The penetration depth of atomic radicals in tubes with catalytic surface properties

Catalysis of molecular radicals is often performed in interesting experimental configurations.One possible configuration is tubular geometry.The radicals are introduced into the tubes on one side,and stable molecules are exhausted on the other side.The penetration depth of radicals depends on numerous parameters,so it is not always feasible to calculate it.This article presents systematic measurements of the penetration depth of oxygen atoms along tubes made from nickel,cobalt,and copper.The source of O atoms was a surfatron-type microwave plasma.The initial density of O atoms depended on the gas flow and was 0.7×10^(21)m^(-3),2.4×10^(21)m^(-3),and 4.2×10^(21)m^(-3)at the flow rates of 50,300,and 600 sccm,and pressures of 10,35,and 60 Pa,respectively.The gas temperature remained at room temperature throughout the experiments.The dissociation fraction decreased exponentially along the length of the tubes in all cases.The penetration depths for well-oxidized nickel were 1.2,1.7,and 2.4 cm,respectively.For cobalt,they were slightly lower at 1.0,1.3,and 1.6 cm,respectively,while for copper,they were 1.1,1.3,and 1.7 cm,respectively.The results were explained by gas dynamics and heterogeneous surface association.These data are useful in any attempt to estimate the loss of molecular fragments along tubes,which serve as catalysts for the association of various radicals to stable molecules.

Effects of surface chlorine atoms on charge distribution and reaction barriers for photocatalytic CO_(2)reduction

Photocatalytic CO_(2)reduction to produce high value-added carbon-based fuel has been proposed as a promising approach to mitigate global warming issues.However,the conversion efficiency and product selectivity are still low due to the sluggish dynamics of transfer processes involved in proton-assisted multi-electron reactions.Lowering the formation energy barriers of intermediate products is an effective method to enhance the selectivity and productivity of final products.In this study,we aim to regulate the surface electronic structure of Bi_(2)WO_(6)by doping surface chlorine atoms to achieve effective photocatalytic CO_(2)reduction.Surface Cl atoms can enhance the absorption ability of light,affect its energy band structure and promote charge separation.Combined with DFT calculations,it is revealed that surface Cl atoms can not only change the surface charge distribution which affects the competitive adsorption of H_(2)O and CO_(2),but also lower the formation energy barrier of intermediate products to generate more intermediate*COOH,thus facilitating CO production.Overall,this study demonstrates a promising surface halogenation strategy to enhance the photocatalytic CO_(2)reduction activity of a layered structure Bi-based catalyst.

Molecular Dynamics, Physical Properties, Diffusion Coefficients and Activation Energy of the Lithium Oxide (Li-O) and Sodium Oxide (Na-O) Electrolyte (Cathode)

This work is a simulation model with the LAMMPS calculation code of an electrode based on alkali metal oxides (lithium, sodium and potassium) using the Lennard Jones potential. For a multiplicity of 8*8*8, we studied a gap-free model using molecular dynamics. Physical quantities such as volume and pressure of the Na-O and Li-O systems exhibit similar behaviors around the thermodynamic ensembles NPT and NVE. However, for the Na2O system, at a minimum temperature value, we observe a range of total energy values;in contrast, for the Li2O system, a minimum energy corresponds to a range of temperatures. Finally, for physicochemical properties, we studied the diffusion coefficient and activation energy of lithium and potassium oxides around their melting temperatures. The order of magnitude of the diffusion coefficients is given by the relation Dli-O >DNa-O for the multiplicity 8*8*8, while for the activation energy, the order is well reversed EaNa-O > EaLi-O.

MD Simulation of Diffusion Behaviors in Collision Welding Processes of Al-Cu, Al-Al, Cu-Cu

To investigate the effects of material combinations and velocity conditions on atomic diffusion behavior near collision interfaces,this study simulates the atomic diffusion behavior near collision interfaces in Cu-Al,Al-Al and Cu-Cu combinations fabricated through collision welding using molecular dynamic(MD)simulation.The atomic diffusion behaviors are compared between similar metal combinations(Al-Al,Cu-Cu)and dissimilar metal combinations(Al-Cu).By combining the simulation results and classical diffusion theory,the diffusion coefficients for similar and dissimilar metal material combinations under different velocity conditions are obtained.The effects of material combinations and collision velocity on diffusion behaviors are also discussed.The diffusion behaviors of dissimilar material combinations strongly depend on the transverse velocity,whereas those of the similar material combinations are more dependent on the longitudinal velocity.These findings can provide guidance for optimizing welding parameters.

Boosting rate performance of layered lithium-rich cathode materials by oxygen vacancy induced surface multicomponent integration

The rapid development of electric vehicles and portable energy storage systems demands improvements in the energy density and cost-effectiveness of lithium-ion batteries,a domain in which Lithium-rich layered cathode(LLO)materials inherently excel.However,these materials face practical challenges,such as low initial Coulombic efficiency,inferior cycle/rate performance,and voltage decline during cycling,which limit practical application.Our study introduces a surface multi-component integration strategy that incorporates oxygen vacancies into the pristine LLO material Li1.2Mn_(0.6)Ni_(0.2)O_(2).This process involves a brief citric acid treatment followed by calcination,aiming to explore rate-dependent degradation behavior.The induced surface oxygen vacancies can reduce surface oxygen partial pressure and diminish the generation of O_(2)and other highly reactive oxygen species on the surface,thereby facilitating the activation of Li ions trapped in tetrahedral sites while overcoming transport barriers.Additionally,the formation of a spinel-like phase with 3D Li+diffusion channels significantly improves Li^(+)diffusion kinetics and stabilizes the surface structure.The optimally modified sample boasts a discharge capacity of 299.5 mA h g^(-1)at a 0.1 C and 251.6 mA h g^(-1)at a 1 C during the initial activation cycle,with an impressive capacity of 222.1 mA h g^(-1)at a 5 C.Most notably,it retained nearly 70%of its capacity after 300 cycles at this elevated rate.This straightforward,effective,and highly viable modification strategy provides a crucial resolution for overcoming challenges associated with LLO materials,making them more suitable for practical application.

Adsorptions and diffusions of carbon atoms on the surface and in the subsurface of Co(200): A first-principles density-functional study

First-principles calculations based on density functional theory are used to investigate the adsorptions and diffusions of carbon atoms on the surface and in the subsurface of Co （200）. The preferred site for the carbon atom on the surface is the hollow site, and the preferred site in the subsurface is the octahedral site. There is charge transfer from the surface to the adsorbed carbon atom, and for the most favorable adsorbed structure the charge transfer is largest. Moreover, the energy barriers for the diffusions of carbon atoms on the surface and from the surface into the subsurface and then back to the surface are calculated in detail. The results indicate that the energy barrier for the diffusion of carbon atoms on the surface is comparable to that from the subsurface to the surface. The results imply that both the direct surface nucleation and the surface segregation from Co bulk can be observed in the chemical vapor deposition growth of graphene on Co （200） substrate, which can gain a new insight into the growth mechanism of graphene.

Surface diffusion of Si, Ge and C adatoms on Si (001) substrate studied by the molecular dynamics simulation

Depositions of Si, Ge and C atoms onto a preliminary Si （001） substrate at different temperatures are investigated by using the molecular dynamics method. The mechanism of atomic self-assembling occurring locally on the flat terraces between steps is suggested. Diffusion and arrangement patterns of adatoms at different temperatures are observed. At 900 K, the deposited atoms are more likely to form dimers in the perpendicular [110] direction due to the more favourable movement along the perpendicular [110] direction. C adatoms are more likely to break or reconstruct the dimers on the substrate surface and have larger diffusion distances than Ge and Si adatoms. Exchange between C adatoms and substrate atoms are obvious and the epitaxial thickness is small. Total potential energies of adatoms and substrate atoms involved in the simulation cell are computed. When a newly arrived adatom reaches the stable position, the potential energy of the system will decrease and the curves turns into a ladder-like shape. It is found that C adatoms can lead to more reduction of the system energy and the potential energy of the system will increase as temperature increases.

Driving the Diffusion of Cesium Atoms of Graphite Monolayers on Metal Surfaces into Rhenium (1010)

It has been shown experimentally for the first time that diffusion of cesium n rhenium takes place at irradiation of atoms flux heated up to Т ≤ 1800 K -C. Analysis of thermal desorption spectra showed that cesium forms two high-temperature phases during adsorption of cesium on graphite monolayer in rhenium heated up to 1800 K. The first, intercalated phase starts filling immediately and grows up to maximum concentration. The second, diffusion phase appears with slight delay and grows incessantly during adsorption. It is for the first time that the Fick Equation has been applied for such kind of diffusion. Correspondences and average displacement L = f(Т,t) have been obtained at diffusion of surface cesium in rhenium in the interval of temperatures 1600 K Т ν = 5 × 1013 cm-2·s-1, U = +2000 V, T = 1700 K, effectiveness of cesium diffusion δCs in the system of Re(1010)-C was identified with application of suggested methods, which showed δCs = 0.45. Activation energies of Сs atoms diffusion in rhenium from rhenium were found and values Е1p = 5.65 ± 0.05 eV and Еp1 = 5.85 ± 0.05 eV were obtained respectively. Effect of electrical field on intercalation and cesium diffusion in Re-C was observed.

Surface Molecular Encapsulation with Cyclodextrin in Promoting the Activity and Stability of Fe Single-Atom Catalyst for Oxygen Reduction Reaction

Fe single-atom catalysts(Fe-SACs)have been extensively studied as a highly efficient electrocatalyst toward the oxygen reduction reaction(ORR).Nonetheless,they suffer from stability issue induced by dissolution of Fe metal center and the OH^(−)blocking.Herein,a surface molecular engineering strategy is developed by usingβ-cyclodextrins(CDs)as a localized molecular encapsulation.The CD-modified Fe-SAC(Fe-SNC-β-CD)shows obviously improved activity toward the ORR with 0.90 V,4.10 and 4.09 mA cm^(-2)for E_(1/2),J_(0)and Jk0.9,respectively.Meanwhile,the Fe-SNC-β-CD shows the excellent long-term stability against aggressive stress and the poisoning.It is confirmed through electrochemical investigation that modification ofβ-CD can,on one hand,regulate the atomic Fe coordination chemistry through the interaction between the CD and FeN_(x) moiety,while on the other mitigate the strong adsorption of OH^(−)and function as protective barrier against the poisoning molecules leading to enhanced ORR activity and stability for the Fe-SACs.The molecular encapsulation strategy demonstrates the uniqueness of post-pyrolysis surface molecular engineering for the design of single-atom catalyst.

Nanoscale guiding for cold atoms based on surface plasmons along the tips of metallic wedges

We propose a novel scheme to guide neutral cold atoms in a nanoscale region based on surface plasmons （SPs） of one pair and two pairs of tips of metallic wedges with locally enhanced light intensity and sub-optical wavelength resolution. We analyze the near-field intensity distribution of the tip of the metallic wedge by the FDTD method, and study the total intensity as well as the total potential of optical potentials and van der Waals potentials for 87 Rb atoms in the light field of one pair and two pairs of tips of metallic wedges. It shows that the total potentials of one pair and two pairs of tips of metallic wedges can generate a gravito-optical trap and a dark closed trap for nanoscale guiding of neutral cold atoms. Guided atoms can be cooled with efficient intensity-gradient Sisyphus cooling by blue-detuned light field. This provides an important step towards the generation of hybrid systems consisting of isolated atoms and solid devices.

The diffusion and concentration effects of formamide on a TiO₂surface in the presence of a water solvent

The formamide-titanium oxide interaction mechanism is a research target of great importance for understanding the elementary events of the origin of life: the synthesis of nucleoside bases and formation of biological molecules needed for life. Titanium oxide (TiO2) can act as a strongly adsorbing surface or a catalytic material. In the present study, a comparative molecular dynamics analysis performed to clarify the adsorbing and diffusion properties of liquid formamide on a TiO2 surface in the presence of water molecules. The structural features of the formamide concentration effect (the accumulation of molecules) on a TiO2 surface in the presence and absence of water solvent are cleared up. Modification of the formamide diffusion abilities mediated by a water solvent is observed to correlate with the formamide-water concentration distribution on the surface.

Synthesis of Y_2O_3:Eu^(3+) phosphors by surface diffusion and their photoluminescence properties

Y2O3:Eu3+ phosphors were synthesized by the surface diffusion method (SDM). X-ray diffractometry (XRD), scanning electron microscopy (SEM), and energy dispersive spectrometry (EDS) were used to characterize the structure, morphology and component of Y2O3:Eu3+ phosphors. The photoluminescent (PL) properties were also investigated. The results reveal that the PL intensity of Y2O3:Eu3+ phosphors prepared by the surface diffusion method (SDM) is much higher than that prepared by homogeneous co-precipitation. The luminescence efficiency of the sample (Y0.997, Eu0.003)2O3 prepared by the SDM is almost 1.9 times that by homogeneous co-precipitation. The concentration of Eu3+ in the phosphor Y2O3:Eu3+ prepared by the surface diffusion can be reduced greatly owing to the activator, Eu3+ ions, distributing mainly in the outer layer of the phosphors where the photon generation process occurs.

Time-Resolved Measurements of the Adsorption/Desorption of Rb Atoms on Octadecyltrichlorosilane Coated Surfaces

We carry out the first time-resolved measurement of Rb atoms desorbing from octadecyltrichlorosilane coated sur- faces by polarizing the atoms near the surface using an evanescent wave pump pulse and watching the subsequent intensity change of another evanescent wave probe beam, and find the mean adsorption （dwell） time to be about 400ns at a cell body temperature of 112℃. The adsorption energy is found to be 0.19eV from the surface tem- perature dependence of the adsorption time. This method can be extended to study the adsorption/desorption process of other alkali atoms on other surfaces of transparent substrates with an ultimate time resolution limited by the flight time of atoms in the evanescent wave which is of the order of nanoseconds.

DETERMINATION OF THE SURFACE BINDING ENERGY OF A Cu/Li ALLOY BY MEASUREMENTS OF ANGULAR DISTRIBUTION OF SPUTTERED ATOMS

A copper based binary alloy containing 16.9 at % lithium has been bombarded with deuterium ions in energy range of 400 eV to 2 keV at the incidence angles of 70° and 80° away from the surface normal. The sputtered flux was condensed on Al- strips arranged arround the target in a cylindrical cup. 1.5 MeV proton backscattering and nuclear reaction 7Li(p, α)4He were used to detect the collected atoms of Cu and Li simultaneously. The angular distribution of sputtered atoms has been shown to be different for two components and strongly anisotropic for the grazing incidence. According to direct knock-on sputtering model and the experimental results the angle for the maximum differential sputtering yield is dependent on the incidence angle α, the bombarding energy E, the energy transfer factor γ= 4M1M2/(M1+ M2)2 and the surface binding energy U. With the assumption that the sputtered particles are diffracted by a planar barrier the surface binding energies of 2.3 eV for the Li component and 3.0 eV for the Cu component have been determined by fitting the measured angles of preferred ejection to the direct knock-on sputtering model, and the results agree well with a pair-binding model.

EVOLUTION OF ROUGHNESS ON THE SURFACE OF A STRAINED ELASTIC MATERIAL DUE TO STRESS-DRIVEN SURFACE DIFFUSION

The free energy of a stressed crystal is assumed to consist of elastic strain energy and surface energy, and the chemical potential for surface diffusion at constant temperature is obtained under this assumption. A gradient in chemical potential results in diffusive mass transport along the surface. The result is applied in considering the phenomena of instability of a flat surface in a stressed material under fluctuations in surface shape, and the transient evolution of surface roughness due to an initial perturbation in the nearly flat free surface of the material, both under plane strain conditions.

First-principles study of diffusion behaviour of point defects in the O-terminated (0001) surface in wurtzite ZnO

A detailed first-principles study of the diffusion behaviour of point defects in the O-terminated （0001） surface in wnrtzite ZnO was performed. The 0 vacancy and interstitial are found to diffuse much more easily in surface than in bulk. The Zn vacancy has a similar migration barrier for both bulk and surface, but has much smaller barrier for the diffuse-in process. The Zn interstitial is difficult to diffuse in the surface directly, but it can diffuse into the bulk relatively easily. Specific values of corresponding migration barriers are obtained.

Size Effects for the Adsorption of Alkali Metal Atoms on the Si(001) Surface

The adsorptions of a series of alkali metal （AM） atoms, Li, Na, K, Rb and Cs, on a Si（001）-2 × 2 surface at 0.25 monolayer coverage have been investigated systematically by means of density functional theory calculations. The effects of the size of AM atoms on the Si（001） surface are focused in the present work by examining the most stable adsorption site, diffusion path, band structure, charge transfer, and the change of work function for different adsorbates. Our results suggest that, when the interactions among AM atoms are neglectable, these AM atoms can be divided into three classes. For Li and Na atoms, they show unique site preferences, and correspond to the strongest and weakest AM-Si interactions, respectively. In particular, the band structure calculation indicates that the nature of Li-Si interaction differs significantly from others. For the adsorptions of other AM atoms with larger size （namely, K, Rb and Cs）, the similarities in the atomic and electronic structures are observed, implying that the atom size has little influence on the adsorption behavior for these large AM atoms on the Si（001） surface.

SURFACE SELF-DIFFUSION ANISOTROPY OF TUNGSTEN ATOMS ON W(112) PLANE

Surface self-diffusion anisotropy of tungsten on W(112)plane has been measured along(Ⅱ)and across(丄)channels existed on this plane by using the field emission fluctuation method in two forms of the probeholes.In the round probehole the thermal activation energy E=13.0kcal,and the prefactor of the surface self-diffusion coefficient Dq=^.5X 70_7cm2s-1;in the long narrow rectangular slit,E(Ⅱ)=13.2kcal,D0(Ⅱ)=7.1×10-7crr^and E(丄)=6.2kcal,Do(丄)=1.8×10^(-9)cm^(2)s^(-1) at T=500-700K.The experimental data suggest that a W atom diffusing across channels should not climb over the channel wall,which would certainly require a much higher activation energy,but instead,displace an atom in the wall.This process reqwes a much smaller activation energy;however,since it involves concerted motion of at least two atoms,it will also have a much smaller prefactor.

SURFACE SELF-DIFFUSION AND THERMAL ROUGHENING OF TUNGSTEN SURFACES STUDIED BY FIELD EMISSION FLUCTUATION METHOD

Surface self-diffusion measurements of tungsten atoms and other defects were carried out by means of field emission fluctuation method at various positions along the zones(011)-(112)and(011)-(001).The experimental results shod that the self-diffusion on stepped surface can be used to investigate thermal roughening procedures.

Molecular dynamics simulation of nanoscale surface diffusion of heterogeneous adatoms clusters

Molecular dynamics simulation employing the embedded atom method potential is utilized to investigate nanoscale surface diffusion mechanisms of binary heterogeneous adatoms clusters at 300 K, 500 K, and 700 K. Surface diffusion of heterogeneous adatoms clusters can be vital for the binary island growth on the surface and can be useful for the formation of alloy-based thin film surface through atomic exchange process. The results of the diffusion process show that at 300 K, the diffusion of small adatoms clusters shows hopping, sliding, and shear motion; whereas for large adatoms clusters（hexamer and above）, the diffusion is negligible. At 500 K, small adatoms clusters, i.e., dimer, show almost all possible diffusion mechanisms including the atomic exchange process; however no such exchange is observed for adatoms clusters greater than dimer. At 700 K, the exchange mechanism dominates for all types of clusters, where Zr adatoms show maximum tendency and Ag adatoms show minimum or no tendency toward the exchange process. Separation and recombination of one or more adatoms are also observed at 500 K and 700 K. The Ag adatoms also occupy pop-up positions over the adatoms clusters for short intervals. At 700 K, the vacancies are also generated in the vicinity of the adatoms cluster,vacancy formation, filling, and shifting can be observed from the results.