Bimetallic NiCo boride nanoparticles confined in a MXene network enable efficient ambient ammonia electrosynthesis

Ambient electrocatalytic nitrogen fixation is an emerging technology for green ammonia synthesis,but the absence of optimized,stable and performant catalysts can render its practical application challenging.Herein,bimetallic NiCo boride nanoparticles confined in MXene are shown to accomplish highperformance nitrogen reduction electrolysis.Ta king advantage of the synergistic effect in specific compositions with unique electronic d and p orbits and typical architecture of rich nanosized particles embedded in the interconnected conductive network,the synthesized MXene@NiCoB composite demonstrates extensive improvements in nitrogen molecule chemisorption,active area exposure and charge transport.As a result,optimal NH3 yield rate of 38.7μg h^(-1) mgcat^(-1).and Faradaic efficiency of 6.92%are acquired in0.1 M Na_(2)SO_(4) electrolyte.Moreover,the great catalytic performance can be almost entirely maintained in the cases of repeatedly-cycled and long-term electrolysis.Theoretical investigations reveal that the nitrogen reduction reaction on MXene@NiCoB catalyst proceeds according to the distal pathway,with a distinctly-reduced energy barrier relative to the Co2B counterpart.This work may inspire a new route towards the rational catalyst design for the nitrogen reduction reaction.

A fresh class of superconducting and hard pentaborides

On the basis of the current theoretical understanding of boron-based hard superconductors under ambient conditions,numerous studies have been conducted with the aim of developing superconducting materials with favorable mechanical properties using boron-rich compounds.In this paper,first-principles calculations reveal the existence of an unprecedented family of tetragonal pentaborides MB_(5)(M=Na,K,Rb,Ca,Sr,Ba,Sc,and Y),comprising B_(20)cages and centered metal atoms acting as stabilizers and electron donors to the boron sublattice.These compounds exhibit both superconductivity and high hardness,with the maximum superconducting transition temperature T_(c)of 18.6 K being achieved in RbB5 and the peak Vickers hardness Hv of 35.1 GPa being achieved in KB_(5)at 1 atm.The combination of these properties is particularly evident in KB_(5),RbB5,and BaB5,with Tc values of∼14.7,18.6,and 16.3 K and H_(v)values of∼35.1,32.4,and 33.8 GPa,respectively.The results presented here reveal that pentaborides can provide a framework for exploring and designing novel superconducting materials with favorable hardness at achievable pressures and even under ambient conditions.

Anisotropic thermal expansion in high-entropy multicomponent AlB_(2)-type diboride solid solutions

High-entropy(HE)ultra-high temperature ceramics have the chance to pave the way for future applications propelling technology advantages in the fields of energy conversion and extreme environmental shielding.Among others,HE diborides stand out owing to their intrinsic anisotropic layered structure and ability to withstand ultra-high temperatures.Herein,we employed in-situ high-resolution synchrotron diffraction over a plethora of multicomponent compositions,with four to seven transition metals,with the intent of understanding the thermal lattice expansion following different composition or synthesis process.As a result,we were able to control the average thermal expansion(TE)from 1.3×10^(−6)to 6.9×10^(−6)K^(−1)depending on the combination of metals,with a variation of in-plane to out-of-plane TE ratio ranging from 1.5 to 2.8.

A first-principle calculation of structural,mechanical and electronic properties of titanium borides

The first-principle calculations are performed to investigate the structural,mechanical and electronic properties of titanium borides （Ti2B,TiB and TiB2）.Those calculated lattice parameters are in good agreement with the experimental data and previous theoretical values.All these borides are found to be mechanically stable at ambient pressure.Compared with parent metal Ti （120 GPa）,the larger bulk modulus of these borides increase successively with the increase of the boron content in three borides,which may be due to direction bonding introduced by the boron atoms in the lattice and the strong covalent Ti-B bonds.Additionally,TiB can be regarded as a candidate of incompressible and hard material besides TiB2.Furthermore,the elastic anisotropy and Debye temperatures are also discussed by investigating the elastic constants and moduli.Electronic density of states and atomic Mulliken charges analysis show that chemical bonding in these titanium borides is a complex mixture of covalent,ionic,and metallic characters.

Microstructure Characteristics and Elevated Temperature Mechanical Properties of a B Containedβ-solidifiedγ-TiAl Alloy

The improved microstructure and enhanced elevated temperature mechanical properties of Ti-44Al-5Nb-(Mo,V,B)alloys were obtained by vacuum arc re-melting(VAR)and primary annealing heat treatment(HT)of 1260℃/6 h/Furnace cooling(FC).The phase transformation,microstructure evolution and tensile properties for as-cast and HTed alloys were investigated.Results indicate that three main phase transformation points are determined,T_(eut)=1164.3℃,T_(γsolv)=1268.3℃and T_(βtrans)=1382.8℃.There are coarse lamellar colonies(300μm in length)and neighbor reticular B2 andγgrain(3-5μm)in as-cast alloy,while lamellar colonies are markedly refined and multi-oriented(20-50μm)as well as the volume fraction and grain sizes of equiaxedγand B2 phases(about 15μm)significantly increase in as-HTed alloy.Phase transformations involvingα+γ→α+γ+β/B2 and discontinuousγcoarsening contribute to the above characteristics.Borides(1-3μm)act as nucleation sites forβ_(eutectic) and produce massiveβgrains with different orientations,thus effectively refining the lamellar colonies and forming homogeneous multi-phase microstructure.Tensile curves show both the alloys exhibit suitable performance at 800℃.As-cast alloy shows a higher ultimate tensile stress of 647 MPa,while a better total elongation of more than 41%is obtained for as-HTed alloy.The mechanical properties improvement is mainly attributed to fine,multi-oriented lamellar colonies,coordinated deformation of homogeneous multi-phase microstructure and borides within lamellar interface preventing crack propagation.

Ballistic performance of titanium-based layered composites made using blended elemental powder metallurgy and hot isostatic pressing

Metal matrix composites tiles based on Ti-6Al-4V(Ti64)alloy,reinforced with 10,20,and 40(vol%)of either TiC or TiB particles were made using press-and-sinter blended elemental powder metallurgy(BEPM)and then bonded together into 3-layer laminated plates using hot isostatic pressing(HIP).The laminates were ballistically tested and demonstrated superior performance.The microstructure and properties of the laminates were analyzed to determine the effect of the BEPM and HIP processing on the ballistic properties of the layered plates.The effect of porosity in sintered composites on further diffusion bonding of the plates during HIP is analyzed to understand the bonding features at the interfaces between different adjacent layers in the laminate.Exceptional ballistic performance of fabricated structures was explained by a significant reduction in the residual porosity of the BEPM products by their additional processing using HIP,which provides an unprecedented increase in the hardness of the layered composites.It is argued that the combination of the used two technologies,BEPM and HIP is principally complimentary for the materials in question with the abilities to solve the essential problems of each used individually.

Research Progress of Non-oxide and High Entropy Ceramic Coatings

Ceramic coatings play a keyrole in extending the service life of materials in aerospaceandenergy fields byprotectingmaterials from high temperature,oxidation,corrosion and thermal stress.Non-oxide and high entropy ceramics are new emerging coating materials which have been researched and developed in recent years.Compared with traditional oxide ceramics,non-oxide ceramics have better high temperature stability,oxidation resistance and erosion resistance.These characteristics make non-oxide ceramics perform well in extreme environments.It is particularly noteworthy that the non-oxide high entropy ceramic is a uniform solid solution composed of at least four or fiveatoms.Their unique structure and outstanding propertiesshow great potential application in the field of coating.In this paper,the researches aboutregulating microstructure,preparation technology and properties of nitride and its high entropy system,carbide and its high entropy system and boride and its high entropy system in coating field are summarized,and their future development and prospects are prospected.

Development Strategies in Transition Metal Borides for Electrochemical Water Splitting

Electrochemical water splitting is a feasible method for producing environmental benignity energy of hydrogen,while high price and low availability on the earth of noble electrocatalysts constrain their global-scale application.Transition metal borides(TMBs)have displayed unique metalloid characteristic and outstanding performance for oxygen evolution reaction(OER)and hydrogen evolution reaction(HER)in the last few decades.Herein,recent developments of the TMBs for HER and OER are summarized.Initially,the impact factors and relevant evaluation of electrocatalytic performance are described,that is,overpotential,Tafel slope and exchange current density,stability,faradaic efficiency,turnover frequency,mass and specific activities.Moreover,the optimization strategies of borides are emphasized,which principally include coupling with effective substrates,elemental doping,phase modification,interfacial engineering,and morphology control.Finally,in order to reach the goal of application,the remaining challenges and perspectives are given to point out a direction for enhancing the performance of borides.

Influence of nickel silicides presence on hardness,elastic modulus and fracture toughness of gas-borided layer produced on Nisil-alloy

The two-stage gas boriding in N_(2)−H_(2)−BCl_(3)atmosphere was applied to producing a two-zoned borided layer on Nisil-alloy.The process was carried out at 910℃ for 2 h.The microstructure consisted of two zones differing in their phase composition.The outer layer contained only a mixture of nickel borides(Ni_(2)B,Ni_(3)B)only.The inner zone contained additionally nickel silicides(Ni_(2)Si,Ni_(3)Si)occurring together with nickel borides.The aim of this study was to determine the presence of nickel silicides on the mechanical properties of the borided layer produced on Ni-based alloy.The hardness and elastic modulus were measured using the nanoindenter with a Berkovich diamond tip under a load of 50 mN.The average values of indentation hardness(HI)and indentation elastic modulus(E_(I))obtained in the outer zone were respectively(16.32±1.03)GPa and(232±16.15)GPa.The presence of nickel silicides in the inner zone reduced the indentation hardness(6.8−12.54 GPa)and elastic modulus(111.79−153.99 GPa).The fracture toughness of the boride layers was investigated using a Vickers microindentation under a load of 0.981 N.It was confirmed that the presence of nickel silicides caused an increase in brittleness(by about 40%)of the gas-borided layer.

Biological,antibacterial activities and electrochemical behavior of borided commercially pure titanium in BSA-containing PBS

The effects of boride coating on the bioactivity, antibacterial activity, and electrochemical behavior of commercially pure titanium(CP-Ti) in phosphate buffer solution(PBS) with bovine serum albumin(BSA) were studied. The grazing incidence X-ray diffraction(GIXRD) pattern confirmed the formation of a Ti B/Ti B2 coating via boriding process. Scanning electron microscopy(SEM) observation indicated that the Ti B2 cross-linked particles covered the Ti B whiskers. Water contact angle measurements revealed that boriding led to the formation of a surface with intermediate water affinity. Potentiodynamic polarization(PDP) assays demonstrated that the Ti B/Ti B2 coating had acceptable passivation behavior in BSA-containing PBS. Electrochemical impedance spectroscopy(EIS) measurements revealed that the passivation behavior of the CP-Ti and the borided samples was improved by increasing exposure time. Based on the Mott-Schottky(M-S) tests, it was realized that the charge carriers of passive films of both samples decreased with increasing exposure time in BSA-containing PBS. The bioactivity test results in a simulated body fluid showed that the Ti B/Ti B2 coating switched the CP-Ti from bioinert to bioactive material. Finally, the antibacterial activity test of the Ti B/Ti B2 coating against Escherichia coli and Staphylococcus aureus indicated 99% antibacterial activity.

Optimizing the nickel boride layer thickness in a spectroelectrochemical ATR-FTIR thin-film flow cell applied in glycerol oxidation

The influence of the drop-casted nickel boride catalyst loading on glassy carbon electrodes was investigated in a spectroelectrochemical ATR-FTIR thin-film flow cell applied in alkaline glycerol electrooxidation.The continuously operated radial flow cell consisted of a borehole electrode positioned 50μm above an internal reflection element enabling operando FTIR spectroscopy.It is identified as a suitable tool for facile and reproducible screening of electrocatalysts under well-defined conditions,additionally providing access to the selectivities in complex reaction networks such as glycerol oxidation.The fast product identification by ATR-IR spectroscopy was validated by the more time-consuming quantitative HPLC analysis of the pumped electrolyte.High degrees of glycerol conversion were achieved under the applied laminar flow conditions using 0.1 M glycerol and 1 M KOH in water and a flow rate of 5μL min^(–1).Conversion and selectivity were found to depend on the catalyst loading,which determined the catalyst layer thickness and roughness.The highest loading of 210μg cm^(–2)resulted in 73%conversion and a higher formate selectivity of almost 80%,which is ascribed to longer residence times in rougher films favoring readsorption and C–C bond scission.The lowest loading of 13μg cm^(–2)was sufficient to reach 63%conversion,a lower formate selectivity of 60%,and,correspondingly,higher selectivities of C_(2)species such as glycolate amounting to 8%.Thus,only low catalyst loadings resulting in very thin films in the fewμm thickness range are suitable for reliable catalyst screening.

Metal phosphides and borides as the catalytic host of sulfur cathode for lithium–sulfur batteries

Lithium−sulfur batteries are one of the most competitive high-energy batteries due to their high theoretical energy density of _(2)600 W·h·kg^(−1).However,their commercialization is limited by poor cycle stability mainly due to the low intrinsic electrical conductivity of sulfur and its discharged products(Li_(2)S_(2)/Li_(2)S),the sluggish reaction kinetics of sulfur cathode,and the“shuttle effect”of soluble intermediate lithi-um polysulfides in ether-based electrolyte.To address these challenges,catalytic hosts have recently been introduced in sulfur cathodes to en-hance the conversion of soluble polysulfides to the final solid products and thus prevent the dissolution and loss of active-sulfur material.In this review,we summarize the recent progress on the use of metal phosphides and borides of different dimensions as the catalytic host of sulfur cathodes and demonstrate the catalytic conversion mechanism of sulfur cathodes with the help of metal phosphides and borides for high-en-ergy and long-life lithium-sulfur batteries.Finally,future outlooks are proposed on developing advanced catalytic host materials to improve battery performance.

Mechanical Properties and Fracture Mechanism of Boron Carbide-Lanthanum Boride Composite

The properties of boron carbide-lanthanum boride composite material prepared by hot pressed sintering method was tested, and lanthanum boride as a sintering aid for boron carbide was investigated. The result shows that the hardness of boron carbide-lanthanum boride increases with the increasing content of lanthanum boride. When the content of the lanthanum boride is 6%, the hardness reaches its supreme value of 31.83 GPa, and its hardness is improved nearly 20.52% compared to monolithic boron carbide. The content of the lanthanum boride does not greatly affect flexibility strength, however, it gives much effect on fracture toughness. The curve of fracture toughness likes the form of saw-toothed wave as the content of lanthanum boride increases in the test. When the content of the lanthanum boride is 6%, the fracture toughness reaches its supreme value of 5.14 MPa·m 1/2, which is improved nearly 39.67% compared with monolithic boron carbide materials. The fracture scanning electric microscope analysis of boron carbide-lanthanum boride composite material shows that, with the increase of the content of lanthanum boride, the interior station of monolithic boron carbide is changed. The crystallite arrangement is so compact that pores disappear gradually. The main fracture way of boron carbide-lanthanum boride composite material is intercrystalline rupture, while the transcrystalline rupture is minor, which is in accordance with fracture mechanism of ceramic material. It indicates that this change of fracture mode by the addition of lanthanum boride gives rise to the improvement of the fracture toughness.

Elastic, thermodynamic, electronic, and optical properties of recently discovered superconducting transition metal boride NbRuB:An ab-initio investigation

The elastic, thermodynamic, electronic, and optical properties of recently discovered and potentially technologically important transition metal boride NbRuB, are investigated using the density functional formalism. Both generalized gradient approximation （GGA） and local density approximation （LDA） are used for optimizing the geometry and for estimating various elastic moduli and constants. The optical properties of NbRuB are studied for the first time with different photon polarizations. The frequency （energy） dependence of various optical constants complement quite well the essential features of the electronic band structure calculations. Debye temperature of NbRuB is estimated from the thermodynamical study. All these theoretical estimates are compared with published results, where available, and discussed in detail. Both electronic band structure and optical conductivity reveal robust metallic characteristics. The NbRuB possesses significant elastic anisotropy. Electronic features, on the other hand, are almost isotropic in nature. The effects of electronic band structure and Debye temperature on the emergence of superconductivity are also analyzed.

Corrosion and wear properties of TB2 titanium alloy borided by pack boriding with La_(2)O_(3)

To improve the surface performance of TB2 alloy,pack boriding was performed at 1100℃ for 20 h with 4 wt.%La_(2)O_(3).The composition and thickness of boride layer and corrosion and wear properties of borided TB2 alloy were measured.The results show that La_(2)O_(3) can promote the growth,continuity,and compactness of boride layer,and the length of TiB whisker increases from 16.80 to 21.84μm.The reason is that La_(2)O_(3) can react with B to form La−B active groups and further to improve the growth of the boride layer.The wear and corrosion resistances of TB2 alloy are enhanced by boriding with La_(2)O_(3).The wear mechanisms are adhesive wear and abrasive wear for unborided and borided TB2 alloys,respectively,and the corrosion mechanism is changed from local corrosion(unborided TB2 alloy)to uniform corrosion(borided TB2 alloy).

TEM OBSERVATION OF NUCLEATION AND GROWTH OF BORIDE DURING BORONIZATION OF STEEL 20 AND INFLUENCE OF PRIOR DEFORMATION

The TEM observation on the single-side thinned specimens was made of the nucleation and growth of boride during boronization for steel 20 and the influence of prior room temperature deformation.The results of X-ray diffraction and electron probe microstructure analysis show that only Fe_2B formed in the surface layer of specimens at the beginning of boronization;the atomic concentration of B in the surface layer increased with the increase of deformation monotonously;and the segregation of B atoms in the dislocation cells hindered the recovery and recrystallization of the deformed structure of the matrix and accelerated the nucleation and growth of boride in the surface layer.

First-principles calculation of structural and thermodynamic properties of titanium boride

The equilibrium lattice parameters, electronic structure, bulk modulus, Debye temperature, heat capacity and Gibbs energy of TiB and TiB2 were investigated using the pseudopotential plane-wave method based on density functional theory (DFT) and the improved quasi-harmonic Debye method. The results show that the total density of states (DOS) of TiB2 is mainly provided by the orbit hybridization of Ti-3d and B-2p states, and the total DOS of TiB is mainly provided by the hybrids bond of Ti-3d and B-2p below the Fermi level and Ti—Ti bond up to the Fermi level. The Ti—B hybrid bond in TiB2 is stronger than that in TiB. Finally, the enthalpy of formation at 0 K, heat capacity and Gibbs free energy of formation at various temperatures were determined. The calculated results are in excellent agreement with the available experimental data.

THE INTERFACE OF TERNARY-BORIDE-BASED HARD CLADDING MATERIAL

The interfacial microstructure of ternary-boride-based hard cladding material (YF-2) has been studied using scanning electron microanalyser (SEM), X-ray diffraction (XRD) and energy disperse spectroscopy (EDS). Results show that there are chemical reactions and elements diffusion in the interfacial zone, which make the interface bonding well and bonding strength ideal at the interface. The results gotten by studying of crack produced by Vickers indentation technique in the interfacial zone show that it is difficult to produce crack in the interface, the crack length in the cladding layer is longer than that to the interface, the crack which propagate to the interface stops at the interface rather than propagates along the interface. This suggests negligible residual stresses have developed because of thermal expansion mismatch. The bonding strength of the interface is 550MPa, which has been gotten by cutting test. The result gotten by analyzing the fracture surface shows that the fracture occurs at the side of cladding layer, which confirms that the bonding strength at the interface is higher than that in the cladding layer.

Synthesis of niobium borides by powder metallurgy methods using Nb_(2)O_(5), B_(2)O_(3) and Mg blends

Niobium boride powders having NbB, NbB2 and Nb3B4 phases in various amounts and single phase NbB powders were successfully synthesized by using powder metallurgy methods from related metal oxide raw materials in the presence of a strong reducing agent. Nb2O5, B2O3 and Mg powder blends were milled at room temperature by a high-energy ball mill for different time. Subsequently, undesired MgO phase was removed from the milled powders by HCl leaching to constitute NbB?NbB2?Nb3B4 as final products and they were subjected to an annealing process at 1500 °C for 4 h to observe probable boride transformation. Characterization was carried out by XRD, DSC, PSA, SEM/EDX, TEM and VSM. The effects of milling time (up to 9 h) on the formation, microstructure and thermal behavior of the final products were investigated. Reduction reaction took place after milling stoichiometric powder blends for 2 h. Nano-sized NbB?NbB2?Nb3B4 powders in high purity were obtained in the absence of any secondary phase and any impurity via mechanochemistry by milling for 5 h and leaching with 4 mol/L HCl. After annealing, pure and nano-sized NbB?NbB2?Nb3B4 powders transformed to a single NbB phase without leaving behind NbB2 and Nb3B4 phases.

Morphology and growth mechanism of borides in Ti-48Al+B alloys

The morphology and growth mechanism of borides in Ti 48Al+(0.2%～0.8%)B (mole fraction) alloys were investigated. The results show that TiB 2 phase are all flakes with width <0.5 μm and aspect ratio >100 in alloys containing 0.2% and 0.5%B, respectively, but there are a few hexagonal blocky borides with habit planes of (0001) and {1010} type besides flakes in the alloy containing 0.8%B. Flake borides are the products of irregular eutectic reactions growing coupled with matrix and blocky borides are primary TiB 2 phases growing unconstrained in melt.