The scarcity of wettability,insufficient active sites,and low surface area of graphite felt(GF)have long been suppressing the performance of vanadium redox flow batteries(VRFBs).Herein,an ultra-homogeneous multipledim...The scarcity of wettability,insufficient active sites,and low surface area of graphite felt(GF)have long been suppressing the performance of vanadium redox flow batteries(VRFBs).Herein,an ultra-homogeneous multipledimensioned defect,including nano-scale etching and atomic-scale N,O codoping,was used to modify GF by the molten salt system.NH_(4)Cl and KClO_(3) were added simultaneously to the system to obtain porous N/O co-doped electrode(GF/ON),where KClO_(3) was used to ultra-homogeneously etch,and O-functionalize electrode,and NH4Cl was used as N dopant,respectively.GF/ON presents better electrochemical catalysis for VO_(2)+/VO_(2)+ and V3+/V2+ reactions than only O-functionalized electrodes(GF/O)and GF.The enhanced electrochemical properties are attributed to an increase in active sites,surface area,and wettability,as well as the synergistic effect of N and O,which is also supported by the density functional theory calculations.Further,the cell using GF/ON shows higher discharge capacity,energy efficiency,and stability for cycling performance than the pristine cell at 140 mA cm^(−2) for 200 cycles.Moreover,the energy efficiency of the modified cell is increased by 9.7% from 55.2% for the pristine cell at 260 mA cm^(−2).Such an ultra-homogeneous etching with N and O co-doping through“boiling”molten salt medium provides an effective and practical application potential way to prepare superior electrodes for VRFB.展开更多
The incorporation of heteroatoms into carbon aerogels(CAs)can lead to structural distortions and changes in active sites due to their smaller size and electronegativity compared to pure carbon.However,the evolution of...The incorporation of heteroatoms into carbon aerogels(CAs)can lead to structural distortions and changes in active sites due to their smaller size and electronegativity compared to pure carbon.However,the evolution of the electronic structure from single-atom doping to heteroatom codoping in CAs has not yet been thoroughly investigated,and the impact of codoping on potassium ion(K+)storage and diffusion pathways as electrode material remains unclear.In this study,experimental and theoretical simulations were conducted to demonstrate that heteroatom codoping,composed of multiple heteroatoms(O/N/B)with different properties,has the potential to improve the electrical properties and stability of CAs compared to single-atom doping.Electronic states near the Fermi level have revealed that doping with O/N/B generates a greater number of active centers on adjacent carbon atoms than doping with O and O/N atoms.As a result of synergy with enhanced wetting ability(contact angle of 9.26°)derived from amino groups and hierarchical porous structure,ON-CA has the most optimized adsorption capacity(−1.62 eV)and diffusion barrier(0.12 eV)of K^(+).The optimal pathway of K^(+)in ON-CA is along the carbon ring with N or O doping.As K^(+)storage material for supercapacitors and ion batteries,it shows an outstanding specific capacity and capacitance,electrochemical stability,and rate performance.Especially,the assembled symmetrical K^(+)supercapacitor demonstrates an energy density of 51.8 Wh kg^(−1),an ultrahigh power density of 443Wkg^(−1),and outstanding cycling stability(maintaining 83.3%after 10,000 cycles in 1M KPF6 organic electrolyte).This research provides valuable insights into the design of highperformance potassium ion storage materials.展开更多
Ensuring a stable power output from renewable energy sources,such as wind and solar energy,depends on the development of large-scale and long-duration energy storage devices.Zinc–bromine fl ow batteries(ZBFBs)have em...Ensuring a stable power output from renewable energy sources,such as wind and solar energy,depends on the development of large-scale and long-duration energy storage devices.Zinc–bromine fl ow batteries(ZBFBs)have emerged as cost-eff ective and high-energy-density solutions,replacing expensive all-vanadium fl ow batteries.However,uneven Zn deposition during charging results in the formation of problematic Zn dendrites,leading to mass transport polarization and self-discharge.Stable Zn plating and stripping are essential for the successful operation of high-areal-capacity ZBFBs.In this study,we successfully synthesized nitrogen and oxygen co-doped functional carbon felt(NOCF4)electrode through the oxidative polymerization of dopamine,followed by calcination under ambient conditions.The NOCF4 electrode eff ectively facilitates effi cient“shuttle deposition”of Zn during charging,signifi cantly enhancing the areal capacity of the electrode.Remarkably,ZBFBs utilizing NOCF4 as the anode material exhibited stable cycling performance for 40 cycles(approximately 240 h)at an areal capacity of 60 mA h/cm^(2).Even at a high areal capacity of 130 mA h/cm^(2),an impressive energy effi ciency of 76.98%was achieved.These fi ndings provide a promising pathway for the development of high-areal-capacity ZBFBs for advanced energy storage systems.展开更多
The electrochemical carbon dioxide reduction reaction(CO_(2)RR),which can produce value-added chemical feedstocks,is a proton-coupled-electron process with sluggish kinetics.Thus,highly efficient,cheap catalysts are u...The electrochemical carbon dioxide reduction reaction(CO_(2)RR),which can produce value-added chemical feedstocks,is a proton-coupled-electron process with sluggish kinetics.Thus,highly efficient,cheap catalysts are urgently required.Transition metal oxides such as CoO_(x),FeO_(x),and NiO_(x)are low-cost,low toxicity,and abundant materials for a wide range of electrochemical reactions,but are almost inert for CO_(2)RR.Here,we report for the first time that nitrogen doped carbon nanotubes(N-CNT)have a surprising activation effect on the activity and selectivity of transition metal-oxide(MO_(x)where M=Fe,Ni,and Co)nanoclusters for CO_(2)RR.MO_(x)supported on N-CNT,MO_(x)/N-CNT,achieves a CO yield of 2.6–2.8 mmol cm−2 min−1 at an overpotential of−0.55 V,which is two orders of magnitude higher than MO_(x)supported on acid treated CNTs(MO_(x)/O-CNT)and four times higher than pristine N-CNT.The faraday efficiency for electrochemical CO_(2)-to-CO conversion is as high as 90.3%at overpotential of 0.44 V.Both in-situ XAS measurements and DFT calculations disclose that MO_(x)nanoclusters can be hydrated in CO_(2)saturated KHCO_(3),and the N defects of N-CNT effectively stabilize these metal hydroxyl species under carbon dioxide reduction reaction conditions,which can split the water molecules and provide local protons to inhibit the poisoning of active sites under carbon dioxide reduction reaction conditions.展开更多
Fluid catalytic cracking (FCC) salty wastewaters, containing quaternary ammonium compounds (QACs), are very difficult to treat by biochemical process. Anoxic/oxic (A/O) biochemical system, based on nitrification and d...Fluid catalytic cracking (FCC) salty wastewaters, containing quaternary ammonium compounds (QACs), are very difficult to treat by biochemical process. Anoxic/oxic (A/O) biochemical system, based on nitrification and denitrification reactions, was used to assess their possible biodegradation. Because of the negative effects of high salt concentration (3%), heavy metals and toxic organic matter on microorganisms’ activities, some techniques consisting of dilution, coagulation and flocculation, and ozonation pretreatments, were gradually tested to evaluate chemical oxygen demand (COD), ammonia-nitrogen (ammonia-N) and total nitrogen (TN) removal rates. In this process of FCC wastewater, starting with university-domesticated sludge, the ammonia-N and TN removal rates were worst. However, when using domesticated SBR’s sludge and operating with five-fold daily diluted influent (thus reducing salt concentration), the ammonia-N removal reached about 57% while the TN removal rate was less than 37% meaning an amelioration of the nitrification process. However, by reducing the dilution factors, these results were inflected after some days of operation, with ammonia-N removal decreasing and TN barely removed meaning a poor nitrification. Even by reducing heavy metals concentration with coagulation/flocculation process, the results never changed. Thereafter, by using ozonation pre-treatment to degrade the detected organic matter of di-tert-butylphenol and certain isoparaffins, COD, ammonia-N and TN removal rates reached 92%, 62% and 61%, respectively. These results showed that the activities of the microorganisms were increased, thus indicating a net denitrification and nitrification reactions improvement.展开更多
基金supported by the National Natural Science Foundation of China(No.51872090)Natural Science Foundation of Hebei Province(No.E2019209433,E2022209158)Colleges and Universities in Hebei Province Science and Technology Research Project(No.JZX2024026).
文摘The scarcity of wettability,insufficient active sites,and low surface area of graphite felt(GF)have long been suppressing the performance of vanadium redox flow batteries(VRFBs).Herein,an ultra-homogeneous multipledimensioned defect,including nano-scale etching and atomic-scale N,O codoping,was used to modify GF by the molten salt system.NH_(4)Cl and KClO_(3) were added simultaneously to the system to obtain porous N/O co-doped electrode(GF/ON),where KClO_(3) was used to ultra-homogeneously etch,and O-functionalize electrode,and NH4Cl was used as N dopant,respectively.GF/ON presents better electrochemical catalysis for VO_(2)+/VO_(2)+ and V3+/V2+ reactions than only O-functionalized electrodes(GF/O)and GF.The enhanced electrochemical properties are attributed to an increase in active sites,surface area,and wettability,as well as the synergistic effect of N and O,which is also supported by the density functional theory calculations.Further,the cell using GF/ON shows higher discharge capacity,energy efficiency,and stability for cycling performance than the pristine cell at 140 mA cm^(−2) for 200 cycles.Moreover,the energy efficiency of the modified cell is increased by 9.7% from 55.2% for the pristine cell at 260 mA cm^(−2).Such an ultra-homogeneous etching with N and O co-doping through“boiling”molten salt medium provides an effective and practical application potential way to prepare superior electrodes for VRFB.
基金This work is supported by the National Natural Science Foundation of China(No.22103075,No.21827804,and No.22173089)the National Key R&D Program of China(No.2021YFA0716801andNo.2017YFA0303502).
基金financially supported by the Natural Science Foundation of China(Grant No.22005165)the Major Science and Technology Innovation Project of Shandong(Grant No.2019JZZY010507)+1 种基金the Qingdao Municipal Science and Technology Bureau(Grant No.17-1-1-86-jch)the Key Technology Research and Development Program of Shandong(Grant No.2018GGX108005).
文摘The incorporation of heteroatoms into carbon aerogels(CAs)can lead to structural distortions and changes in active sites due to their smaller size and electronegativity compared to pure carbon.However,the evolution of the electronic structure from single-atom doping to heteroatom codoping in CAs has not yet been thoroughly investigated,and the impact of codoping on potassium ion(K+)storage and diffusion pathways as electrode material remains unclear.In this study,experimental and theoretical simulations were conducted to demonstrate that heteroatom codoping,composed of multiple heteroatoms(O/N/B)with different properties,has the potential to improve the electrical properties and stability of CAs compared to single-atom doping.Electronic states near the Fermi level have revealed that doping with O/N/B generates a greater number of active centers on adjacent carbon atoms than doping with O and O/N atoms.As a result of synergy with enhanced wetting ability(contact angle of 9.26°)derived from amino groups and hierarchical porous structure,ON-CA has the most optimized adsorption capacity(−1.62 eV)and diffusion barrier(0.12 eV)of K^(+).The optimal pathway of K^(+)in ON-CA is along the carbon ring with N or O doping.As K^(+)storage material for supercapacitors and ion batteries,it shows an outstanding specific capacity and capacitance,electrochemical stability,and rate performance.Especially,the assembled symmetrical K^(+)supercapacitor demonstrates an energy density of 51.8 Wh kg^(−1),an ultrahigh power density of 443Wkg^(−1),and outstanding cycling stability(maintaining 83.3%after 10,000 cycles in 1M KPF6 organic electrolyte).This research provides valuable insights into the design of highperformance potassium ion storage materials.
基金supported by Natural Science Foundation of Anhui Higher Education Institution of China(2023AH051318).
文摘Ensuring a stable power output from renewable energy sources,such as wind and solar energy,depends on the development of large-scale and long-duration energy storage devices.Zinc–bromine fl ow batteries(ZBFBs)have emerged as cost-eff ective and high-energy-density solutions,replacing expensive all-vanadium fl ow batteries.However,uneven Zn deposition during charging results in the formation of problematic Zn dendrites,leading to mass transport polarization and self-discharge.Stable Zn plating and stripping are essential for the successful operation of high-areal-capacity ZBFBs.In this study,we successfully synthesized nitrogen and oxygen co-doped functional carbon felt(NOCF4)electrode through the oxidative polymerization of dopamine,followed by calcination under ambient conditions.The NOCF4 electrode eff ectively facilitates effi cient“shuttle deposition”of Zn during charging,signifi cantly enhancing the areal capacity of the electrode.Remarkably,ZBFBs utilizing NOCF4 as the anode material exhibited stable cycling performance for 40 cycles(approximately 240 h)at an areal capacity of 60 mA h/cm^(2).Even at a high areal capacity of 130 mA h/cm^(2),an impressive energy effi ciency of 76.98%was achieved.These fi ndings provide a promising pathway for the development of high-areal-capacity ZBFBs for advanced energy storage systems.
基金Y.C.and J.C.are contributed equally to the paper.Project supported by the National Natural Science Foundation of China (U19A2017)the Fundamental Research Funds for the Central South University and the Australian Research Council (DP180100731 and DP180100568)。
文摘The electrochemical carbon dioxide reduction reaction(CO_(2)RR),which can produce value-added chemical feedstocks,is a proton-coupled-electron process with sluggish kinetics.Thus,highly efficient,cheap catalysts are urgently required.Transition metal oxides such as CoO_(x),FeO_(x),and NiO_(x)are low-cost,low toxicity,and abundant materials for a wide range of electrochemical reactions,but are almost inert for CO_(2)RR.Here,we report for the first time that nitrogen doped carbon nanotubes(N-CNT)have a surprising activation effect on the activity and selectivity of transition metal-oxide(MO_(x)where M=Fe,Ni,and Co)nanoclusters for CO_(2)RR.MO_(x)supported on N-CNT,MO_(x)/N-CNT,achieves a CO yield of 2.6–2.8 mmol cm−2 min−1 at an overpotential of−0.55 V,which is two orders of magnitude higher than MO_(x)supported on acid treated CNTs(MO_(x)/O-CNT)and four times higher than pristine N-CNT.The faraday efficiency for electrochemical CO_(2)-to-CO conversion is as high as 90.3%at overpotential of 0.44 V.Both in-situ XAS measurements and DFT calculations disclose that MO_(x)nanoclusters can be hydrated in CO_(2)saturated KHCO_(3),and the N defects of N-CNT effectively stabilize these metal hydroxyl species under carbon dioxide reduction reaction conditions,which can split the water molecules and provide local protons to inhibit the poisoning of active sites under carbon dioxide reduction reaction conditions.
文摘Fluid catalytic cracking (FCC) salty wastewaters, containing quaternary ammonium compounds (QACs), are very difficult to treat by biochemical process. Anoxic/oxic (A/O) biochemical system, based on nitrification and denitrification reactions, was used to assess their possible biodegradation. Because of the negative effects of high salt concentration (3%), heavy metals and toxic organic matter on microorganisms’ activities, some techniques consisting of dilution, coagulation and flocculation, and ozonation pretreatments, were gradually tested to evaluate chemical oxygen demand (COD), ammonia-nitrogen (ammonia-N) and total nitrogen (TN) removal rates. In this process of FCC wastewater, starting with university-domesticated sludge, the ammonia-N and TN removal rates were worst. However, when using domesticated SBR’s sludge and operating with five-fold daily diluted influent (thus reducing salt concentration), the ammonia-N removal reached about 57% while the TN removal rate was less than 37% meaning an amelioration of the nitrification process. However, by reducing the dilution factors, these results were inflected after some days of operation, with ammonia-N removal decreasing and TN barely removed meaning a poor nitrification. Even by reducing heavy metals concentration with coagulation/flocculation process, the results never changed. Thereafter, by using ozonation pre-treatment to degrade the detected organic matter of di-tert-butylphenol and certain isoparaffins, COD, ammonia-N and TN removal rates reached 92%, 62% and 61%, respectively. These results showed that the activities of the microorganisms were increased, thus indicating a net denitrification and nitrification reactions improvement.
