Optimizing the oxygen reduction reaction(ORR)kinetics requires precise control of intermediate adsorption at active sites,which can be achieved through orbital engineering by regulating the electronic structure.This s...Optimizing the oxygen reduction reaction(ORR)kinetics requires precise control of intermediate adsorption at active sites,which can be achieved through orbital engineering by regulating the electronic structure.This study addresses the challenge by exploring how modulation of the 3d-orbital electronic structure of FeN_(4) active sites influences ORR electrocatalysis.To realize this,a catalyst composed of Fe_(3)C nanoparticles and FeN_(4) single atoms anchored on carbon black(Fe_(3)C-FeN_(4)/CB)was synthesized via a synergistic strategy of spatial confinement and atmosphere control.This unique heterostructure creates interfaces between Fe_(3)C and FeN_(4) that modulate the electronic configuration of the FeN_(4) center,transforming its geometry from square-planar to quasi-octahedral.Spectroscopic characterizations and theoretical calculations reveal that this orbital modulation results in a downward shift of the Fe dband center,altering the reaction pathway and lowering the energy barrier for ORR.Consequently,the Fe_(3)C-FeN_(4)/CB catalyst exhibits outstanding ORR activity,four-electron selectivity,excellent methanol tolerance,and remarkable electrochemical stability.When applied in a zinc-air battery,it achieves a peak power density of 178.4 mW cm^(-2)and superior cycling stability compared to commercial Pt/C catalysts.This work provides valuable insights into heterointerface-induced orbital modulation as a promising design principle for high-performance ORR electrocatalysts.展开更多
Nitric oxide(NO),which generally originates from vehicle exhaust and industrial flue gases,is one of the most serious air pollutants.In this case,the electrochemical NO reduction reaction(NORR)not only removes the atm...Nitric oxide(NO),which generally originates from vehicle exhaust and industrial flue gases,is one of the most serious air pollutants.In this case,the electrochemical NO reduction reaction(NORR)not only removes the atmospheric pollutant NO but also produces valuable ammonia(NH_(3)).Hence,through the synthesis and modification of Fe_(3)C nanocrystal cata-lysts,the as-obtained optimal sample of Fe_(3)C/C-900 was adopted as the NORR catalyst at ambient conditions.As a result,the Fe_(3)C/C-900 catalyst showed an NH_(3)Faraday efficiency of 76.5%and an NH_(3)yield rate of 177.5μmol·h^(-1)·cm^(-2)at the working potentials of-0.8 and-1.2 V versus reversible hydrogen electrode(vs.RHE),respectively.And it delivered a stable NORR activity during the electrolysis.Moreover,we attribute the high NORR properties of Fe_(3)C/C-900 to two aspects:one is the enhanced intrinsic activity of Fe_(3)C nanocrystals,including the lowering of the energy barrier of rate-limiting step(*NOH→*N)and the inhibition of hydrogen evolution;on the other hand,the favorable dispersion of active components,the effective adsorption of gaseous NO,and the release of liquid NH_(3)products facilitated by the porous carbon substrate.展开更多
The practical applications of carbon anode for lithium-ion batteries(LIBs)are largely obstructed by their moderate rate capability and cyclic stability.Herein,we report a N,S-codoped porous carbon nanosheet(NSC)decora...The practical applications of carbon anode for lithium-ion batteries(LIBs)are largely obstructed by their moderate rate capability and cyclic stability.Herein,we report a N,S-codoped porous carbon nanosheet(NSC)decorated with Fe_(3)C nanoparticles(Fe_(3)C/NSC)by a one-pot pyrolysis process.The high surface area and abundant defects of NSC can not only promote electrons and ions transfer,but also induce high pseudocapacitive contribution.More importantly,the synergistic catalysis effect of Fe-Nx and Fe_(3)C can catalyze the reversible conversion of some solid electrolyte interface(SEI)components to offer excess capacity during cycling.As expected,the Fe_(3)C-NSC anode delivers a discharge capacity of750 mAh·g^(-1)under a current density of 0.5 A·g^(-1)through 500 cycles and retains a dis-charge capacity of 366 mAh·g^(-1)at 4 A·g^(-1)after 1600 cycles,respectively.Most importantly,the lithium-ion capacitors based on Fe_(3)C/NSC anode demonstrate a high energy density of 249.5 Wh·kg^(-1)at 560 W·kg^(-1).展开更多
基金supported by the National Natural Science Foundation of China(Grant Nos.22272105 and 22572118)Natural Science Foundation of Shanghai(Grant No.23ZR1423900)。
文摘Optimizing the oxygen reduction reaction(ORR)kinetics requires precise control of intermediate adsorption at active sites,which can be achieved through orbital engineering by regulating the electronic structure.This study addresses the challenge by exploring how modulation of the 3d-orbital electronic structure of FeN_(4) active sites influences ORR electrocatalysis.To realize this,a catalyst composed of Fe_(3)C nanoparticles and FeN_(4) single atoms anchored on carbon black(Fe_(3)C-FeN_(4)/CB)was synthesized via a synergistic strategy of spatial confinement and atmosphere control.This unique heterostructure creates interfaces between Fe_(3)C and FeN_(4) that modulate the electronic configuration of the FeN_(4) center,transforming its geometry from square-planar to quasi-octahedral.Spectroscopic characterizations and theoretical calculations reveal that this orbital modulation results in a downward shift of the Fe dband center,altering the reaction pathway and lowering the energy barrier for ORR.Consequently,the Fe_(3)C-FeN_(4)/CB catalyst exhibits outstanding ORR activity,four-electron selectivity,excellent methanol tolerance,and remarkable electrochemical stability.When applied in a zinc-air battery,it achieves a peak power density of 178.4 mW cm^(-2)and superior cycling stability compared to commercial Pt/C catalysts.This work provides valuable insights into heterointerface-induced orbital modulation as a promising design principle for high-performance ORR electrocatalysts.
基金supported by the Guangxi Natural Science Fund for Distinguished Young Scholars(2024GXNSFFA010008)Shenzhen Science and Technology Program(JCYJ20230807112503008).
文摘Nitric oxide(NO),which generally originates from vehicle exhaust and industrial flue gases,is one of the most serious air pollutants.In this case,the electrochemical NO reduction reaction(NORR)not only removes the atmospheric pollutant NO but also produces valuable ammonia(NH_(3)).Hence,through the synthesis and modification of Fe_(3)C nanocrystal cata-lysts,the as-obtained optimal sample of Fe_(3)C/C-900 was adopted as the NORR catalyst at ambient conditions.As a result,the Fe_(3)C/C-900 catalyst showed an NH_(3)Faraday efficiency of 76.5%and an NH_(3)yield rate of 177.5μmol·h^(-1)·cm^(-2)at the working potentials of-0.8 and-1.2 V versus reversible hydrogen electrode(vs.RHE),respectively.And it delivered a stable NORR activity during the electrolysis.Moreover,we attribute the high NORR properties of Fe_(3)C/C-900 to two aspects:one is the enhanced intrinsic activity of Fe_(3)C nanocrystals,including the lowering of the energy barrier of rate-limiting step(*NOH→*N)and the inhibition of hydrogen evolution;on the other hand,the favorable dispersion of active components,the effective adsorption of gaseous NO,and the release of liquid NH_(3)products facilitated by the porous carbon substrate.
基金financially supported by the National Science Foundation of China (Nos. 51772169, 52072217 and 51802261)the National Key R&D Program of China (No. 2018YFB0905400)+2 种基金the Major Technological Innovation Project of Hubei Science and Technology Department (No. 2019AAA164)the Natural Science Foundation of Hubei Province of China (No. 2019CFB337)the Natural Science Foundation of Hubei Provincial Department of Education (No. Q20191204)
文摘The practical applications of carbon anode for lithium-ion batteries(LIBs)are largely obstructed by their moderate rate capability and cyclic stability.Herein,we report a N,S-codoped porous carbon nanosheet(NSC)decorated with Fe_(3)C nanoparticles(Fe_(3)C/NSC)by a one-pot pyrolysis process.The high surface area and abundant defects of NSC can not only promote electrons and ions transfer,but also induce high pseudocapacitive contribution.More importantly,the synergistic catalysis effect of Fe-Nx and Fe_(3)C can catalyze the reversible conversion of some solid electrolyte interface(SEI)components to offer excess capacity during cycling.As expected,the Fe_(3)C-NSC anode delivers a discharge capacity of750 mAh·g^(-1)under a current density of 0.5 A·g^(-1)through 500 cycles and retains a dis-charge capacity of 366 mAh·g^(-1)at 4 A·g^(-1)after 1600 cycles,respectively.Most importantly,the lithium-ion capacitors based on Fe_(3)C/NSC anode demonstrate a high energy density of 249.5 Wh·kg^(-1)at 560 W·kg^(-1).
