In studying interactions between intense laser fields and atoms or molecules,the role of electron correlation effects on the dynamical response is an important and pressing issue to address.Utilizing Bohmian mechanics...In studying interactions between intense laser fields and atoms or molecules,the role of electron correlation effects on the dynamical response is an important and pressing issue to address.Utilizing Bohmian mechanics(BM),we have theoretically explored the two-electron correlation characteristics while generating high-order harmonics in xenon atoms subjected to intense laser fields.We initially employed Bohmian trajectories to reproduce the dynamics of the electrons and subsequently utilized time-frequency analysis spectra to ascertain the emission time windows for high-order harmonics.Within these time windows,we classified the nuclear region Bohmian trajectories and observed that intense high-order harmonics are solely generated when paired Bohmian particles(BPs)concurrently appear in the nuclear region and reside there for a duration within a re-collision time window.Furthermore,our analysis of characteristic trajectories producing high-order harmonics led us to propose a two-electron re-collision model to elucidate this phenomenon.The study demonstrates that intense high-order harmonics are only generated when both electrons are in the ground state within the re-collision time window.This work discusses the implications of correlation effects between two electrons and offers valuable insights for studying correlation in multi-electron high-order harmonic generation.展开更多
The x-ray energies and transition rates associated with single and double electron radiative transitions from the double K hole state 2s2p to the 1s2s and 1s^2 configurations of 11 selected He-like ions(10 ≤ Z ≤ 47)...The x-ray energies and transition rates associated with single and double electron radiative transitions from the double K hole state 2s2p to the 1s2s and 1s^2 configurations of 11 selected He-like ions(10 ≤ Z ≤ 47) are calculated using the fully relativistic multi-configuration Dirac–Fock method(MCDF). An appropriate electron correlation model is constructed with the aid of the active space method, which allows the electron correlation effects to be studied efficiently. The contributions of the electron correlation and the Breit interaction to the transition properties are analyzed in detail. It is found that the two-electron one-photon(TEOP) transition is correlation sensitive. The Breit interaction and electron correlation both contribute significantly to the radiative transition properties of the double K hole state of the He-like ions. Good agreement between the present calculation and previous work is achieved. The calculated data will be helpful to future investigations on double K hole decay processes of He-like ions.展开更多
Hydrogen peroxide(H_(2)O_(2))is an eco-friendly chemical with widespread industrial applications.However,the commercial anthraquinone process for H_(2)O_(2) production is energy-intensive and environmentally harmful,h...Hydrogen peroxide(H_(2)O_(2))is an eco-friendly chemical with widespread industrial applications.However,the commercial anthraquinone process for H_(2)O_(2) production is energy-intensive and environmentally harmful,highlighting the need for more sustainable alternatives.The electrochemical production of H_(2)O_(2) via the two-electron water oxidation reaction(2e^(−)WOR)presents a promising route but is often hindered by low efficiency and selectivity,due to the competition with the oxygen evolution reaction.In this study,we employed high-throughput computational screening and microkinetic modeling to design a series of efficient 2e^(−)WOR electrocatalysts from a library of 240 single-metal-embedded nitrogen heterocycle aromatic molecules(M-NHAMs).These catalysts,primarily comprising post-transition metals,such as Cu,Ni,Zn,and Pd,exhibit high activity for H_(2)O_(2) conversion with a limiting potential approaching the optimal value of 1.76 V.Additionally,they exhibit excellent selectivity,with Faradaic efficiencies exceeding 80%at overpotentials below 300 mV.Structure-performance analysis reveals that the d-band center and magnetic moment of the metal center correlated strongly with the oxygen adsorption free energy(ΔGO*),suggesting these parameters as key catalytic descriptors for efficient screening and performance optimization.This study contributes to the rational design of highly efficient and selective electrocatalysts for electrochemical production of H_(2)O_(2),offering a sustainable solution for green energy and industrial applications.展开更多
Hydrogen peroxide(H_(2)O_(2))electrosynthesis via two-electron oxygen reduction reaction(2e-ORR)is a promising alternative for the energy-intensive anthraquinone process.However,the instability of the catalytic metal ...Hydrogen peroxide(H_(2)O_(2))electrosynthesis via two-electron oxygen reduction reaction(2e-ORR)is a promising alternative for the energy-intensive anthraquinone process.However,the instability of the catalytic metal sites in the state-of-the-art metal single-atom catalysts(M-SACs)hinders their further industrial applications,and the high potential and valueless oxygen product of the conventional anodic oxygen evolution reaction(OER)further limit the economic efficiency of this technology.To address this,a dynamically local structure reconstruction strategy is proposed to in situ transfer the active sites from unstable metal sites to the stable surrounding carbon sites for efficient and durable 2e^(-)ORR electrocatalysis.For the as-designed Mn-N_(3)O-C catalyst,by reconstructing Mn sites into Mn(^(*)OH),the Mn sites were passivated and carbon sites adjacent to the O atom were verified to be the actual active sites by in situ characterization and theoretical calculation.Consequently,Mn-N_(3)O-C exhibited>80%Faradaic efficiency and superior long-term durability over 100 h for H_(2)O_(2)electrosynthesis at~120 mA cm^(-2).In addition,coupling anodic ethylene glycol oxidation reaction(EGOR)further improves the efficiency and economic viability of the H_(2)O_(2)electrosynthesis system.This two-pronged strategy thus opens up a new opportunity for the development of stable H_(2)O_(2)electrosynthesis with low energy consumption and superior economic performance.展开更多
Derivatives of metal-organic frameworks(MOFs)are a promising bifunctional electrocatalysts in electrochemical advanced oxidation processes(EAOPs).These metal/carbon materials overcome the limitations of individual com...Derivatives of metal-organic frameworks(MOFs)are a promising bifunctional electrocatalysts in electrochemical advanced oxidation processes(EAOPs).These metal/carbon materials overcome the limitations of individual components by creating synergistic effects.EAOPs is primarily constrained by the generation and activation of H_(2)O_(2).This article examines the regulatory strategies employed in MOFs derivatives to enhance the production of H_(2)O_(2)via 2e^(-)pathways and its activation to·OH,focusing on preparation techniques,structures,and compositions.The design of these derivatives involves methods such as metal dispersion on the surface of nanocarbons,embedding in carbon shells,and atomic dispersion of metals anchored in porous carbon.MOFs derivatives promote·OH production and enhance wastewater purification through mechanisms such as boosting the Fe(Ⅱ)/Fe(Ⅲ)cycle,facilitating direct 3e^(-)reactions of O_(2),and interacting of O_(2)^(·-).Moreover,the performance and durability of MOFs derivatives in wastewater treatment,particularly in influencing·OH generation within EAOPs,were investigated.This review addresses current challenges and future prospects,offering valuable insights for the development of MOFs derivatives as 3e^(-)ORR electrocatalysts and the advancement of sustainable water treatment technologies.展开更多
Photocatalytic fuel cells provide promising opportunities for sustainable wastewater treatment and energy conversion.However,their applications are challenged by the sluggish oxygen reducton reaction(ORR)kinetics at c...Photocatalytic fuel cells provide promising opportunities for sustainable wastewater treatment and energy conversion.However,their applications are challenged by the sluggish oxygen reducton reaction(ORR)kinetics at cathodes owning to the low O_(2) solubility and diffusion rate.Herein,we proposed a photobiocatalytic fuel cell(PBFC) with a novel hybrid biocathode based on artificially engineered algal cells coated by ZIF-8 confined carbon dots/bilirubin oxidase(ZIF-8/CDs/BOD@algae).Microalgae absorbed CO_(2) and provided O_(2) in situ for BOD catalysts.Due to effective absorption of O_(2) by imidazole and confinement of hydrophobic porous ZIF-8,oxygen diffusion has been accelerated in MOF/enzyme systems.Importantly,the introduction of CDs alleviated the poor conductivity of ZIF-8 and improved the electron transfer rate of BOD.Thus,the biocathode exhibited a high current density of 1767 μA/cm^(2),a 2.26-fold increase compared with that of CDs/BOD/algae biocathode.Also,it displayed enduring operational stability for up to 60 h since the firmly wrapped ZIF-8 shells could encapsulate proteins and protect algae from the external stimulation.When coupled with Mo:BiVO_(4) photoanodes,the PBFC exhibited a remarkable power output of 131.8 μW/cm^(2) using tetracycline hydrochloride(TCH) as a fuel and an increased degradation rate of TCH.Therefore,this work not only establishs an effective confinement strategy for enzyme to enrich oxygen,but also unveils new possibilities for modified microalgal cells aiding photoelectrocatalytic systems to recover energy from wastewater treatment.展开更多
Carbon-based air cathodes offer low cost,high electrical conductivity,and structural tunability.However,they suffer from limited catalytic activity and inefficient gas transport,and they typically rely on noble metal ...Carbon-based air cathodes offer low cost,high electrical conductivity,and structural tunability.However,they suffer from limited catalytic activity and inefficient gas transport,and they typically rely on noble metal additives or complex multilayer configurations.To tackle these issues,this study devised a self-activated integrated carbon-based air cathode.By integrating in situ catalytic site construction with structural optimization,the strategy not only induces the formation of oxygen functional groups(─C─OH,─C═O,─COOH),hierarchical pores,and uniformly distributed active sites,but also establishes a favorable electronic and mass-transport environment.Furthermore,the roll-pressing-based integrated design streamlines electrode construction,reinforces interfacial bonding,and significantly enhances mechanical stability.Density functional theory(DFT)calculations show that oxygen functional groups initiate hydrogen bonding interaction and promote charge enrichment,which improves the activity of the cathode and facilitates intermediate adsorption/desorption in oxygen reduction and evolution reactions processes.As a result,the integrated air cathode-based rechargeable zinc-air batteries(RZABs)achieve a high specific capacity of 811 mAh g^(-1).It also performs well in quasi-solid-state RZABs and silicon-air batteries systems across a wide temperature range,demonstrating strong adaptability and application potential.This study provides a scalable and cost-effective design strategy for high-performance carbon-based air cathodes,offering new insights into advancing durable and practical metal-air energy systems.展开更多
基金Project supported by the Natural Science Foundation(General Project)of Jilin Province,China(Grant No.20230101283JC)。
文摘In studying interactions between intense laser fields and atoms or molecules,the role of electron correlation effects on the dynamical response is an important and pressing issue to address.Utilizing Bohmian mechanics(BM),we have theoretically explored the two-electron correlation characteristics while generating high-order harmonics in xenon atoms subjected to intense laser fields.We initially employed Bohmian trajectories to reproduce the dynamics of the electrons and subsequently utilized time-frequency analysis spectra to ascertain the emission time windows for high-order harmonics.Within these time windows,we classified the nuclear region Bohmian trajectories and observed that intense high-order harmonics are solely generated when paired Bohmian particles(BPs)concurrently appear in the nuclear region and reside there for a duration within a re-collision time window.Furthermore,our analysis of characteristic trajectories producing high-order harmonics led us to propose a two-electron re-collision model to elucidate this phenomenon.The study demonstrates that intense high-order harmonics are only generated when both electrons are in the ground state within the re-collision time window.This work discusses the implications of correlation effects between two electrons and offers valuable insights for studying correlation in multi-electron high-order harmonic generation.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.U1832126 and 11874051)the National Key Research and Development Program of China(Grant No.2017YFA0402300)。
文摘The x-ray energies and transition rates associated with single and double electron radiative transitions from the double K hole state 2s2p to the 1s2s and 1s^2 configurations of 11 selected He-like ions(10 ≤ Z ≤ 47) are calculated using the fully relativistic multi-configuration Dirac–Fock method(MCDF). An appropriate electron correlation model is constructed with the aid of the active space method, which allows the electron correlation effects to be studied efficiently. The contributions of the electron correlation and the Breit interaction to the transition properties are analyzed in detail. It is found that the two-electron one-photon(TEOP) transition is correlation sensitive. The Breit interaction and electron correlation both contribute significantly to the radiative transition properties of the double K hole state of the He-like ions. Good agreement between the present calculation and previous work is achieved. The calculated data will be helpful to future investigations on double K hole decay processes of He-like ions.
基金supported by the National Natural Science Foundation of China (22209061 and 22462006)Start-up Fund for Senior Talents in Jiangsu University (21JDG060)the Fundamental Research Funds for the Central Universities (20720220009)
文摘Hydrogen peroxide(H_(2)O_(2))is an eco-friendly chemical with widespread industrial applications.However,the commercial anthraquinone process for H_(2)O_(2) production is energy-intensive and environmentally harmful,highlighting the need for more sustainable alternatives.The electrochemical production of H_(2)O_(2) via the two-electron water oxidation reaction(2e^(−)WOR)presents a promising route but is often hindered by low efficiency and selectivity,due to the competition with the oxygen evolution reaction.In this study,we employed high-throughput computational screening and microkinetic modeling to design a series of efficient 2e^(−)WOR electrocatalysts from a library of 240 single-metal-embedded nitrogen heterocycle aromatic molecules(M-NHAMs).These catalysts,primarily comprising post-transition metals,such as Cu,Ni,Zn,and Pd,exhibit high activity for H_(2)O_(2) conversion with a limiting potential approaching the optimal value of 1.76 V.Additionally,they exhibit excellent selectivity,with Faradaic efficiencies exceeding 80%at overpotentials below 300 mV.Structure-performance analysis reveals that the d-band center and magnetic moment of the metal center correlated strongly with the oxygen adsorption free energy(ΔGO*),suggesting these parameters as key catalytic descriptors for efficient screening and performance optimization.This study contributes to the rational design of highly efficient and selective electrocatalysts for electrochemical production of H_(2)O_(2),offering a sustainable solution for green energy and industrial applications.
基金supported by the National Natural Science Foundation of China(22379111 and 22179093)。
文摘Hydrogen peroxide(H_(2)O_(2))electrosynthesis via two-electron oxygen reduction reaction(2e-ORR)is a promising alternative for the energy-intensive anthraquinone process.However,the instability of the catalytic metal sites in the state-of-the-art metal single-atom catalysts(M-SACs)hinders their further industrial applications,and the high potential and valueless oxygen product of the conventional anodic oxygen evolution reaction(OER)further limit the economic efficiency of this technology.To address this,a dynamically local structure reconstruction strategy is proposed to in situ transfer the active sites from unstable metal sites to the stable surrounding carbon sites for efficient and durable 2e^(-)ORR electrocatalysis.For the as-designed Mn-N_(3)O-C catalyst,by reconstructing Mn sites into Mn(^(*)OH),the Mn sites were passivated and carbon sites adjacent to the O atom were verified to be the actual active sites by in situ characterization and theoretical calculation.Consequently,Mn-N_(3)O-C exhibited>80%Faradaic efficiency and superior long-term durability over 100 h for H_(2)O_(2)electrosynthesis at~120 mA cm^(-2).In addition,coupling anodic ethylene glycol oxidation reaction(EGOR)further improves the efficiency and economic viability of the H_(2)O_(2)electrosynthesis system.This two-pronged strategy thus opens up a new opportunity for the development of stable H_(2)O_(2)electrosynthesis with low energy consumption and superior economic performance.
基金financially supported by National Natural Science Foundation of China(No.22302170)Science Research Project of Hebei Education Department(No.QN2024256)。
文摘Derivatives of metal-organic frameworks(MOFs)are a promising bifunctional electrocatalysts in electrochemical advanced oxidation processes(EAOPs).These metal/carbon materials overcome the limitations of individual components by creating synergistic effects.EAOPs is primarily constrained by the generation and activation of H_(2)O_(2).This article examines the regulatory strategies employed in MOFs derivatives to enhance the production of H_(2)O_(2)via 2e^(-)pathways and its activation to·OH,focusing on preparation techniques,structures,and compositions.The design of these derivatives involves methods such as metal dispersion on the surface of nanocarbons,embedding in carbon shells,and atomic dispersion of metals anchored in porous carbon.MOFs derivatives promote·OH production and enhance wastewater purification through mechanisms such as boosting the Fe(Ⅱ)/Fe(Ⅲ)cycle,facilitating direct 3e^(-)reactions of O_(2),and interacting of O_(2)^(·-).Moreover,the performance and durability of MOFs derivatives in wastewater treatment,particularly in influencing·OH generation within EAOPs,were investigated.This review addresses current challenges and future prospects,offering valuable insights for the development of MOFs derivatives as 3e^(-)ORR electrocatalysts and the advancement of sustainable water treatment technologies.
基金support from National Natural Science Foundation of China (Nos.22176086,52100014)Natural Science Foundation of Jiangsu Province (No.BK20210189)+7 种基金State Key laboratory of Pollution Control and Resource Reuse,the Fundamental Research Funds for the Central Universities (Nos.021114380183,021114380189,021114380199)the Research Funds from Frontiers Science Center for Critical Earth Material Cycling of Nanjing UniversityResearch Funds for Jiangsu Distinguished ProfessorCarbon Peaking and Carbon Neutrality Technological Innovation Foundation of Jiangsu Province (No.BE2022861)the Central Universities - Cemac “Geo X” Interdisciplinary Program (No.021114380217)Frontiers Science Center for Critical Earth Material Cycling of Nanjing University (No.2024QNXZ07)Postdoctoral Fellowship Program of CPSF (No.GZC20231105)the Jiangsu Funding Program for Excellent Postdoctoral Talent (No.2023ZB226)。
文摘Photocatalytic fuel cells provide promising opportunities for sustainable wastewater treatment and energy conversion.However,their applications are challenged by the sluggish oxygen reducton reaction(ORR)kinetics at cathodes owning to the low O_(2) solubility and diffusion rate.Herein,we proposed a photobiocatalytic fuel cell(PBFC) with a novel hybrid biocathode based on artificially engineered algal cells coated by ZIF-8 confined carbon dots/bilirubin oxidase(ZIF-8/CDs/BOD@algae).Microalgae absorbed CO_(2) and provided O_(2) in situ for BOD catalysts.Due to effective absorption of O_(2) by imidazole and confinement of hydrophobic porous ZIF-8,oxygen diffusion has been accelerated in MOF/enzyme systems.Importantly,the introduction of CDs alleviated the poor conductivity of ZIF-8 and improved the electron transfer rate of BOD.Thus,the biocathode exhibited a high current density of 1767 μA/cm^(2),a 2.26-fold increase compared with that of CDs/BOD/algae biocathode.Also,it displayed enduring operational stability for up to 60 h since the firmly wrapped ZIF-8 shells could encapsulate proteins and protect algae from the external stimulation.When coupled with Mo:BiVO_(4) photoanodes,the PBFC exhibited a remarkable power output of 131.8 μW/cm^(2) using tetracycline hydrochloride(TCH) as a fuel and an increased degradation rate of TCH.Therefore,this work not only establishs an effective confinement strategy for enzyme to enrich oxygen,but also unveils new possibilities for modified microalgal cells aiding photoelectrocatalytic systems to recover energy from wastewater treatment.
基金funded by the National Nature Science Foundation of China(62264006,62574102)“Thousand Talents Program”of Yunnan Province for Young Talents,Innovative Research Teams(in Science and Technology)in the University of Yunnan Province(IRTSTYN),XingDian Talent Support Program for Young Talents,and Frontier Research Team of Kunming University 2023,The Basic Research Project of Yunnan Province(Nos.202201AU070022)+2 种基金Kunming University Talent Introduction Fund(Nos.YJL20024)Yunnan Province Education Department Scientific Research Fund Project(Nos.2024Y759)Undergraduate Innovation and Entrepreneurship Training Program Project of Yunnan Provincial(202411393005)。
文摘Carbon-based air cathodes offer low cost,high electrical conductivity,and structural tunability.However,they suffer from limited catalytic activity and inefficient gas transport,and they typically rely on noble metal additives or complex multilayer configurations.To tackle these issues,this study devised a self-activated integrated carbon-based air cathode.By integrating in situ catalytic site construction with structural optimization,the strategy not only induces the formation of oxygen functional groups(─C─OH,─C═O,─COOH),hierarchical pores,and uniformly distributed active sites,but also establishes a favorable electronic and mass-transport environment.Furthermore,the roll-pressing-based integrated design streamlines electrode construction,reinforces interfacial bonding,and significantly enhances mechanical stability.Density functional theory(DFT)calculations show that oxygen functional groups initiate hydrogen bonding interaction and promote charge enrichment,which improves the activity of the cathode and facilitates intermediate adsorption/desorption in oxygen reduction and evolution reactions processes.As a result,the integrated air cathode-based rechargeable zinc-air batteries(RZABs)achieve a high specific capacity of 811 mAh g^(-1).It also performs well in quasi-solid-state RZABs and silicon-air batteries systems across a wide temperature range,demonstrating strong adaptability and application potential.This study provides a scalable and cost-effective design strategy for high-performance carbon-based air cathodes,offering new insights into advancing durable and practical metal-air energy systems.
