In this work,p⁃phenylenediamine and L⁃cysteine were used as raw materials,and water⁃soluble N,S co⁃doped carbon dots(N,S⁃CDs)with excellent performance were prepared through a one⁃step solvothermal method.The morpholo...In this work,p⁃phenylenediamine and L⁃cysteine were used as raw materials,and water⁃soluble N,S co⁃doped carbon dots(N,S⁃CDs)with excellent performance were prepared through a one⁃step solvothermal method.The morphology and structure of N,S⁃CDs were characterized by transmission electron microscope,X⁃ray diffrac⁃tion,Fourier transform infrared spectroscopy,and X⁃ray photoelectron spectroscopy,and the basic photophysical properties were investigated via UV⁃Vis absorption spectra and fluorescence spectra.Meanwhile,the N,S⁃CDs have excellent luminescence stability with pH,ionic strength,radiation time,and storage time.Experimental results illus⁃trated the present sensor platform exhibited high sensitivity and selectivity in response to baicalein with a detection limit of 85 nmol·L-1.The quenching mechanism is proved to be the inner filter effect.In addition,this sensor can also detect baicalein in biofluids(serum and urine)with good accuracy and reproducibility.展开更多
The development of an efficient artificial H_(2)O_(2) photosynthesis system is a challenging work using H_(2)O and O_(2) as starting materials.Herein,3D In_(2.77)S_(4) nanoflower precursor was in-situ deposited on K^(...The development of an efficient artificial H_(2)O_(2) photosynthesis system is a challenging work using H_(2)O and O_(2) as starting materials.Herein,3D In_(2.77)S_(4) nanoflower precursor was in-situ deposited on K^(+)-doped g-C_(3)N_(4)(KCN)nanosheets using a solvothermal method,then In_(2.77)S_(4)/KCN(IS/KCN)het-erojunction with an intimate interface was obtained after a calcination process.The investigation shows that the photocatalytic H_(2)O_(2) production rate of 50IS/KCN can reach up to 1.36 mmol g^(-1)h^(-1)without any sacrificial reagents under visible light irradiation,which is 9.2 times and 4.1 times higher than that of KCN and In_(2.77)S_(4)/respectively.The enhanced activity of the above composite can be mainly attributed to the S-scheme charge transfer route between KCN and In_(2.77)S_(4) according to density functional theory calculations,electron paramagnetic resonance and free radical capture tests,leading to an expanded light response range and rapid charge separation at their interface,as well as preserving the active electrons and holes for H_(2)O_(2) production.Besides,the unique 3D nanostructure and surface hydrophobicity of IS/KCN facilitate the diffusion and transportation of O_(2) around the active centers,the energy barriers of O_(2) protonation and H_(2)O_(2) desorption steps are ef-fectively reduced over the composite.In addition,this system also exhibits excellent light harvesting ability and stability.This work provides a potential strategy to explore a sustainable H_(2)O_(2) photo-synthesis pathway through the design of heterojunctions with intimate interfaces and desired reac-tion thermodynamics and kinetics.展开更多
Shuttle effect,poor conductivity and large volume expansion are the main factors that hinder the practical application of sulfur cathodes.Currently,rational structure designing of carbon-based sulfur hosts is the most...Shuttle effect,poor conductivity and large volume expansion are the main factors that hinder the practical application of sulfur cathodes.Currently,rational structure designing of carbon-based sulfur hosts is the most effective strategy to address the above issues.However,the preparation process of carbon-based sulfur hosts is usually complex and costly.Therefore,it is necessary to develop an efficient and cost-effective method to fabricate carbon hosts for high-performance sulfur cathodes.Herein,we reported the fabrication of a bio-derived nitrogen doped porous carbon materials(BNPC)via a molten-salt method for high performance sulfur cathodes.The long-range-ordered honeycomb structure of BNPC is favorable for the trapping of polysulfide(PS)species and accommodates the volumetric variation of sulfur during cycling,while the high graphitization degree of BNPC favors the redox kinetics of sulfur cathodes.Moreover,the nitrogen doping content not only enhances the electrical conductivity of BNPC,but also provides ample anchoring sites for the immobilization of PS,which plays a key role in suppressing the shuttle effect.As a result,the S@BNPC cathode exhibits a high initial specific capacity of 1189.4 mA·h/g at 0.2C.After 300 cycles,S@BNPC still maintains a capacity of 703.2 mA·h/g which corresponds to a fading rate of 0.13%per cycle after the second cycle.This work offers vast opportunities for the large-scale application of high performance carbon-based sulfur hosts.展开更多
Proton exchange membrane fuel cells suffer from the sluggish kinetics of the oxygen reduction reaction(ORR)and the high cost of Pt catalysts.In the present work,a high‐performance ORR catalystbased on Fe,N,S‐doped p...Proton exchange membrane fuel cells suffer from the sluggish kinetics of the oxygen reduction reaction(ORR)and the high cost of Pt catalysts.In the present work,a high‐performance ORR catalystbased on Fe,N,S‐doped porous carbon(FeNS‐PC)was synthesized using melamine formaldehyderesin as C and N precursors,Fe(SCN)3as Fe and S precursors,and CaCl2as a template via a two‐stepheat treatment without a harsh template removal step.The results show that the catalyst treated at900℃(FeNS‐PC‐900)had a high surface area of775m2/g,a high mass activity of10.2A/g in anacidic medium,and excellent durability;the half‐wave potential decreased by only20mV after10000potential cycles.The FeNS‐PC‐900catalyst was used as the cathode in a proton exchangemembrane fuel cell and delivered a peak power density of0.49W/cm2.FeNS‐PC‐900therefore hasgood potential for use in practical applications.展开更多
Ultrathin small MoS2nanosheets exhibit a higher electrocatalytic activity for the hydrogen evolution reaction.However,strong interactions between MoS2layers may result in aggregation;together with the low conductivity...Ultrathin small MoS2nanosheets exhibit a higher electrocatalytic activity for the hydrogen evolution reaction.However,strong interactions between MoS2layers may result in aggregation;together with the low conductivity of MoS2,this may lower its electrocatalytic activity.In this paper we present a method that we developed to directly produce solid S,N co‐doped carbon(SNC)with a graphite structure and multiple surface groups through a hydrothermal route.When Na2MoO4was added to the reaction,polymolybdate could be anchored into the carbon materials via a chemical interaction that helps polymolybdate disperse uniformly into the SNC.After a high temperature treatment,polymolybdate transformed into MoS2at800°C for6h in a N2atmosphere at a heating rate of5°C/min,owing to S2?being released from the SNC during the treatment(denoted as MoS2/SNC‐800‐6h).The SNC effectively prevents MoS2from aggregating into large particles,and we successfully prepared highly dispersed MoS2in the SNC matrix.Electrochemical characterizations indicate that MoS2/SNC‐900‐12h exhibits a low onset potential of115mV and a low overpotential of237mV at a current density of10mA/cm2.Furthermore,MoS2/SNC‐900‐12h also had an excellent stability with only^2.6%decay at a current density of10mA/cm2after5000test cycles.展开更多
Metal doping for active sites exhibits remarkable potential for improving the hydrogen evolution reaction(HER).Multi-doping and the use of a conductive substrate can further modulate catalytic performance.Herein,Nb-Co...Metal doping for active sites exhibits remarkable potential for improving the hydrogen evolution reaction(HER).Multi-doping and the use of a conductive substrate can further modulate catalytic performance.Herein,Nb-CoSe well dispersed in N-doped carbon nanospheres(NCs,Nb-CoSe@NC)was synthesized to serve as a conductive substrate and facilitated good dispersion of active sites for the HER.Nb doping can also change the electronic structure of CoSe,which facilitates the activity for the HER.In order to further improve the conductivity and intrinsic activity of Nb-CoSe@NC,dual,nonmetal doping was realized through gas sulfurization to prepare hierarchical Nb-CoSeS@NC.The prepared Nb-CoSeS@NC,with a core-shell structure,exhibited a low overpotential of 115 mV at 10 mA cm–2,which is smaller than that of the most doped catalysts.In addition,NCs not only improved the dispersion and conductivity of the catalyst but also prevented metal corrosion in an electrolyte,thus facilitating the long-term stability of Nb-CoSeS@NC.Moreover,the synergistic effect of the multi-doping of Nb,S,and Se was explained.This work provides a promising,multi-doping strategy for the large-scale application of transition-metal-based electrocatalysts for the HER.展开更多
Reversible oxygen reaction plays a crucial role in rechargeable battery systems,but it is limited by the slow reaction kinetics.Herein,the ionic modulation of cobalt pentlandite coupled with nitrogen‐doped bowl‐like...Reversible oxygen reaction plays a crucial role in rechargeable battery systems,but it is limited by the slow reaction kinetics.Herein,the ionic modulation of cobalt pentlandite coupled with nitrogen‐doped bowl‐like hollow carbon sphere is well designed on octahedral and tetrahedral sites.The robust FexCo9−xS8‐NHCS‐V with iron replacing at the octahedron possesses prolonged metal sulfur bond and exhibits excellent bifunctional electrocatalytic performance towards oxygen reduction reaction(ORR,E_(1/2)=0.80 V vs.RHE)and excellent oxygen evolution reaction(OER,E_(j=10)=1.53 V vs.RHE)in 0.1 mol/L KOH.Accordingly,a rechargeable Zn‐air battery of Fe_(x)Co_(9−x)S_(8)‐NHCS‐V cathode endows high energy efficiency(102 mW cm^(−2)),and a microbial fuel cell achieves a high‐power density(791±42 mW m^(−2)),outperforming the benchmark Pt/C catalyst.展开更多
The N,S co-doped porous carbon nanofibers were fabricated by the carbonization of[Zn_(2)(tdc)_(2)(MA)]n MOFs/polyacrylonitrile nanofibers composite,which was produced by the electrospinning technology.The electrochemi...The N,S co-doped porous carbon nanofibers were fabricated by the carbonization of[Zn_(2)(tdc)_(2)(MA)]n MOFs/polyacrylonitrile nanofibers composite,which was produced by the electrospinning technology.The electrochemical results show that the N,S co-doped porous carbon nanofibers can achieve capacity of 201.2 mAh·g^(-1)at the current density of 0.05 A·g^(-1).Furthermore,the reversible capacity still has 161.3 mAh·g^(-1)even at a high current density of 1 A·g^(-1)after 600 cycles.The superior electrochemical performance shows that the N,S co-doped porous carbon nanofibers electrode material can be used as an ideal anode material for sodium-ion batteries.展开更多
Heteroatom doping, especially dual-doped carbon materials have attracted much attention for the past few years, and have been regarded as one of the most efficient strategies to enhance the capacitance behavior of por...Heteroatom doping, especially dual-doped carbon materials have attracted much attention for the past few years, and have been regarded as one of the most efficient strategies to enhance the capacitance behavior of porous carbon materials. In this work, a facile two-step synthetic route was developed to fab- ricate nitrogen and sulfur co-doped carbon microsphere （NSCM） by using thiourea as dopant. The NJS doping content is controlled via varying the carbonization temperature. It has been proved that a suitable quantity of N and S groups could not only provide pseudo-capacitance but also promote the electron transfer for carbon materials, which ensures the further utilization of the exposed surfaces for charge storage. The optimized NSCM prepared at a carbonization temperature of 800 ℃ （NSCM-800） achieves a capacitance of 277.1 F g^-1 at a current density of 0.3 A g^-1 in 6.0 mol L^-1 KOH electrolyte, which is 71% higher than that of undoped carbon microsphere. Besides, NSCM-800 shows an excellent cycling stability, 98.2% of the initial capacitance is retained after 5,000 cvcles at a current densitv of 3.0 A g^-1.展开更多
基金supported by the National Nature Science Foundation of China(51474255)the Hunan Provincial Science and Technology Plan Project,China(2016TP1007)the Open Research Fund Program of Key Laboratory of Metallogenic Prediction of Nonferrous Metals and Geological Environment Monitoring,China(Central South University),Ministry of Education,the Fundamental Research Funds for the Central Universities of Central South University,China~~
文摘In this work,p⁃phenylenediamine and L⁃cysteine were used as raw materials,and water⁃soluble N,S co⁃doped carbon dots(N,S⁃CDs)with excellent performance were prepared through a one⁃step solvothermal method.The morphology and structure of N,S⁃CDs were characterized by transmission electron microscope,X⁃ray diffrac⁃tion,Fourier transform infrared spectroscopy,and X⁃ray photoelectron spectroscopy,and the basic photophysical properties were investigated via UV⁃Vis absorption spectra and fluorescence spectra.Meanwhile,the N,S⁃CDs have excellent luminescence stability with pH,ionic strength,radiation time,and storage time.Experimental results illus⁃trated the present sensor platform exhibited high sensitivity and selectivity in response to baicalein with a detection limit of 85 nmol·L-1.The quenching mechanism is proved to be the inner filter effect.In addition,this sensor can also detect baicalein in biofluids(serum and urine)with good accuracy and reproducibility.
文摘The development of an efficient artificial H_(2)O_(2) photosynthesis system is a challenging work using H_(2)O and O_(2) as starting materials.Herein,3D In_(2.77)S_(4) nanoflower precursor was in-situ deposited on K^(+)-doped g-C_(3)N_(4)(KCN)nanosheets using a solvothermal method,then In_(2.77)S_(4)/KCN(IS/KCN)het-erojunction with an intimate interface was obtained after a calcination process.The investigation shows that the photocatalytic H_(2)O_(2) production rate of 50IS/KCN can reach up to 1.36 mmol g^(-1)h^(-1)without any sacrificial reagents under visible light irradiation,which is 9.2 times and 4.1 times higher than that of KCN and In_(2.77)S_(4)/respectively.The enhanced activity of the above composite can be mainly attributed to the S-scheme charge transfer route between KCN and In_(2.77)S_(4) according to density functional theory calculations,electron paramagnetic resonance and free radical capture tests,leading to an expanded light response range and rapid charge separation at their interface,as well as preserving the active electrons and holes for H_(2)O_(2) production.Besides,the unique 3D nanostructure and surface hydrophobicity of IS/KCN facilitate the diffusion and transportation of O_(2) around the active centers,the energy barriers of O_(2) protonation and H_(2)O_(2) desorption steps are ef-fectively reduced over the composite.In addition,this system also exhibits excellent light harvesting ability and stability.This work provides a potential strategy to explore a sustainable H_(2)O_(2) photo-synthesis pathway through the design of heterojunctions with intimate interfaces and desired reac-tion thermodynamics and kinetics.
基金Project(2018YFB0104300)supported by the National Key R&D Program of ChinaProject(51774150)supported by the National Natural Science Foundation of China
文摘Shuttle effect,poor conductivity and large volume expansion are the main factors that hinder the practical application of sulfur cathodes.Currently,rational structure designing of carbon-based sulfur hosts is the most effective strategy to address the above issues.However,the preparation process of carbon-based sulfur hosts is usually complex and costly.Therefore,it is necessary to develop an efficient and cost-effective method to fabricate carbon hosts for high-performance sulfur cathodes.Herein,we reported the fabrication of a bio-derived nitrogen doped porous carbon materials(BNPC)via a molten-salt method for high performance sulfur cathodes.The long-range-ordered honeycomb structure of BNPC is favorable for the trapping of polysulfide(PS)species and accommodates the volumetric variation of sulfur during cycling,while the high graphitization degree of BNPC favors the redox kinetics of sulfur cathodes.Moreover,the nitrogen doping content not only enhances the electrical conductivity of BNPC,but also provides ample anchoring sites for the immobilization of PS,which plays a key role in suppressing the shuttle effect.As a result,the S@BNPC cathode exhibits a high initial specific capacity of 1189.4 mA·h/g at 0.2C.After 300 cycles,S@BNPC still maintains a capacity of 703.2 mA·h/g which corresponds to a fading rate of 0.13%per cycle after the second cycle.This work offers vast opportunities for the large-scale application of high performance carbon-based sulfur hosts.
基金supported by the National Basic Research Program of China (973 Program,2015CB932303)the National Natural Science Founda-tion of China (21373175,21621091)~~
文摘Proton exchange membrane fuel cells suffer from the sluggish kinetics of the oxygen reduction reaction(ORR)and the high cost of Pt catalysts.In the present work,a high‐performance ORR catalystbased on Fe,N,S‐doped porous carbon(FeNS‐PC)was synthesized using melamine formaldehyderesin as C and N precursors,Fe(SCN)3as Fe and S precursors,and CaCl2as a template via a two‐stepheat treatment without a harsh template removal step.The results show that the catalyst treated at900℃(FeNS‐PC‐900)had a high surface area of775m2/g,a high mass activity of10.2A/g in anacidic medium,and excellent durability;the half‐wave potential decreased by only20mV after10000potential cycles.The FeNS‐PC‐900catalyst was used as the cathode in a proton exchangemembrane fuel cell and delivered a peak power density of0.49W/cm2.FeNS‐PC‐900therefore hasgood potential for use in practical applications.
基金supported by the National Natural Science Foundation of China(21671011)Beijing High-Level Talent program~~
文摘Ultrathin small MoS2nanosheets exhibit a higher electrocatalytic activity for the hydrogen evolution reaction.However,strong interactions between MoS2layers may result in aggregation;together with the low conductivity of MoS2,this may lower its electrocatalytic activity.In this paper we present a method that we developed to directly produce solid S,N co‐doped carbon(SNC)with a graphite structure and multiple surface groups through a hydrothermal route.When Na2MoO4was added to the reaction,polymolybdate could be anchored into the carbon materials via a chemical interaction that helps polymolybdate disperse uniformly into the SNC.After a high temperature treatment,polymolybdate transformed into MoS2at800°C for6h in a N2atmosphere at a heating rate of5°C/min,owing to S2?being released from the SNC during the treatment(denoted as MoS2/SNC‐800‐6h).The SNC effectively prevents MoS2from aggregating into large particles,and we successfully prepared highly dispersed MoS2in the SNC matrix.Electrochemical characterizations indicate that MoS2/SNC‐900‐12h exhibits a low onset potential of115mV and a low overpotential of237mV at a current density of10mA/cm2.Furthermore,MoS2/SNC‐900‐12h also had an excellent stability with only^2.6%decay at a current density of10mA/cm2after5000test cycles.
文摘Metal doping for active sites exhibits remarkable potential for improving the hydrogen evolution reaction(HER).Multi-doping and the use of a conductive substrate can further modulate catalytic performance.Herein,Nb-CoSe well dispersed in N-doped carbon nanospheres(NCs,Nb-CoSe@NC)was synthesized to serve as a conductive substrate and facilitated good dispersion of active sites for the HER.Nb doping can also change the electronic structure of CoSe,which facilitates the activity for the HER.In order to further improve the conductivity and intrinsic activity of Nb-CoSe@NC,dual,nonmetal doping was realized through gas sulfurization to prepare hierarchical Nb-CoSeS@NC.The prepared Nb-CoSeS@NC,with a core-shell structure,exhibited a low overpotential of 115 mV at 10 mA cm–2,which is smaller than that of the most doped catalysts.In addition,NCs not only improved the dispersion and conductivity of the catalyst but also prevented metal corrosion in an electrolyte,thus facilitating the long-term stability of Nb-CoSeS@NC.Moreover,the synergistic effect of the multi-doping of Nb,S,and Se was explained.This work provides a promising,multi-doping strategy for the large-scale application of transition-metal-based electrocatalysts for the HER.
文摘Reversible oxygen reaction plays a crucial role in rechargeable battery systems,but it is limited by the slow reaction kinetics.Herein,the ionic modulation of cobalt pentlandite coupled with nitrogen‐doped bowl‐like hollow carbon sphere is well designed on octahedral and tetrahedral sites.The robust FexCo9−xS8‐NHCS‐V with iron replacing at the octahedron possesses prolonged metal sulfur bond and exhibits excellent bifunctional electrocatalytic performance towards oxygen reduction reaction(ORR,E_(1/2)=0.80 V vs.RHE)and excellent oxygen evolution reaction(OER,E_(j=10)=1.53 V vs.RHE)in 0.1 mol/L KOH.Accordingly,a rechargeable Zn‐air battery of Fe_(x)Co_(9−x)S_(8)‐NHCS‐V cathode endows high energy efficiency(102 mW cm^(−2)),and a microbial fuel cell achieves a high‐power density(791±42 mW m^(−2)),outperforming the benchmark Pt/C catalyst.
文摘The N,S co-doped porous carbon nanofibers were fabricated by the carbonization of[Zn_(2)(tdc)_(2)(MA)]n MOFs/polyacrylonitrile nanofibers composite,which was produced by the electrospinning technology.The electrochemical results show that the N,S co-doped porous carbon nanofibers can achieve capacity of 201.2 mAh·g^(-1)at the current density of 0.05 A·g^(-1).Furthermore,the reversible capacity still has 161.3 mAh·g^(-1)even at a high current density of 1 A·g^(-1)after 600 cycles.The superior electrochemical performance shows that the N,S co-doped porous carbon nanofibers electrode material can be used as an ideal anode material for sodium-ion batteries.
基金supported by the National Natural Science Foundation of China(21306060,21573083)the Program for New Century Excellent Talents in Universities of China(NCET-13-0237)+3 种基金the Doctoral Fund of Ministry of Education of China(20130142120039)the Thousand Talents Plan,and the Initiatory Financial Support from Huazhong University of Science and Technology(HUST)Analytical and Testing Center of Huazhong University of Science and Technologythe support of the China Scholarship Council(CSC)
文摘Heteroatom doping, especially dual-doped carbon materials have attracted much attention for the past few years, and have been regarded as one of the most efficient strategies to enhance the capacitance behavior of porous carbon materials. In this work, a facile two-step synthetic route was developed to fab- ricate nitrogen and sulfur co-doped carbon microsphere （NSCM） by using thiourea as dopant. The NJS doping content is controlled via varying the carbonization temperature. It has been proved that a suitable quantity of N and S groups could not only provide pseudo-capacitance but also promote the electron transfer for carbon materials, which ensures the further utilization of the exposed surfaces for charge storage. The optimized NSCM prepared at a carbonization temperature of 800 ℃ （NSCM-800） achieves a capacitance of 277.1 F g^-1 at a current density of 0.3 A g^-1 in 6.0 mol L^-1 KOH electrolyte, which is 71% higher than that of undoped carbon microsphere. Besides, NSCM-800 shows an excellent cycling stability, 98.2% of the initial capacitance is retained after 5,000 cvcles at a current densitv of 3.0 A g^-1.
