Hydrogen peroxide(H_(2)O_(2))is a versatile oxidant with significant applications,particularly in regulating the microenvironment for healthcare purposes.Herein,a rational design of the photoanode is implemented to en...Hydrogen peroxide(H_(2)O_(2))is a versatile oxidant with significant applications,particularly in regulating the microenvironment for healthcare purposes.Herein,a rational design of the photoanode is implemented to enhance H_(2)O_(2) production by oxidizing H_(2)O in a portable photoelectrocatalysis(PEC)device.The obtained solution from this system is demonstrated for effective bactericidal activity against Staphylococcus aureus and Escherichia coli,while maintaining low toxicity toward hippocampal neuronal cells.The photoanode is achieved by Mo-doped BiVO4 films,which are subsequently loaded with cobalt-porphyrin(Co-py)molecules as a co-catalyst.As a result,the optimal performance for H_(2)O_(2) production rate was achieved at 8.4μmol h^(−1) cm^(−2),which is 1.8 times that of the pristine BiVO4 photoanode.Density functional theory(DFT)simulations reveal that the improved performance results from a 1.1 eV reduction in the energy of the rate-determining step of·OH adsorption by the optimal photoanode.This study demonstrates a PEC approach for promoting H_(2)O_(2) production by converting H_(2)O for antibacterial purposes,offering potential applications in conventionally controlling microenvironments for healthcare applications.展开更多
Flash Joule heating(FJH),as a high-efficiency and low-energy consumption technology for advanced materials synthesis,has shown significant potential in the synthesis of graphene and other functional carbon materials.B...Flash Joule heating(FJH),as a high-efficiency and low-energy consumption technology for advanced materials synthesis,has shown significant potential in the synthesis of graphene and other functional carbon materials.Based on the Joule effect,the solid carbon sources can be rapidly heated to ultra-high temperatures(>3000 K)through instantaneous high-energy current pulses during FJH,thus driving the rapid rearrangement and graphitization of carbon atoms.This technology demonstrates numerous advantages,such as solvent-and catalyst-free features,high energy conversion efficiency,and a short process cycle.In this review,we have systematically summarized the technology principle and equipment design for FJH,as well as its raw materials selection and pretreatment strategies.The research progress in the FJH synthesis of flash graphene,carbon nanotubes,graphene fibers,and anode hard carbon,as well as its by-products,is also presented.FJH can precisely optimize the microstructures of carbon materials(e.g.,interlayer spacing of turbostratic graphene,defect concentration,and heteroatom doping)by regulating its operation parameters like flash voltage and flash time,thereby enhancing their performances in various applications,such as composite reinforcement,metal-ion battery electrodes,supercapacitors,and electrocatalysts.However,this technology is still challenged by low process yield,macroscopic material uniformity,and green power supply system construction.More research efforts are also required to promote the transition of FJH from laboratory to industrial-scale applications,thus providing innovative solutions for advanced carbon materials manufacturing and waste management toward carbon neutrality.展开更多
Photocatalytic oxygen reduction provides a sustainable method for on-site hydrogen peroxide(H_(2)O_(2))synthesis.However,most photocatalysts suffer from moderate kinetics due to sluggish electron transfer and ineffici...Photocatalytic oxygen reduction provides a sustainable method for on-site hydrogen peroxide(H_(2)O_(2))synthesis.However,most photocatalysts suffer from moderate kinetics due to sluggish electron transfer and inefficient oxygen adsorption and activation.Herein,sodium(Na)and potassium(K)are co-incorporated into graphitic carbon nitride(g-C_(3)N_(4))via a stepwise co-doping strategy combining sodium chloride-induced and molten salt-assisted polymerization.Experimental results and density functional theory calculations demonstrate that the synergistic interaction between intralayer Na+ions and interlayer K^(+)ions facilitates charge carrier separation and migration both within and between g-C_(3)N_(4)layers.Additionally,multiple heteroatom sites enhance surface charge polarization and introduce cyano groups,which synergistically promote oxygen molecule(O_(2))adsorption and elevate local proton coverage.Simultaneously,the energy barrier for H_(2)O_(2)desorption on the optimal photocatalyst(5Na/3.3K-CN)is lowered,thus improving H_(2)O_(2)production efficiency.Eventually,5Na/3.3K-CN exhibits an impressive H_(2)O_(2)yield of 2541.6μmol·g^(-1)·h^(-1) in an artificial reactor,which is 10.6 times higher than that of pure g-C_(3)N_(4)(240.2μmol·g^(-1)·h^(-1)).Under natural sunlight outdoors,5Na/3.3K-CN still maintains ultrahigh H_(2)O_(2)photosynthesis efficiency,achieving an H_(2)O_(2)photosynthesis rate of 2068.7μmol·g^(-1)·h^(-1).This work introduces a straightforward method to simultaneously optimize charge transfer and O_(2)activation for boosting H_(2)O_(2)photosynthesis,offering valuable insights toward the real-world deployment of g-C_(3)N_(4)-based photocatalysts in environmental protection and energy conversion.展开更多
Photosynthesis is a promising method for H_(2)O_(2)production,but its application in pure water is limited by slow oxidation kinetics and rapid photocarrier recombination of photocatalysts.Herein,a novel defective car...Photosynthesis is a promising method for H_(2)O_(2)production,but its application in pure water is limited by slow oxidation kinetics and rapid photocarrier recombination of photocatalysts.Herein,a novel defective carbon nitride photocatalyst(D-C3-xN4)containing the C vacancies and the frustrated Lewis pairs(B and N of cyano group)is designed for H_(2)O_(2)photosynthesis,and the role of C vacancies on the electron transfer mechanism during photocatalysis is systematically investigated.The D-C_(3-x)N_(4) exhibits a H_(2)O_(2)production rate of 140.1μmol·g^(-1)·h^(-1) in pure water,which is 87.6 times that of C_(3)N_(4).Such superior performance for H_(2)O_(2)photosynthesis is found to arise from the C vacancies and frustrated Lewis pairs(FLPs).The C vacancies have strong electron-trapping ability,which greatly enhances the separation of photocarriers.The C vacancies can also effectively reduce O_(2)to*OOH via a proton-coupled process,which significantly accelerates the O_(2)reduction kinetics.Meanwhile,the FLPs show an outstanding catalytic activity for H_(2)O oxidation.This study not only provides a new structure for highly active photocatalysts,but also deepens the understanding of the electron transfer mechanism of photocatalysts with trapped sites.展开更多
Carbon superstructures with multiscale hierarchies and functional attributes represent an appealing cathode candidate for zinc hybrid capacitors,but their tailor-made design to optimize the capacitive activity remains...Carbon superstructures with multiscale hierarchies and functional attributes represent an appealing cathode candidate for zinc hybrid capacitors,but their tailor-made design to optimize the capacitive activity remains a confusing topic.Here we develop a hydrogen-bond-oriented interfacial super-assembly strategy to custom-tailor nanosheet-intertwined spherical carbon superstructures(SCSs)for Zn-ion storage with double-high capacitive activity and durability.Tetrachlorobenzoquinone(H-bond acceptor)and dimethylbenzidine(H-bond donator)can interact to form organic nanosheet modules,which are sequentially assembled,orientally compacted and densified into well-orchestrated superstructures through multiple H-bonds(N-H···O).Featured with rich surface-active heterodiatomic motifs,more exposed nanoporous channels,and successive charge migration paths,SCSs cathode promises high accessibility of built-in zincophilic sites and rapid ion diffusion with low energy barriers(3.3Ωs-0.5).Consequently,the assembled Zn||SCSs capacitor harvests all-round improvement in Zn-ion storage metrics,including high energy density(166 Wh kg-1),high-rate performance(172 m Ah g^(-1)at 20 A g^(-1)),and long-lasting cycling lifespan(95.5%capacity retention after 500,000 cycles).An opposite chargecarrier storage mechanism is rationalized for SCSs cathode to maximize spatial capacitive charge storage,involving high-kinetics physical Zn^(2+)/CF_(3)SO_(3)-adsorption and chemical Zn^(2+)redox with carbonyl/pyridine groups.This work gives insights into H-bond-guided interfacial superassembly design of superstructural carbons toward advanced energy storage.展开更多
Graphite,encompassing both natural graphite and synthetic graphite,and graphene,have been extensively utilized and investigated as anode materials and additives in lithium-ion batteries(LIBs).In the pursuit of carbon ...Graphite,encompassing both natural graphite and synthetic graphite,and graphene,have been extensively utilized and investigated as anode materials and additives in lithium-ion batteries(LIBs).In the pursuit of carbon neutrality,LIBs are expected to play a pivotal role in reducing CO_(2)emissions by decreasing reliance on fossil fuels and enabling the integration of renewable energy sources.Owing to their technological maturity and exceptional electrochemical performance,the global production of graphite and graphene for LIBs is projected to continue expanding.Over the past decades,numerous researchers have concentrated on reducing the material and energy input whilst optimising the electrochemical performance of graphite and graphene,through novel synthesis methods and various modifications at the laboratory scale.This review provides a comprehensive examination of the manufacturing methods,environmental impact,research progress,and challenges associated with graphite and graphene in LIBs from an industrial perspective,with a particular focus on the carbon footprint of production processes.Additionally,it considers emerging challenges and future development directions of graphite and graphene,offering significant insights for ongoing and future research in the field of green LIBs.展开更多
Large-area graphene films with defined uniformity,thickness and morphology are crucial for their applications in optoelectronic and photothermal devices.Herein,we demonstrate that oriented arrangement and ordered asse...Large-area graphene films with defined uniformity,thickness and morphology are crucial for their applications in optoelectronic and photothermal devices.Herein,we demonstrate that oriented arrangement and ordered assembly of graphene oxide(GO)nanosheets in solution films can be realized to obtain the high-quality and large-area reduced GO(rGO)films.The key to the success of this process primarily lies in the control of GO solution shear force direction with array capillaries,achieving oriented arrangement of GO nanosheets in the solution film.Secondly,the control of GO nanosheet concentration and solution viscosity during solvent evaporation of solution film is key to achieve the ordered and disordered assembly of GO,featuring the smooth and wrinkled structure rGO films,respectively.Subsequently,the resultant smooth rGO film with ordered assembly exhibits excellent thermal conductivity and electronic conductivity(over 1800 S·cm-1).Meanwhile,the wrinkled rGO film with disordered assembly can be used as a coating layer on Al current collectors,demonstrating anticorrosion properties and enhanced material adhesive stability.As a result,with such collectors,the high-voltage Li//NCM811 batteries show a 6-fold increase in cycle stability,and the lithium-sulfur batteries with high sulfur loading show a 3-fold increase in cycle stability.展开更多
Electrosynthesis of hydrogen peroxide through the two-electron oxygen reduction pathway provides a crucial alternative to the energy-intensive anthraquinone process.Nevertheless,the efficicency for hydrogen peroxide g...Electrosynthesis of hydrogen peroxide through the two-electron oxygen reduction pathway provides a crucial alternative to the energy-intensive anthraquinone process.Nevertheless,the efficicency for hydrogen peroxide generation is limited by the competitive four-electron pathway.In this work,we report a noncovalent modulation strategy for the isolated CoN_(4) sites by metal-phthalocyanine molecules confinement,which boosts the two-electron oxygen reduction towards generating hydrogen peroxide.The confined Co-phthalocyanine molecules on CoN_(4) sites through π-π interactions induce the competitive*OOH adsorption between the two Co sites formed nanochannel.This noncovalent modulation contributes to the weakened*OOH binding on CoN_(4) sites and thus suppresses its further dissociation,achieving the maximum selectivity of 95% with high activity for H_(2)O_(2)production.This work shows that tailoring noncovalent interactions beyond the binding sites is a promising approach to modulate the local structure of isolated metal sites and related catalytic performance.展开更多
Hard carbons(HCs)are commercial anode materials for sodium-ion batteries(SIBs),yet their electrochemical performance remains limited by intrinsic structural deficiencies and insufficient Na+storage kinetics.Herein,we ...Hard carbons(HCs)are commercial anode materials for sodium-ion batteries(SIBs),yet their electrochemical performance remains limited by intrinsic structural deficiencies and insufficient Na+storage kinetics.Herein,we report oxygen manipulation in hard carbon,enabled by plasma and laser beam,for improved Na^(+)storage.Starting with commercial HC electrodes,oxygen atoms were first implanted into carbon layers via atmospheric plasma treatment under controlled oxygen partial pressure.Subsequent laser irradiation induced localized thermal shocks that selectively remove oxygen atoms from edge sites,triggering transient carbon lattice rearrangement to simultaneously generate intrinsic defects and optimally sized closed nanopores(1.2-2.0 nm).This dual-stage regulation yielded HC anodes with exceptional Na^(+)storage properties,achieving a high reversible capacity of 335 mAh·g^(-1)at 30 mA·g^(-1)(with 36% enhancement compared with pristine HC)and enhanced Na+diffusion.Through in situ Raman and correlated ex situ spectroscopy analyses(electron paramagnetic resonance(EPR)and X-ray photoelectron spectroscopy(XPS)),we systematically decode the multiscale Na^(+)storage mechanism involving defect adsorption,interlayer intercalation,and nanopore filling.The proposed methodology bridges atomic-scale structural engineering with macroscopic electrode performance optimization,offering a scalable green manufacturing pathway for next-generation SIBs.展开更多
基金support from the National Key Technologies R&D Program of China(2022YFE0114800)National Natural Science Foundation of China(22075047),and the 111 Project(D16008)。
文摘Hydrogen peroxide(H_(2)O_(2))is a versatile oxidant with significant applications,particularly in regulating the microenvironment for healthcare purposes.Herein,a rational design of the photoanode is implemented to enhance H_(2)O_(2) production by oxidizing H_(2)O in a portable photoelectrocatalysis(PEC)device.The obtained solution from this system is demonstrated for effective bactericidal activity against Staphylococcus aureus and Escherichia coli,while maintaining low toxicity toward hippocampal neuronal cells.The photoanode is achieved by Mo-doped BiVO4 films,which are subsequently loaded with cobalt-porphyrin(Co-py)molecules as a co-catalyst.As a result,the optimal performance for H_(2)O_(2) production rate was achieved at 8.4μmol h^(−1) cm^(−2),which is 1.8 times that of the pristine BiVO4 photoanode.Density functional theory(DFT)simulations reveal that the improved performance results from a 1.1 eV reduction in the energy of the rate-determining step of·OH adsorption by the optimal photoanode.This study demonstrates a PEC approach for promoting H_(2)O_(2) production by converting H_(2)O for antibacterial purposes,offering potential applications in conventionally controlling microenvironments for healthcare applications.
基金supported by the National Natural Science Foundation of China(52276196)the Foundation of State Key Laboratory of Coal Combustion(FSKLCCA2508)the High-level Talent Foundation of Anhui Agricultural University(rc412307).
文摘Flash Joule heating(FJH),as a high-efficiency and low-energy consumption technology for advanced materials synthesis,has shown significant potential in the synthesis of graphene and other functional carbon materials.Based on the Joule effect,the solid carbon sources can be rapidly heated to ultra-high temperatures(>3000 K)through instantaneous high-energy current pulses during FJH,thus driving the rapid rearrangement and graphitization of carbon atoms.This technology demonstrates numerous advantages,such as solvent-and catalyst-free features,high energy conversion efficiency,and a short process cycle.In this review,we have systematically summarized the technology principle and equipment design for FJH,as well as its raw materials selection and pretreatment strategies.The research progress in the FJH synthesis of flash graphene,carbon nanotubes,graphene fibers,and anode hard carbon,as well as its by-products,is also presented.FJH can precisely optimize the microstructures of carbon materials(e.g.,interlayer spacing of turbostratic graphene,defect concentration,and heteroatom doping)by regulating its operation parameters like flash voltage and flash time,thereby enhancing their performances in various applications,such as composite reinforcement,metal-ion battery electrodes,supercapacitors,and electrocatalysts.However,this technology is still challenged by low process yield,macroscopic material uniformity,and green power supply system construction.More research efforts are also required to promote the transition of FJH from laboratory to industrial-scale applications,thus providing innovative solutions for advanced carbon materials manufacturing and waste management toward carbon neutrality.
基金supported by the Program for New Century Talents in University(No.NCET-11-0951)from the Ministry of Education of ChinaKey Laboratory Project Fund of CAS(No.2005DP173065-2016-04).
文摘Photocatalytic oxygen reduction provides a sustainable method for on-site hydrogen peroxide(H_(2)O_(2))synthesis.However,most photocatalysts suffer from moderate kinetics due to sluggish electron transfer and inefficient oxygen adsorption and activation.Herein,sodium(Na)and potassium(K)are co-incorporated into graphitic carbon nitride(g-C_(3)N_(4))via a stepwise co-doping strategy combining sodium chloride-induced and molten salt-assisted polymerization.Experimental results and density functional theory calculations demonstrate that the synergistic interaction between intralayer Na+ions and interlayer K^(+)ions facilitates charge carrier separation and migration both within and between g-C_(3)N_(4)layers.Additionally,multiple heteroatom sites enhance surface charge polarization and introduce cyano groups,which synergistically promote oxygen molecule(O_(2))adsorption and elevate local proton coverage.Simultaneously,the energy barrier for H_(2)O_(2)desorption on the optimal photocatalyst(5Na/3.3K-CN)is lowered,thus improving H_(2)O_(2)production efficiency.Eventually,5Na/3.3K-CN exhibits an impressive H_(2)O_(2)yield of 2541.6μmol·g^(-1)·h^(-1) in an artificial reactor,which is 10.6 times higher than that of pure g-C_(3)N_(4)(240.2μmol·g^(-1)·h^(-1)).Under natural sunlight outdoors,5Na/3.3K-CN still maintains ultrahigh H_(2)O_(2)photosynthesis efficiency,achieving an H_(2)O_(2)photosynthesis rate of 2068.7μmol·g^(-1)·h^(-1).This work introduces a straightforward method to simultaneously optimize charge transfer and O_(2)activation for boosting H_(2)O_(2)photosynthesis,offering valuable insights toward the real-world deployment of g-C_(3)N_(4)-based photocatalysts in environmental protection and energy conversion.
基金supported by the Shaanxi Sanqin Scholars Innovation Team,the Science and Technology Project of Yan’an City(No.2023-CYL-193)the Key Science Research Plan of Department of Education in Shaanxi Province(No.23JS070)the Science Research Training Project(No.CLXZ2207).
文摘Photosynthesis is a promising method for H_(2)O_(2)production,but its application in pure water is limited by slow oxidation kinetics and rapid photocarrier recombination of photocatalysts.Herein,a novel defective carbon nitride photocatalyst(D-C3-xN4)containing the C vacancies and the frustrated Lewis pairs(B and N of cyano group)is designed for H_(2)O_(2)photosynthesis,and the role of C vacancies on the electron transfer mechanism during photocatalysis is systematically investigated.The D-C_(3-x)N_(4) exhibits a H_(2)O_(2)production rate of 140.1μmol·g^(-1)·h^(-1) in pure water,which is 87.6 times that of C_(3)N_(4).Such superior performance for H_(2)O_(2)photosynthesis is found to arise from the C vacancies and frustrated Lewis pairs(FLPs).The C vacancies have strong electron-trapping ability,which greatly enhances the separation of photocarriers.The C vacancies can also effectively reduce O_(2)to*OOH via a proton-coupled process,which significantly accelerates the O_(2)reduction kinetics.Meanwhile,the FLPs show an outstanding catalytic activity for H_(2)O oxidation.This study not only provides a new structure for highly active photocatalysts,but also deepens the understanding of the electron transfer mechanism of photocatalysts with trapped sites.
基金financially supported by the National Natural Science Foundation of China(Nos.22272118,22172111,and 22309134)the Science and Technology Commission of Shanghai Municipality,China(Nos.22ZR1464100,20ZR1460300,and 19DZ2271500)+2 种基金the China Postdoctoral Science Foundation(2022M712402),the Shanghai Rising-Star Program(23YF1449200)the Zhejiang Provincial Science and Technology Project(2022C01182)the Fundamental Research Funds for the Central Universities(2023-3-YB-07)。
文摘Carbon superstructures with multiscale hierarchies and functional attributes represent an appealing cathode candidate for zinc hybrid capacitors,but their tailor-made design to optimize the capacitive activity remains a confusing topic.Here we develop a hydrogen-bond-oriented interfacial super-assembly strategy to custom-tailor nanosheet-intertwined spherical carbon superstructures(SCSs)for Zn-ion storage with double-high capacitive activity and durability.Tetrachlorobenzoquinone(H-bond acceptor)and dimethylbenzidine(H-bond donator)can interact to form organic nanosheet modules,which are sequentially assembled,orientally compacted and densified into well-orchestrated superstructures through multiple H-bonds(N-H···O).Featured with rich surface-active heterodiatomic motifs,more exposed nanoporous channels,and successive charge migration paths,SCSs cathode promises high accessibility of built-in zincophilic sites and rapid ion diffusion with low energy barriers(3.3Ωs-0.5).Consequently,the assembled Zn||SCSs capacitor harvests all-round improvement in Zn-ion storage metrics,including high energy density(166 Wh kg-1),high-rate performance(172 m Ah g^(-1)at 20 A g^(-1)),and long-lasting cycling lifespan(95.5%capacity retention after 500,000 cycles).An opposite chargecarrier storage mechanism is rationalized for SCSs cathode to maximize spatial capacitive charge storage,involving high-kinetics physical Zn^(2+)/CF_(3)SO_(3)-adsorption and chemical Zn^(2+)redox with carbonyl/pyridine groups.This work gives insights into H-bond-guided interfacial superassembly design of superstructural carbons toward advanced energy storage.
基金supported by European Union's Horizon Europe,UK Research and Innovation(UKRI).
文摘Graphite,encompassing both natural graphite and synthetic graphite,and graphene,have been extensively utilized and investigated as anode materials and additives in lithium-ion batteries(LIBs).In the pursuit of carbon neutrality,LIBs are expected to play a pivotal role in reducing CO_(2)emissions by decreasing reliance on fossil fuels and enabling the integration of renewable energy sources.Owing to their technological maturity and exceptional electrochemical performance,the global production of graphite and graphene for LIBs is projected to continue expanding.Over the past decades,numerous researchers have concentrated on reducing the material and energy input whilst optimising the electrochemical performance of graphite and graphene,through novel synthesis methods and various modifications at the laboratory scale.This review provides a comprehensive examination of the manufacturing methods,environmental impact,research progress,and challenges associated with graphite and graphene in LIBs from an industrial perspective,with a particular focus on the carbon footprint of production processes.Additionally,it considers emerging challenges and future development directions of graphite and graphene,offering significant insights for ongoing and future research in the field of green LIBs.
基金the National Natural Science Foundation of China(No.U22A20437)Joint Fund of Science and Technology R&D Plan of Henan Province(No.222301420005)Program for Innovative Research Team(in Science and Technology)in University of Henan Province(No.24IRTSTHN001)for financial support.
文摘Large-area graphene films with defined uniformity,thickness and morphology are crucial for their applications in optoelectronic and photothermal devices.Herein,we demonstrate that oriented arrangement and ordered assembly of graphene oxide(GO)nanosheets in solution films can be realized to obtain the high-quality and large-area reduced GO(rGO)films.The key to the success of this process primarily lies in the control of GO solution shear force direction with array capillaries,achieving oriented arrangement of GO nanosheets in the solution film.Secondly,the control of GO nanosheet concentration and solution viscosity during solvent evaporation of solution film is key to achieve the ordered and disordered assembly of GO,featuring the smooth and wrinkled structure rGO films,respectively.Subsequently,the resultant smooth rGO film with ordered assembly exhibits excellent thermal conductivity and electronic conductivity(over 1800 S·cm-1).Meanwhile,the wrinkled rGO film with disordered assembly can be used as a coating layer on Al current collectors,demonstrating anticorrosion properties and enhanced material adhesive stability.As a result,with such collectors,the high-voltage Li//NCM811 batteries show a 6-fold increase in cycle stability,and the lithium-sulfur batteries with high sulfur loading show a 3-fold increase in cycle stability.
基金financially supported by the National Natural Science Foundation of China(No.U21A2077)the Natural Science Foundation of Shandong Province(Nos.ZR2022JQ08 and 2023HWYQ-028)+4 种基金the Taishan Scholar Project Foundation of Shandong Province(Nos.tsqn202211028 and tsqn202306080)the City University of Hong Kong(Nos.9020005,9610663,and 7020103)ITF-RTH-Global STEM Professorship(No.9446008)Hong Kong Branch of National Precious Metals Material Engineering Research Center—ITC FundGeneral Research Fund(No.9043720)from the Research Grants Council of Hong Kong SAR,China.
文摘Electrosynthesis of hydrogen peroxide through the two-electron oxygen reduction pathway provides a crucial alternative to the energy-intensive anthraquinone process.Nevertheless,the efficicency for hydrogen peroxide generation is limited by the competitive four-electron pathway.In this work,we report a noncovalent modulation strategy for the isolated CoN_(4) sites by metal-phthalocyanine molecules confinement,which boosts the two-electron oxygen reduction towards generating hydrogen peroxide.The confined Co-phthalocyanine molecules on CoN_(4) sites through π-π interactions induce the competitive*OOH adsorption between the two Co sites formed nanochannel.This noncovalent modulation contributes to the weakened*OOH binding on CoN_(4) sites and thus suppresses its further dissociation,achieving the maximum selectivity of 95% with high activity for H_(2)O_(2)production.This work shows that tailoring noncovalent interactions beyond the binding sites is a promising approach to modulate the local structure of isolated metal sites and related catalytic performance.
基金financially supported by the National Key Research and Development Program of China(No.2023YFB4203702)the National Natural Science Foundation of China(Nos.22179145,22005341,and 22309206)+4 种基金Shandong Provincial Natural Science Foundation(No.ZR2020QB128)Taishan Scholars Program of Shandong Province(No.tsqn20221117)Shandong Provincial Excellent Young Scientists Fund Program(Overseas)(No.2024HWYQ-047)Qingdao Natural Science Foundation(Nos.24-8-4-zrjj-jch and 23-2-1-24-zyyd-jch)Science and Technology Park Incubation Program Project of Qingdao City(No.25-1-1-yqpy-33-qy).
文摘Hard carbons(HCs)are commercial anode materials for sodium-ion batteries(SIBs),yet their electrochemical performance remains limited by intrinsic structural deficiencies and insufficient Na+storage kinetics.Herein,we report oxygen manipulation in hard carbon,enabled by plasma and laser beam,for improved Na^(+)storage.Starting with commercial HC electrodes,oxygen atoms were first implanted into carbon layers via atmospheric plasma treatment under controlled oxygen partial pressure.Subsequent laser irradiation induced localized thermal shocks that selectively remove oxygen atoms from edge sites,triggering transient carbon lattice rearrangement to simultaneously generate intrinsic defects and optimally sized closed nanopores(1.2-2.0 nm).This dual-stage regulation yielded HC anodes with exceptional Na^(+)storage properties,achieving a high reversible capacity of 335 mAh·g^(-1)at 30 mA·g^(-1)(with 36% enhancement compared with pristine HC)and enhanced Na+diffusion.Through in situ Raman and correlated ex situ spectroscopy analyses(electron paramagnetic resonance(EPR)and X-ray photoelectron spectroscopy(XPS)),we systematically decode the multiscale Na^(+)storage mechanism involving defect adsorption,interlayer intercalation,and nanopore filling.The proposed methodology bridges atomic-scale structural engineering with macroscopic electrode performance optimization,offering a scalable green manufacturing pathway for next-generation SIBs.
