Aqueous zinc(Zn)-ion batteries(AZIBs)have gained significant interest in energy storage due to several unique advantages.Utilizing waterbased electrolytes enhances environmental sustainability,while the abundance and ...Aqueous zinc(Zn)-ion batteries(AZIBs)have gained significant interest in energy storage due to several unique advantages.Utilizing waterbased electrolytes enhances environmental sustainability,while the abundance and affordability of Zn offer economic benefits.Manganese(Mn)-based materials,commonly used as cathodes in these batteries,provide high theoretical capacity,high electrical conductivity,and good structural stability.However,these materials suffer from capacity degradation over repeated cycles due to structural collapse and limited conductivity.To address this problem,we synthesized a magnesium(Mg)-and Mn-based composite,Mg^(2+)-Mn_(3)O_(4),using the hydrothermal method with an optimized amount of ammonium hydroxide(NH_(4)OH)solution.This approach effectively stabilizes the structure during cycling,enhancing both capacity retention and conductivity.The Zn^(2+)/H+intercalation/deintercalation process was confirmed by experimental results and ex-situ X-ray diffraction analysis,which demonstrates that Mg^(2+),along with optimized NH_(4)OH amount,prevents structural collapse and improves conductivity.Under optimal process conditions,the composite electrode(Mg^(2+)-Mn_(3)O_(4)–8 ml)achieved a capacity of 173.58 mA h g^(-1) at 0.5 A g^(-1),with excellent rate performance of 71.39 mA h g^(-1) at 10 A g^(-1).Remarkably,even at 5 A g^(-1),the electrode maintained a capacity of 86.87 mA h g^(-1) over 2100 cycles,underscoring the role of Mg^(2+)and NH_(4)OH in enhancing the reversible insertion/extraction stability of Zn^(2+)in Mn-based layered materials.This study presents a novel strategy for metal-ion incorporation in Mn-based AZIBs,offering insights into the optimization of cathode materials and advancing research on associated storage mechanisms.展开更多
The preparation of Cu nanoparticles by the aqueous solution reduction method was investigated. The effects of different reaction parameters on the preparation of Cu nanoparticles were studied. The optimum conditions f...The preparation of Cu nanoparticles by the aqueous solution reduction method was investigated. The effects of different reaction parameters on the preparation of Cu nanoparticles were studied. The optimum conditions for preparing well-dispersed nanoparticles were found as follows: 0.4 mol/L NaBH4 was added into solution containing 0.2 mol/L Cu2+, 1.0% gelatin dispersant in mass fraction, and 1.2 mol/L NH3?H2O at pH 12 and 313 K. In addition, a series of experiments were performed to discover the reaction process. NH3?H2O was found to be able to modulate the reaction process. At pH=10, Cu2+ was transformed to Cu(NH3)42+ as precursor after the addition of NH3?H2O, and then Cu(NH3)42+ was reduced by NaBH4 solution. At pH=12, Cu2+ was transformed to Cu(OH)2 as precursor after the addition of NH3?H2O, and Cu(OH)2 was then reduced by NaBH4 solution.展开更多
Li_(6)ZnO_(4)was chemically modified by nickel addition,in order to develop different compositions of the solid solution Li_(6)Zn_(1-x)Ni_(x)O_(4).These materials were evaluated bifunctionally;analyzing their CO_(2)ca...Li_(6)ZnO_(4)was chemically modified by nickel addition,in order to develop different compositions of the solid solution Li_(6)Zn_(1-x)Ni_(x)O_(4).These materials were evaluated bifunctionally;analyzing their CO_(2)capture performances,aswell as on their catalytic properties for H_(2)production via dry reforming of methane(DRM).The crystal structures of Li_(6)Zn_(1-x)Ni_(x)O_(4)solid solution samples were determined through X-ray diffraction,which confirmed the integration of nickel ions up to a concentration around 20 mol%,meanwhile beyond this value,a secondary phase was detected.These results were supported by XPS and TEM analyses.Then,dynamic and isothermal thermogravimetric analyses of CO_(2)capture revealed that Li_(6)Zn_(1-x)Ni_(x)O_(4)solid solution samples exhibited good CO_(2)chemisorption efficiencies,similarly to the pristine Li_(6)ZnO_(4)chemisorption trends observed.Moreover,a kinetic analysis of CO_(2)isothermal chemisorptions,using the Avrami-Erofeev model,evidenced an increment of the constant rates as a function of the Ni content.Since Ni^(2+)ions incorporation did not reduce the CO_(2)capture efficiency and kinetics,the catalytic properties of thesematerialswere evaluated in the DRM process.Results demonstrated that nickel ions favored hydrogen(H_(2))production over the pristine Li_(6)ZnO_(4)phase,despite a second H2 production reaction was determined,methane decomposition.Thereby,Li_(6)Zn_(1-x)Ni_(x)O_(4)ceramics can be employed as bifunctional materials.展开更多
The 2024 anodized aluminum alloy film was sealed by KAl(SO_(4))_(2)solution and the effect of sealing on corrosion resistance was investigated by means of potentiodynamic polarization curves,electrochemical impedance ...The 2024 anodized aluminum alloy film was sealed by KAl(SO_(4))_(2)solution and the effect of sealing on corrosion resistance was investigated by means of potentiodynamic polarization curves,electrochemical impedance spectroscopy,and X-ray photoelectron spectroscopy.The experimental results show that the optimal parameters for KAl(SO_(4))_(2)sealing are 35℃,with the pH value of 8,the concentration of 8 g/L,and the sealing time of 3 min.The corrosion resistance of the KAl(SO_(4))_(2)sealed sample can be significantly improved than that of unsealed one,and is obviously superior to that of the conventional hydrothermal sealed sample.Furthermore,X-ray photoelectron spectroscopy demonstrates that more Al(OH)_(3)will be formed in the process of KAl(SO_(4))_(2)sealing,which will shrink the diameter of the microporous and therefore results in the excellent corrosion resistance.展开更多
Ammonium vanadate has been considered as a competitive high-performance cathode material for aqueous Zn-ion batteries.However,it still suffers from insufficient rate capability and poor cyclability due to the low elec...Ammonium vanadate has been considered as a competitive high-performance cathode material for aqueous Zn-ion batteries.However,it still suffers from insufficient rate capability and poor cyclability due to the low electronic conductivity.Herein,(NH_(4))_(2)V_(6)O_(16).0.9H_(2)Onanobelts with reduced graphene oxide(RGO)modification are synthesized by one-step hydrothermal reaction.Benefiting from the addition of RGO,an excellent electrochemical performance of(NH_(4))_(2)V_(6)O_(16).0.9H_(2)O@RGO nanobelts can be obtained.The(NH_(4))_(2)V_(6)O_(16).0.9H_(2)O@RGO displays a high-rate capacity and a high energy density of 386 Wh/kg at 72 W/kg.In particular,after 1000 cycles at 5 A/g,the capacity remains at 322 mAh/g with 92.8%capacity retention.In addition,the key reaction mechanisms of reversible Zn^(2+)insertion/extraction in(NH_(4))_(2)V_(6)O_(16).0.9H_(2)O@RGO are clarified.展开更多
In this study,the benign target double terpyridine parts based amphiphilic ionic molecules(AIMs 1,2)and the reference single terpyridine segment included AIMs(AIMs 3,4)were synthesized through a multi-step method,and ...In this study,the benign target double terpyridine parts based amphiphilic ionic molecules(AIMs 1,2)and the reference single terpyridine segment included AIMs(AIMs 3,4)were synthesized through a multi-step method,and the molecular structures were fully characterized.The excellent anticorrosion of the target AIMs for copper surface in H_(2)SO_(4) solution was demonstrated by the electrochemistry analysis,which was more superior over those of the reference AIMs.The standard adsorption free energy changes of the target AIMs calculated by the adsorption isotherms were lower than -40 kJ·mol^(-1),suggesting an intensified chemical adsorption on metal surface.The molecular modeling and molecular dynamic computation of the studied AIMs were performed,demonstrating that the target AIMs exhibited lower highest occupied molecular orbital-lowest unoccupied molecular orbital energy gaps and greater adsorption energies than the reference ones.The chemical adsorption of the AIMs on metal surface was revealed by various spectroscopic methods including scanning electron microscopy,atomic force microscopy,Fourier transform infrared spectroscopy,attenuated total reflection infrared spectroscopy,Raman and X-ray diffraction.展开更多
The formation of oligomeric hydrogen peroxide triggered by Criegee intermediate maybe contributes significantly to the formation and growth of secondary organic aerosol(SOA).However,to date,the reactivity of C2 Criege...The formation of oligomeric hydrogen peroxide triggered by Criegee intermediate maybe contributes significantly to the formation and growth of secondary organic aerosol(SOA).However,to date,the reactivity of C2 Criegee intermediates(CH_(3)CHOO)in areas contaminated with acidic gas remains poorly understood.Herein,high-level quantum chemical calculations and Born-Oppenheimer molecular dynamics(BOMD)simulations are used to explore the reaction of CH_(3)CHOO and H_(2)SO_(4)both in the gas phase and at the airwater interface.In the gas phase,the addition reaction of CH_(3)CHOO with H_(2)SO_(4)to generate CH_(3)HC(OOH)OSO_(3)H(HPES)is near-barrierless,regardless of the presence of water molecules.BOMD simulations showthat the reaction at the air-water interface is even faster than that in the gas phase.Further calculations reveal that the HPES has a tendency to aggregate with sulfuric acids,ammonias,and water molecules to form stable clusters,meanwhile the oligomerization reaction of CH_(3)CHOO with HPES in the gas phase is both thermochemically and kinetically favored.Also,it is noted that the interfacial HPES−ion can attract H_(2)SO_(4),NH_(3),(COOH)_(2)and HNO_(3)for particle formation from the gas phase to the water surface.Thus,the results of this work not only elucidate the high atmospheric reactivity of C2 Criegee intermediates in polluted regions,but also deepen our understanding of the formation process of atmospheric SOA induced by Criegee intermediates.展开更多
基金supported by a National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIT)(No.2018R1A6A1A03025708).
文摘Aqueous zinc(Zn)-ion batteries(AZIBs)have gained significant interest in energy storage due to several unique advantages.Utilizing waterbased electrolytes enhances environmental sustainability,while the abundance and affordability of Zn offer economic benefits.Manganese(Mn)-based materials,commonly used as cathodes in these batteries,provide high theoretical capacity,high electrical conductivity,and good structural stability.However,these materials suffer from capacity degradation over repeated cycles due to structural collapse and limited conductivity.To address this problem,we synthesized a magnesium(Mg)-and Mn-based composite,Mg^(2+)-Mn_(3)O_(4),using the hydrothermal method with an optimized amount of ammonium hydroxide(NH_(4)OH)solution.This approach effectively stabilizes the structure during cycling,enhancing both capacity retention and conductivity.The Zn^(2+)/H+intercalation/deintercalation process was confirmed by experimental results and ex-situ X-ray diffraction analysis,which demonstrates that Mg^(2+),along with optimized NH_(4)OH amount,prevents structural collapse and improves conductivity.Under optimal process conditions,the composite electrode(Mg^(2+)-Mn_(3)O_(4)–8 ml)achieved a capacity of 173.58 mA h g^(-1) at 0.5 A g^(-1),with excellent rate performance of 71.39 mA h g^(-1) at 10 A g^(-1).Remarkably,even at 5 A g^(-1),the electrode maintained a capacity of 86.87 mA h g^(-1) over 2100 cycles,underscoring the role of Mg^(2+)and NH_(4)OH in enhancing the reversible insertion/extraction stability of Zn^(2+)in Mn-based layered materials.This study presents a novel strategy for metal-ion incorporation in Mn-based AZIBs,offering insights into the optimization of cathode materials and advancing research on associated storage mechanisms.
文摘The preparation of Cu nanoparticles by the aqueous solution reduction method was investigated. The effects of different reaction parameters on the preparation of Cu nanoparticles were studied. The optimum conditions for preparing well-dispersed nanoparticles were found as follows: 0.4 mol/L NaBH4 was added into solution containing 0.2 mol/L Cu2+, 1.0% gelatin dispersant in mass fraction, and 1.2 mol/L NH3?H2O at pH 12 and 313 K. In addition, a series of experiments were performed to discover the reaction process. NH3?H2O was found to be able to modulate the reaction process. At pH=10, Cu2+ was transformed to Cu(NH3)42+ as precursor after the addition of NH3?H2O, and then Cu(NH3)42+ was reduced by NaBH4 solution. At pH=12, Cu2+ was transformed to Cu(OH)2 as precursor after the addition of NH3?H2O, and Cu(OH)2 was then reduced by NaBH4 solution.
基金This work was carried out in the framework of PAPIIT-UNAM(IN-205823)project.
文摘Li_(6)ZnO_(4)was chemically modified by nickel addition,in order to develop different compositions of the solid solution Li_(6)Zn_(1-x)Ni_(x)O_(4).These materials were evaluated bifunctionally;analyzing their CO_(2)capture performances,aswell as on their catalytic properties for H_(2)production via dry reforming of methane(DRM).The crystal structures of Li_(6)Zn_(1-x)Ni_(x)O_(4)solid solution samples were determined through X-ray diffraction,which confirmed the integration of nickel ions up to a concentration around 20 mol%,meanwhile beyond this value,a secondary phase was detected.These results were supported by XPS and TEM analyses.Then,dynamic and isothermal thermogravimetric analyses of CO_(2)capture revealed that Li_(6)Zn_(1-x)Ni_(x)O_(4)solid solution samples exhibited good CO_(2)chemisorption efficiencies,similarly to the pristine Li_(6)ZnO_(4)chemisorption trends observed.Moreover,a kinetic analysis of CO_(2)isothermal chemisorptions,using the Avrami-Erofeev model,evidenced an increment of the constant rates as a function of the Ni content.Since Ni^(2+)ions incorporation did not reduce the CO_(2)capture efficiency and kinetics,the catalytic properties of thesematerialswere evaluated in the DRM process.Results demonstrated that nickel ions favored hydrogen(H_(2))production over the pristine Li_(6)ZnO_(4)phase,despite a second H2 production reaction was determined,methane decomposition.Thereby,Li_(6)Zn_(1-x)Ni_(x)O_(4)ceramics can be employed as bifunctional materials.
基金Funded by the National Natural Science Foundation of China(No.12175107)the Natural Science Foundation of Nanjing University of Posts and Telecommunications(No.NY220030)
文摘The 2024 anodized aluminum alloy film was sealed by KAl(SO_(4))_(2)solution and the effect of sealing on corrosion resistance was investigated by means of potentiodynamic polarization curves,electrochemical impedance spectroscopy,and X-ray photoelectron spectroscopy.The experimental results show that the optimal parameters for KAl(SO_(4))_(2)sealing are 35℃,with the pH value of 8,the concentration of 8 g/L,and the sealing time of 3 min.The corrosion resistance of the KAl(SO_(4))_(2)sealed sample can be significantly improved than that of unsealed one,and is obviously superior to that of the conventional hydrothermal sealed sample.Furthermore,X-ray photoelectron spectroscopy demonstrates that more Al(OH)_(3)will be formed in the process of KAl(SO_(4))_(2)sealing,which will shrink the diameter of the microporous and therefore results in the excellent corrosion resistance.
基金partly supported by the National Natural Science Foundation of China (No. 51772193)China Postdoctoral Science Foundation (No. 2019T120254)Hong Kong Scholar Program (No. XJ2019024)。
文摘Ammonium vanadate has been considered as a competitive high-performance cathode material for aqueous Zn-ion batteries.However,it still suffers from insufficient rate capability and poor cyclability due to the low electronic conductivity.Herein,(NH_(4))_(2)V_(6)O_(16).0.9H_(2)Onanobelts with reduced graphene oxide(RGO)modification are synthesized by one-step hydrothermal reaction.Benefiting from the addition of RGO,an excellent electrochemical performance of(NH_(4))_(2)V_(6)O_(16).0.9H_(2)O@RGO nanobelts can be obtained.The(NH_(4))_(2)V_(6)O_(16).0.9H_(2)O@RGO displays a high-rate capacity and a high energy density of 386 Wh/kg at 72 W/kg.In particular,after 1000 cycles at 5 A/g,the capacity remains at 322 mAh/g with 92.8%capacity retention.In addition,the key reaction mechanisms of reversible Zn^(2+)insertion/extraction in(NH_(4))_(2)V_(6)O_(16).0.9H_(2)O@RGO are clarified.
基金the National Natural Science Foundation of China (21376282,21676035,21878029)Chongqing Science and Technology Commission (cstc2018jcyjAX0668)+2 种基金Shandong Province Natural Science Foundation (ZR2020QB18)China Postdoctoral Science Foundation (22012 T50762&2011 M501388)Graduate Student Research Innovation Project,Chongqing University (CYB18046)。
文摘In this study,the benign target double terpyridine parts based amphiphilic ionic molecules(AIMs 1,2)and the reference single terpyridine segment included AIMs(AIMs 3,4)were synthesized through a multi-step method,and the molecular structures were fully characterized.The excellent anticorrosion of the target AIMs for copper surface in H_(2)SO_(4) solution was demonstrated by the electrochemistry analysis,which was more superior over those of the reference AIMs.The standard adsorption free energy changes of the target AIMs calculated by the adsorption isotherms were lower than -40 kJ·mol^(-1),suggesting an intensified chemical adsorption on metal surface.The molecular modeling and molecular dynamic computation of the studied AIMs were performed,demonstrating that the target AIMs exhibited lower highest occupied molecular orbital-lowest unoccupied molecular orbital energy gaps and greater adsorption energies than the reference ones.The chemical adsorption of the AIMs on metal surface was revealed by various spectroscopic methods including scanning electron microscopy,atomic force microscopy,Fourier transform infrared spectroscopy,attenuated total reflection infrared spectroscopy,Raman and X-ray diffraction.
基金supported by the National Natural Science Foundation of China(Nos.22073059 and 22203052)the Natural Science Foundation of Shaanxi Province(No.2022JM-060)+1 种基金the Education Department of Shaanxi Provincial Government(No.23JC023)the Key Cultivation Project of Shaanxi University of Technology(No.SLG2101)。
文摘The formation of oligomeric hydrogen peroxide triggered by Criegee intermediate maybe contributes significantly to the formation and growth of secondary organic aerosol(SOA).However,to date,the reactivity of C2 Criegee intermediates(CH_(3)CHOO)in areas contaminated with acidic gas remains poorly understood.Herein,high-level quantum chemical calculations and Born-Oppenheimer molecular dynamics(BOMD)simulations are used to explore the reaction of CH_(3)CHOO and H_(2)SO_(4)both in the gas phase and at the airwater interface.In the gas phase,the addition reaction of CH_(3)CHOO with H_(2)SO_(4)to generate CH_(3)HC(OOH)OSO_(3)H(HPES)is near-barrierless,regardless of the presence of water molecules.BOMD simulations showthat the reaction at the air-water interface is even faster than that in the gas phase.Further calculations reveal that the HPES has a tendency to aggregate with sulfuric acids,ammonias,and water molecules to form stable clusters,meanwhile the oligomerization reaction of CH_(3)CHOO with HPES in the gas phase is both thermochemically and kinetically favored.Also,it is noted that the interfacial HPES−ion can attract H_(2)SO_(4),NH_(3),(COOH)_(2)and HNO_(3)for particle formation from the gas phase to the water surface.Thus,the results of this work not only elucidate the high atmospheric reactivity of C2 Criegee intermediates in polluted regions,but also deepen our understanding of the formation process of atmospheric SOA induced by Criegee intermediates.
