Accelerated prediction of Cu-based single-atom alloy catalysts for CO_(2) reduction by machine learning

Various strategies,including controls of morphology,oxidation state,defect,and doping,have been developed to improve the performance of Cu-based catalysts for CO_(2) reduction reaction(CO_(2)RR),generating a large amount of data.However,a unified understanding of underlying mechanism for further optimization is still lacking.In this work,combining first-principles calculations and machine learning(ML)techniques,we elucidate critical factors influencing the catalytic properties,taking Cu-based single atom alloys(SAAs)as examples.Our method relies on high-throughput calculations of 2669 CO adsorption configurations on 43 types of Cu-based SAAs with various surfaces.Extensive ML analyses reveal that low generalized coordination numbers and valence electron number are key features to determine catalytic performance.Applying our ML model with cross-group learning scheme,we demonstrate the model generalizes well between Cu-based SAAs with different alloying elements.Further,electronic structure calculations suggest surface negative center could enhance CO adsorption by back donating electrons to antibonding orbitals of CO.Finally,several SAAs,including PCu,AgCu,GaCu,ZnCu,SnCu,GeCu,InCu,and SiCu,are identified as promising CO_(2)RR catalysts.Our work provides a paradigm for the rational design and fast screening of SAAs for various electrocatalytic reactions.

Charge-asymmetry Fe_(1)Cu single-atom alloy catalyst for efficient oxygen reduction reaction

The development of high-efficient and low-cost oxygen reduction reaction(ORR)electrocatalysts is crucial for the practical applications of metal-air batteries.One promising way is to develop Fe single-atom catalysts.However,the single active center and inherent electronic structure of Fe single-atom catalysts lead to the undesirable adsorption of multiple ORR intermediates.Herein,a charge-asymmetry single-atom alloy(SAA)catalyst with Fe-Cu dual sites supported on nitrogen-doped carbon nanosheet(Fe_(1)Cu SAA/NC)was constructed.Various characterizations manifest the existence of electron interaction between Fe and Cu in Fe_(1)Cu SAA/NC,which facilitates the adsorption of ORR intermediate for fast kinetics.Consequently,the charge-asymmetry Fe_(1)Cu SAA/NC exhibits much faster ORR kinetics with a half-wave potential of 0.917 V vs.reversible hydrogen electrode(RHE),outperforming its counterparts in the references.Furthermore,Fe_(1)Cu SAA/NC still maintains a high half-wave potential with only a drop of 5 mV after 5000 cycles,indicating excellent stability.This work provides a new strategy to design highly active and non-noble metal ORR electrocatalysts,which hold great potential for various catalytic applications.

Single-atom alloys prepared by two-step thermal evaporation

Single-atom alloys(SAAs)have gained significant attention due to their remarkable atomic utilization efficiency,interactions between single atoms(SAs)and metal supports,and free-atom-like electronic structure of dopant elements.In this work,we observed the formation of SAs in pre-deposited metal particles by a two-step thermal evaporation technique,thereby establishing the first instance of discovering SAAs by thermal evaporation.The discovery of SAAs by thermal evaporation extends the range of SAAs preparation methods to include this traditional synthetic technique,which offers convenience,cost-efficiency,and universality.The formation mechanism of SAAs prepared using this technique was elucidated by density functional theory calculations.It was demonstrated that thermal evaporation can be utilized to prepare SAAs with multiple SAs,further highlighting its universal applicability.

The applications of single-atom alloys in electrocatalysis:Progress and challenges

The development of cost-effective and highly efficient electrocatalysts to accelerate distinct electrochemical reactions is essential to help the industry to achieve a low-carbon footprint.Single-atom alloys(SAAs)with the characteristics of unique electronic structures,well-defined active sites,and maximum atom utilization demonstrate promising potential to replace traditional noble metal catalysts.SAAs are expected to tailor the adsorption properties of reaction species,thus promoting electrocatalytic behaviors.Herein,representative synthetic strategies including wet chemistry,galvanic replacement,dealloying,and atomic layer deposition are introduced,followed by a summary of applications of SAAs in hydrogen evolution reaction,oxygen evolution reaction,oxygen reduction reaction,carbon dioxide reduction reaction,and ethanol electro-oxidation to provide an in-depth understanding of the structure–activity relationship.Moreover,the challenges and perspectives in this emerging field of SAAs are discussed.

Effect of hafnium and molybdenum addition on inclusion characteristics in Co-based dual-phase high-entropy alloys

Specific grades of high-entropy alloys(HEAs)can provide opportunities for optimizing properties toward high-temperature applications.In this work,the Co-based HEA with a chemical composition of Co_(47.5)Cr_(30)Fe_(7.5)Mn_(7.5)Ni_(7.5)(at%)was chosen.The refractory metallic elements hafnium(Hf)and molybdenum(Mo)were added in small amounts(1.5at%)because of their well-known positive effects on high-temperature properties.Inclusion characteristics were comprehensively explored by using a two-dimensional cross-sectional method and extracted by using a three-dimensional electrolytic extraction method.The results revealed that the addition of Hf can reduce Al_(2)O_(3)inclusions and lead to the formation of more stable Hf-rich inclusions as the main phase.Mo addition cannot influence the inclusion type but could influence the inclusion characteristics by affecting the physical parameters of the HEA melt.The calculated coagulation coefficient and collision rate of Al_(2)O_(3)inclusions were higher than those of HfO_(2)inclusions,but the inclusion amount played a larger role in the agglomeration behavior of HfO_(2)and Al_(2)O_(3)inclusions.The impurity level and active elements in HEAs were the crucial factors affecting inclusion formation.

Design of high-temperature superconductors at moderate pressures by alloying AlH3 or GaH3

Since the discovery of hydride superconductors,a significant challenge has been to reduce the pressure required for their stabilization.In this context,we propose that alloying could be an effective strategy to achieve this.We focus on a series of alloyed hydrides with the AMH_(6)composition,which can be made via alloying A15 AH_(3)(A=Al or Ga)with M(M=a group IIIB or IVB metal),and study their behavior under pressure.Seven of them are predicted to maintain the A15-type structure,similar to AH_(3)under pressure,providing a platform for studying the effects of alloying on the stability and superconductivity of AH_(3).Among these,the A15-type phases of AlZrH_(6)and AlHfH_(6)are found to be thermodynamically stable in the pressure ranges of 40–150 and 30–181 GPa,respectively.Furthermore,they remain dynamically stable at even lower pressures,as low as 13 GPa for AlZrH_(6)and 6 GPa for AlHfH_(6).These pressures are significantly lower than that required for stabilizing A15 AlH3.Additionally,the introduction of Zr or Hf increases the electronic density of states at the Fermi level compared with AlH3.This enhancement leads to higher critical temperatures(Tc)of 75 and 76 K for AlZrH_(6)and AlHfH_(6)at 20 and 10 GPa,respectively.In the case of GaMH_(6)alloys,where M represents Sc,Ti,Zr,or Hf,these metals reinforce the stability of the A15-type structure and reduce the lowest thermodynamically stable pressure for GaH_(3) from 160 GPa to 116,95,80,and 85 GPa,respectively.Particularly noteworthy are the A15-type GaMH_(6)alloys,which remain dynamically stable at low pressures of 97,28,5,and 6 GPa,simultaneously exhibiting high Tc of 88,39,70,and 49 K at 100,35,10,and 10 GPa,respectively.Overall,these findings enrich the family of A15-type superconductors and provide insights for the future exploration of high-temperature hydride superconductors that can be stabilized at lower pressures.

Microstructure and mechanical properties stability of pre-hardening treatment in Al-Cu alloys for pre-hardening forming process

The stability of the microstructure and mechanical properties of the pre-hardened sheets during the pre-hardening forming(PHF)process directly determines the quality of the formed components.The microstructure stability of the pre-hardened sheets was in-vestigated by differential scanning calorimetry(DSC),transmission electron microscopy(TEM),and small angle X-ray scattering(SAXS),while the mechanical properties and formability were analyzed through uniaxial tensile tests and formability tests.The results in-dicate that the mechanical properties of the pre-hardened alloys exhibited negligible changes after experiencing 1-month natural aging(NA).The deviations of ultimate tensile strength(UTS),yield strength(YS),and sheet formability(Erichsen value)are all less than 2%.Also,after different NA time(from 48 h to 1 month)is applied to alloys before pre-hardening treatment,the pre-hardened alloys possess stable microstructure and mechanical properties as well.Interestingly,with the extension of NA time before pre-hardening treatment from 48 h to 1 month,the contribution of NA to the pre-hardening treatment is limited.Only a yield strength increment of 20 MPa is achieved,with no loss in elongation.The limited enhancement is mainly attributed to the fact that only a limited number of clusters are transformed into Guinier-Preston(GP)zones at the early stage of pre-hardening treatment,and the formation ofθ''phase inhibits the nucleation and growth of GP zones as the precipitated phase evolves.

Relationship between the unique microstructures and behaviors of high-entropy alloys

High-entropy alloys(HEAs),which were introduced as a pioneering concept in 2004,have captured the keen interest of nu-merous researchers.Entropy,in this context,can be perceived as representing disorder and randomness.By contrast,elemental composi-tions within alloy systems occupy specific structural sites in space,a concept referred to as structure.In accordance with Shannon entropy,structure is analogous to information.Generally,the arrangement of atoms within a material,termed its structure,plays a pivotal role in dictating its properties.In addition to expanding the array of options for alloy composites,HEAs afford ample opportunities for diverse structural designs.The profound influence of distinct structural features on the exceptional behaviors of alloys is underscored by numer-ous examples.These features include remarkably high fracture strength with excellent ductility,antiballistic capability,exceptional radi-ation resistance,and corrosion resistance.In this paper,we delve into various unique material structures and properties while elucidating the intricate relationship between structure and performance.

Accelerated design of high-performance Mg-Mn-based magnesium alloys based on novel bayesian optimization

Magnesium(Mg),being the lightest structural metal,holds immense potential for widespread applications in various fields.The development of high-performance and cost-effective Mg alloys is crucial to further advancing their commercial utilization.With the rapid advancement of machine learning(ML)technology in recent years,the“data-driven''approach for alloy design has provided new perspectives and opportunities for enhancing the performance of Mg alloys.This paper introduces a novel regression-based Bayesian optimization active learning model(RBOALM)for the development of high-performance Mg-Mn-based wrought alloys.RBOALM employs active learning to automatically explore optimal alloy compositions and process parameters within predefined ranges,facilitating the discovery of superior alloy combinations.This model further integrates pre-established regression models as surrogate functions in Bayesian optimization,significantly enhancing the precision of the design process.Leveraging RBOALM,several new high-performance alloys have been successfully designed and prepared.Notably,after mechanical property testing of the designed alloys,the Mg-2.1Zn-2.0Mn-0.5Sn-0.1Ca alloy demonstrates exceptional mechanical properties,including an ultimate tensile strength of 406 MPa,a yield strength of 287 MPa,and a 23%fracture elongation.Furthermore,the Mg-2.7Mn-0.5Al-0.1Ca alloy exhibits an ultimate tensile strength of 211 MPa,coupled with a remarkable 41%fracture elongation.

Single-atom catalysts for the electrochemical reduction of carbon dioxide into hydrocarbons and oxygenates

The electrochemical reduction of carbon dioxide offers a sound and economically viable technology for the electrification and decarbonization of the chemical and fuel industries.In this technology,an electrocatalytic material and renewable energy-generated electricity drive the conversion of carbon dioxide into high-value chemicals and carbon-neutral fuels.Over the past few years,single-atom catalysts have been intensively studied as they could provide near-unity atom utilization and unique catalytic performance.Single-atom catalysts have become one of the state-of-the-art catalyst materials for the electrochemical reduction of carbon dioxide into carbon monoxide.However,it remains a challenge for single-atom catalysts to facilitate the efficient conversion of carbon dioxide into products beyond carbon monoxide.In this review,we summarize and present important findings and critical insights from studies on the electrochemical carbon dioxide reduction reaction into hydrocarbons and oxygenates using single-atom catalysts.It is hoped that this review gives a thorough recapitulation and analysis of the science behind the catalysis of carbon dioxide into more reduced products through singleatom catalysts so that it can be a guide for future research and development on catalysts with industry-ready performance for the electrochemical reduction of carbon dioxide into high-value chemicals and carbon-neutral fuels.

Insight into demand-driven preparation of single-atomic mediators for lithium–sulfur batteries

Lithium-sulfur(Li-S) batteries have attracted considerable attention as one of the most appealing energy storage systems.Strenuous efforts have been devoted to tackling the tremendous challenges,mainly pertaining to the severe shuttle effect,sluggish redox kinetics and lithium dendritic growth.Single-atomic mediators as promising candidates exhibit impressive performance in addressing these intractable issues.Related research often utilizes a trial-and-error approach,proposing solutions to fabricate single-atomic materials with diversified features.However,comprehensive review articles especially targeting demand-driven preparation are still in a nascent stage.Inspired by these considerations,this review summarizes the design of single-atomic mediators based on the application case-studies in LiS batteries and other metal-sulfur systems.Emerging preparation routes represented by chemical vapor deposition technology are introduced in a demand-oriented classification.Finally,future research directions are proposed to foster the advancement of single-atomic mediators in Li-S realm.

Microstructure and damping properties of LPSO phase dominant Mg-Ni-Y and Mg-Zn-Ni-Y alloys

This work studied the microstructure,mechanical properties and damping properties of Mg_(95.34)Ni_(2)Y_(2.66) and Mg_(95.34)Zn_(1)Ni_(1)Y_(2.66)alloys systematically.The difference in the evolution of the long-period stacked ordered(LPSO)phase in the two alloys during heat treatment was the focus.The morphology of the as-cast Mg_(95.34)Ni_(2)Y_(2.66)presented a disordered network.After heat treatment at 773 K for 2 hours,the eutectic phase was integrated into the matrix,and the LPSO phase maintained the 18R structure.As Zn partially replaced Ni,the crystal grains became rounded in the cast alloy,and lamellar LPSO phases and more solid solution atoms were contained in the matrix after heat treatment of the Mg_(95.34)Zn_(1)Ni_(1)Y_(2.66)alloy.Both Zn and the heat treatment had a significant effect on damping.Obvious dislocation internal friction peaks and grain boundary internal friction peaks were found after temperature-dependent damping of the Mg_(95.34)Ni_(2)Y_(2.66)and Mg_(95.34)Zn_(1)Ni_(1)Y_(2.66)alloys.After heat treatment,the dislocation peak was significantly increased,especially in the alloy Mg_(95.34)Ni_(2)Y_(2).66.The annealed Mg_(95.34)Ni_(2)Y_(2.66)alloy with a rod-shaped LPSO phase exhibited a good damping performance of 0.14 atε=10^(−3),which was due to the difference between the second phase and solid solution atom content.These factors also affected the dynamic modulus of the alloy.The results of this study will help in further development of high-damping magnesium alloys.

Effect of pre-twinning and heat treatment on formability of AZX311 Mg alloy

In this study,the effects of pre-strain-induced tensile twins(TTWs)and controlled heat treatment on the formability behavior of AZX311 Mg alloy sheets were investigated.A 4%compressive strain was applied to pre-strain the sheets using the in-plane compression(IPC)technique along the rolling direction(RD)to introduce TTWs.The pre-strained(PS)samples were subsequently heat-treated at 250℃,350℃,and 400℃ independently for 1 hr,and are termed as PSA1,PSA2,and PSA3,respectively.Erichsen cupping tests were conducted to assess the formability of the sheet samples under different initial conditions.The results showed that the PS sample heat-treated at 250℃ for 1hr exhibited a decrease in the Erichsen index(IE)compared to the as-rolled sample,whereas PSA2 and PSA3 samples showed an increase in IE values.Microtexture analysis revealed that most of the TTWs generated through pre-twinning were stable at 250℃;however,the twin volume fraction reduced to 41%at 350℃ compared to the PS samples due to enhanced thermal activity at that temperature.Furthermore,PSA2 samples showed severe grain coarsening in some areas of the sample,and the fraction of such grains increased in the PSA3 samples.The stretch formability(IE value)of PSA2 samples showed a 32.3%increase compared to the as-rolled specimens.Additionally,the analysis of the deformed specimen at failure under the Erichsen test indicated that considerable detwinning occurs in the PS and PSA1 samples,whereas dislocation slip activity dominates in the PSA2 and PSA3 samples during stretch forming.Apart from detwinning and dislocation slip,deformation twins were also observed in all samples after the Erichsen test.Thus,this work highlights the importance of texture control and its underlying mechanisms via pre-twinning followed by heat treatment and their impact on the room temperature(RT)stretch formability of AZX311 Mg alloy sheets.

Surface morphologies of Mg-Gd alloy particle during its reactions with O_(2) and Teflon

Mg-Gd alloy particle has exhibited its unique combustion properties as the fuel of Mg/Teflon/Viton(MTV).Mg-Gd alloy/Teflon/Viton(MGTV)could burn at lower ambient pressure than MTV.To further investigate the reaction of MGTV in air,it was investigated via thermo gravity-differential scanning calorimetry(TG-DSC).Meanwhile,the morphologies and element distributions on the alloy surface during the reaction of MGTV in air were investigated via scanning electronic microscope-mapping-electronic differential spectrometer.Meanwhile,a similar experimental protocol on the Mg-Gd alloy particle during oxidation was also applied.The results showed that owning to a protective oxide shell,the onset oxidation temperature of Mg-Gd alloy is higher than Mg.However,the onset oxidation temperature of the exceeded Mg-Gd alloy in MGTV is significantly lower than that of the exceeded Mg in MTV.It was due to the existence of GdOF,which could significantly lower the oxidation temperature of the exceeded fuel.Furthermore,a possible reaction mechanism was proposed.The fascinating oxidation properties of Mg-Gd alloy suggested its promising applications in energetic materials.

Oxidation behavior and improvement in nonflammability of LPSO-type Mg–Zn–Y–Sr alloy

Mg_(97)Zn_(1)Y_(2)alloys with high ignition temperatures were developed by adding Sr.The addition of Sr resulted in the formation of a uniform and thin Y_(2)O_(3)film.Mg–Zn–Y alloys containing at least 0.25 at.%Sr exhibited ignition temperatures of 1270–1320 K.As a result of EDS measurement,Sr was found to be concentrated in the Y_(2)O_(3)film.In addition,a mixed film of MgO and Sr O formed on the outer layer in the 1.5 at.%Sr-containing Mg_(97)Zn_(1)Y_(2)alloy.These findings suggest that the uniform and thin Y_(2)O_(3)film that maintains high soundness at high temperatures was formed owing to valence control and the formation of a protective outer oxide film.

Revealing the role of pyramidal slip in the high ductility of Mg-Li alloy

The high ductility of Mg-Li alloy has been mainly ascribed to a high activity of pyramidal<c+a>slip to accommodate plastic strain.In the present study,however,a quantitative analysis reveals that Li-addition can only slightly stimulate the activation of pyramidal<c+a>slip under compression along the normal direction of a hot-rolled Mg-4.5 wt.%Li plate,with a relative activity of approximately 18%.Although the limited activity of pyramidal<c+a>slip alone cannot accommodate a large plastic strain,it effectively reduces the number of{10.11}−{10.12}double twins,which are believed to be favorable sites for crack initiation.The evidently reduced activity of double twins leads to a lower cracking tendency,and therefore improves ductility.

Recent progress in the research on magnesium and magnesium alloy foils:A short review

Magnesium and magnesium alloy foils have great potential for application in battery anodes,electromagnetic shielding,optics and acoustics,and biology because of their excellent specific damping,internal dissipation coefficients,magnetic and electrical conductivities,as well as high theoretical specific capacity.However,magnesium alloys exhibit poor deformation ability due to their hexagonal close-packed crystal structure.Preparing magnesium and magnesium alloy foils with thicknesses of less than 0.1 mm is difficult because of surface oxidation and grain growth at high temperatures or severe anisotropy after cold rolling that leads to cracks.Numerous methods have been applied to prepare magnesium alloy foils.They include warm rolling,cold rolling,accumulative roll bonding,electric plastic rolling,and on-line heating rolling.Defects of magnesium and magnesium alloy foils during preparation,such as edge cracks and breakage,are important factors for consideration.Herein,the current status of the research on magnesium and magnesium alloy foils is summarized from the aspects of foil preparation,defect control,performance characterization,and application prospects.The advantages and disadvantages of different preparation methods and defect(edge cracks and breakage)mechanisms in the preparation of foils are identified.

High corrosion and wear resistant electroless Ni–P gradient coatings on aviation aluminum alloy parts

A Ni–P alloy gradient coating consisting of multiple electroless Ni–P layers with various phosphorus contents was prepared on the aviation aluminum alloy. Several characterization and electrochemical techniques were used to characterize the different Ni–P coatings’ morphologies, phase structures, elemental compositions, and corrosion protection. The gradient coating showed good adhesion and high corrosion and wear resistance, enabling the application of aluminum alloy in harsh environments. The results showed that the double zinc immersion was vital in obtaining excellent adhesion (81.2 N). The optimal coating was not peeled and shredded even after bending tests with angles higher than 90°and was not corroded visually after 500 h of neutral salt spray test at 35℃. The high corrosion resistance was attributed to the misaligning of these micro defects in the three different nickel alloy layers and the amorphous structure of the high P content in the outer layer. These findings guide the exploration of functional gradient coatings that meet the high application requirement of aluminum alloy parts in complicated and harsh aviation environments.

High-entropy alloys in thermoelectric application:A selective review

Since the superior mechanical,chemical and physical properties of high-entropy alloys(HEAs)were discovered,they have gradually become new emerging candidates for renewable energy applications.This review presents the novel applications of HEAs in thermoelectric energy conversion.Firstly,the basic concepts and structural properties of HEAs are introduced.Then,we discuss a number of promising thermoelectric materials based on HEAs.Finally,the conclusion and outlook are presented.This article presents an advanced understanding of the thermoelectric properties of HEAs,which provides new opportunities for promoting their applications in renewable energy.

Enhancing the mechanical properties of casting eutectic high -entropy alloys via W addition

The effect of W element on the microstructure evolution and mechanical properties of Al_(1.25)CoCrFeNi3 eutectic high-entropy alloy and Al_(1.25)CoCrFeNi_(3-x)W_(x)(x=0,0.05,0.1,0.3,and 0.5;atomic ratio)high-entropy alloys(HEAs)were explored.Results show that the Al_(1.25)CoCrFeNi_(3-x)W_(x) HEAs are composed of face-centered cubic and body-centered cubic(BCC)phases.As W content increases,the microstructure changes from eutectic to dendritic.The addition of W lowers the nucleation barrier of the BCC phase,decreases the valence electron concentration of the HEAs,and replaces Al in the BCC phase,thus facilitating the nucleation of the BCC phase.Tensile results show that the addition of W greatly improves the mechanical properties,and solid-solution,heterogeneous-interface,and second-phase strengthening are the main strengthening mechanisms.The yield strength,tensile strength,and elongation of the Al_(1.25)CoCrFeNi2.95W0.05 HEA are 601.44 MPa,1132.26 MPa,and 15.94%,respectively,realizing a balance between strength and plasti-city.The fracture mode of the Al_(1.25)CoCrFeNi_(3-x)W_(x) HEAs is ductile–brittle mixed fracture,and the crack propagates and initiates in the BCC phase.The eutectic lamellar structure impedes crack propagation and maintains plasticity.