Reshaping Li–Mg hybrid batteries:Epitaxial electrodeposition and spatial confinement on MgMOF substrates via the lattice‐matching strategy

The emergence of Li–Mg hybrid batteries has been receiving attention,owing to their enhanced electrochemical kinetics and reduced overpotential.Nevertheless,the persistent challenge of uneven Mg electrodeposition remains a significant impediment to their practical integration.Herein,we developed an ingenious approach that centered around epitaxial electrocrystallization and meticulously controlled growth of magnesium crystals on a specialized MgMOF substrate.The chosen MgMOF substrate demonstrated a robust affinity for magnesium and showed minimal lattice misfit with Mg,establishing the crucial prerequisites for successful heteroepitaxial electrocrystallization.Moreover,the incorporation of periodic electric fields and successive nanochannels within the MgMOF structure created a spatially confined environment that considerably promoted uniform magnesium nucleation at the molecular scale.Taking inspiration from the“blockchain”concept prevalent in the realm of big data,we seamlessly integrated a conductive polypyrrole framework,acting as a connecting“chain,”to interlink the“blocks”comprising the MgMOF cavities.This innovative design significantly amplified charge‐transfer efficiency,thereby increasing overall electrochemical kinetics.The resulting architecture(MgMOF@PPy@CC)served as an exceptional host for heteroepitaxial Mg electrodeposition,showcasing remarkable electrostripping/plating kinetics and excellent cycling performance.Surprisingly,a symmetrical cell incorporating the MgMOF@PPy@CC electrode demonstrated impressive stability even under ultrahigh current density conditions(10mAcm^(–2)),maintaining operation for an extended 1200 h,surpassing previously reported benchmarks.Significantly,on coupling the MgMOF@PPy@CC anode with a Mo_(6)S_(8) cathode,the assembled battery showed an extended lifespan of 10,000 cycles at 70 C,with an outstanding capacity retention of 96.23%.This study provides a fresh perspective on the rational design of epitaxial electrocrystallization driven by metal–organic framework(MOF)substrates,paving the way toward the advancement of cuttingedge batteries.

Multiscale confinement nitridation in molybdenum carbide for efficient hydrogen production

The molybdenum carbide(Mo_(2)C)has been regarded as one of the most cost-efficient and stable electrocatalyst for the hydrogen evolution reaction(HER)by the virtue of its Pt-like electronic structures.However,the inherent limitation of high density of empty valence band significantly reduces its catalytic reactivity by reason of strong hydrogen desorption resistance.Herein,we propose a multiscale confinement synthesis method to design the nitrogen-rich Mo_(2)C for modulating the band structure via decomposing the pre-coordination bonded polymer in a pressure-tight tube sealing system.Pre-bonded c/N-Mo in the coordination precursor constructs a micro-confinement space,enabling the homogeneous nitrogenization in-situ happened during the formation of Mo_(2)C.Simultaneously,the evolved gases from the precursor decomposition in tube sealing system establish a macro-confinement environment,preventing the lattice N escape and further endowing a continuous nitridation.Combining the multiscale confinement effects,the nitrogen-rich Mo2C displays as high as 25%N-Mo concentration in carbide lattice,leading to a satisfactory band structure.Accordingly,the constructed nitrogen-rich Mo_(2)C reveals an adorable catalytic activity for HER in both alkaline and acid solution.It is anticipated that the multiscale confinement synthesis strategy presents guideline for the rational design of electrocatalysts and beyond.

Quantum confinement of carriers in the type-I quantum wells structure

Quantum confinement is recognized to be an inherent property in low-dimensional structures.Traditionally,it is believed that the carriers trapped within the well cannot escape due to the discrete energy levels.However,our previous research has revealed efficient carrier escape in low-dimensional structures,contradicting this conventional understanding.In this study,we review the energy band structure of quantum wells along the growth direction considering it as a superposition of the bulk material dispersion and quantization energy dispersion resulting from the quantum confinement across the whole Brillouin zone.By accounting for all wave vectors,we obtain a certain distribution of carrier energy at each quantized energy level,giving rise to the energy subbands.These results enable carriers to escape from the well under the influence of an electric field.Additionally,we have compiled a comprehensive summary of various energy band scenarios in quantum well structures relevant to carrier transport.Such a new interpretation holds significant value in deepening our comprehension of low-dimensional energy bands,discovering new physical phenomena,and designing novel devices with superior performance.

Enhancing I^(0)/I^(-)Conversion Efficiency by Starch Confinement in Zinc-lodine Battery

The redox couple of I^(0)/I^(-)in aqueous rechargeable iodine–zinc(I^(2)-Zn)batteries is a promising energy storage resource since it is safe and cost-effective,and provides steady output voltage.However,the cycle life and efficiency of these batteries remain unsatisfactory due to the uncontrolled shuttling of polyiodide(I_(3)^(-)and I_(5)^(-))and side reactions on the Zn anode.Starch is a very low-cost and widely sourced food used daily around the world.“Starch turns blue when it encounters iodine”is a classic chemical reaction,which results from the unique structure of the helix starch molecule–iodine complex.Inspired by this,we employ starch to confine the shuttling of polyiodide,and thus,the I^(0)/I^(-)conversion efficiency of an I^(2)-Zn battery is clearly enhanced.According to the detailed characterizations and theoretical DFT calculation results,the enhancement of I^(0)/I^(-)conversion efficiency is mainly originated from the strong bonding between the charged products of I_(3)^(-)and I_(5)^(-)and the rich hydroxyl groups in starch.This work provides inspiration for the rational design of high-performance and low-cost I^(2)-Zn in AZIBs.

Ethylene purification in a metal–organic framework over a wide temperature range via pore confinement

The separation of C2H4from C_(2)H_(6)/C_(2)H_(4)mixture is of great importance but difficult and energy intensive. Adsorptive separation provides an alternative approach to ameliorate this situation. Here, we report a microporous metal–organic framework(MOF) BUT-315-a as a C_(2)H_(6)-selective adsorbent for the separation of C2H6/C2H4gas mixture. BUT-315-a combines good IAST selectivity of 2.35 with high C_(2)H_(6)uptake of 97.5 cm^(3)g^(-1), giving superior high separation potential ΔQ(2226 mmol L^(-1)) for equimolar C_(2)H_(6)/C_(2)H_(4) at 298 K. Impressively, such excellent performance can be preserved at higher temperatures of 313 and 323 K to accommodate industrial conditions. Efficient dynamic separation performance of BUT-315-a has been demonstrated by column breakthrough experiments under varied temperatures and gas ratios. Theoretical calculations further reveal multiple synergistic interactions between C_(2)H_(6) and the framework. This work highlights a new benchmark material for C_(2)H_(6)/C_(2)H_(4)separation and provides guidance for designing adsorbent for separation applications.

Bacterial turbulence in gradient confinement

We investigate a novel form of non-uniform living turbulence at an extremely low Reynolds number using a bacterial suspension confined within a sessile droplet. This turbulence differs from homogeneous active turbulences in two or threedimensional geometries. The heterogeneity arises from a gradient of bacterial activity due to oxygen depletion along the droplet’s radial direction. Motile bacteria inject energy at individual scales, resulting in local anisotropic energy fluctuations that collectively give rise to isotropic turbulence. We find that the total kinetic energy and enstrophy decrease as distance from the drop contact line increases, due to the weakening of bacterial activity caused by oxygen depletion. While the balance between kinetic energy and enstrophy establishes a characteristic vortex scale depending on the contact angle of the sessile drop. The energy spectrum exhibits diverse scaling behaviors at large wavenumber, ranging from k-1/5to k-1,depending on the geometric confinement. Our findings demonstrate how spatial regulation of turbulence can be achieved by tuning the activity of driving units, offering insights into the dynamic behavior of living systems and the potential for controlling turbulence through gradient confinements.

Anion type-dependent confinement effect on glass transitions of solutions of LiTFSI and LiFSI

We present findings on the effect of nanometer-sized silica-based pores on the glass transition of aqueous solutions of lithium bis(trifluoromethane)sulfonimide(LiTFSI)and lithium difluorosulfimide(LiFSI),respectively.Our experimental results demonstrate a clear dependence of the confinement effect on the anion type,particularly for water-rich solutions,in which the precipitation of crystalized ice under cooling process induces the formation of freeze-concentrated phase confined between pore wall and core ice.As this liquid layer becomes thinner,the freeze-concentrated phase experiences glass transition at increasingly higher temperatures in solutions of LiTFSI.However,differently,for solutions of LiFSI and LiCl,this secondary confinement has a negligible effect on the glass transition of solutions confined wherein.These different behaviors emphasize the obvious difference in the dynamic properties’response of LiTFSI and LiFSI solutions to spatial confinement and particularly to the presence of the hydrophilic pore wall.

Experimental study of density gradient-driven micro-instabilities and the confinement degradation during H-mode in EAST

A broadband(BB)mode is observed by collective Thomson scattering diagnostics in repeatable shots of EAST and analyzed for the first time.This BB mode usually grows during L–H transitions,featuring a BB quasi-coherent mode with increasing frequency.During H-mode operations,it is characterized by steady-state BB in the high-frequency range(f~200–2000 k Hz),at the electron scale(k_(θ)ρ_(s)=1–2),mainly driven by the density gradient,and is sensitive to the value ofηein the region of interest(ρ=0.4–0.8),wherehe=(R/L_(Te))/(R/L_(ne))is the ratio of the normalized electron temperature gradient and density gradient,and the regionρ=0.4–0.8 usually has a relatively low collisionality(v_(eff)<5).The frequency of BB is found to be dependent on the electron temperature and density gradient,which is a typical feature of electron-driven turbulence.A negative correlation between the energy confinement and the intensity of the BB turbulence during H-mode has been found,which indicates a strong electron thermal transport induced by the BB turbulence.The BB significantly decreases the electron temperature and causes flatter electron temperature profiles in the region of interest(ρ=0.4–0.8),thus makingηedecrease and the BB destabilize further.These characteristics of BB are related to the theoretical density gradient-driven trapped electron mode.It should be noted that this mode is not observed by other diagnostics in EAST,and shows very different features to the coherent modes in the edge.

Single-Molecule Confinement Induced Intrinsic Multi-Electron Redox-Activity to Enhance Supercapacitor Performance

Aggregation of polyoxometalates(POM)is largely responsible for the reduced performance of POM-based energy-storage systems.To address this challenge,here,the precise confinement of single Keggin-type POM molecule in a porous carbon(PC)of unimodal super-micropore(micro-PC)is realized.Such precise single-molecule confinement enables sufficient activity center exposure and maximum electron-transfer from micro-PC to POM,which well stabilizes the electron-accepting molecules and thoroughly activates its inherent multi-electron redox-activity.In particular,the redox-activities and electron-accepting properties of the confined POM molecule are revealed to be super-micropore pore size-dependent by experiment and spectroscopy as well as theoretical calculation.Meanwhile,the molecularly dispersed POM molecules confined steadily in the“cage”of micro-PC exhibit unprecedented large-negative-potential stability and multiple-peak redox-activity at an ultra-low loading of~11.4 wt%.As a result,the fabricated solid-state supercapacitor achieves a remarkable areal capacitance,ultrahigh energy and power density of 443 mF cm^(-2),0.12 mWh cm^(-2)and 21.1 mW cm^(-2),respectively.This work establishes a novel strategy for the precise confinement of single POM molecule,providing a versatile approach to inducing the intrinsic activity of POMs for advanced energy-storage systems.

Implosion Plasma Driven Fusion Pellet of Inertial Confinement(A Short Memorandum)

The implosion plasma drive fusion pellet of inertial confinement is a concept related to nuclear fusion,a process in which atomic nuclei combine to form heavier nuclei,releasing a large amount of energy in the process.The implosion plasma drive fusion pellet is a potential fuel source for achieving controlled nuclear fusion.ICF(inertial confinement fusion)is a technique used to achieve fusion by compressing a small target containing fusion fuel to extremely high densities and temperatures using lasers or other methods.The implosion plasma drive fusion pellet concept involves using a small pellet of deuterium and tritium(two isotopes of hydrogen)as fusion fuel,and then rapidly heating and compressing it using a pulsed power system.The implosion process creates a high-pressure plasma that ignites the fusion reactions,releasing energy in the form of neutrons and charged particles.The resulting energy can be captured and used for power generation.This technology is still in the experimental stage,and significant research and development is required to make it commercially viable.However,it has the potential to provide a virtually limitless source of clean energy with no greenhouse gas emissions or long-term radioactive waste.Be that as it may,ICF has to get exact control of the implosion process,mitigate insecurities,and create modern materials and advances to resist the extraordinary conditions of the combined response.

Measurements of Carrier Confinement at β-FeSi_2-Si Heterojunction by Electroluminescence

A Si p-π-n diode with β-FeSi 2 particles embedded in the unintentionally doped Si (p--type) was designed for determining the band offset at β-FeSi 2-Si heterojunction.When the diode is under forward bias,the electrons injected via the Si n-p- junction diffuse to and are confined in the β-FeSi 2 particles due to the band offset.The storage charge at the β-FeSi 2-Si heterojunction inversely hamper the further diffusion of electrons,giving rise to the localization of electrons in the p--Si near the Si junction,which prevents them from nonradiative recombination channels.This results in electroluminescence (EL) intensity from both Si and β-FeSi 2 quenching slowly up to room temperature.The temperature dependent ratio of EL intensity of β-FeSi 2 to Si indicates the loss of electron confinement following thermal excitation model.The conduction band offset between Si and β-FeSi 2 is determined to be about 0 2eV.

Manifestation of Color Confinement in the YY Model for Atomic Nuclei

In this paper, a manifestation of the well-known color confinement from the QCD (quantum chromodynamics) in the newly developed YY model for the atomic nucleus is presented. There is a wonderful correspondence between the structural requirements from the YY model and some elementary properties of the color dynamics from QCD. The open questions in the YY model, namely the holding forces for triple nodes and for pairing space links, are exactly covered by the three-color compensation or by the paired color anti-color balance. We will see what colors and anti-colors do mean in the YY model, how up quarks and down quarks get assigned a color or anti-color. We will discover some relationships between gluon-based interactions as described in the standard model and pairing space links in the YY model.

A 1.3μm Low-Threshold Edge-Emitting Laser with AlInAs-Oxide Confinement Layers

A 1.3μm low-threshold edge-emitting AlGaInAs multiple-quantum-well(MQW) laser with AlInAs-oxide confinement layers is fabricated.The Al-contained waveguide layers upper and low the active layers are oxidized as current-confined layers using wet-oxidation technique.This structure provides excellent current and optical confinement,resulting in 12.9mA of a low continuous wave threshold current and 0.47W/A of a high slope efficiency of per facet at room temperature for a 5-μm-wide current aperture.Compared with the ridge waveguide laser with the same-width ridge,the threshold current of the AlInAs-oxide confinement laser has decreased by 31.7% and the slope efficiency has increased a little.Both low threshold and high slope efficiency indicate that lateral current confinement can be realized by oxidizing AlInAs waveguide layers.The full width of half maximum angles of the Al-InAs-oxide confinement laser are 21.6° for the horizontal and 36.1° for the vertical,which demonstrate the ability of the AlInAs oxide in preventing the optical field from spreading laterally.

Numerical analysis of confinement effect on crack propagation mechanism from a flaw in a pre-cracked rock under compression

In many situations rocks are subjected to biaxial loading and the failure process is controlled by the lateral confinement stresses. The importance of confinement stresses has been recognized in the literature by many researchers, in particular, its influence on strength and on the angle of fracture, but still there is not a clear description for the influence of confining stress on the crack propagation mechanism of rocks. This paper presents a numerical pro- cedure for the analysis of crack propagation in rock-like ma- terials under compressive biaxial loads. Several numerical simulations of biaxial tests on the rock specimen have been carried out by a bonded particle model （BPM） and the influ- ence of confinement on the mechanism of crack propagation from a single flaw in rock specimens is studied. For this purpose, several biaxial compressive tests on rectangular spec- imens under different confinement stresses were modeled in （2 dimensional particle flow code） PFC2D. The results show that wing cracks initiate perpendicular to the flaw and trend toward the direction of major stress, however, when the lat- eral stresses increase, this initiation angle gets wider. Also it is concluded that in addition to the material type, the initiation direction of the secondary cracks depends on confine- ment stresses, too. Besides, it is understood that secondary cracks may be produced from both tensile and shear mechanisms.

Recent progress on confinement of polysulfides through physical andchemical methods

With high theoretical energy density and the natural abundance of S, lithium-sulfur （Li-S） batteries areconsidered to be the promising next generation high-energy rechargeable energy storage devices. How-ever, issues including electronical insulation of S, the lithium polysulfides （LiPSs） dissolution and the shortcycle lifespan have prevented Li-S batteries from being practical applied. Feasible settlements of confiningLiPSs to reduce the loss of active substances and improve the cycle stability include wrapping sulfur withcompact layers, designing matrix with porous or hollow structures, adding adsorbents owning stronginteraction with sulfur and inserting polysulfide barriers between cathodes and separators. This reviewcategorizes them into physical and chemical confinements according to the influencing mechanism. Withfurther discussion of their merits and flaws, synergy of the physical and chemical confinement is believedto be the feasible avenue that can guide Li-S batteries to the practical application.

Dielectric Confinement Effect on Calculating the Band Gap of PbSe Quantum Dots

Considering the dielectric confinement effect on excitonics of PbSe quantum dots （QDs）, a correction factor in the wave function was introduced to propose a new band gap calculation model for QDs. The modified model showed great consistency with the experimental data, especially in small size range. According to the variation of confined barrier, the band gap calculation model of PbSe QDs was analyzed in different solvents. The calculating results showed that the modified model was almost solvent-independent, which was consistent with our experimental results and related reports.

Sandwiching Sulfur into the Dents Between N,O Co-Doped Graphene Layered Blocks with Strong Physicochemical Confinements for Stable and High-Rate Li-S Batteries

The development of lithium-sulfur batteries(LSBs)is restricted by their poor cycle stability and rate performance due to the low conductivity of sulfur and severe shuttle effect.Herein,an N,O co-doped graphene layered block(NOGB)with many dents on the graphene sheets is designed as effective sulfur host for high-performance LSB s.The sulfur platelets are physically confined into the dents and closely contacted with the graphene scaffold,ensuring structural stability and high conductivity.The highly doped N and O atoms can prevent the shuttle effect of sulfur species by strong chemical adsorption.Moreover,the micropores on the graphene sheets enable fast Li^+transport through the blocks.As a result,the obtained NOGB/S composite with 76 wt%sulfur content shows a high capacity of 1413 mAh g^-1 at 0.1 C,good rate performance of 433 mAh g^-1 at 10 C,and remarkable stability with 526 mAh g^-1 at after 1000 cycles at 1 C(average decay rate:0.038%per cycle).Our design provides a comprehensive route for simultaneously improving the conductivity,ion transport kinetics,and preventing the shuttle effect in LSBs.

Effects of confinement on rock mass modulus:A synthetic rock mass modelling(SRM) study

The main objective of this paper is to examine the influence of the applied confining stress on the rock mass modulus of moderately jointed rocks（well interlocked undisturbed rock mass with blocks formed by three or less intersecting joints）. A synthetic rock mass modelling（SRM） approach is employed to determine the mechanical properties of the rock mass. In this approach, the intact body of rock is represented by the discrete element method（DEM）-Voronoi grains with the ability of simulating the initiation and propagation of microcracks within the intact part of the model. The geometry of the preexisting joints is generated by employing discrete fracture network（DFN） modelling based on field joint data collected from the Brockville Tunnel using LiDAR scanning. The geometrical characteristics of the simulated joints at a representative sample size are first validated against the field data, and then used to measure the rock quality designation（RQD）, joint spacing, areal fracture intensity（P21）, and block volumes. These geometrical quantities are used to quantitatively determine a representative range of the geological strength index（GSI）. The results show that estimating the GSI using the RQD tends to make a closer estimate of the degree of blockiness that leads to GSI values corresponding to those obtained from direct visual observations of the rock mass conditions in the field. The use of joint spacing and block volume in order to quantify the GSI value range for the studied rock mass suggests a lower range compared to that evaluated in situ. Based on numerical modelling results and laboratory data of rock testing reported in the literature, a semi-empirical equation is proposed that relates the rock mass modulus to confinement as a function of the areal fracture intensity and joint stiffness.

Experimental investigations on mechanical performance of rocks under fatigue loads and biaxial confinements

In this research,a series of biaxial compression and biaxial fatigue tests were conducted to investigate the mechanical behaviors of marble and sandstone under biaxial confinements.Experimental results demonstrate that the biaxial compressive strength of rocks under biaxial compression increases firstly,and subsequently decreases with increase of the intermediate principal stress.The fatigue failure characteristics of the rocks in biaxial fatigue tests are functions of the peak value of fatigue loads,the intermediate principal stress and the rock lithology.With the increase of the peak values of fatigue loads,the fatigue lives of rocks decrease.The intermediate principal stress strengthens the resistance ability of rocks to fatigue loads except considering the strength increasing under biaxial confinements.The fatigue lives of rocks increase with the increase of the intermediate principal stress under the same ratio of the fatigue load and their biaxial compressive strength.The acoustic emission(AE)and fragments studies showed that the sandstone has higher ability to resist the fatigue loads compared to the marble,and the marble generated a greater number of smaller fragments after fatigue failure compared to the sandstone.So,it can be inferred that the rock breaking efficiency and rock burst is higher or severer induced by fatigue loading than that induced by monotonous quasi-static loading,especially for hard rocks.

Heavy Metal Detection in Soils by Laser Induced Breakdown Spectroscopy Using Hemispherical Spatial Confinement

Spatial confinement has great potential for Laser Induced Breakdown Spectroscopy （LIBS） instruments after it has been proven that it has the ability to enhance the LIBS signal strength and repeatability. In order to achieve in-situ measurement of heavy metals in farmland soils by LIBS, a hemispherical spatial confinement device is designed and used to collect plasma spectra, in which the optical fibers directly collect the breakdown spectroscopy of the soil samples. This device could effectively increase the stability of the spectrum intensity of soil. It also has other advantages, such as ease of installation, and its small and compact size. The relationship between the spectrum intensity and the laser pulse energy is studied for this device. It is found that the breakdown threshold is 160 cm-2, and when the laser fluence increases to 250 J/cm2, the spectrum intensity reaches its maximum. Four different kinds of laser pulse energy were set up and in each case the limits of detection of Cd, Cu, Ni, Pb and Zn were calculated. The results show that when the laser pulse fluence was 2.12 GW/cm2, we obtained the smallest limits of detection of these heavy metals, which are all under 10 mg/kg. This device can satisfy the needs of heavy metal in-situ detection, and in the next step it will be integrated into a portable LIBS instrument.