“Buckets effect”in the kinetics of electrocatalytic reactions

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.

Collisionless shock acceleration of protons in a plasma slab produced in a gas jet by the collision of two laser-driven hydrodynamic shockwaves

We have recently proposed a new technique of plasma tailoring by laser-driven hydrodynamic shockwaves generated on both sides of a gas jet[Marquès et al.,Phys.Plasmas 28,023103(2021)].In a continuation of this numerical work,we study experimentally the influence of the tailoring on proton acceleration driven by a high-intensity picosecond laser in three cases:without tailoring,by tailoring only the entrance side of the picosecond laser,and by tailoring both sides of the gas jet.Without tailoring,the acceleration is transverse to the laser axis,with a low-energy exponential spectrum,produced by Coulomb explosion.When the front side of the gas jet is tailored,a forward acceleration appears,which is significantly enhanced when both the front and back sides of the plasma are tailored.This forward acceleration produces higher-energy protons,with a peaked spectrum,and is in good agreement with the mechanism of collisionless shock acceleration(CSA).The spatiotemporal evolution of the plasma profile is characterized by optical shadowgraphy of a probe beam.The refraction and absorption of this beam are simulated by post-processing 3D hydrodynamic simulations of the plasma tailoring.Comparison with the experimental results allows estimation of the thickness and near-critical density of the plasma slab produced by tailoring both sides of the gas jet.These parameters are in good agreement with those required for CSA.

A Moving Mesh Method for Kinetic/Hydrodynamic Coupling

This paper deals with the application of a moving mesh method for kinetic/hydrodynamic coupling model in two dimensions.With some criteria,the domain is dynamically decomposed into three parts:kinetic regions where fluids are far from equilibrium,hydrodynamic regions where fluids are near thermodynamical equilibrium and buffer regions which are used as a smooth transition.The Boltzmann-BGK equation is solved in kinetic regions,while Euler equations in hydrodynamic regions and both equations in buffer regions.By a well defined monitor function,our moving mesh method smoothly concentrate the mesh grids to the regions containing rapid variation of the solutions.In each moving mesh step,the solutions are conservatively updated to the new mesh and the cut-off function is rebuilt first to consist with the region decomposition after the mesh motion.In such a framework,the evolution of the hybrid model and the moving mesh procedure can be implemented independently,therefore keep the advantages of both approaches.Numerical examples are presented to demonstrate the efficiency of the method.

Diagnosis of the Kinetic Energy of the“21·7”Extreme Torrential Rainfall Event in Henan Province,China

An extreme torrential rain(ETR)event occurred in Henan Province,China,during 18-21 July 2021.Based on hourly rain-gauge observations and ERA5 reanalysis data,the ETR was studied from the perspective of kinetic energy(K),which can be divided into rotational wind(V_(R))kinetic energy(K_(R)),divergent wind kinetic energy(K_(D)),and the kinetic energy of the interaction between the divergent and rotational winds(K_(RD)).According to the hourly precipitation intensity variability,the ETR process was divided into an initial stage,a rapid increase stage,and maintenance stage.Results showed that the intensification and maintenance of ETR were closely related to the upper-level K,and most closely related to the upperlevel K_(R),with a correlation coefficient of up to 0.9.In particular,the peak value of hourly rainfall intensity lagged behind the K_(R) by 8 h.Furthermore,diagnosis showed that K transformation from unresolvable to resolvable scales made the ETR increase slowly.The meridional rotational wind(u_(R))and meridional gradient of the geopotential(φ)jointly determined the conversion of available potential energy(APE)to K_(R) through the barotropic process,which dominated the rapid enhancement of K_(R) and then caused the rapid increase in ETR.The transportation of K by rotational wind consumed K_(R),and basically offset the K_(R) produced by the barotropic process,which basically kept K_(R) stable at a high value,thus maintaining the ETR.

Electron kinetic effects in back-stimulated Raman scattering bursts driven by broadband laser pulses

We examine electron kinetic effects in broadband-laser-driven back-stimulated Raman scattering(BSRS)bursts using particle-in-cell simulations.These bursts occur during the nonlinear stage,causing reflectivity spikes and generating large numbers of hot electrons.Long-duration simulations are performed to observe burst events,and a simplified model is developed to eliminate the interference of the broadband laser’s random intensity fluctuations.Using the simplified model,we isolate and characterize the spectrum of electron plasma waves.The spectrum changes from a sideband structure to a turbulence-like structure during the burst.A significant asymmetry in the spectrum is observed.This asymmetry is amplified and transferred to electron phase space by high-intensity broadband laser pulses,leading to violent vortex-merging and generation of hot electrons.The proportion of hot electrons increases from 6.76%to 14.7%during a single violent burst event.We demonstrate that kinetic effects profoundly influence the BSRS evolution driven by broadband lasers.

Hydrodynamic Cavitation Enhanced SR-Aops Degradation of Organic Pollutants in Water:A Review

SR-AOP(sulfate radical advanced oxidation process)is a novel water treatment method able to eliminate refractory organic pollutants.Hydrodynamic cavitation(HC)is a novel green technology,that can effectively produce strong oxidizing sulfate radicals.This paper presents a comprehensive review of the research advancements in these fields and a critical discussion of the principal factors influencing HC-enhanced SR-AOP and the mechanisms of synergistic degradation.Furthermore,some insights into the industrial application of HC/PS are also provided.Current research shows that this technology is feasible at the laboratory stage,but its application on larger scales requires further understanding and exploration.In this review,some attention is also paid to the design of the hydrodynamic cavitation reactor and the related operating parameters.

Growth kinetics of titanium carbide coating by molten salt synthesis process on graphite sheet surface

The synthesis of carbide coatings on graphite substrates using molten salt synthesis(MSS),has garnered significant interest due to its cost-effective nature.This study investigates the reaction process and growth kinetics involved in MSS,shedding light on key aspects of the process.The involvement of Ti powder through liquid-phase mass transfer is revealed,where the diffusion distance and quantity of Ti powder play a crucial role in determining the reaction rate by influencing the C content gradient on both sides of the carbide.Furthermore,the growth kinetics of the carbide coating are predominantly governed by the diffusion behavior of C within the carbide layer,rather than the chemical reaction rate.To analyze the kinetics,the thickness of the carbide layer is measured with respect to heat treatment time and temperature,unveiling a parabolic relationship within the temperature range of 700-1300℃.The estimated activation energy for the reaction is determined to be 179283 J·mol^(-1).These findings offer valuable insights into the synthesis of carbide coatings via MSS,facilitating their optimization and enhancing our understanding of their growth mechanisms and properties for various applications.

Particle aggregation and breakage kinetics in cemented paste backfill

The macroscopic flow behavior and rheological properties of cemented paste backfill(CPB)are highly impacted by the inherent structure of the paste matrix.In this study,the effects of shear-induced forces and proportioning parameters on the microstructure of fresh CPB were studied.The size evolution and distribution of floc/agglomerate/particles of paste were monitored by focused beam reflection measuring(FBRM)technique,and the influencing factors of aggregation and breakage kinetics of CPB were discussed.The results indicate that influenced by both internal and external factors,the paste kinetics evolution covers the dynamic phase and the stable phase.Increasing the mass content or the cement-tailings ratio can accelerate aggregation kinetics,which is advantageous for the rise of average floc size.Besides,the admixture and high shear can improve breaking kinetics,which is beneficial to reduce the average floc size.The chord length resembles a normal distribution somewhat,with a peak value of approximate 20μm.The particle disaggregation con-stant(k_(2))is positively correlated with the agitation rate,and k_(2) is five orders of magnitude greater than the particle aggregation constant(k1).The kinetics model depicts the evolution law of particles over time quantitatively and provides a theoretical foundation for the micromechanics of complicated rheological behavior of paste.

An Innovative Coupled Common-Node Discrete Element Method-Smoothed Particle Hydrodynamics Model Developed with LS-DYNA and Its Applications

In this study,a common-node DEM-SPH coupling model based on the shared node method is proposed,and a fluid–structure coupling method using the common-node discrete element method-smoothed particle hydrodynamics(DS-SPH)method is developed using LS-DYNA software.The DEM and SPH are established on the same node to create common-node DEM-SPH particles,allowing for fluid–structure interactions.Numerical simulations of various scenarios,including water entry of a rigid sphere,dam-break propagation over wet beds,impact on an ice plate floating on water and ice accumulation on offshore structures,are conducted.The interaction between DS particles and SPH fluid and the crack generation mechanism and expansion characteristics of the ice plate under the interaction of structure and fluid are also studied.The results are compared with available data to verify the proposed coupling method.Notably,the simulation results demonstrated that controlling the cutoff pressure of internal SPH particles could effectively control particle splashing during ice crushing failure.

Tuning the crystallinity of titanium nitride on copper-embedded carbon nanofiber interlayers for accelerated electrochemical kinetics in lithium-sulfur batteries

The development of lithium-sulfur(Li-S)batteries is hindered by the disadvantages of shuttling of polysulfides and the sluggish redox kinetics of the conversion of sulfur species during discharge and charge.Herein,the crystallinities of a titanium nitride(TiN)film on copper-embedded carbon nanofibers(Cu-CNFs)are regulated and the nanofibers are used as interlayers to resolve the aforementioned crucial issues.A low-crystalline TiN-coated Cu-CNF(L-TiN-Cu-CNF)interlayer is compared with its highly crystalline counterpart(H-TiN-Cu-CNFs).It is demonstrated that the L-TiN coating not only strengthens the chemical adsorption toward polysulfides but also greatly accelerates the electrochemical conversion of polysulfides.Due to robust carbon frameworks and enhanced kinetics,impressive highrate performance at 2 C(913 mAh g^(-1)based on sulfur)as well as remarkable cyclic stability up to 300 cycles(626 mAh g^(-1))with capacity retention of 46.5%is realized for L-TiN-Cu-CNF interlayer-configured Li-S batteries.Even under high loading(3.8 mg cm^(-2))of sulfur and relatively lean electrolyte(10μL electrolyte per milligram sulfur)conditions,the Li-S battery equipped with L-TiN-Cu-CNF interlayers delivers a high capacity of 1144 mAh g^(-1)with cathodic capacity of 4.25 mAh cm^(-2)at 0.1 C,providing a potential pathway toward the design of multifunctional interlayers for highly efficient Li-S batteries.

A modified smoothed particle hydrodynamics method considering residual stress for simulating failure and its application in layered rock mass

Residual strength is an indispensable factor in evaluating rock fracture,yet the current Smoothed Particle Hydrodynamics(SPH)framework rarely considers its influence when simulating fracture.An improved cracking strategy considering residual stress in the base bond SPH method was proposed to simulate failures in layered rocks and slopes and verified by experimental results and other simulation methods(i.e.,the discrete element method).Modified Mohr–Coulomb failure criterion was applied to distinguish the mixed failure of tensile and shear.Bond fracture markψwas introduced to improve the kernel function after tensile damage,and the calculation of residual stress after the damage was derived after shear damage.Numerical simulations were carried out to evaluate its performance under different stress and scale conditions and to verify its effectiveness in realistically reproducing crack initiation and propagation and coalescence,even fracture and separation.The results indicate that the improved cracking strategy precisely captures the fracture and failure pattern in layered rocks and rock slopes.The residual stress of brittle tock is correctly captured by the improved SPH method.The improved SPH method that considers residual strength shows an approximately 13%improvement in accuracy for the safety factor of anti-dip layered slopes compared to the method that does not consider residual strength,as validated against analytical solutions.We infer that the improved SPH method is effective and shows promise for applications to continuous and discontinuous rock masses.

Simulating the Escaping Atmosphere of GJ 436 b with Two-fluid Magnetohydrodynamic Models

Observations of transmission spectra reveal that hot Jupiters and Neptunes are likely to possess escaping atmospheres driven by stellar radiation.Numerous models predict that magnetic fields may exert significant influences on the atmospheres of hot planets.Generally,the escaping atmospheres are not entirely ionized,and magnetic fields only directly affect the escape of ionized components within them.Considering the chemical reactions between ionized components and neutral atoms,as well as collision processes,magnetic fields indirectly impact the escape of neutral atoms,thereby influencing the detection signals of planetary atmospheres in transmission spectra.In order to simulate this process,we developed a magnetohydrodynamic multi-fluid model based on MHD code PLUTO.As an initial exploration,we investigated the impact of magnetic fields on the decoupling of H^(+)and H in the escaping atmosphere of the hot Neptune GJ436b.Due to the strong resonant interactions between H and H^(+),the coupling between them is tight even if the magnetic field is strong.Of course,alternatively,our work also suggests that merging H and H^(+)into a single flow can be a reasonable assumption in MHD simulations of escaping atmospheres.However,our simulation results indicate that under the influence of magnetic fields,there are noticeable regional differences in the decoupling of H^(+)and H.With the increase of magnetic field strength,the degree of decoupling also increases.For heavier particles such as O,the decoupling between O and H^(+)is more pronounced.Our findings provide important insights for future studies on the decoupling processes of heavy atoms in the escaping atmospheres of hot Jupiters and hot Neptunes under the influence of magnetic fields.

Boosting kinetic separation of ethylene and ethane on microporous materials via crystal size control

The adsorptive separation of C_(2)H_(4)and C_(2)H_(6),as an alternative to distillation units consuming high energy,is a promising yet challenging research.The great similarity in the molecular size of C_(2)H_(4)and C_(2)H_(6)brings challenges to the regulation of adsorbents to realize efficient dynamic separation.Herein,we reported the enhancement of the kinetic separation of C_(2)H_(4)/C_(2)H_(6)by controlling the crystal size of ZnAtzPO_(4)(Atz=3-amino-1,2,4-triazole)to amplify the diffusion difference of C_(2)H_(4)and C_(2)H_(6).Through adjusting the synthesis temperature,reactant concentration,and ligands/metal ions molar ratio,ZnAtzPO4 crystals with different sizes were obtained.Both single-component kinetic adsorption tests and binary-component dynamic breakthrough experiments confirmed the enhancement of the dynamic separation of C_(2)H_(4)/C_(2)H_(6)with the increase in the crystal size of ZnAtzPO_(4).The separation selectivity of C_(2)H_(4)/C_(2)H_(6)increased from 1.3 to 98.5 with the increase in the crystal size of ZnAtzPO_(4).This work demonstrated the role of morphology and size control of adsorbent crystals in the improvement of the C_(2)H_(4)/C_(2)H_(6)kinetic separation performance.

Improving hydrogen storage thermodynamics and kinetics of Ce-Mg-Ni-based alloy by mechanical milling with TiF_(3)

Mg-based hydrides are too stable and the kinetics of hydrogen absorption and desorption is not satisfactory.An efficient way to improve these shortcomings is to employ reactive ball milling to synthesize the nanocomposite materials of Mg and additives.In this experiment,TiF_(3)was selected as an additive,and the mechanical milling method was employed to prepare the experimental alloys.The alloys used in this experiment were the as-cast Ce_(5)Mg_(85)Ni_(10),as-milled Ce_(5)Mg_(85)Ni_(10)and Ce_(5)Mg_(85)Ni_(10)+3 wt.%TiF3.The phase transformation,structural evolution,isothermal and non-isothermal hydrogenation and dehydrogenation performances of the alloys were inspected by XRD,SEM,TEM,Sievert apparatus,DSC and TGA.It revealed that nanocrystalline appeared in the as-milled samples.Compared with the as-cast alloy,ball milling made the particle dimension and grain size decrease dramatically and the defect density increase significantly.The addition of TiF_(3)made the surface of ball milling alloy particles markedly coarser and more irregular.Ball milling and adding TiF_(3)distinctly improved the activation and kinetics of the alloys.Moreover,ball milling along with TiF_(3)can decrease the onset dehydrogenation temperature of Mg-based hydrides and slightly ameliorate their thermodynamics.

All‑Covalent Organic Framework Nanofilms Assembled Lithium‑Ion Capacitor to Solve the Imbalanced Charge Storage Kinetics

Free-standing covalent organic framework(COFs)nanofilms exhibit a remarkable ability to rapidly intercalate/de-intercalate Li^(+) in lithium-ion batteries,while simultaneously exposing affluent active sites in supercapacitors.The development of these nanofilms offers a promising solution to address the persistent challenge of imbalanced charge storage kinetics between battery-type anode and capacitor-type cathode in lithium-ion capacitors(LICs).Herein,for the first time,custom-made COFBTMB-TP and COFTAPB-BPY nanofilms are synthesized as the anode and cathode,respectively,for an all-COF nanofilm-structured LIC.The COFBTMB-TP nanofilm with strong electronegative–CF3 groups enables tuning the partial electron cloud density for Li^(+) migration to ensure the rapid anode kinetic process.The thickness-regulated cathodic COFTAPB-BPY nanofilm can fit the anodic COF nanofilm in the capacity.Due to the aligned 1D channel,2D aromatic skeleton and accessible active sites of COF nanofilms,the whole COFTAPB-BPY//COFBTMB-TP LIC demonstrates a high energy density of 318 mWh cm^(−3) at a high-power density of 6 W cm^(−3),excellent rate capability,good cycle stability with the capacity retention rate of 77%after 5000-cycle.The COFTAPB-BPY//COFBTMB-TP LIC represents a new benchmark for currently reported film-type LICs and even film-type supercapacitors.After being comprehensively explored via ex situ XPS,7Li solid-state NMR analyses,and DFT calculation,it is found that the COFBTMB-TP nanofilm facilitates the reversible conversion of semi-ionic to ionic C–F bonds during lithium storage.COFBTMB-TP exhibits a strong interaction with Li^(+) due to the C–F,C=O,and C–N bonds,facilitating Li^(+) desolation and absorption from the electrolyte.This work addresses the challenge of imbalanced charge storage kinetics and capacity between the anode and cathode and also pave the way for future miniaturized and wearable LIC devices.

Hydrodynamic characteristics and particle tracking of 90° lateral intakes at an inclined river slope

Lateral intakes are common in rivers.The pump effciency and sediment deposition are determined by the local hydrodynamic characteristics and mainstream division width.The hydraulic characteristics of lateral withdrawal from inclined river slopes at different intake elevations should be investigated.Meanwhile,the division width exhibits significant vertical non-uniformity at an inclined river slope,which should be clarified.Hence,a three-dimensional(3-D)hydrodynamic and particle-tracking model was developed with the Open Source Field Operation and Manipulation(Open FOAM),and the model was validated with physical model tests for 90°lateral withdrawal from an inclined side bank.The flow fields,withdrawal sources,and division widths were investigated with different intake bottom elevations,withdrawal discharges,and main channel velocities.This study showed that under inclined side bank conditions,water entered the intake at an oblique angle,causing significant 3-D spiral flows in the intake rather than two-dimensional closed recirculation.A lower withdrawal discharge,a lower bottom elevation of the intake,or a higher main channel velocity could further strengthen this phenomenon.The average division width and turbulent kinetic energy were smaller under inclined side bank conditions than under vertical bank conditions.With a low intake bottom elevation,a low withdrawal discharge,or a high main channel velocity,the sources of lateral withdrawal were in similar ranges near the local inclined bank in the vertical direction.Under inclined slope conditions,sediment deposition near the intake entrance could be reduced,compared to that under vertical slope conditions.The results provide hydrodynamic and sediment references for engineering designs for natural rivers with inclined terrains.

Mass transfer enhancement and hydrodynamic performance with wire mesh coupling solid particles in bubble column reactor

It is of vital significance to investigate mass transfer enhancements for chemical engineering processes.This work focuses on investigating the coupling influence of embedding wire mesh and adding solid particles on bubble motion and gas-liquid mass transfer process in a bubble column.Particle image velocimetry(PIV)technology was employed to analyze the flow field and bubble motion behavior,and dynamic oxygen absorption technology was used to measure the gas-liquid volumetric mass transfer coefficient(kLa).The effect of embedding wire mesh,adding solid particles,and wire mesh coupling solid particles on the flow characteristic and kLa were analyzed and compared.The results show that the gas-liquid interface area increases by 33%-72%when using the wire mesh coupling solid particles strategy compared to the gas-liquid two-phase flow,which is superior to the other two strengthening methods.Compared with the system without reinforcement,kLa in the bubble column increased by 0.5-1.8 times with wire mesh coupling solid particles method,which is higher than the sum of kLa increases with inserting wire mesh and adding particles,and the coupling reinforcement mechanism for affecting gas-liquid mass transfer process was discussed to provide a new idea for enhancing gas-liquid mass transfer.

Description of martensitic transformation kinetics in Fe-C-X(X = Ni,Cr,Mn,Si) system by a modified model

Controlling the content of athermal martensite and retained austenite is important to improving the mechanical properties of high-strength steels,but a mechanism for the accurate description of martensitic transformation during the cooling process must be addressed.At present,frequently used semi-empirical kinetics models suffer from huge errors at the beginning of transformation,and most of them fail to exhibit the sigmoidal shape characteristic of transformation curves.To describe the martensitic transformation process accurately,based on the Magee model,we introduced the changes in the nucleation activation energy of martensite with temperature,which led to the varying nucleation rates of this model during martensitic transformation.According to the calculation results,the relative error of the modified model for the martensitic transformation kinetics curves of Fe-C-X(X = Ni,Cr,Mn,Si) alloys reached 9.5% compared with those measured via the thermal expansion method.The relative error was approximately reduced by two-thirds compared with that of the Magee model.The incorporation of nucleation activation energy into the kinetics model contributes to the improvement of its precision.

Kinetic equilibrium reconstruction with internal safety factor profile constraints on EAST tokamak

Reconstruction of plasma equilibrium plays an important role in the analysis and simulation of plasma experiments. The kinetic equilibrium reconstruction with pressure and edge current constraints has been employed on EAST tokamak. However, the internal safety factor(q) profile is not accurate. This paper proposes a new way of incorporating q profile constraints into kinetic equilibrium reconstruction. The q profile is yielded from the Polarimeter Interferometer(POINT)reconstruction. Virtual probes containing information on q profile constraints are added to inputs of the kinetic equilibrium reconstruction program to obtain the final equilibrium. The new equilibrium produces a more accurate internal q profile. This improved method would help analyze EAST experiments.

A comparative study on kinetics and dynamics of two dump truck lifting mechanisms using MATLAB simscape

In this paper,two lifting mechanism models with opposing placements,which use the same hydraulic hoist model and have the same angle of 50°,have been developed.The mechanical and hydraulic simulation models are established using MATLAB Simscape to analyze their kinetics and dynamics in the lifting and holding stages.The simulation findings are compared to the analytical calculation results in the steady state,and both methods show good agreement.In the early lifting stage,Model 1 produces greater force and discharges goods in the container faster than Model 2.Meanwhile,Model 2 reaches a higher force and ejects goods from the container cleaner than its counterpart at the end lifting stage.The established simulation models can consider the effects of dynamic loads due to inertial moments and forces generated during the system operation.It is crucial in studying,designing,and optimizing the structure of hydraulic-mechanical systems.