Catalytic effect in lithium metal batteries: From heterogeneous catalyst to homogenous catalyst

Lithium metal batteries are regarded as prominent contenders to address the pressing needs owing to the high theoretical capacity.Toward the broader implementation,the primary obstacle lies in the intricate multi-electron,multi-step redox reaction associated with sluggish conversion kinetics,subsequently giving rise to a cascade of parasitic issues.In order to smooth reaction kinetics,catalysts are widely introduced to accelerate reaction rate via modulating the energy barrier.Over past decades,a large amount of research has been devoted to the catalyst design and catalytic mechanism exploration,and thus the great progress in electrochemical performance has been realized.Therefore,it is necessary to make a comprehensive review toward key progress in catalyst design and future development pathway.In this review,the basic mechanism of lithium metal batteries is provided along with corresponding advantages and existing challenges detailly described.The main catalysts employed to accelerate cathode reaction with emphasis on their catalytic mechanism are summarized as well.Finally,the rational design and innovative direction toward efficient catalysts are suggested for future application in metal-sulfur/gas battery and beyond.This review is expected to drive and benefit future research on rational catalyst design with multi-parameter synergistic impacts on the activity and stability of next-generation metal battery,thus opening new avenue for sustainable solution to climate change,energy and environmental issues,and the potential industrial economy.

A cloud model target damage effectiveness assessment algorithm based on spatio-temporal sequence finite multilayer fragments dispersion

To solve the problem of target damage assessment when fragments attack target under uncertain projectile and target intersection in an air defense intercept,this paper proposes a method for calculating target damage probability leveraging spatio-temporal finite multilayer fragments distribution and the target damage assessment algorithm based on cloud model theory.Drawing on the spatial dispersion characteristics of fragments of projectile proximity explosion,we divide into a finite number of fragments distribution planes based on the time series in space,set up a fragment layer dispersion model grounded in the time series and intersection criterion for determining the effective penetration of each layer of fragments into the target.Building on the precondition that the multilayer fragments of the time series effectively assail the target,we also establish the damage criterion of the perforation and penetration damage and deduce the damage probability calculation model.Taking the damage probability of the fragment layer in the spatio-temporal sequence to the target as the input state variable,we introduce cloud model theory to research the target damage assessment method.Combining the equivalent simulation experiment,the scientific and rational nature of the proposed method were validated through quantitative calculations and comparative analysis.

Effect of boundary conditions on shakedown analysis of heterogeneous materials

The determination of the ultimate load-bearing capacity of structures made of elastoplastic heterogeneous materials under varying loads is of great importance for engineering analysis and design. Therefore, it is necessary to accurately predict the shakedown domains of these materials. The static shakedown theorem, also known as Melan's theorem, is a fundamental method used to predict the shakedown domains of structures and materials. Within this method, a key aspect lies in the construction and application of an appropriate self-equilibrium stress field(SSF). In the structural shakedown analysis, the SSF is typically constructed by governing equations that satisfy no external force(NEF) boundary conditions. However, we discover that directly applying these governing equations is not suitable for the shakedown analysis of heterogeneous materials. Researchers must consider the requirements imposed by the Hill-Mandel condition for boundary conditions and the physical significance of representative volume elements(RVEs). This paper addresses this issue and demonstrates that the sizes of SSFs vary under different boundary conditions, such as uniform displacement boundary conditions(DBCs), uniform traction boundary conditions(TBCs), and periodic boundary conditions(PBCs). As a result, significant discrepancies arise in the predicted shakedown domain sizes of heterogeneous materials. Built on the demonstrated relationship between SSFs under different boundary conditions, this study explores the conservative relationships among different shakedown domains, and provides proof of the relationship between the elastic limit(EL) factors and the shakedown loading factors under the loading domain of two load vertices. By utilizing numerical examples, we highlight the conservatism present in certain results reported in the existing literature. Among the investigated boundary conditions, the obtained shakedown domain is the most conservative under TBCs.Conversely, utilizing PBCs to construct an SSF for the shakedown analysis leads to less conservative lower bounds, indicating that PBCs should be employed as the preferred boundary conditions for the shakedown analysis of heterogeneous materials.

On the Determination and Characteristics of Effective Roughness Length for Heterogeneous Terrain

A new method is proposed for the effective roughness length (ERL) in heterogeneous terrain based on the principle of equalisation of momentum or heat fluxes calculated by the drag coefficient parameterization scheme used in the ECMWF numerical model. Compared with the area-weighted logarithmically averaged ERL (drag coefficient), the newly calculated ERL (drag coefficient) is about 40% (16%) larger with a roughness step of 2.3. These differences reach their maximum values when the ratio of smooth to rough surface is 60% to 40%. Since the determination by this method is not sensitive to the atmospheric stratification, it is suitable for use in climate models.

A THEORY OF EFFECTIVE THERMAL CONDUCTIVITY FOR MATRIX-INCLUSION-MICROCRACK THREE-PHASE HETEROGENEOUS MATERIALS BASED ON MICROMECHANICS

The effective thermal conductivity of matrix-inclusion-microcrack three-phase heterogeneous materials is investigated with a self-consistent micromechanical method (SCM) and a random microstructure finite element method(RMFEM). In the SCM, microcracks are assumed to be randomly distributed and penny-shaped and inclusions to be spherical, the crack effect is accounted for by introducing a crack density parameter, the effective thermal conductivity is derived which relates the macroscopic behavior to the crack density parameter. In the RMFEM, the highly irregular microstructure of the heterogeneous media is accurately described, the interaction among the matrix-inclusion-microcracks is exactly treated, the inclusion shape effect and crack size effect are considered. A Ni/ZrO2 particulate composite material containing randomly distributed, penny-shaped cracks is examined as an example. The main results obtained are: (1) the effective thermal conductivity is sensitive to the crack density and exhibits essentially a linear relationship with the density parameter: (2) the inclusion shape has a significant effect on the effective thermal conductivity and a polygon-shaped inclusion is more effective in increasing or decreasing the effective thermal conductivity than a sphere-shaped one; and (3) the SCM and RMFEM are compared and the two methods give the same effective property in the case in which the matrix thermal conductivity A, is greater than the inclusion one lambda(2). In the inverse case of lambda(1) < lambda(2), the two methods as the as the inclusion volume fraction and crack density are low and differ as they are high. A reasonable explanation for the agreement and deviation between the two methods in the case of lambda(1) < lambda(2) is made.

Modeling the heterogeneous traffic flow considering the effect of self-stabilizing and autonomous vehicles

With the increasing maturity of automatic driving technology,the homogeneous traffic flow will gradually evolve into the heterogeneous traffic flow,which consists of human-driving and autonomous vehicles.To better study the characteristics of the heterogeneous traffic system,this paper proposes a new car-following model for autonomous vehicles and heterogeneous traffic flow,which considers the self-stabilizing effect of vehicles.Through linear and nonlinear methods,this paper deduces and analyzes the stability of such a car-following model with the self-stabilizing effect.Finally,the model is verified by numerical simulation.Numerical results show that the self-stabilizing effect can make the heterogeneous traffic flow more stable,and that increasing the self-stabilizing coefficient or historical time length can strengthen the stability of heterogeneous traffic flow and alleviate traffic congestion effectively.In addition,the heterogeneous traffic flow can also be stabilized with a higher proportion of autonomous vehicles.

Modeling Strain Rate Effect for Heterogeneous Brittle Materials

Rocks are heterogeneous from the point of dynamic failure behavior. Both the compressive and microstructure which is of significance to their tensile strength of rock-like materials is regarded different from the static strength. The present study adopts smoothed particle hydrodynamics （SPH） which is a virtual particle based meshfree method to investigate strain rate effect for heterogeneous brittle materials. The SPH method is capable of simulating rock fracture, free of the mesh constraint of the traditional FEM and FDM models. A pressure dependent J-H constitutive model involving heterogeneity is employed in the numerical modeling. The results show the compressive strength increases with the increase of strain rate as well as the tensile strength, which is important to the engineering design.

Visual representation and characterization of three-dimensional hydrofracturing cracks within heterogeneous rock through 3D printing and transparent models

The heterogeneity of unconventional reservoir rock tremendously affects its hydrofracturing behavior. A visual representation and accurate characterization of the three-dimensional （3D） growth and distribution of hydrofracturing cracks within heterogeneous rocks is of particular use to the design and implementation of hydrofracturing stimulation of unconventional reservoirs. However, because of the difficulties involved in visually representing and quantitatively characterizing a 3D hydrofracturing crack-network, this issue remains a challenge. In this paper, a novel method is proposed for physically visualizing and quantitatively characterizing the 3D hydrofracturing crack-network distributed through a heterogeneous structure based on a natural glutenite sample. This method incorporates X-ray microfocus computed tomography （μCT）, 3D printing models and hydrofracturing triaxial tests to represent visually the heterogeneous structure, and the 3D crack growth and distribution within a transparent rock model during hydrofracturing. The coupled effects of material heterogeneity and confining geostress on the 3D crack initiation and propagation were analyzed. The results indicate that the breakdown pressure of a heterogeneous rock model is significantly affected by material heterogeneity and confining geostress. The measured breakdown pressures of heterogeneous models are apparently different from those predicted by traditional theories. This study helps to elucidate the quantitative visualization and characterization of the mechanism and influencing factors that determine the hydrofracturing crack initiation and propagation in heterogeneous reservoir rocks.

Metal-doped(Cu,Zn)Fe2O4 from integral utilization of toxic Zn-containing electric arc furnace dust: An environment-friendly heterogeneous Fenton-like catalyst

Pure metal-doped(Cu,Zn)Fe2O4 was synthesized from Zn-containing electric arc furnace dust(EAFD)by solid-state reaction using copper salt as additive.The effects of pretreated EAFD-to-Cu2(OH)2CO3·6H2O mass ratio,calcination time,and calcination temperature on the structure and catalytic ability were systematically studied.Under the optimum conditions,the decolorization efficiency and total organic carbon(TOC)removal efficiency of the as-prepared ferrite for treating a Rhodamine B solution were approximately 90.0%and 45.0%,respectively,and the decolorization efficiency remained 83.0%after five recycles,suggesting that the as-prepared(Cu,Zn)Fe2O4 was an efficient heterogeneous Fenton-like catalyst with high stability.The high catalytic activity mainly depended on the synergistic effect of iron and copper ions occupying octahedral positions.More importantly,the toxicity characteristic leaching procedure(TCLP)analysis illustrated that the toxic Zncontaining EAFD was transformed into harmless(Cu,Zn)Fe2O4 and that the concentrations of toxic ions in the degraded solution were all lower than the national emission standard(GB/31574-2015),further confirming that the as obtained sample is an environment-friendly heterogeneous Fenton-like catalyst.

Revisiting anisotropy in the tensile and fracture behavior of cold-rolled316L stainless steel with heterogeneous nano-lamellar structures

We produced a 316 L stainless steel with heterogeneous nanometer-thick lamellar structures by severe cold-rolling at room temperature,and conducted micro-scale tensile tests in different orientations to evaluate both the inplane(parallel to the nano-lamellae)and out-of-plane(normal and 45inclined to the nano-lamellae)mechanical anisotropy.The parallel orientation demonstrates the greatest tensile strength while the inclined orientation exhibits the least strength.The tensile tests in normal and inclined directions also indicate significant transient elastic-plastic response due to the strain path change.Fractographic examination demonstrates that the specimen fails in the normal direction by premature micro-void nucleation and growth,which restricts its tensile strength;however,we identified zig-zag cracking associated with lamellar shear cracking in the inclined direction.

Heterogeneous Quality of Experience Guarantees Over Wireless Networks

Quality of experience(Qo E), which is very critical for the experience of users in wireless networks, has been extensively studied. However, due to different human perceptions, quantifying the effective capacity of wireless network subject to diverse Qo E is very difficult, which leads to many new challenges regarding Qo E guarantees in wireless networks. In this paper, we formulate the Qo E guarantees model for cellular wireless networks. Based on the model, we convert the effective capacity maximization problem into the equivalent convex optimization problem. Then, we develop the optimal Qo E-driven power allocation scheme, which can maximize the effective capacity. The obtained simulation results verified our proposed power allocation scheme, showing that the effective capacity can be significantly increased compared with that of traditional Qo E guarantees based schemes.

Spatio-temporal variability in sea surface wind stress near and off the east coast of Korea

Sea surface wind stress variabilities near and off the east coast of Korea, are examined using 7 kinds of wind datasets from measurements at 2 coastal (land) stations and 2 ocean buoys,satellite scatterometer (QuikSCAT), and global reanalyzed products (ECMWF,NOGAPS,and NCEP/NCAR). Temporal variabilities are analyzed at 3 frequency bands; synoptic (2-20 d), intra-seasonal (20-90 d),and seasonal (>90 d).Synoptic and intra-seasonal variations are predominant near and off the Donghae City due to the passage of the mesoscale weather system. Seasonal variation is caused by southeastward wind stress during Asian winter monsoon. The sea surface wind stress from reanalyzed datasets.QuikSCAT and KMA-B measurements off the coast show good agreement in the magnitude and direction,which are strongly aligned with the alongshore direction.At the land-based sites,wind stresses are much weaker by factors of 3-10 due to the mountainous landmass on the east parts of Korea Peninsula.The first EOF modes(67%-70%) of wind stresses from reanalyzed and QuikSCAT data have similar structures of the strong southeastward wind stress in winter along the coast but show different curl structures at scales less than 200 km due to the orographic effects.The second EOF modes (23%-25%) show southwestward wind stress in every September along the east coast of the North Korea

Characteristics and displacement mechanisms of the dispersed particle gel soft heterogeneous compound flooding system

Considering high temperature and high salinity in the reservoirs, a dispersed particle gel soft heterogeneous compound(SHC) flooding system was prepared to improve the micro-profile control and displacement efficiency. The characteristics and displacement mechanisms of the system were investigated via core flow tests and visual simulation experiments. The SHC flooding system composed of DPG particles and surfactants was suitable for the reservoirs with the temperature of 80-110 °C and the salinity of 1×10~4-10×10~4 mg/L. The system presented good characteristics: low viscosity, weak negatively charged, temperature and salinity resistance, particles aggregation capacity, wettability alteration on oil wet surface, wettability weaken on water wet surface, and interfacial tension(IFT) still less than 1×10^(-1) mN/m after aging at high temperature. The SHC flooding system achieved the micro-profile control by entering formations deeply and the better performance was found in the formation with the higher permeability difference existing between the layers, which suggested that the flooding system was superior to the surfactants, DPG particles, and polymer/surfactant compound flooding systems. The system could effectively enhance the micro-profile control in porous media through four behaviors, including direct plugging, bridging, adsorption, and retention. Moreover, the surfactant in the system magnified the deep migration capability and oil displacement capacity of the SHC flooding system, and the impact was strengthened through the mechanisms of improved displacement capacity, synergistic emulsification, enhanced wettability alteration ability and coalescence of oil belts. The synergistic effect of the two components of SHC flooding system improved oil displacement efficiency and subsequently enhanced oil recovery.

Mechanism of heterogeneous distribution of Cr-containing dispersoids in DC casting 7475 aluminum alloy

The actual effective partition coefficients of Mg and Cr in a cross-section of a dendrite arm in a direct-chill(DC)-casting ingot of 7475 aluminum alloy are obtained.Meanwhile,by analyzing the microstructure,the mechanism of the heterogeneous distribution of E(Al_(18)Mg_(3)Cr_(2))dispersoids in this DC ingot is revealed.The results show that the actual effective partition coefficients of Mg and Cr are 0.650 and 1.392,respectively,and they describe the heterogeneous distributions of Mg and Cr along the direction of radius of the cross-section of the dendrite arm of the alloy.After homogenization treatment at 470℃ for 24 h,Mg diffuses uniformly,but Cr hardly diffuses.Both the concentrations of Mg and Cr and the sites of heterogeneous nucleation in the alloy are the determinants of the formation of E dispersoids simultaneously.The heat treatment at 250℃ for 72 h provides a large number of the sites of heterogeneous nucleation of the formation of fine E dispersoids that will be formed in the center of the cross-section during the subsequent heat treatment at higher temperature.

Effects of amygdale heterogeneity and sample size on the mechanical properties of basalt

Due to the complex diagenesis process,basalt usually contains defects in the form of amygdales formed by diagenetic bubbles,which affect its mechanical properties.In this study,a synthetic rock mass method(SRM)based on the combination of discrete fracture network(DFN)and finite-discrete element method(FDEM)is applied to characterizing the amygdaloidal basalt,and to systematically exploring the effects of the development characteristics of amygdales and sample sizes on the mechanical properties of basalt.The results show that with increasing amygdale content,the elastic modulus(E)increases linearly,while the uniaxial compressive strength(UCS)shows an exponential or logarithmic decay.When the orientation of amygdales is between 0°and 90°,basalt shows a relatively pronounced strength and stiffness anisotropy.Based on the analysis of the geometric and mechanical properties,the representative element volume(REV)size of amygdaloidal basalt blocks is determined to be 200 mm,and the mechanical properties obtained on this scale can be regarded as the properties of the equivalent continuum.The results of this research are of value to the understanding of the mechanical properties of amygdaloidal basalt,so as to guide the formulation of engineering design schemes more accurately.

Spatio-temporal Changes and Associated Uncertainties of CENTURYmodelled SOC for Chinese Upland Soils, 1980-2010

Detailed information on the spatio-temporal changes of cropland soil organic carbon(SOC) can significantly contribute to the improvement of soil fertility and mitigate climate change. Nonetheless, information and knowledge on the national scale spatio-temporal changes and the corresponding uncertainties of SOC in Chinese upland soils remain limited. The CENTURY model was used to estimate the SOC storages and their changes in Chinese uplands from 1980 to 2010. With the Monte Carlo method, the uncertainties of CENTURY-modelled SOC dynamics associated with the spatial heterogeneous model inputs were quantified. Results revealed that the SOC storage in Chinese uplands increased from 3.03(1.59 to 4.78) Pg C in 1980 to 3.40(2.39 to 4.62) Pg C in 2010. Increment of SOC storage during this period was 370 Tg C, with an uncertainty interval of –440 to 1110 Tg C. The regional disparities of SOC changes reached a significant level, with considerable SOC accumulation in the Huang-Huai-Hai Plain of China and SOC loss in the northeastern China. The SOC lost from Meadow soils, Black soils and Chernozems was most severe, whilst SOC accumulation in Fluvo-aquic soils, Cinnamon soils and Purplish soils was most significant. In modelling large-scale SOC dynamics, the initial soil properties were major sources of uncertainty. Hence, more detailed information concerning the soil properties must be collected. The SOC stock of Chinese uplands in 2010 was still relatively low, manifesting that recommended agricultural management practices in conjunction with effectively economic and policy incentives to farmers for soil fertility improvement were indispensable for future carbon sequestration in these regions.

The influence of heterogeneous environmental regulation on the green development of the mining industry: empirical analysis based on the system GMM and dynamic panel data model

The intensity of environmental regulation (ERI) affects the short-term effect of the level of green mining (GML),and which structure determines the long-term mechanism.Based on the panel data from 2001 to 2015,with the dynamic panel model and system GMM estimation method were employed to test the influence of heterogeneous environmental regulation on green mining and its transmission mechanism.The results show that,there is a 'U' type nonlinear relationship between the ERI and GML.The direct effect of command-control-based (CAC) and the market incentive-based (MBI) environmental regulation on green development of mining shows the characteristics of inhibition and promotion.There is a 'U' type of indirectly moderating effect between technological innovation and the energy consumption structure on the GML.The technological innovation promotes the green development of the mining industry only after pass the inflection point of MBI,while the CAC plays a significant guiding role in upgrading of the energy consumption structure.There is an inhibition and promotion effect of MBI on the GML in the southeast coastal area,and the CAC is not significantly.Meanwhile,both of the ERI shows no positive effects in the central and western inland region.

Investigating Spatio-Temporal Pattern of Relative Risk of Tuberculosis in Kenya Using Bayesian Hierarchical Approaches

Proper understanding of global distribution of infectious diseases is an important part of disease management and policy making. However, data are subject to complexities caused by heterogeneities across host classes and space-time epidemic processes. This paper seeks to suggest or propose Bayesian spatio-temporal model for modeling and mapping tuberculosis relative risks in space and time as well identify risks factors associated with the tuberculosis and counties in Kenya with high tuberculosis relative risks. In this paper, we used spatio-temporal Bayesian hierarchical models to study the pattern of tuberculosis relative risks in Kenya. The Markov Chain Monte Carlo method via WinBUGS and R packages were used for simulations and estimation of the parameter estimates. The best fitting model is selected using the Deviance Information Criterion proposed by Spiegelhalter and colleagues. Among the spatio-temporal models used, the Knorr-Held model with space-time interaction type III and IV fit the data well but type IV appears better than type III. Variation in tuberculosis risk is observed among Kenya counties and clustering among counties with high tuberculosis relative risks. The prevalence of HIV is identified as the determinant of TB. We found clustering and heterogeneity of TB risk among high rate counties and the overall tuberculosis risk is slightly decreasing from 2002-2009. We proposed that the Knorr-Held model with interaction type IV should be used to model and map Kenyan tuberculosis relative risks. Interaction of TB relative risk in space and time increases among rural counties that share boundaries with urban counties with high tuberculosis risk. This is due to the ability of models to borrow strength from neighboring counties, such that nearby counties have similar risk. Although the approaches are less than ideal, we hope that our study provide a useful stepping stone in the development of spatial and spatio-temporal methodology for the statistical analysis of risk from tuberculosis in Kenya.

EFFECT OF ELECTRON DONORS ON THE SELECTIVE HYDROGENATION OF DIENE TO MONOENE OVER HETEROGENIZED Pd CATALYST

In the selective hydrogenation of diene (or alkyne) using heterogenized homogeneous catalyst, the high selectivity of monoene formation only appears in a very short time interval. The addition of suitable electron donors can decrease or even cease the monoene hydrogenation and thereby keep the high monoene selectivity after reaching its maximum.

Novel miR-490-3p/hnRNPA1-b/PKM2 axis mediates the Warburg effect and proliferation of colon cancer cells via the PI3K/AKT pathway

BACKGROUND Heterogeneous ribonucleoprotein A1(hnRNPA1)has been reported to enhance the Warburg effect and promote colon cancer(CC)cell proliferation,but the role and mechanism of the miR-490-3p/hnRNPA1-b/PKM2 axis in CC have not yet been elucidated.AIM To investigate the role and mechanism of a novel miR-490-3p/hnRNPA1-b/PKM2 axis in enhancing the Warburg effect and promoting CC cell proliferation through the PI3K/AKT pathway.METHODS Paraffin-embedded pathological sections from 220 CC patients were collected and subjected to immunohistochemical analysis to determine the expression of hnRNPA1-b.The relationship between the expression values and the clinicopathological features of the patients was investigated.Differences in mRNA expression were analyzed using quantitative real-time polymerase chain reaction,while differences in protein expression were analyzed using western blot.Cell proliferation was evaluated using the cell counting kit-8 and 5-ethynyl-2’-deoxyuridine assays,and cell cycle and apoptosis were detected using flow cytometric assays.The targeted binding of miR-490-3p to hnRNPA1-b was validated using a dual luciferase reporter assay.The Warburg effect was evaluated by glucose uptake and lactic acid production assays.RESULTS The expression of hnRNPA1-b was significantly increased in CC tissues and cells compared to normal controls(P<0.05).Immunohistochemical results demonstrated significant variations in the expression of the hnRNPA1-b antigen in different stages of CC,including stage I,II-III,and IV.Furthermore,the clinicopathologic characterization revealed a significant correlation between hnRNPA1-b expression and clinical stage as well as T classification.HnRNPA1-b was found to enhance the Warburg effect through the PI3K/AKT pathway,thereby promoting proliferation of HCT116 and SW620 cells.However,the proliferation of HCT116 and SW620 cells was inhibited when miR-490-3p targeted and bound to hnRNPA1-b,effectively blocking the Warburg effect.CONCLUSION These findings suggest that the novel miR-490-3p/hnRNPA1-b/PKM2 axis could provide a new strategy for the diagnosis and treatment of CC.