TiO 2 films are anatase in structure as characterized by X-ray diffraction.The electrochemical measurements show that the equilibrium corrosion potential positively shifts from-0.275 eV for bare stainless steel to-0.267 eV for C,N-codoped TiO 2 coated stainless steel,and the corrosion current density decreases from 1.3×10-5 A/cm2 to 4.1×10-6 A/cm2.The corrosion resistance obtained by electrochemistry noise also reveals that the C,N-codoped TiO 2 films provide good protection for stainless steel against corrosion in stimulated body fluid.The above results indicate that C,N-codoped TiO 2 films deposited by plasma surface alloying and thermal oxidation duplex process are effective in protecting stainless steel from corrosion.
