The poor stability of RuO_(2)electrocatalysts has been the primary obstacles for their practical application in polymer electrolyte membrane electrolyzers.To dramatically enhance the durability of RuO_(2)to construct ...The poor stability of RuO_(2)electrocatalysts has been the primary obstacles for their practical application in polymer electrolyte membrane electrolyzers.To dramatically enhance the durability of RuO_(2)to construct activity-stability trade-off model is full of significance but challenging.Herein,a single atom Zn stabilized RuO_(2)with enriched oxygen vacancies(SA Zn-RuO_(2))is developed as a promising alternative to iridium oxide for acidic oxygen evolution reaction(OER).Compared with commercial RuO_(2),the enhanced Ru–O bond strength of SA Zn-RuO_(2)by forming Zn-O-Ru local structure motif is favorable to stabilize surface Ru,while the electrons transferred from Zn single atoms to adjacent Ru atoms protects the Ru active sites from overoxidation.Simultaneously,the optimized surrounding electronic structure of Ru sites in SA ZnRuO_(2)decreases the adsorption energies of OER intermediates to reduce the reaction barrier.As a result,the representative SA Zn-RuO_(2)exhibits a low overpotential of 210 mV to achieve 10 mA cm^(-2)and a greatly enhanced durability than commercial RuO_(2).This work provides a promising dual-engineering strategy by coupling single atom doping and vacancy for the tradeoff of high activity and catalytic stability toward acidic OER.展开更多
High-pressure nanosecond pulsed discharges(NPDs)have attracted increasing attention in recent years due to their wide potential applications.In this study,a barrier-free NPD in pure helium plasma at 120 Torr was numer...High-pressure nanosecond pulsed discharges(NPDs)have attracted increasing attention in recent years due to their wide potential applications.In this study,a barrier-free NPD in pure helium plasma at 120 Torr was numerically investigated by a one-dimensional self-consistent fluid model,and its current–voltage characteristics show very different behaviors from those in pulsed dielectric barrier discharges(DBDs),indicating an entirely distinctive discharge evolution in pulsed discharges with or without barriers on electrodes.Without the control of barriers,the computational data suggest that the discharge current increases very sharply during the plateau phase of the pulsed voltage and reaches its peak value at approximately the instant when the pulsed voltage starts to drop,together with a gradual reduction in the sheath thickness and an increase in electric field in the sheath region,which is in good agreement with experimental observations.By increasing the voltage plateau width and repetition frequency,the discharge current density from the simulation can be substantially enhanced,which cannot be observed in conventional pulsed DBDs,and the spatial distributions of the electric field and charged particles are given to unravel the underlying physics.From the computational data,the distinctive discharge characteristics in barrier-free NPDs are deeply understood,and could be further optimized by tailoring the waveform of the pulsed voltage to obtain desirable plasmas for applications.展开更多
Deformable catalytic material with excellent flexible structure is a new type of catalyst that has been applied in various chemical reactions,especially electrocatalytic hydrogen evolution reaction(HER).In recent year...Deformable catalytic material with excellent flexible structure is a new type of catalyst that has been applied in various chemical reactions,especially electrocatalytic hydrogen evolution reaction(HER).In recent years,deformable catalysts for HER have made great progress and would become a research hotspot.The catalytic activities of deformable catalysts could be adjustable by the strain engineering and surface reconfiguration.The surface curvature of flexible catalytic materials is closely related to the electrocatalytic HER properties.Here,firstly,we systematically summarized self-adaptive catalytic performance of deformable catalysts and various micro–nanostructures evolution in catalytic HER process.Secondly,a series of strategies to design highly active catalysts based on the mechanical flexibility of lowdimensional nanomaterials were summarized.Last but not least,we presented the challenges and prospects of the study of flexible and deformable micro–nanostructures of electrocatalysts,which would further deepen the understanding of catalytic mechanisms of deformable HER catalyst.展开更多
In this study,we systematically investigated the effect of proton concentration on the kinetics of the oxygen reduction reaction(ORR)on Pt(111)in acidic solutions.Experimental results demonstrate a rectangular hyperbo...In this study,we systematically investigated the effect of proton concentration on the kinetics of the oxygen reduction reaction(ORR)on Pt(111)in acidic solutions.Experimental results demonstrate a rectangular hyperbolic relationship,i.e.,the ORR current excluding the effect of other variables increases with proton concentration and then tends to a constant value.We consider that this is caused by the limitation of ORR kinetics by the trace oxygen concentration in the solution,which determines the upper limit of ORR kinetics.A model of effective concentration is further proposed for rectangular hyperbolic relationships:when the reactant concentration is high enough to reach a critical saturation concentration,the effective reactant concentration will become a constant value.This could be due to the limited concentration of a certain reactant for reactions involving more than one reactant or the limited number of active sites available on the catalyst.Our study provides new insights into the kinetics of electrocatalytic reactions,and it is important for the proper evaluation of catalyst activity and the study of structureperformance relationships.展开更多
We investigated the role of metal atomization and solvent decomposition into reductive species and carbon clusters in the phase formation of transition-metal carbides(TMCs;namely,Co_(3)C,Fe_(3)C,TiC,and MoC)by pulsed ...We investigated the role of metal atomization and solvent decomposition into reductive species and carbon clusters in the phase formation of transition-metal carbides(TMCs;namely,Co_(3)C,Fe_(3)C,TiC,and MoC)by pulsed laser ablation of Co,Fe,Ti,and Mo metals in acetone.The interaction between carbon s-p-orbitals and metal d-orbitals causes a redistribution of valence structure through charge transfer,leading to the formation of surface defects as observed by X-ray photoelectron spectroscopy.These defects influence the evolved TMCs,making them effective for hydrogen and oxygen evolution reactions(HER and OER)in an alkaline medium.Co_(3)C with more oxygen affinity promoted CoO(OH)intermediates,and the electrochemical surface oxidation to Co_(3)O_(4)was captured via in situ/operando electrochemical Raman probes,increasing the number of active sites for OER activity.MoC with more d-vacancies exhibits strong hydrogen binding,promoting HER kinetics,whereas Fe_(3)C and TiC with more defect states to trap charge carriers may hinder both OER and HER activities.The results show that the assembled membrane-less electrolyzer with Co_(3)C∥Co_(3)C and MoC∥MoC electrodes requires~2.01 and 1.99 V,respectively,to deliver a 10 mA cm−2 with excellent electrochemical and structural stability.In addition,the ascertained pulsed laser synthesis mechanism and unit-cell packing relations will open up sustainable pathways for obtaining highly stable electrocatalysts for electrolyzers.展开更多
Copper-based metal-organic frameworks(Cu-MOFs)are a promising multiphase catalyst for catalyzing C-S coupling reactions by virtue of their diverse structures and functions.However,the unpleasant odor and instability o...Copper-based metal-organic frameworks(Cu-MOFs)are a promising multiphase catalyst for catalyzing C-S coupling reactions by virtue of their diverse structures and functions.However,the unpleasant odor and instability of the organosulfur,as well as the mass-transfer resistance that exists in multiphase catalysis,have often limited the catalytic application of Cu-MOFs in C-S coupling reactions.In this paper,a Cu-MOFs catalyst modified by cetyltrimethylammonium bromide(CTAB)was designed to enhance mass transfer by increasing the adsorption of organic substrates using the long alkanes of CTAB.Concurrently,elemental sulfur was used to replace organosulfur to achieve a highly efficient and atom-economical multicomponent C-S coupling reaction.展开更多
Nyquist pulses have wide applications in many areas,from electronics to optics.Mode-locked lasers are ideal platforms to generate such pulses.However,how to generate high-quality Nyquist pulses in mode-locked lasers r...Nyquist pulses have wide applications in many areas,from electronics to optics.Mode-locked lasers are ideal platforms to generate such pulses.However,how to generate high-quality Nyquist pulses in mode-locked lasers remains elusive.We address this problem by managing different physical effects in mode-locked fiber lasers through extensive numerical simulations.We find that net dispersion,linear loss,gain and filter shaping can affect the quality of Nyquist pulses significantly.We also demonstrate that Nyquist pulses experience similariton shaping due to the nonlinear attractor effect in the gain medium.Our work may contribute to the design of Nyquist pulse sources and enrich the understanding of pulse shaping dynamics in mode-locked lasers.展开更多
Relativistic femtosecond mid-infrared pulses can be generated efficiently by laser interaction with near-criticaldensity plasmas.It is found theoretically and numerically that the radiation pressure of a circularly po...Relativistic femtosecond mid-infrared pulses can be generated efficiently by laser interaction with near-criticaldensity plasmas.It is found theoretically and numerically that the radiation pressure of a circularly polarized laser pulse first compresses the plasma electrons to form a dense flying mirror with a relativistic high speed.The pulse reflected by the mirror is red-shifted to the mid-infrared range.Full three-dimensional simulations demonstrate that the central wavelength of the mid-infrared pulse is tunable from 3µm to 14µm,and the laser energy conversion efficiency can reach as high as 13%.With a 0.5–10 PW incident laser pulse,the generated mid-infrared pulse reaches a peak power of 10–180 TW,which is interesting for various applications in ultrafast and high-field sciences.展开更多
A high-power laser ablating solid targets induces giant electromagnetic pulses(EMPs),which are intimately pertinent to laser parameters,such as energy and pulse width.In this study,we reveal the features of EMPs gener...A high-power laser ablating solid targets induces giant electromagnetic pulses(EMPs),which are intimately pertinent to laser parameters,such as energy and pulse width.In this study,we reveal the features of EMPs generated from a picosecond(ps)laser irradiating solid targets at the SG-Ⅱpicosecond petawatt(PSPW)laser facility.The laser energy and pulse,as well as target material and thickness,show determinative effects on the EMPs’amplitude.More intense EMPs are detected behind targets compared to those at the other three positions,and the EMP amplitude decreases from 90.09 kV/m to 17.8 kV/m with the gold target thickness increasing from 10μm to 20μm,which is suppressed when the laser pulse width is enlarged.The results are expected to provide more insight into EMPs produced by ps lasers coupling with targets and lay the foundation for an effective EMP shielding design in high-power laser infrastructures.展开更多
Pulse rate is one of the important characteristics of traditional Chinese medicine pulse diagnosis,and it is of great significance for determining the nature of cold and heat in diseases.The prediction of pulse rate b...Pulse rate is one of the important characteristics of traditional Chinese medicine pulse diagnosis,and it is of great significance for determining the nature of cold and heat in diseases.The prediction of pulse rate based on facial video is an exciting research field for getting palpation information by observation diagnosis.However,most studies focus on optimizing the algorithm based on a small sample of participants without systematically investigating multiple influencing factors.A total of 209 participants and 2,435 facial videos,based on our self-constructed Multi-Scene Sign Dataset and the public datasets,were used to perform a multi-level and multi-factor comprehensive comparison.The effects of different datasets,blood volume pulse signal extraction algorithms,region of interests,time windows,color spaces,pulse rate calculation methods,and video recording scenes were analyzed.Furthermore,we proposed a blood volume pulse signal quality optimization strategy based on the inverse Fourier transform and an improvement strategy for pulse rate estimation based on signal-to-noise ratio threshold sliding.We found that the effects of video estimation of pulse rate in the Multi-Scene Sign Dataset and Pulse Rate Detection Dataset were better than in other datasets.Compared with Fast independent component analysis and Single Channel algorithms,chrominance-based method and plane-orthogonal-to-skin algorithms have a more vital anti-interference ability and higher robustness.The performances of the five-organs fusion area and the full-face area were better than that of single sub-regions,and the fewer motion artifacts and better lighting can improve the precision of pulse rate estimation.展开更多
The shock-induced reaction mechanism and characteristics of Ni/Al system,considering an Al nanoparticle-embedded Ni single crystal,are investigated through molecular dynamics simulation.For the shock melting of Al nan...The shock-induced reaction mechanism and characteristics of Ni/Al system,considering an Al nanoparticle-embedded Ni single crystal,are investigated through molecular dynamics simulation.For the shock melting of Al nanoparticle,interfacial crystallization and dissolution are the main characteristics.The reaction degree of Al particle first increases linearly and then logarithmically with time driven by rapid mechanical mixing and following dissolution.The reaction rate increases with the decrease of particle diameter,however,the reaction is seriously hindered by interfacial crystallization when the diameter is lower than 9 nm in our simulations.Meanwhile,we found a negative exponential growth in the fraction of crystallized Al atoms,and the crystallinity of B2-NiAl(up to 20%)is positively correlated with the specific surface area of Al particle.This can be attributed to the formation mechanism of B2-NiAl by structural evolution of finite mixing layer near the collapsed interface.For shock melting of both Al particle and Ni matrix,the liquid-liquid phase inter-diffusion is the main reaction mechanism that can be enhanced by the formation of internal jet.In addition,the enhanced diffusion is manifested in the logarithmic growth law of mean square displacement,which results in an almost constant reaction rate similar to the mechanical mixing process.展开更多
Slits have been widely used in laser-plasma interactions as plasma optical components for generating high-harmonic light and controlling laser-driven particle beams.Here,we propose and demonstrate that periodic thin s...Slits have been widely used in laser-plasma interactions as plasma optical components for generating high-harmonic light and controlling laser-driven particle beams.Here,we propose and demonstrate that periodic thin slits can be regarded as a new breed of optical elements for efficient focusing and guiding of intense laser pulse.The fundamental physics of intense laser interaction with thin slits is studied,and it is revealed that relativistic effects can lead to enhanced laser focusing far beyond the pure diffractive focusing regime.In addition,the interaction of an intense laser pulse with periodic thin slits makes it feasible to achieve multifold enhancement in both laser intensity and energy transfer efficiency compared with conventional waveguides.These results provide a novel method for manipulating ultra-intense laser pulses and should be of interest for many laser-based applications.展开更多
High efficiency,cost-effective and durable electrocatalysts are of pivotal importance in energy conversion and storage systems.The electro-oxidation of water to oxygen plays a crucial role in such energy conversion te...High efficiency,cost-effective and durable electrocatalysts are of pivotal importance in energy conversion and storage systems.The electro-oxidation of water to oxygen plays a crucial role in such energy conversion technologies.Herein,we report a robust method for the synthesis of a bimetallic alkoxide for efficient oxygen evolution reaction(OER)for alkaline electrolysis,which yields current density of 10 mA cm^(-2)at an overpotential of 215 mV in 0.1 M KOH electrolyte.The catalyst demonstrates an excellent durability for more than 540 h operation with negligible degradation in activity.Raman spectra revealed that the catalyst underwent structure reconstruction during OER,evolving into oxyhydroxide,which was the active site proceeding OER in alkaline electrolyte.In-situ synchrotron X-ray absorption experiment combined with density functional theory calculation suggests a lattice oxygen involved electrocatalytic reaction mechanism for the in-situ generated nickel–iron bimetal-oxyhydroxide catalyst.This mechanism together with the synergy between nickel and iron are responsible for the enhanced catalytic activity and durability.These findings provide promising strategies for the rational design of nonnoble metal OER catalysts.展开更多
Extensive experimental studies have been performed on the Diels-Alder(DA)reactions in ionic liquids(ILs),which demonstrate that the IL environment can significantly influence the reaction rates and selectivity.However...Extensive experimental studies have been performed on the Diels-Alder(DA)reactions in ionic liquids(ILs),which demonstrate that the IL environment can significantly influence the reaction rates and selectivity.However,the underlying microscopic mechanism remains ambiguous.In this work,the multiscale reaction density functional theory is applied to explore the effect of 1-butyl-3-methylimidazolium hexafluorophosphate([BMIM][PF_(6)])solvent on the reaction of cyclopentadiene(CP)with acrolein,methyl acrylate,or acrylonitrile.By analyzing the free energy landscape during the reaction,it is found that the polarization effect has a relatively small influence,while the solvation effect makes both the activation free energy and reaction free energy decrease.In addition,the rearrangement of local solvent structure shows that the cation spatial distribution responds more evidently to the reaction than the anion,and this indicates that the cation plays a dominant role in the solvation effect and so as to affect the reaction rates and selectivity of the DA reactions.展开更多
Hydrogen production by water reduction reactions has received considerable attention because hydrogen is considered a clean-energy carrier,key for a sustainable energy future.Computational methods have been widely use...Hydrogen production by water reduction reactions has received considerable attention because hydrogen is considered a clean-energy carrier,key for a sustainable energy future.Computational methods have been widely used to study the reaction mechanism of the hydrogen evolution reaction(HER),but the calculation results need to be supported by experimental results and direct evidence to confirm the mechanistic insights.In this review,we discuss the fundamental principles of the in situ spectroscopic strategy and a theoretical model for a mechanistic understanding of the HER.In addition,we investigate recent studies by in situ Fourier transform infrared(FTIR),Raman spectroscopy,and X-ray absorption spectroscopy(XAS) and cover new findings that occur at the catalyst-electrolyte interface during HER.These spectroscopic strategies provide practical ways to elucidate catalyst phase,reaction intermediate,catalyst-electrolyte interface,intermediate binding energy,metal valency state,and coordination environment during HER.展开更多
In this study,a pulsed,high voltage driven hollow-cathode electron beam sources through an optical trigger is designed with characteristics of simple structure,low cost,and easy triggering.To validate the new design,t...In this study,a pulsed,high voltage driven hollow-cathode electron beam sources through an optical trigger is designed with characteristics of simple structure,low cost,and easy triggering.To validate the new design,the characteristics of hollow-cathode discharge and electron beam characterization under pulsed high voltage drive are studied experimentally and discussed by discharge characteristics and analyses of waveform details,respectively.The validation experiments indicate that the pulsed high voltage supply significantly improves the frequency and stability of the discharge,which provides a new solution for the realization of a high-frequency,high-energy electron beam source.The peak current amplitude in the high-energy electron beam increases from 6.2 A to 79.6 A,which indicates the pulsed power mode significantly improves the electron beam performance.Besides,increasing the capacitance significantly affects the highcurrent,lower-energy electron beam more than the high-energy electron beam.展开更多
Giant electromagnetic pulses(EMPs) induced by high-power laser irradiating solid targets interfere with various experimental diagnoses and even damage equipment,so unveiling the evolution of EMPs inside the laser cham...Giant electromagnetic pulses(EMPs) induced by high-power laser irradiating solid targets interfere with various experimental diagnoses and even damage equipment,so unveiling the evolution of EMPs inside the laser chamber is crucial for designing effective EMP shielding.In this work,the transmission characteristics of EMPs as a function of distances from the target chamber center(TCC) are studied using B-dot probes.The mean EMP amplitude generated by picosecond laser-target interaction reaches 561 kV m^(-1),357 kV m^(-1),395 kV m^(-1),and 341 kV m^(-1)at 0.32 m,0.53 m,0.76 m,and 1 m from TCC,which decreases dramatically from 0.32 m to 0.53 m.However,it shows a fluctuation from 0.53 m to 1 m.The temporal features of EMPs indicate that time-domain EMP signals near the target chamber wall have a wider full width at half maximum compared to that close to TCC,mainly due to the echo oscillation of electromagnetic waves inside the target chamber based on simulation and experimentation.The conclusions of this study will provide a new approach to mitigate strong electromagnetic pulses by decreasing the echo oscillation of electromagnetic waves inside the target chamber during laser coupling with targets.展开更多
Molecular-frame photoelectron momentum distributions(MF-PMDs) of an H_(2)^(+) molecule ion in the presence of a pair of counter-rotating circularly polarized attosecond extreme ultraviolet laser pulses is studied by n...Molecular-frame photoelectron momentum distributions(MF-PMDs) of an H_(2)^(+) molecule ion in the presence of a pair of counter-rotating circularly polarized attosecond extreme ultraviolet laser pulses is studied by numerically solving the two-dimensional time-dependent Schrodinger equation within the frozen-nuclei approximation. At small time delay, our simulations show that the electron vortex structure is sensitive to the time delay and relative phase between the counterrotating pulses when they are partially overlapped. By adjusting time delay and relative phase, we have the ability to manipulate the MF-PMDs and the appearance of spiral arms. We further show that the internuclear distance can affect the spiral vortices due to its different transition cross sections in the parallel and perpendicular geometries. The lowest-order perturbation theory is employed to interpret these phenomena qualitatively. It is concluded that the internuclear distancedependent transition cross sections and the confinement effect in diatomic molecules are responsible for the variation of vortex structures in the MF-PMDs.展开更多
In seismology and earthquake engineering,it is fundamental to identify and characterize the pulse-like features in pulse-type ground motions.To capture the pulses that dominate structural responses,this study establis...In seismology and earthquake engineering,it is fundamental to identify and characterize the pulse-like features in pulse-type ground motions.To capture the pulses that dominate structural responses,this study establishes congruence and shift relationships between response spectrum surfaces.A similarity search between spectrum surfaces,supplemented with a similarity search in time series,has been applied to characterize the pulse-like features in pulse-type ground motions.The identified pulses are tested in predicting the rocking consequences of slender rectangular blocks under the original ground motions.Generally,the prediction is promising for the majority of the ground motions where the dominant pulse is correctly identified.展开更多
基金supported by the Taishan Scholar Program of Shandong Province,China (tsqn202211162)the National Natural Science Foundation of China (22102079)the Natural Science Foundation of Shandong Province of China (ZR2021YQ10,ZR2022QB163)。
文摘The poor stability of RuO_(2)electrocatalysts has been the primary obstacles for their practical application in polymer electrolyte membrane electrolyzers.To dramatically enhance the durability of RuO_(2)to construct activity-stability trade-off model is full of significance but challenging.Herein,a single atom Zn stabilized RuO_(2)with enriched oxygen vacancies(SA Zn-RuO_(2))is developed as a promising alternative to iridium oxide for acidic oxygen evolution reaction(OER).Compared with commercial RuO_(2),the enhanced Ru–O bond strength of SA Zn-RuO_(2)by forming Zn-O-Ru local structure motif is favorable to stabilize surface Ru,while the electrons transferred from Zn single atoms to adjacent Ru atoms protects the Ru active sites from overoxidation.Simultaneously,the optimized surrounding electronic structure of Ru sites in SA ZnRuO_(2)decreases the adsorption energies of OER intermediates to reduce the reaction barrier.As a result,the representative SA Zn-RuO_(2)exhibits a low overpotential of 210 mV to achieve 10 mA cm^(-2)and a greatly enhanced durability than commercial RuO_(2).This work provides a promising dual-engineering strategy by coupling single atom doping and vacancy for the tradeoff of high activity and catalytic stability toward acidic OER.
基金supported by National Natural Science Foundation of China(No.11975142)。
文摘High-pressure nanosecond pulsed discharges(NPDs)have attracted increasing attention in recent years due to their wide potential applications.In this study,a barrier-free NPD in pure helium plasma at 120 Torr was numerically investigated by a one-dimensional self-consistent fluid model,and its current–voltage characteristics show very different behaviors from those in pulsed dielectric barrier discharges(DBDs),indicating an entirely distinctive discharge evolution in pulsed discharges with or without barriers on electrodes.Without the control of barriers,the computational data suggest that the discharge current increases very sharply during the plateau phase of the pulsed voltage and reaches its peak value at approximately the instant when the pulsed voltage starts to drop,together with a gradual reduction in the sheath thickness and an increase in electric field in the sheath region,which is in good agreement with experimental observations.By increasing the voltage plateau width and repetition frequency,the discharge current density from the simulation can be substantially enhanced,which cannot be observed in conventional pulsed DBDs,and the spatial distributions of the electric field and charged particles are given to unravel the underlying physics.From the computational data,the distinctive discharge characteristics in barrier-free NPDs are deeply understood,and could be further optimized by tailoring the waveform of the pulsed voltage to obtain desirable plasmas for applications.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.51902101 and 21875203)the Natural Science Foundation of Hunan Province(Nos.2021JJ40044 and 2023JJ50287)Natural Science Foundation of Jiangsu Province(No.BK20201381).
文摘Deformable catalytic material with excellent flexible structure is a new type of catalyst that has been applied in various chemical reactions,especially electrocatalytic hydrogen evolution reaction(HER).In recent years,deformable catalysts for HER have made great progress and would become a research hotspot.The catalytic activities of deformable catalysts could be adjustable by the strain engineering and surface reconfiguration.The surface curvature of flexible catalytic materials is closely related to the electrocatalytic HER properties.Here,firstly,we systematically summarized self-adaptive catalytic performance of deformable catalysts and various micro–nanostructures evolution in catalytic HER process.Secondly,a series of strategies to design highly active catalysts based on the mechanical flexibility of lowdimensional nanomaterials were summarized.Last but not least,we presented the challenges and prospects of the study of flexible and deformable micro–nanostructures of electrocatalysts,which would further deepen the understanding of catalytic mechanisms of deformable HER catalyst.
基金supported by the National Natural Science Foundation of China(21972131)。
文摘In this study,we systematically investigated the effect of proton concentration on the kinetics of the oxygen reduction reaction(ORR)on Pt(111)in acidic solutions.Experimental results demonstrate a rectangular hyperbolic relationship,i.e.,the ORR current excluding the effect of other variables increases with proton concentration and then tends to a constant value.We consider that this is caused by the limitation of ORR kinetics by the trace oxygen concentration in the solution,which determines the upper limit of ORR kinetics.A model of effective concentration is further proposed for rectangular hyperbolic relationships:when the reactant concentration is high enough to reach a critical saturation concentration,the effective reactant concentration will become a constant value.This could be due to the limited concentration of a certain reactant for reactions involving more than one reactant or the limited number of active sites available on the catalyst.Our study provides new insights into the kinetics of electrocatalytic reactions,and it is important for the proper evaluation of catalyst activity and the study of structureperformance relationships.
基金National Research Foundation of Korea,Grant/Award Numbers:2019H1D3A1A01071209,2021R1I1A1A01060380,2022R1A2C2010686,2022R1A4A3033528Korea Basic Science Institute,Grant/Award Numbers:2019R1A6C1010042,2021R1A6C103A427。
文摘We investigated the role of metal atomization and solvent decomposition into reductive species and carbon clusters in the phase formation of transition-metal carbides(TMCs;namely,Co_(3)C,Fe_(3)C,TiC,and MoC)by pulsed laser ablation of Co,Fe,Ti,and Mo metals in acetone.The interaction between carbon s-p-orbitals and metal d-orbitals causes a redistribution of valence structure through charge transfer,leading to the formation of surface defects as observed by X-ray photoelectron spectroscopy.These defects influence the evolved TMCs,making them effective for hydrogen and oxygen evolution reactions(HER and OER)in an alkaline medium.Co_(3)C with more oxygen affinity promoted CoO(OH)intermediates,and the electrochemical surface oxidation to Co_(3)O_(4)was captured via in situ/operando electrochemical Raman probes,increasing the number of active sites for OER activity.MoC with more d-vacancies exhibits strong hydrogen binding,promoting HER kinetics,whereas Fe_(3)C and TiC with more defect states to trap charge carriers may hinder both OER and HER activities.The results show that the assembled membrane-less electrolyzer with Co_(3)C∥Co_(3)C and MoC∥MoC electrodes requires~2.01 and 1.99 V,respectively,to deliver a 10 mA cm−2 with excellent electrochemical and structural stability.In addition,the ascertained pulsed laser synthesis mechanism and unit-cell packing relations will open up sustainable pathways for obtaining highly stable electrocatalysts for electrolyzers.
基金support from the National Natural Science Foundation of China(22078130)the Fundamental Research Funds for the Central Universities(1042050205225990/010)and Starting Research Fund of Qingyuan Innovation Laboratory(00523001).
文摘Copper-based metal-organic frameworks(Cu-MOFs)are a promising multiphase catalyst for catalyzing C-S coupling reactions by virtue of their diverse structures and functions.However,the unpleasant odor and instability of the organosulfur,as well as the mass-transfer resistance that exists in multiphase catalysis,have often limited the catalytic application of Cu-MOFs in C-S coupling reactions.In this paper,a Cu-MOFs catalyst modified by cetyltrimethylammonium bromide(CTAB)was designed to enhance mass transfer by increasing the adsorption of organic substrates using the long alkanes of CTAB.Concurrently,elemental sulfur was used to replace organosulfur to achieve a highly efficient and atom-economical multicomponent C-S coupling reaction.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.11621404,11561121003,11727812,61775059,12074122,62022033,and 11704123)Shanghai Rising-Star Program,the Sustainedly Supported Foundation by the National Key Laboratory of Science and Technology on Space Microwave(Grant No.HTKT2022KL504008)+1 种基金Shanghai Natural Science Foundation(Grant No.23ZR1419000)the National Key Laboratory Foundation of China(Grant No.6142411196307).
文摘Nyquist pulses have wide applications in many areas,from electronics to optics.Mode-locked lasers are ideal platforms to generate such pulses.However,how to generate high-quality Nyquist pulses in mode-locked lasers remains elusive.We address this problem by managing different physical effects in mode-locked fiber lasers through extensive numerical simulations.We find that net dispersion,linear loss,gain and filter shaping can affect the quality of Nyquist pulses significantly.We also demonstrate that Nyquist pulses experience similariton shaping due to the nonlinear attractor effect in the gain medium.Our work may contribute to the design of Nyquist pulse sources and enrich the understanding of pulse shaping dynamics in mode-locked lasers.
基金supported by the National Natural Science Foundation of China(Grant Nos.12375244,12135009,and 12275356)the Hunan Provincial Innovation Foun-dation for Postgraduate(Grant Nos.CX20210062 and CX20230006).
文摘Relativistic femtosecond mid-infrared pulses can be generated efficiently by laser interaction with near-criticaldensity plasmas.It is found theoretically and numerically that the radiation pressure of a circularly polarized laser pulse first compresses the plasma electrons to form a dense flying mirror with a relativistic high speed.The pulse reflected by the mirror is red-shifted to the mid-infrared range.Full three-dimensional simulations demonstrate that the central wavelength of the mid-infrared pulse is tunable from 3µm to 14µm,and the laser energy conversion efficiency can reach as high as 13%.With a 0.5–10 PW incident laser pulse,the generated mid-infrared pulse reaches a peak power of 10–180 TW,which is interesting for various applications in ultrafast and high-field sciences.
基金Project supported by the Strategic Priority Research Program of the Chinese Academy of Sciences(Grant No.XDA25020205)the program of Science and Technology on Plasma Physics Laboratory,China Academy of Engineering Physics(Grant No.6142A04220108)。
文摘A high-power laser ablating solid targets induces giant electromagnetic pulses(EMPs),which are intimately pertinent to laser parameters,such as energy and pulse width.In this study,we reveal the features of EMPs generated from a picosecond(ps)laser irradiating solid targets at the SG-Ⅱpicosecond petawatt(PSPW)laser facility.The laser energy and pulse,as well as target material and thickness,show determinative effects on the EMPs’amplitude.More intense EMPs are detected behind targets compared to those at the other three positions,and the EMP amplitude decreases from 90.09 kV/m to 17.8 kV/m with the gold target thickness increasing from 10μm to 20μm,which is suppressed when the laser pulse width is enlarged.The results are expected to provide more insight into EMPs produced by ps lasers coupling with targets and lay the foundation for an effective EMP shielding design in high-power laser infrastructures.
基金supported by the Key Research Program of the Chinese Academy of Sciences(grant number ZDRW-ZS-2021-1-2).
文摘Pulse rate is one of the important characteristics of traditional Chinese medicine pulse diagnosis,and it is of great significance for determining the nature of cold and heat in diseases.The prediction of pulse rate based on facial video is an exciting research field for getting palpation information by observation diagnosis.However,most studies focus on optimizing the algorithm based on a small sample of participants without systematically investigating multiple influencing factors.A total of 209 participants and 2,435 facial videos,based on our self-constructed Multi-Scene Sign Dataset and the public datasets,were used to perform a multi-level and multi-factor comprehensive comparison.The effects of different datasets,blood volume pulse signal extraction algorithms,region of interests,time windows,color spaces,pulse rate calculation methods,and video recording scenes were analyzed.Furthermore,we proposed a blood volume pulse signal quality optimization strategy based on the inverse Fourier transform and an improvement strategy for pulse rate estimation based on signal-to-noise ratio threshold sliding.We found that the effects of video estimation of pulse rate in the Multi-Scene Sign Dataset and Pulse Rate Detection Dataset were better than in other datasets.Compared with Fast independent component analysis and Single Channel algorithms,chrominance-based method and plane-orthogonal-to-skin algorithms have a more vital anti-interference ability and higher robustness.The performances of the five-organs fusion area and the full-face area were better than that of single sub-regions,and the fewer motion artifacts and better lighting can improve the precision of pulse rate estimation.
基金supported by the State Key Program of National Natural Science Foundation of China(Grant No.12132003)State Key Laboratory of Explosion Science and Technology(Grant No.QNKT20-07)。
文摘The shock-induced reaction mechanism and characteristics of Ni/Al system,considering an Al nanoparticle-embedded Ni single crystal,are investigated through molecular dynamics simulation.For the shock melting of Al nanoparticle,interfacial crystallization and dissolution are the main characteristics.The reaction degree of Al particle first increases linearly and then logarithmically with time driven by rapid mechanical mixing and following dissolution.The reaction rate increases with the decrease of particle diameter,however,the reaction is seriously hindered by interfacial crystallization when the diameter is lower than 9 nm in our simulations.Meanwhile,we found a negative exponential growth in the fraction of crystallized Al atoms,and the crystallinity of B2-NiAl(up to 20%)is positively correlated with the specific surface area of Al particle.This can be attributed to the formation mechanism of B2-NiAl by structural evolution of finite mixing layer near the collapsed interface.For shock melting of both Al particle and Ni matrix,the liquid-liquid phase inter-diffusion is the main reaction mechanism that can be enhanced by the formation of internal jet.In addition,the enhanced diffusion is manifested in the logarithmic growth law of mean square displacement,which results in an almost constant reaction rate similar to the mechanical mixing process.
基金supported by the National Key R&D Program of China(Grant No.2022YFA1603300)the National Natural Science Foundation of China(Grant Nos.12175154,12205201,12005149,and 11975214)+1 种基金the Shenzhen Science and Technology Program(Grant No.RCYX20221008092851073)used under UK EPSRC Contract Nos.EP/G055165/1 and EP/G056803/1.
文摘Slits have been widely used in laser-plasma interactions as plasma optical components for generating high-harmonic light and controlling laser-driven particle beams.Here,we propose and demonstrate that periodic thin slits can be regarded as a new breed of optical elements for efficient focusing and guiding of intense laser pulse.The fundamental physics of intense laser interaction with thin slits is studied,and it is revealed that relativistic effects can lead to enhanced laser focusing far beyond the pure diffractive focusing regime.In addition,the interaction of an intense laser pulse with periodic thin slits makes it feasible to achieve multifold enhancement in both laser intensity and energy transfer efficiency compared with conventional waveguides.These results provide a novel method for manipulating ultra-intense laser pulses and should be of interest for many laser-based applications.
基金the staff at Beamline (BL08U1-A and BL11B)of the Shanghai Synchrotron Radiation Facility (SSRF)the support from the National Key Research&Development Program of China (2022YFB3803700)+2 种基金the National Natural Science Foundation of China (52171186)the support through the Overseas Outstanding Youth Fund and Shanghai Pujiang Talent Project (21PJ1408500)the financial support from the Center of Hydrogen Science,Shanghai Jiao Tong University。
文摘High efficiency,cost-effective and durable electrocatalysts are of pivotal importance in energy conversion and storage systems.The electro-oxidation of water to oxygen plays a crucial role in such energy conversion technologies.Herein,we report a robust method for the synthesis of a bimetallic alkoxide for efficient oxygen evolution reaction(OER)for alkaline electrolysis,which yields current density of 10 mA cm^(-2)at an overpotential of 215 mV in 0.1 M KOH electrolyte.The catalyst demonstrates an excellent durability for more than 540 h operation with negligible degradation in activity.Raman spectra revealed that the catalyst underwent structure reconstruction during OER,evolving into oxyhydroxide,which was the active site proceeding OER in alkaline electrolyte.In-situ synchrotron X-ray absorption experiment combined with density functional theory calculation suggests a lattice oxygen involved electrocatalytic reaction mechanism for the in-situ generated nickel–iron bimetal-oxyhydroxide catalyst.This mechanism together with the synergy between nickel and iron are responsible for the enhanced catalytic activity and durability.These findings provide promising strategies for the rational design of nonnoble metal OER catalysts.
基金supported by the National Natural Science Foundation of China(22168002,22108070,21878078)the Natural Science Foundation of Guangxi Province(2020GXNSFAA159119)+2 种基金the Dean Project of Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology(2021Z012)the Open Fund of the State Key Laboratory of Molecular Reaction Dynamics in DICP(SKLMRD-K202106)the Young Elite Scientists Sponsorship Program by CAST(2022QNRC001)。
文摘Extensive experimental studies have been performed on the Diels-Alder(DA)reactions in ionic liquids(ILs),which demonstrate that the IL environment can significantly influence the reaction rates and selectivity.However,the underlying microscopic mechanism remains ambiguous.In this work,the multiscale reaction density functional theory is applied to explore the effect of 1-butyl-3-methylimidazolium hexafluorophosphate([BMIM][PF_(6)])solvent on the reaction of cyclopentadiene(CP)with acrolein,methyl acrylate,or acrylonitrile.By analyzing the free energy landscape during the reaction,it is found that the polarization effect has a relatively small influence,while the solvation effect makes both the activation free energy and reaction free energy decrease.In addition,the rearrangement of local solvent structure shows that the cation spatial distribution responds more evidently to the reaction than the anion,and this indicates that the cation plays a dominant role in the solvation effect and so as to affect the reaction rates and selectivity of the DA reactions.
基金the immense support provided by the National Research Foundation of Korea(NRF)Grant funded by the Korean Government(MSIT)(RS-2023–00210114)the National R&D Program through the National Research Foundation of Korea(NRF)funded by Ministry of Science and ICT(2021M3D1A2051636)。
文摘Hydrogen production by water reduction reactions has received considerable attention because hydrogen is considered a clean-energy carrier,key for a sustainable energy future.Computational methods have been widely used to study the reaction mechanism of the hydrogen evolution reaction(HER),but the calculation results need to be supported by experimental results and direct evidence to confirm the mechanistic insights.In this review,we discuss the fundamental principles of the in situ spectroscopic strategy and a theoretical model for a mechanistic understanding of the HER.In addition,we investigate recent studies by in situ Fourier transform infrared(FTIR),Raman spectroscopy,and X-ray absorption spectroscopy(XAS) and cover new findings that occur at the catalyst-electrolyte interface during HER.These spectroscopic strategies provide practical ways to elucidate catalyst phase,reaction intermediate,catalyst-electrolyte interface,intermediate binding energy,metal valency state,and coordination environment during HER.
基金supported by National Natural Science Foundation of China(No.12102099)the National Key R&D Program of China(No.2021YFC2202700)the Outstanding Academic Leader Project of Shanghai(Youth)(No.23XD1421700),respectively。
文摘In this study,a pulsed,high voltage driven hollow-cathode electron beam sources through an optical trigger is designed with characteristics of simple structure,low cost,and easy triggering.To validate the new design,the characteristics of hollow-cathode discharge and electron beam characterization under pulsed high voltage drive are studied experimentally and discussed by discharge characteristics and analyses of waveform details,respectively.The validation experiments indicate that the pulsed high voltage supply significantly improves the frequency and stability of the discharge,which provides a new solution for the realization of a high-frequency,high-energy electron beam source.The peak current amplitude in the high-energy electron beam increases from 6.2 A to 79.6 A,which indicates the pulsed power mode significantly improves the electron beam performance.Besides,increasing the capacitance significantly affects the highcurrent,lower-energy electron beam more than the high-energy electron beam.
基金supported by National Grand Instrument Project (No.2019YFF01014404)the National Key Program for S & T Research and Development (No. 2022YFA1603202)+1 种基金National Natural Science Foundation of China (Nos.U2241281 and 11975037)the Foundation of Science and Technology on Plasma Physics Laboratory (No.6142A04220108)。
文摘Giant electromagnetic pulses(EMPs) induced by high-power laser irradiating solid targets interfere with various experimental diagnoses and even damage equipment,so unveiling the evolution of EMPs inside the laser chamber is crucial for designing effective EMP shielding.In this work,the transmission characteristics of EMPs as a function of distances from the target chamber center(TCC) are studied using B-dot probes.The mean EMP amplitude generated by picosecond laser-target interaction reaches 561 kV m^(-1),357 kV m^(-1),395 kV m^(-1),and 341 kV m^(-1)at 0.32 m,0.53 m,0.76 m,and 1 m from TCC,which decreases dramatically from 0.32 m to 0.53 m.However,it shows a fluctuation from 0.53 m to 1 m.The temporal features of EMPs indicate that time-domain EMP signals near the target chamber wall have a wider full width at half maximum compared to that close to TCC,mainly due to the echo oscillation of electromagnetic waves inside the target chamber based on simulation and experimentation.The conclusions of this study will provide a new approach to mitigate strong electromagnetic pulses by decreasing the echo oscillation of electromagnetic waves inside the target chamber during laser coupling with targets.
基金Project supported by the Natural Science Foundation of Jilin Province,China (Grant No.20220101016JC)the National Key Research and Development Program of China (Grant No.2022YFE0134200)+1 种基金the National Natural Science Foundation of China (Grant Nos.12174147,91850114,and 11774131)the Open Research Fund of State Key Laboratory of Transient Optics and Photonics。
文摘Molecular-frame photoelectron momentum distributions(MF-PMDs) of an H_(2)^(+) molecule ion in the presence of a pair of counter-rotating circularly polarized attosecond extreme ultraviolet laser pulses is studied by numerically solving the two-dimensional time-dependent Schrodinger equation within the frozen-nuclei approximation. At small time delay, our simulations show that the electron vortex structure is sensitive to the time delay and relative phase between the counterrotating pulses when they are partially overlapped. By adjusting time delay and relative phase, we have the ability to manipulate the MF-PMDs and the appearance of spiral arms. We further show that the internuclear distance can affect the spiral vortices due to its different transition cross sections in the parallel and perpendicular geometries. The lowest-order perturbation theory is employed to interpret these phenomena qualitatively. It is concluded that the internuclear distancedependent transition cross sections and the confinement effect in diatomic molecules are responsible for the variation of vortex structures in the MF-PMDs.
基金National Key Research and Development Program,Ministry of Science and Technology of China under Grant No.2022YFC3803004the National Natural Science Foundation of China under Grant No.51838004。
文摘In seismology and earthquake engineering,it is fundamental to identify and characterize the pulse-like features in pulse-type ground motions.To capture the pulses that dominate structural responses,this study establishes congruence and shift relationships between response spectrum surfaces.A similarity search between spectrum surfaces,supplemented with a similarity search in time series,has been applied to characterize the pulse-like features in pulse-type ground motions.The identified pulses are tested in predicting the rocking consequences of slender rectangular blocks under the original ground motions.Generally,the prediction is promising for the majority of the ground motions where the dominant pulse is correctly identified.