Relationship between partial and average atomic volumes of components in Au-Ni alloys

In the framework of systematic science of alloys,the average molar property（volume and potential energy） functions of disordered alloys were established.From these functions,the average molar property functions,partial molar property functions,derivative functions with respect to composition,general equation of relationship between partial and average molar properties of components,difference equation and constraining equation of different values between partial and average molar properties,as well as general Gibbs-Duhem formula were derived.It was proved that the partial molar properties calculated from various combinative functions of average molar properties of alloys are equal,but in general,the partial molar properties are not equal to the average molar properties of a given component.This means that the partial molar properties cannot represent the corresponding properties of the component.All the equations and functions established in this work were proved to be correct by calculating the results of partial and average atomic volumes of components as well as average atomic volumes of alloys in the Au-Ni system.

Linear correlations of formation enthalpies/bulk modules and atomic volumes observed in Pt-Zr compounds by ab initio calculation

118 kinds of Pt-Zr phases were established and investigated by considering various structures. Then the related physical properties, such as structural stability, lattice constants, formation enthalpies, elastic constants and bulk moduli, are obtained by ab initio calculations. Based on the calculated results of formation enthalpies, the ground-state convex hull is derived for the Pt-Zr system. The calculated physical data would provide a basis for further thermodynamic calculations and atomistic simulations. For these Pt-Zr compounds, it is found there are a positive linear correlation between the formation enthalpies and atomic volumes, and a negative linear correlation between the bulk modules and atomic volumes.

Atomic volumes and volume functions for Ag-Cu alloys

Nine functions of atomic volume interaction have been established. The values of average atomic volumes and lattice constants of Ag-Cu alloys obtained from each V-function are, respectively, equal to each other and in good agreement with experimental values. But the average atomic volumes of components and the volumes of characteristic atoms obtained from each V-function are different from each other. Only after the correlative study of energy, volume and electronic structure is carried out, can the V-function be correctly chosen, can a knowledge system about the alloys be established, thus providing the base for scientific design of new alloys. The relationships between lattice parameters of metastable phases of Ag-Cu alloys and composition and between average properties and partial molar properties of components are discussed.

A combined multiscale modeling and experimental study on surface modification of high-volume micro-nanoparticles with atomic accuracy

Surface modification for micro-nanoparticles at the atomic and close-to-atomic scales is of great importance to enhance their performance in various applications,including high-volume battery,persistent luminescence,etc.Fluidized bed atomic layer deposition(FB-ALD)is a promising atomic-scale manufacturing technology that offers ultrathin films on large amounts of particulate materials.Nevertheless,nanoparticles tend to agglomerate due to the strong cohesive forces,which is much unfavorable to the film conformality and also hinders their real applications.In this paper,the particle fluidization process in an ultrasonic vibration-assisted FB-ALD reactor is numerically investigated from micro-scale to macro-scale through the multiscale computational fluid dynamics and discrete element method(CFD-DEM)modeling with experimental verification.Various vibration amplitudes and frequencies are investigated in terms of their effects on the fluid dynamics,distribution of particle velocity and solid volume fraction,as well as the size of agglomerates.Results show that the fluid turbulent kinetic energy,which is the key power source for the particles to obtain the kinetic energy for overcoming the interparticle agglomeration forces,can be strengthened obviously by the ultrasonic vibration.Besides,the application of ultrasonic vibration is found to reduce the mean agglomerate size in the FB.This is bound to facilitate the heat transfer and precursor diffusion in the entire FB-ALD reactor and the agglomerates,which can largely shorten the coating time and improve the film conformality as well as precursor utilization.The simulation results also agree well with our battery experimental results,verifying the validity of the multiscale CFD-DEM model.This work has provided momentous guidance to the mass manufacturing of atomic-scale particle coating from lab-scale to industrial applications.

Strong synergy between physical and chemical properties:Insight into optimization of atomically dispersed oxygen reduction catalysts

Atomically dispersed catalysts exhibit significant influence on facilitating the sluggish oxygen reduction reaction(ORR)kinetics with high atom economy,owing to remarkable attributes including nearly 100%atomic utilization and exceptional catalytic functionality.Furthermore,accurately controlling atomic physical properties including spin,charge,orbital,and lattice degrees of atomically dispersed catalysts can realize the optimized chemical properties including maximum atom utilization efficiency,homogenous active centers,and satisfactory catalytic performance,but remains elusive.Here,through physical and chemical insight,we review and systematically summarize the strategies to optimize atomically dispersed ORR catalysts including adjusting the atomic coordination environment,adjacent electronic orbital and site density,and the choice of dual-atom sites.Then the emphasis is on the fundamental understanding of the correlation between the physical property and the catalytic behavior for atomically dispersed catalysts.Finally,an overview of the existing challenges and prospects to illustrate the current obstacles and potential opportunities for the advancement of atomically dispersed catalysts in the realm of electrocatalytic reactions is offered.

Synthesis and Modulation of Low-Dimensional Transition Metal Chalcogenide Materials via Atomic Substitution

In recent years,low-dimensional transition metal chalcogenide(TMC)materials have garnered growing research attention due to their superior electronic,optical,and catalytic properties compared to their bulk counterparts.The controllable synthesis and manipulation of these materials are crucial for tailoring their properties and unlocking their full potential in various applications.In this context,the atomic substitution method has emerged as a favorable approach.It involves the replacement of specific atoms within TMC structures with other elements and possesses the capability to regulate the compositions finely,crystal structures,and inherent properties of the resulting materials.In this review,we present a comprehensive overview on various strategies of atomic substitution employed in the synthesis of zero-dimensional,one-dimensional and two-dimensional TMC materials.The effects of substituting elements,substitution ratios,and substitution positions on the structures and morphologies of resulting material are discussed.The enhanced electrocatalytic performance and photovoltaic properties of the obtained materials are also provided,emphasizing the role of atomic substitution in achieving these advancements.Finally,challenges and future prospects in the field of atomic substitution for fabricating low-dimensional TMC materials are summarized.

Building Feedback-Regulation System Through Atomic Design for Highly Active SO_(2)Sensing

Reasonably constructing an atomic interface is pronouncedly essential for surface-related gas-sensing reaction.Herein,we present an ingen-ious feedback-regulation system by changing the interactional mode between single Pt atoms and adjacent S species for high-efficiency SO_(2)sensing.We found that the single Pt sites on the MoS_(2)surface can induce easier volatiliza-tion of adjacent S species to activate the whole inert S plane.Reversely,the activated S species can provide a feedback role in tailoring the antibonding-orbital electronic occupancy state of Pt atoms,thus creating a combined system involving S vacancy-assisted single Pt sites(Pt-Vs)to synergistically improve the adsorption ability of SO_(2)gas molecules.Further-more,in situ Raman,ex situ X-ray photoelectron spectroscopy testing and density functional theory analysis demonstrate the intact feedback-regulation system can expand the electron transfer path from single Pt sites to whole Pt-MoS_(2)supports in SO_(2)gas atmosphere.Equipped with wireless-sensing modules,the final Pt1-MoS_(2)-def sensors array can further realize real-time monitoring of SO_(2)levels and cloud-data storage for plant growth.Such a fundamental understanding of the intrinsic link between atomic interface and sensing mechanism is thus expected to broaden the rational design of highly effective gas sensors.

A frequency servo SoC with output power stabilization loop technology for miniaturized atomic clocks

A frequency servo system-on-chip(FS-SoC)featuring output power stabilization technology is introduced in this study for high-precision and miniaturized cesium(Cs)atomic clocks.The proposed power stabilization loop(PSL)technique,incorporating an off-chip power detector(PD),ensures that the output power of the FS-SoC remains stable,mitigating the impact of power fluctuations on the atomic clock's stability.Additionally,a one-pulse-per-second(1PPS)is employed to syn-chronize the clock with GPS.Fabricated using 65 nm CMOS technology,the measured phase noise of the FS-SoC stands at-69.5 dBc/Hz@100 Hz offset and-83.9 dBc/Hz@1 kHz offset,accompanied by a power dissipation of 19.7 mW.The Cs atomic clock employing the proposed FS-SoC and PSL obtains an Allan deviation of 1.7×10^(-11) with 1-s averaging time.

Atomically dispersed Ni electrocatalyst for superior urea-assisted water splitting

Urea oxidation reaction(UOR) has been selected as substitution for oxygen evolution reaction ascribing to its low thermodynamic voltage as well as utilization of nickel as electrocatalyst.Herein,we report the formation of nickel single atoms(Ni-SAs) as exceptional bifunctional electrocatalyst toward UOR and hydrogen evolution reaction(HER) in urea-assisted water splitting.In UOR catalysis,Ni-SAs perform a superior catalytic performance than Ni-NP/NC and Pt/C ascribing to the formation of HOO-Ni-N_(4) structure evidenced by in-situ Raman spectroscopy,corresponding to a boosted mass activity by 175-fold at 1.4 V vs.RHE than Ni-NP/NC.Furthermore,Ni-SAs requires only 450 mV overpotential to obtain HER current density of 500 mA cm^(-2).136 mA cm^(-2) is achieved in urea-assisted water splitting at1.7 V for Ni-SAs,boosted by 5.7 times than Pt/C-IrO_(2) driven water splitting.

Atomically Substitutional Engineering of Transition Metal Dichalcogenide Layers for Enhancing Tailored Properties and Superior Applications

Transition metal dichalcogenides(TMDs)are a promising class of layered materials in the post-graphene era,with extensive research attention due to their diverse alternative elements and fascinating semiconductor behavior.Binary MX2 layers with different metal and/or chalcogen elements have similar structural parameters but varied optoelectronic properties,providing opportunities for atomically substitutional engineering via partial alteration of metal or/and chalcogenide atoms to produce ternary or quaternary TMDs.The resulting multinary TMD layers still maintain structural integrity and homogeneity while achieving tunable(opto)electronic properties across a full range of composition with arbitrary ratios of introduced metal or chalcogen to original counterparts(0–100%).Atomic substitution in TMD layers offers new adjustable degrees of freedom for tailoring crystal phase,band alignment/structure,carrier density,and surface reactive activity,enabling novel and promising applications.This review comprehensively elaborates on atomically substitutional engineering in TMD layers,including theoretical foundations,synthetic strategies,tailored properties,and superior applications.The emerging type of ternary TMDs,Janus TMDs,is presented specifically to highlight their typical compounds,fabrication methods,and potential applications.Finally,opportunities and challenges for further development of multinary TMDs are envisioned to expedite the evolution of this pivotal field.

Atomic layer deposition in advanced display technologies:from photoluminescence to encapsulation

Driven by the growing demand for next-generation displays,the development of advanced luminescent materials with exceptional photoelectric properties is rapidly accelerating,with such materials including quantum dots and phosphors,etc.Nevertheless,the primary challenge preventing the practical application of these luminescent materials lies in meeting the required durability standards.Atomic layer deposition(ALD)has,therefore,been employed to stabilize luminescent materials,and as a result,flexible display devices have been fabricated through material modification,surface and interface engineering,encapsulation,cross-scale manufacturing,and simulations.In addition,the appropriate equipment has been developed for both spatial ALD and fluidized ALD to satisfy the low-cost,high-efficiency,and high-reliability manufacturing requirements.This strategic approach establishes the groundwork for the development of ultra-stable luminescent materials,highly efficient light-emitting diodes(LEDs),and thin-film packaging.Ultimately,this significantly enhances their potential applicability in LED illumination and backlighted displays,marking a notable advancement in the display industry.

Asymmetric Zn-N_4 atomic sites embedded hollow fibers as stable Zn anode for high-performance Zn-ion hybrid capacitor

Zn based electrochemical energy storage systems(EES)have attracted tremendous interests owing to their low cost and high intrinsic safety.Nevertheless,the uncontrolled growth of Zn dendrites and the side reactions of Zn metal anodes(ZMAs)severely restrict their applications.To address these issues,we design the asymmetric Zn-N_(4) atomic sites embedded hollow fibers(AS-IHF)as the flexible host for stable ZMAs.Through introducing different nitrogen resources in the synthesis,two kinds of coordination,i,e.Zn-N(pyridinic)and Zn-N(pyrrolic),are introduced in the Zn-N_(4) atomic module synchronously.The asymmetric Zn-N_(4) module with regulated micro-environment facilitates the superior zincophilic features and promotes the Zn adsorption.Meanwhile,the highly porous structure of the hollow fiber effectively reduces local current density,homogenize Zn ion flux,and alleviate structure stress.All the advantages endow the high efficiency and good stability for Zn plating/stripping.Both theoretical and experimental results demonstrate the high reversibility,low nucleation overpotential,and dendritefree behavior of the AS-IHF@Zn anode,which afford the high stability in high-rate and long-term cycling.Moreover,the solid-state Zn-ion hybrid capacitor(ZIHC)based on AS-IHF@Zn anode shows the high flexibility,reliability,and superior long-term cycling capability in a wide-range of temperatures(-20-25℃).Therefore,the present work not only gives a new strategy for modulating local environments of single atomic sites,but also propels the development of flexible power sources for diverse electronics.

Unveiling the early stage evolution of local atomic structures in the crystallization process of a metallic glass

The early stage evolution of local atomic structures in a multicomponent metallic glass during its crystallization process has been investigated via molecular dynamics simulation.It is found that the initial thermal stability and earliest stage evolution of the local atomic clusters show no strong correlation with their initial short-range orders,and this leads to an observation of a novel symmetry convergence phenomenon,which can be understood as an atomic structure manifestation of the ergodicity.Furthermore,in our system we have quantitatively proved that the crucial factor for the thermal stability against crystallization exhibited by the metallic glass is not the total amount of icosahedral clusters,but the degree of global connectivity among them.

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.

Precise construction of RuPt dual single-atomic sites to optimize oxygen electrocatalytic behaviors for high-performance Zn-air batteries

The development of redox bifunctional electrocatalysts with high performance,low cost,and long lifetimes is essential for achieving clean energy goals.This study proposed an atom capture strategy for anchoring dual single atoms(DSAs)in a zinc-zeolitic imidazolate framework(Zn-ZIF),followed by calcination under an N_(2) atmosphere to synthesize ruthenium-platinum DSAs supported on a nitrogendoped carbon substrate(RuPt DSAs-NC).Theoretical calculations showed that the degree of Ru 5dxz-~*O 2p_x orbital hybridization was high when^(*)O was adsorbed at the Ru site,indicating enhanced covalent hybridization of metal sites and oxygen ligands,which benefited the adsorption of intermediate species.The presence of the RuPtN_6 active center optimized the absorption-desorption behavior of intermediates,improving the electrocatalytic performance of the oxygen reduction reaction(ORR)and the oxygen evolution reaction(DER),RuPt DSAs-NC exhibited a 0.87 V high half-wave potential and a 268 mV low overpotential at 10 mA cm^(-2)in an alkaline environment.Furthermore,rechargeable zinc-air batteries(ZABs)achieved a peak power density of 171 MW cm^(-2).The RuPt DSAs-NC demonstrated long-term cycling for up to 500 h with superior round-trip efficiency.This study provided an effective structural design strategy to construct DSAs active sites for enhanced electrocata lytic performance.

Hydrogen Spillover Effect in Electrocatalysis:Delving into the Mysteries of the Atomic Migration

Hydrogen spillover effect has recently garnered a lot of attention in the field of electrocatalytic hydrogen evolution reactions.A new avenue for understanding the dynamic behavior of atomic migration in which hydrogen atoms moving on a catalyst surface was opened up by the setup of the word"hydrogen spillover."However,there is currently a dearth of thorough knowledge regarding the hydrogen spillover effect.Currently,the advancement of sophisticated characterization procedures offers progressively useful information to enhance our grasp of the hydrogen spillover effect.The understanding of material fabrication for hydrogen spillover effect has erupted.Considering these factors,we made an effort to review most of the articles published on the hydrogen spillover effect and carefully analyzed the aspect of material fabrication.All of our attention has been directed toward the molecular pathway that leads to improve hydrogen evolution reactions performance.In addition,we have attempted to elucidate the spillover paths through the utilization of DFT calculations.Furthermore,we provide some preliminary research suggestions and highlight the opportunities and obstacles that are still to be confronted in this study area.

Influence of anodization conditions on deposition of hydroxyapatite onα/βTi alloys for osseointegration:Atomic force microscopy analysis

Integrating titanium-based implants with the surrounding bone tissue remains challenging.This study aims to explore the impact of different anodization voltages(20−80 V)on the surface topography of two-phase(α/β)Ti alloys and to produce TiO_(2) films with enhanced bone formation abilities.Scanning electron microscopy coupled with energy dispersive spectroscopy(SEM−EDS)and atomic force microscopy(AFM)were applied to investigate the morphological,chemical,and surface topography of the prepared alloys and to confirm the growth of hydroxyapatite(HA)on their surfaces.Results disclosed that the surface roughness of TiO_(2) films formed on Ti−6Al−7Nb alloys was superior to that of Ti−6Al−4V alloys.Ti−6Al−7Nb alloy anodized at 80 V had the highest yields of HA after immersion in simulated body fluid with enhanced HA surface coverage.The developed HA layer had a mean thickness of(128.38±18.13)μm,suggesting its potential use as an orthopedic implantable material due to its promising bone integration and,hence,remarkable stability inside the human body.

Atomic Dispersed Hetero‑Pairs for Enhanced Electrocatalytic CO_(2)Reduction

Electrochemical carbon dioxide reduction reaction(CO_(2)RR)involves a variety of intermediates with highly correlated reaction and ad-desorption energies,hindering optimization of the catalytic activity.For example,increasing the binding of the*COOH to the active site will generally increase the*CO desorption energy.Breaking this relationship may be expected to dramatically improve the intrinsic activity of CO_(2)RR,but remains an unsolved challenge.Herein,we addressed this conundrum by constructing a unique atomic dispersed hetero-pair consisting of Mo-Fe di-atoms anchored on N-doped carbon carrier.This system shows an unprecedented CO_(2)RR intrinsic activity with TOF of 3336 h−1,high selectivity toward CO production,Faradaic efficiency of 95.96%at−0.60 V and excellent stability.Theoretical calculations show that the Mo-Fe diatomic sites increased the*COOH intermediate adsorption energy by bridging adsorption of*COOH intermediates.At the same time,d-d orbital coupling in the Mo-Fe di-atom results in electron delocalization and facilitates desorption of*CO intermediates.Thus,the undesirable correlation between these steps is broken.This work provides a promising approach,specifically the use of di-atoms,for breaking unfavorable relationships based on understanding of the catalytic mechanisms at the atomic scale.

Performance optimization of a SERF atomic magnetometer based on flat-top light beam

We explore the impact of pumping beams with different transverse intensity profiles on the performance of the spinexchange relaxation-free(SERF) atomic magnetometers(AMs). We conduct experiments comparing the traditional Gaussian optically-pumped AM with that utilizing the flat-top optically-pumped(FTOP) method. Our findings reveal that the FTOP-based approach outperforms the conventional method, exhibiting a larger response, a narrower magnetic resonance linewidth, and a superior low-frequency noise performance. Specifically, the use of FTOP method leads to a 16% enhancement in average sensitivity within 1 Hz–30 Hz frequency range. Our research emphasizes the significance of achieving transverse polarization uniformity in AMs, providing insights for future optimization efforts and sensitivity improvements in miniaturized magnetometers.

Regulating the coordination microenvironment of atomic bismuth sites in nitrogen-rich carbon nanosheets as anode for superior potassium-ion batteries

Carbon-based materials are recognized as anodes fulling of promise for potassium ion batteries(PIBs)due to advantages of affordable cost and high conductivity.However,they still face challenges including structural unstability and slow kinetics.It is difficult to achieve efficient potassium storage with unmodified carbonaceous anode.Herein,atomic bismuth(Bi)sites with different atom coordinations anchored on carbon nanosheets(CNSs)have been synthesized through a template method.The properties of prepared multi-doping carbon anodes Bi-N_(3)S_(1)/CNSs,Bi-N_(3)P_(1)/CNSs and Bi-N_(4)/CNSs were probed in PIBs.The configuration Bi-N_(3)S_(1) with stronger charge asymmetry exhibits superior potassium storage performance compared to Bi-N_(3)P_(1) and Bi-N_(4) configurations.The Bi-N_(3)S_(1)/CNSs display a rate capacity of 129.2 mAh g^(-1)even at 10 A g^(-1)and an impressive cyclability characterized by over 5000 cycles at 5 A g^(-1),on account of its optimal coordination environment with more active Bi centers and K^(+)adsorption sites.Notably,assembled potassium-ion full cell Mg-KVO//Bi-N_(3)S_(1)/CNSs also shows an outstanding cycling stability,enduring 3000 cycles at 2 A g^(-1).Therefore,it can be demonstrated that regulating the electronic structure of metallic centre M-N_(4) via changing the type of ligating atom is a feasible strategy for modifying carbon anodes,on the base of co-doping metal and non-metal.