Metastable face-centered cubic ruthenium-based binary alloy for efficient alkaline hydrogen oxidation electrocatalysis

Metastable nanostructured electrocatalyst with a completely different surface environment compared to conventional phase-based electrocatalyst often shows distinctive catalytic property.Although Ru-based electrocatalysts have been widely investigated toward hydrogen oxidation reaction(HOR)under alkaline electrolytes,these studies are mostly limited to conventional hexagonal-close-packed(hcp)phase,mainly arising from the lack of sufficient synthesis strategies.In this study,we report the precise synthesis of metastable binary RuW alloy with face-centered-cubic(fcc)phase.We find that the introduction of W can serve as fcc phase seeds and reduce the formation energy of metastable fcc-RuW alloy.Impressively,fcc-RuW exhibits remarkable alkaline HOR performance and stability with the activity of 0.67 mA cm_(Ru)^(-2)which is almost five and three times higher than that of hcp-Ru and commercial Pt/C,respectively,which is attributed to the optimized binding strength of adsorbed hydroxide intermediate derived from tailored electronic structure through W doping and phase engineering.Moreover,this strategy can also be applied to synthesize other metastable fcc-RuCr and fcc-RuMo alloys with enhanced HOR performances.

Chemical Bonds between Charged Atoms in the Even-Odd Rule and a Limitation to Eight Covalent Bonds per Atom in Centered-Cubic and Single Face-Centered-Cubic Crystals

A crystal is a highly organized arrangement of atoms in a solid, wherein a unit cell is periodically repeated to form the crystal pattern. A unit cell is composed of atoms that are connected to some of their first neighbors by chemical bonds. A recent rule, entitled the even-odd rule, introduced a new way to calculate the number of covalent bonds around an atom. It states that around an uncharged atom, the number of bonds and the number of electrons have the same parity. In the case of a charged atom on the contrary, both numbers have different parity. The aim of the present paper is to challenge the even-odd rule on chemical bonds in well-known crystal structures. According to the rule, atoms are supposed to be bonded exclusively through single-covalent bonds. A distinctive criterion, only applicable to crystals, states that atoms cannot build more than 8 chemical bonds, as opposed to the classical model, where each atom in a crystal is connected to every first neighbor without limitation. Electrical charges can be assigned to specific atoms in order to compensate for extra or missing bonds. More specifically the article considers di-atomic body-centered-cubic, tetra-atomic and dodeca-atomic single-face-centered-cubic crystals. In body-centered crystals, atoms are interconnected by 8 covalent bonds. In face-centered crystal, the unit cell contains 4 or 12 atoms. For di-element crystals, the total number of bonds for both elements is found to be identical. The neutrality of the unit cell is obtained with an opposite charge on the nearest or second-nearest neighbor. To conclude, the even-odd rule is applicable to a wide number of compounds in known cubic structures and the number of chemical bonds per atom is not related to the valence of the elements in the periodic table.

The Even-Odd and the Isoelectronicity Rules Applied to Single Covalent Bonds in Ionic, Double-Face-Centered Cubic and Diamond-Like Crystals

Although atom configuration in crystals is precisely known thanks to imaging techniques, there is no experimental way to know the exact location of bonds or charges. Many different representations have been proposed, yet no theory to unify conceptions. The present paper describes methods to derive bonds and charge location in double-face-centered cubic crystals with 4 and 6 atoms per unit cell using two novel rules introduced in earlier works: the even-odd and the isoelectronicity rules. Both of these rules were previously applied to ions, molecules and some solids, and the even-odd rule was also tested on two covalent crystal structures: centered-cubic and single-face-centered cubic crystals. In the present study, the diamond-like structure was subjected to the isoelectronicity rule in order to derive Zinc-blende structures. Rock-salt-like crystals were derived from each other using both rules. These structures represent together more than 230 different crystals. Findings for these structures are threefold: both rules describe a very sure method to obtain valid single covalent-bonded structures;single covalent structures can be used in every case instead of the classical ionic model;covalent bonds and charges positions do not have any relation with the valence number given in the periodic table.

Discrete gap breathers in a two-dimensional diatomic face-centered square lattice

In this paper we study the existence and stability of two-dimensional discrete gap breathers in a two-dimensional diatomic face-centered square lattice consisting of alternating light and heavy atoms, with on-site potential and coupling potential. This study is focused on two-dimensional breathers with their frequency in the gap that separates the acoustic and optical bands of the phonon spectrum. We demonstrate the possibility of the existence of two-dimensional gap breathers by using a numerical method. Six types of two-dimensional gap breathers are obtained, i.e., symmetric, mirror-symmetric and asymmetric, whether the center of the breather is on a light or a heavy atom. The difference between one-dimensional discrete gap breathers and two-dimensional discrete gap breathers is also discussed. We use Aubry＇s theory to analyze the stability of discrete gap breathers in the two-dimensional diatomic face-centered square lattice.

Instantaneous Creep in Face-centered Cubic Metals at Ultra- low Strain Rates by a High-resolution Strain Measurement

Instantaneous creep in face-centered cubic metals, 5N Al（99.999%）, 2N Al （99%） and 4N Cu （99.99%） with different grain sizes, was firstly investigated by sudden stress-change experiments at ultra- low strain rates ε ≤10-10 s-1 and temperature T 〈 0.32 Tn. The experimental results indicate that the observed instantaneous creep is strongly dependent on grain size, the concentration of impurity, and stacking fault energy. Creep in high-purity aluminum, 5N Al, with a very large grain size, d 〉 1600μm, shows non-viscous behavior, and is controlled by the recovery of dislocations in the boundary of dislocation cells. On the other hand, for 5N A1 with a small grain size, d=30μm, and low-purity aluminum, 2N A1, with d8= 25μm, creep shows viscous behavior and may be related to ＇low temperature grain boundary sliding＇. For high-purity copper, 4N Cu, with d= 40 grn and lower stacking fault energy, creep shows a non-viscous behavior, and is controlled by the recovery process of dislocations. For all of the samples, creep shows anelastic behavior.

Metastable Face-Centered Cubic Structure and Structural Transition of Sn on 2H-NbSe2(0001)

Surface structures and properties of Sn islands grown on superconducting substrate 2H-NbSe2（0001）are studied using low temperature scanning tunneling microscopy or spectroscopy.The pure face-centered cubic（fee）structure of Sn surface is obtained.Superconductivity is also detected on the fcc-Sn（111）surface,and the size of superconducting gap on the Sn surface is nearly the same as that on the superconducting substrate.Furthermore,phase transition occurs from fcc-Sn（111）toβ-Sn（001）by keeping the sample at room temperature for a certain time.Due to the strain relaxation on theβ-Sn islands,both the in-plane unit cell and out-of-plane structures distort,and the height of surface atoms varies periodically to form a universal ripple structure.

Direct observation of metastable face-centered cubic Sb2Te3 crystal

Although phase change memory technology has developed drastically in the past two decades, the cognition of the key switching materials still ignores an important member, the face-centered cubic Sb2Te3. Apart from the well-known equilibrium hexagonal Sb2Te3 crystal, we prove the metastable face-centered cubic Sb2Te3 phase does exist. Such a metastable crystal contains a large concentration of vacancies randomly occupying the cationic lattice sites. The face-centered cubic to hexagonal phase transformation of Sb2Te3, accompanied by vacancy aggregation, occurs at a quite lower temperature compared to that of Ge2Sb2Te5 alloy. We prove that the covalent-like bonds prevail in the metastable Sb2Te3 crystal, deviating from the ideal resonant features. If a proper doping technique is adopted, the metastable Sb2Te3 phase could be promising for realizing reversibly swift and low-energy phase change memory applications. Our study may offer a new insight into commercialized Ge-Sb-Te systems and help in the design of novel phase change materials to boost the performances of the phase change memorv device.

Face-centered cubic structured RuCu hollow urchin-like nanospheres enable remarkable hydrogen evolution catalysis

Ruthenium(Ru)is one of the most promising metals for its versatility in driving a wide range of catalytic reactions.However,owing to the intrinsic preference of hexagonal close-packed(hcp)phase for bulk Ru,currently,it is still challenging to construct Ru-based nanomaterials with face-centered-cubic(fcc)phase for optimizing their performance towards potential applications.Herein,we report a facile wet-chemical method to directly create unconventional fcc-structured Ru-copper hollow urchin-like nanospheres(fcc-RuCu HUNSs)as a class of efficient pH-universal hydrogen evolution reaction(HER)electrocatalyst.Interestingly,this synthetic strategy can be expanded to prepare other fcc-Ru-based alloy nanomaterials.Significantly,the novel fcc-RuCu HUNSs exhibit superior HER performance with the overpotential of only 25,34,40,and 26 m V to reach the current density of 10 mA cm^(-2)in 0.5 M H_(2)SO_(4),0.05 M H_(2)SO_(4),0.1 M KOH,and 1 M KOH,respectively,much lower than those of hcpRuCu HUNSs and commercial Pt/C.Density functional theory(DFT)calculations further indicate that their excellent pH-universal HER performance results from the optimized adsorption free energy of H and work functions.Our work highlights the importance of phase control to design high-efficiency nanocatalysts for relevant catalytic reactions in energy conversion.

Effective Stacking Fault Energy in Face-Centered Cubic Metals

As a typical configuration in plastic deformations, dislocation arrays possess a large variation of the separation of the partial dislocation pairs in face-centered cubic（fcc） metals. This can be manifested conveniently by an effective stacking fault energy（SFE）. The effective SFE of dislocation arrays is described within the elastic theory of dislocations and verified by atomistic simulations. The atomistic modeling results reveal that the general formulae of the effective SFE can give a reasonably satisfactory prediction for all dislocation types, especially for edge dislocation arrays. Furthermore, the predicted variation of the effective SFE is consistent with several previous experiments, in which the measured SFE is not definite, changing with dislocation density. Our approach could provide better understandings of cross-slip and the competition between slip and twinning during plastic deformations in fcc metals.

Mechanism transition of cross slip with stress and temperature in face-centered cubic metals

A<110>/2 screw dislocation is commonly dissociated into two <112>/6 Shockley partial dislocations on{111} planes in face-centered cubic metals.As the two partials are not purely screw,different mechanisms of cross-slip could take place,depending on the stacking fault energy,applied stress and tempe rature.It is crucial to classify the mechanisms of cross-slip because each mechanism possesses its own reaction path with a special activation process.In this work,molecular dynamics simulations have been performed systematically to explore the cross-slip mechanism under different stresses and temperatures in three different metals Ag,Cu and Ni that have different stacking fault energies of 17.8,44.4 and 126.8 mJ/m^2,re spectively.In Ag and Cu with low stacking fault energy,it is observed that the cross-slip mechanism of screw dislocations changes from the Fleischer obtuse angle(FLOA),to the Friedel-Escaig(FE),and then to the FL acute angle(FLAA) at low temperatures,with increasing the applied stress.However,when the temperature increases,the FE mechanism gradually becomes dominant,while the FLAA only occurs at the high stress region.In particular,the FLOA has not been observed in Ni because of its high stacking fault energy.

Consistent Analytic Embedded Atom Potential for Face-Centered Cubic Metals and Alloys

A consistent empirical embedded-atom potential that includes a long range force was developed for fcc （face-centered cubic） metals and alloys. The proposed potential for pure metals does not require modification of the initial function form when being applied to alloy systems. The potential parameters of this model were determined by fitting lattice constant, three elastic constants, cohesive energy, and vacancy formation energies of the pure metals and the heats of solution of the binary alloys via an optimization technique. Parameters for Ag, AI, Au, Cu, Ni, Pd and Pt were obtained. The obtained parameters were used to calculate the bulk modulus, divacancy formation energy, crystal stability, stacking fault energy, vacancy migration energy, and melting point for each pure metal and the heats of formation and lattice constants for binary alloys. The predicted values were in good agreement with experimental results.

A New Modified Conductivity Model for Prediction of Shear Yield Stress of Electrorheological Fluids Based on Face-center Square Structure

A new modified conductivity model was established to predict the shear yield stress of electrorheological fluids (ERF). By using a cell equivalent method, the present model can deal with the face-center square structure of ERF. Combining the scheme of the classical conductivity model for the single-chain structure, a new formula for the prediction of the shear yield stress of ERF was set up. The influences of the separation distance of the particles, the volume fraction of the particles and the applied electric field on the shear yield stress were investigated.

Spray drying of fenofibrate loaded nanostructured lipid carriers

The conversion of aqueous dispersion of nanostructured lipid carriers(NLCs) into dry powder by spray drying could be a useful approach to render NLCs with better physical chemical stability than the aqueous dispersion. In this study, aqueous NLC dispersion containing fenofibrate was converted into dry, easily reconstitutable powder using spray drying. A central composite face centered design(CCFD) was used to investigate the influence of the ratio of lipid to protectant(mannitol and trehalose) and crystallinity of spray-dried powder on the particle size, yield and residual moisture content of the dried powder. A linear relationship(R2= 0.9915) was established between the crystalline content of the spray-dried powders against the ratio of mannitol to trehalose from 3:7 to 10:0(w/w). Spray drying of NLC aqueous dispersion using a mannitol and trehalose mixture resulted in an increase in particle size of the NLCs after reconstitution in water as compared to that in the initial aqueous dispersion. The decrease in crystallinity of the dry powder by reducing the ratio of mannitol to trehalose could improve the reconstitution of the NLCs in water. However the yield and residual moisture content of dry powder decreased with an increase in the ratio of mannitol to trehalose. Lipid nanoparticles were able to retain the drug incorporation and the prolonged drug release profile after spray drying. The experimental model was robust, and suggested that spray drying is a viable technique for the conversion of NLCs into dry powder.

Study on Ultra-Short Laser Pulse Ablation of Metals by Molecular Dynamics Simulation

The dynamical progresses involved in ultra-short laser pulse ablation of face-centered cubic metals under stress confinement condition are described completely using molecular dynamics method. The laser beam absorption and thermal energy turning into kinetics energy of. atoms are taken into account to give a detailed picture of laser metal interaction. Superheating phenomenon is observed, and the phase change from solid to liquid is characterized by a destroyed atom configuration and a decreased number density. The steep velocity gradients are found in the systems of Cu and Ni after pulse in consequence of located heating and exponential decrease of fluences following the Lambert-Beer expression. The shock wave velocities are predicted to be about 5 000 m/s in Cu and 7 200 m/s in Ni. The higher ablation rates are obtained from simulations compared with experimental data as a result of a well-defined crystalline surface irradiated by a single pulse. Simulation results show that the main mechanisms of ablation are evaporation and thermoelastic stress due to located heating.

STUDY ON FRACTOGRAPHY OF TRANSGRANULAR SCC OF 70Cu-3OZn IN AN AMMONIACAL SOLUTION

The microfractography of transgranular stress corrosion cracking (TSCC) of 70Cu-30Zn a-brass in ammoniacal solution was studied. The observations indicate that on a very microscale, the crack path of TSCC of or-brass follows {111} planes. The crack path very often alternates between {111} Planes to result in 'cleavage-like'facet, the usual average orientation of which is {110} with preferential microscopic crack propagation in (100) and (112) directions. The average orientation of wide secondary facets is often close to {100}. The size of {111} microfacets increases with incrmsing stress intensity K, which indicates that the microscopic crack path follows {111} planes on which some localized slip has occurred. Possible TSCC mechanisms which appear to be consistent with the microfraphic features observed in the present study are also discussed.

Experimental and numerical simulation of bird-strike performance of lattice-material-infilled curved plate

The anti-bird-strike performance of a lattice-material-infilled curved plate is investigated herein.Since automatically filling the curved structure by classical lattice material filling methods will cause a large number of manufacturing defects,a space-dependent lattice material filling method for the curved plate is firstly proposed in this paper Next,using a face-centered cubic lattice,a lattice-material-infilled test piece with a hollow ratio of 40.8%is built.The test pieces are manufactured via additive manufacturing using titanium alloy.In bird-strike experimental tests,the test pieces are crashed against gelatin birds at an impact velocity of 200 m/s.Dynamic strain gauges are used to record the crash history and the results are discussed.Furthermore,a numerical analysis to simulate the bird-strike experiment is performed.The results from the experimental tests and numerical simulation agree well.This work shows that the lattice-material-infilled curved plate yields promising bird-strike resistance.Therefore,lattice-infilled materials are feasible for protecting aerospace components against bird-strike as well as for reducing the component weight.

Synthesis of MoX2 (X =Se or S) monolayers with high-concentration 1T'phase on 4H/fcc-Au nanorods for hydrogen evolution

Controlled synthesis of transition metal dichalcogenide (TMD) monolayers with unusual crystal phases has attracted increasing attention due to their promising applications in electrocatalysis.However,the facile and large-scale preparation of TMD monolayers with high-concentration unusual crystal phase still remains a challenge.Herein,we report the synthesis of MoX2 (X =Se or S) monolayers with high-concentration semimetallic 1T'phase by using the 4H/face-centered cubic (fcc)-Au nanorod as template to form the 4H/fcc-Au@MoX2 nanocomposite.The concentrations of 1T'phase in the prepared MoSe2 and MoS2 monolayers are up to 86% and 81%,respectively.As a proof-of-concept application,the obtained Au@MoS2 nanocomposite is used for the electrocatalytic hydrogen evolution reaction (HER) in acid medium,exhibiting excellent performance with a low overpotential of 178 mV at the current density of 10 mNcm^2,a small Tafel slope of 43.3 mV/dec,and excellent HER stability.This work paves a way for direct synthesis of TMD monolayers with high-concentration of unusual crystal phase for the electrocatalytic application.