Collaborative effect between single-atom Re and S vacancy on modulating localized electronic structure of MoS_(2) catalysts for alkaline hydrogen evolution

Optimizing the catalytic activity and stability of molybdenum disulfide (MoS_(2)) towards alkaline hydrogen evolution reaction (HER) is significant for sustaining green hydrogen. A moderate localized electronic structure of active sites plays a crucial role in determining the activity and stability of the catalysts, yet how to construct such localized electronic structure still remains indeterminacy. Enlightened by theoretical prediction, herein, the introduction of both single-atom Re and the adjacent S vacancy in MoS_(2) (denoted as Re-MoS_(2)-Vs) exhibits collaborative effect on regulating the localized electronic structure of active sites (viz. Re-(S, Vs)-Mo). Such regulated electronic structure helps to decrease the energy barrier of the water dissociation and optimize hydrogen adsorption energy for enhancing alkaline HER performance. Most importantly, Mo-S bonds in the above local Re-(S, Vs)-Mo configurations are also strengthened for preventing the leaching of Mo and S atoms and then ensuring the long-time stability. Consequently, the deliberately designed Re-MoS_(2)-Vs with a Re coordination number of ~ 5.0 is experimentally verified to exhibit a comparable electrocatalytic performance and robust operational stability over 120 h. This strategy provides a promising guidance for modulating the electronic structure of MoS_(2) based catalysts via double-tuning atomic-scale local configuration for HER applications.

Tailoring local structures of atomically dispersed copper sites for highly selective CO_(2) electroreduction

Atomically‐dispersed copper sites coordinated with nitrogen‐doped carbon(Cu–N–C)can provide novel possibilities to enable highly selective and active electrochemical CO_(2) reduction reactions.However,the construction of optimal local electronic structures for nitrogen‐coordinated Cu sites(Cu–N_(4))on carbon remains challenging.Here,we synthesized the Cu–N–C catalysts with atomically‐dispersed edge‐hosted Cu–N_(4) sites(Cu–N_(4)C_(8))located in a micropore between two graphitic sheets via a facile method to control the concentration of metal precursor.Edge‐hosted Cu–N_(4)C_(8) catalysts outperformed the previously reported M–N–C catalysts for CO_(2)‐to‐CO conversion,achieving a maximum CO Faradaic efficiency(FECO)of 96%,a CO current density of–8.97 mA cm^(–2) at–0.8 V versus reversible hydrogen electrode(RHE),and over FECO of 90%from–0.6 to–1.0 V versus RHE.Computational studies revealed that the micropore of the graphitic layer in edge‐hosted Cu–N_(4)C_(8) sites causes the d‐orbital energy level of the Cu atom to shift upward,which in return decreases the occupancy of antibonding states in the*COOH binding.This research suggests new insights into tailoring the locally coordinated structure of the electrocatalyst at the atomic scale to achieve highly selective electrocatalytic reactions.

Multi-Material Topology Optimization for Spatial-Varying Porous Structures

This paper aims to propose a topology optimization method on generating porous structures comprising multiple materials.The mathematical optimization formulation is established under the constraints of individual volume fraction of constituent phase or total mass,as well as the local volume fraction of all phases.The original optimization problem with numerous constraints is converted into a box-constrained optimization problem by incorporating all constraints to the augmented Lagrangian function,avoiding the parameter dependence in the conventional aggregation process.Furthermore,the local volume percentage can be precisely satisfied.The effects including the globalmass bound,the influence radius and local volume percentage on final designs are exploited through numerical examples.The numerical results also reveal that porous structures keep a balance between the bulk design and periodic design in terms of the resulting compliance.All results,including those for irregular structures andmultiple volume fraction constraints,demonstrate that the proposedmethod can provide an efficient solution for multiple material infill structures.

Ultrafast dynamics of femtosecond laser-induced high spatial frequency periodic structures on silicon surfaces

Femtosecond laser-induced periodic surface structures(LIPSS)have been extensively studied over the past few decades.In particular,the period and groove width of high-spatial-frequency LIPSS(HSFL)is much smaller than the diffraction limit,making it a useful method for efficient nanomanufacturing.However,compared with the low-spatial-frequency LIPSS(LSFL),the structure size of the HSFL is smaller,and it is more easily submerged.Therefore,the formation mechanism of HSFL is complex and has always been a research hotspot in this field.In this study,regular LSFL with a period of 760 nm was fabricated in advance on a silicon surface with two-beam interference using an 800 nm,50 fs femtosecond laser.The ultrafast dynamics of HSFL formation on the silicon surface of prefabricated LSFL under single femtosecond laser pulse irradiation were observed and analyzed for the first time using collinear pump-probe imaging method.In general,the evolution of the surface structure undergoes five sequential stages:the LSFL begins to split,becomes uniform HSFL,degenerates into an irregular LSFL,undergoes secondary splitting into a weakly uniform HSFL,and evolves into an irregular LSFL or is submerged.The results indicate that the local enhancement of the submerged nanocavity,or the nanoplasma,in the prefabricated LSFL ridge led to the splitting of the LSFL,and the thermodynamic effect drove the homogenization of the splitting LSFL,which evolved into HSFL.

Regulating Anderson localization with structural defect disorder

Localization due to disorder has been one of the most intriguing theoretical concepts that evolved in condensed matter physics.Here,we expand the theory of localization by considering two types of disorders at the same time,namely,the original Anderson’s disorder and the structural defect disorder,which has been suggested to be a key component in recently discovered two-dimensional amorphous materials.While increasing the degree of both disorders could induce localization of wavefunction in real space,we find that a small degree of structural defect disorder can significantly enhance the localization.As the degree of structural defect disorder increases,localized states quickly appear within the extended phase to enter a broad crossover region with mixed phases.We establish two-dimensional diagrams for the wavefunction localization and conductivity to highlight the interplay between the two types of disorders.Our theoretical model provides a comprehensive understanding of localization in two-dimensional amorphous materials and highlights the promising tunability of their transport properties.

Revealing structure correlation between ionic liquid and metal-organic framework matrix

Solid-state batteries are rising rapidly in response to the fast-increasing energy demand.Metal-organic framework(MOF) loaded with ionic liquids has brought new opportunities for solid-state batteries owing to its good interfacial compatibility and high ionic conductivity. MOF-808 is selected to be filled with Li-contained ionic liquid for structure and ion dynamics investigation using nuclear magnetic resonance(NMR) and X-ray diffraction.This study finds that the introduced ionic liquid would partially soften the matrix of MOF-808 and thus yield amorphous phase. By selective isotope replacement under cycling symmetric ^(6)Li metal cell, Li^(+)ion is observed to mainly go cross ionic liquid in the open channel of matrix under potential polarization.

Wave localization in randomly disordered periodic layered piezoelectric structures

Considering the mechnoelectrical coupling, the localization of SH-waves in disordered periodic layered piezoelectric structures is studied. The waves propagating in directions normal and tangential to the layers are considered. The transfer matrices between two consecutive unit cells are obtained according to the continuity conditions. The expressions of localization factor and localization length in the disordered periodic structures are presented. For the disordered periodic piezoelectric structures, the numerical results of localization factor and localization length are presented and discussed. It can be seen from the results that the frequency passbands and stopbands appear for the ordered periodic structures and the wave localization phenomenon occurs in the disordered periodic ones, and the larger the coefficient of variation is, the greater the degree of wave localization is. The widths of stopbands in the ordered periodic structures are very narrow when the properties of the consecutive piezoelectric materials are similar and the intervals of stopbands become broader when a certain material parameter has large changes. For the wave propagating in the direction normal to the layers the localization length has less dependence on the frequency, but for the wave propagating in the direction tangential to the layers the localization length is strongly dependent on the frequency.

Research on mode localization of reticulated shell structures

Reticulated shell structures （RSSs） are characterized as cyclically periodic structures. Mistuning of RSSs will induce structural mode localization. Mode localization has the following two features： some modal vectors of the structure change remarkably when the values of its physical parameters （mass or stiffness） have a slight change; and the vibration of some modes is mainly restricted in some local areas of the structure. In this paper, two quantitative assessment indexes are introduced that correspond to these two features. The first feature is studied through a numerical example of a RSS, and its induced causes are analyzed by using the perturbation theory. The analysis showed that internally, mode localization is closely related to structural frequencies and externally, slight changes of the physical parameters of the structure cause instability to the RSS. A scaled model experiment to examine mode localization was carried out on a Kiewit single-layer spherical RSS, and both features of mode localization are studied. Eight tests that measured the changes of the physical parameters were carried out in the experiment. Since many modes make their contribution in structural dynamic response, six strong vibration modes were tested at random in the experimental analysis. The change and localization of the six modes are analyzed for each test. The results show that slight changes to the physical parameters are likely to induce remarkable changes and localization of some modal vectors in the RSSs.

Theoretical Investigations of the Local Structure Distortion and EPR Parameter for Ni2＋-doped Perovskite Fluorides

By analyzing the optical spectra and electron paramagnetic resonance parameter D, the local structure distortion of （NiF6）4- clusters in AMF3 （A=K, Rb; M=Zn, Cd, Ca） and K2ZnF4 series are studied using the complete energy matrix based on the double spin-orbit coupling parameter model for configuration ions in a tetragonal ligand field. The results indicate that the contribution of ligand to spin-orbit coupling interaction should be considered for our studied systems. Moreover, the relationships between D and the spin-obit coupling coefficients as well as the average parameter and the divergent parameter are discussed.

Wave propagation control in periodic track structure through local resonance mechanism

Excessive vibration and noise radiation of the track structure can be caused by the operation of high speed trains.Though the track structure is characterized by obvious periodic properties and band gaps,the bandwidth is narrow and the elastic wave attenuation capability within the band gap is weak.In order to effectively control the vibration and noise of track structure,the local resonance mechanism is introduced to broaden the band gap and realize wave propagation control.The locally resonant units are attached periodically on the rail,forming a new locally resonant phononic crystal structure.Then the tuning of the elastic wave band gaps of track structure is discussed,and the formation mechanism of the band gap is explicated.The research results show that a new wide and adjustable locally resonant band gap is formed after the resonant units are introduced.The phenomenon of coupling and transition can be observed between the new locally resonant band gap and the original band gap of the periodic track structure with the band gap width reaching the maximum at the coupling position.The broader band gap can be applied for vibration and noise reduction in high speed railway track structure.

Analytic model of non-uniform corrosion induced cracking of reinforced concrete structure

In order to perfectly reflect the dynamic corrosion of reinforced concrete (RC) cover in practical engineering,an analytic model of non-uniform corrosion induced cracking was presented based on the elastic-plastic fracture mechanics theory.Comparisons with the published experimental data show that the predictions given by the present model are in good agreement with the results both for natural exposed experiments and short-time indoor tests (the best difference is about 2.7%).Also it obviously provides much better precision than those models under the assumption of uniform corrosion (the maximal improved precision is about 48%).Therefore,it is pointed out that the so-called uniform corrosion models to describe the cover cracking of RC should be adopted cautiously.Finally,the influences of thickness of local rusty layer around the reinforcing steel bar on the critical corrosion-induced crack indexes were investigated.It is found that the thickness of local rusty layer has great effect on the critical mass loss of reinforcing steel,threshold expansion pressure,and time to cover cracking.For local rusty layer thickness with a size of a=0.5 mm,the time to cover cracking will increase by about one times when a/b (a,semi-minor axis;b,semi-major axis) changes from 0.1 to 1 mm.

MULTI-SCALE COHERENT STRUCTURES IN TURBULENT BOUNDARY LAYER DETECTED BY LOCALLY AVERAGED VELOCITY STRUCTURE FUNCTIONS

The time sequence of longitudinal velocity component at different vertical locations in turbulent boundary layer was finely measured in a wind tunnel. The concept of coarse_grained velocity structure functions, which describes the relative motions of straining and compressing for multi_scale eddy structures in turbulent flows, was put forward based on the theory of locally multi_scale average. Based on the consistency between coarse_grained velocity structure function and Harr wavelet transformation,detecting method was presented, by which the coherent structures and their intermittency was identified by multi_scale flatness factor calculated by locally average structure function. Phase_averaged evolution course for multi_scale coherent eddy structures in wall turbulence were extracted by this conditional sampling to educe scheme. The dynamics course of multi_scale coherent eddy structures and their effects on statistics of turbulent flows were studied.

Functionally Graded Cellular Structure Design Using the Subdomain Level Set Method with Local Volume Constraints

Functional graded cellular structure(FGCS)usually shows superiormechanical behaviorwith lowdensity and high stiffness.With the development of additivemanufacturing,functional graded cellular structure gains its popularity in industries.In this paper,a novel approach for designing functionally graded cellular structure is proposed based on a subdomain parameterized level set method(PLSM)under local volume constraints(LVC).In this method,a subdomain level set function is defined,parameterized and updated on each subdomain independently making the proposed approach much faster and more cost-effective.Additionally,the microstructures on arbitrary two adjacent subdomains can be connected perfectly without any additional constraint.Furthermore,the local volume constraint for each subdomain is applied by virtue of the augmented Lagrange multiplier method.Finally,several numerical examples are given to verify the correctness and effectiveness of the proposed approach in designing the functionally graded cellular structure.From the optimized results,it is also found that the number of local volume constraints has little influence on the convergence speed of the developed approach.

Probing microstructure of solid-state synthesized LiCoO_(2)with MAS NMR spectroscopy

LiCoO_(2)is an important category of active cathode materials in lithium-ion batteries due to its high compacted electrode density,good thermal stability,and stable voltage platform.Recent works on LiCoO_(2)have focused on the realization of higher charging voltages to fully utilize its high theoretical capacity.However,an unambiguous atomic-level local probe is essential for the understanding of structure-function correlation.Here we employ highresolution solid-state nuclear magnetic resonance(NMR)spectroscopy to study the local atomic environments in LiCoO_(2)synthesized with three common sintering methods.While one-dimensional 7Li NMR shows distinct linewidth and subtle dependence on lithium over-stoichiometry,both 7Li and 59Co relaxation times are highly dependent on the sintering method.We prove that the two-step sintering method favors the elimination of unreacted Co3O4,thereby enabling the best discharge capacity in all-solid-state lithium batteries assembled with LiCoO_(2)/LGPS/LiIn,which is in accordance with its narrowest 7Li linewidth and the longest 7Li/59Co T1.

Quantum Chemistry Study on Local Structure and Properties of Amorphous Fe80P20 Alloy

According to the structure features of Fe80P20, A series of clusters Fe4P were designed and focused on studying the stability of local structure, charge distribution and chemical bond, Using the DFT method, energy and structure of Fe4P clusters were optimized and analyzed. The computational results showed that the energy of cluster 1（2） has the lowest energy, and the possibility of its existence in the Fe80P20 is high. Analyzing the transition states among the clusters, it was found that the clusters in the doublet state are more stable than those in the quartet state. The numbers of the Fe-P bond in the clusters play important roles in the cluster stability and electrons transfer properties, The more numbers of Fe-P bonds in the clusters, the higher the cluster stability, and the weaker the ability of P atom to get electron, The number of Fe atoms, which has bonding interactions with the P atom, is direct proportional to the average 3d orbit population of Fe atom. Basing on the orbital population, average magnetic moments of each Fe atom in the Fe4P clusters were calculated, and they are all smaller than that of single metal Fe atom. This suggests that all Fe4P clusters have soft magnetic property and they are expected to be perfect material for preparing soft magnetic apparatus.

Supervised local and non-local structure preserving projections with application to just-in-time learning for adaptive soft sensor

In soft sensor field, just-in-time learning(JITL) is an effective approach to model nonlinear and time varying processes. However, most similarity criterions in JITL are computed in the input space only while ignoring important output information, which may lead to inaccurate construction of relevant sample set. To solve this problem, we propose a novel supervised feature extraction method suitable for the regression problem called supervised local and non-local structure preserving projections(SLNSPP), in which both input and output information can be easily and effectively incorporated through a newly defined similarity index. The SLNSPP can not only retain the virtue of locality preserving projections but also prevent faraway points from nearing after projection,which endues SLNSPP with powerful discriminating ability. Such two good properties of SLNSPP are desirable for JITL as they are expected to enhance the accuracy of similar sample selection. Consequently, we present a SLNSPP-JITL framework for developing adaptive soft sensor, including a sparse learning strategy to limit the scale and update the frequency of database. Finally, two case studies are conducted with benchmark datasets to evaluate the performance of the proposed schemes. The results demonstrate the effectiveness of LNSPP and SLNSPP.

Investigation on Surface Plasmon Polaritons and Localized Surface Plasmon Production Mechanism in Micro-Nano Structures

The simulation mechanism of surface plasmon polaritons(SPPs)and localized surface plasmon(LSP)in different structures was studied,including the Au reflection grating(Au grating),Au substrate with dielectric ribbons grating(Au substrate grating),and pure electric conductor(PEC)substrate with Au ribbons grating(Au ribbons grating).And the characteristics of the Smith-Purcell radiation in these structures were presented.Simulation results show that SPPs are excited on the bottom surface of Au substrate grating grooves and LSP is stimulated on the upper surface both of Au ribbons grating grooves and Au grating grooves.Owing to the irreconcilable contradiction between optimizing the grating diffraction radiation efficiency and optimizing the SPPs excitation efficiency in the Au substrate grating,only 40-times enhancement of the radiation intensity was obtained by excited SPPs.However,the LSP enhanced structure overcomes the above problem and gains much better radiation enhancement ability,with about 200-times enhancement obtained in the Au ribbons grating and more than 500-times enhancement obtained in the Au grating.The results presented here provide a way of developing miniature,integratable,tunable,high-power-density radiation sources from visible light to ultraviolet rays at room temperature.

Ultra-high-density local structure in liquid water

We employ multiple order parameters to analyze the local structure of liquid water obtained from all-atom simulations,and accordingly identify three types of molecules in water. In addition to the well-known low-density-liquid and highdensity-liquid molecules, the newly identified third type possesses an ultra-high density and over-coordinated H-bonds.The existence of this third type decreases the probability of transition of high-density-liquid molecules to low-densityliquid molecules and increases the probability of the reverse one.

Variations of water's local-structure induced by solvation of NaCl

The researches on the structure of water and its changes induced by solutes are of enduring interests. The changes of the local structure of liquid water induced by NaCl solute under ambient conditions are studied and presented quantitatively with some order parameters and visualized with 2-body and 3-body correlation functions. The results show that, after the NaCl are solvated, the translational order t of water is decreased for the suppression of the second hydration shells around H20 molecules; the tetrahedral order （q） of water is also decreased and its favorite distribution peak moves from 0.76 to 0.5. In addition, the orientational freedom k and the diffusion coefficient D of water molecules are reduced because of new formed hydrogen-bonding structures between water and solvated ions.