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,bim...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.展开更多
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 favorab...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.展开更多
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 oth...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.展开更多
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 wit...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.展开更多
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 a...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.展开更多
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 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.展开更多
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 c...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.展开更多
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 sta...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.展开更多
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 tha...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.展开更多
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. B...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.展开更多
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 di...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.展开更多
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 ...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.展开更多
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). Result...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.展开更多
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 p...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.展开更多
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 all...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.展开更多
The recent discovery of the novel boron-framework in boron-rich metal borides with complex structures and intriguing features under high pressure has stimulated the search into the unique boron-network in the metal mo...The recent discovery of the novel boron-framework in boron-rich metal borides with complex structures and intriguing features under high pressure has stimulated the search into the unique boron-network in the metal monoborides or boron-deficient metal borides at high pressure.Herein,based on the particle swarm optimization algorithm combined with first-principles calculations,we thoroughly explored the structural evolution and properties of TiB up to 200 GPa.This material undergoes a pressure-induced phase transition of Pnma→Cmcm→Pmmm.Besides of two known phases Pnma and Cmcm,an unexpected orthorhombic Pmmm structure was predicted to be energetically favored in the pressure range of 110.88–200 GPa.Intriguingly,the B covalent network eventually evolved from a one-dimensional zigzag chain in Pnma-TiB and Cmcm-TiB to a graphene-like B-sheet in Pmmm-TiB.On the basis of the microscopic hardness model,the calculated hardness(H_(v))values of Pnma at 1 atm,Cmcm at 100 GPa,and Pmmm at 140 GPa are 36.81 GPa,25.17 GPa,and15.36 GPa,respectively.Remarkably,analyses of the density of states,electron localization function and the crystal orbital Hamilton population(COHP)exhibit that the bonding nature in the three TiB structures can be considered as a combination of the B–B and Ti–B covalent interactions.Moreover,the high hardness and excellent mechanical properties of the three Ti B polymorphs can be ascribed to the strong B–B and Ti–B covalent bonds.展开更多
To strengthen the face-centered-cubic(FCC)type CoCrFeNi high-entropy alloy(HEA)by in-situ reinforced phase,(CoCrFeNi)_(100-x)(NbB_(2))_(x)(x=0,2,4,6,8,at.%)alloys were prepared.Phase constitution,microstructure,tensil...To strengthen the face-centered-cubic(FCC)type CoCrFeNi high-entropy alloy(HEA)by in-situ reinforced phase,(CoCrFeNi)_(100-x)(NbB_(2))_(x)(x=0,2,4,6,8,at.%)alloys were prepared.Phase constitution,microstructure,tensile mechanical properties of the alloys were studied,and the mechanisms were discussed.Results show that the microstructure of all the reinforced alloys consists of the matrix FCC phase,Laves phase,and(Cr_(3)Fe)B_(x) phase.The eutectic structure and(Cr_(3)Fe)B_(x) phases are formed in the interdendritic region,and the eutectic structure is composed of Laves and FCC phases.When x increases from 0 to 8,i.e.,with increase of Nb and B elements,the volume fraction of Laves and(Cr_(3)Fe)B_(x) phases increases gradually from 0 to 5.84%and 8.3%,respectively.Tensile testing results show that the ultimate strength of the alloys increases gradually from 409 MPa to 658 MPa,while the fracture strain decreases from 75%to 1.6%.Fracture analysis shows that the crack originates from the(Cr_(3)Fe)B_(x) phase.The CoCrFeNi alloys are mainly strengthened by the second phase(Laves phase and boride phase).展开更多
In recent years,transition metal borides(TMBs)have attracted much attention because they are considered as potential superhard materials and have more abundant crystal structures compared with traditional superhard ma...In recent years,transition metal borides(TMBs)have attracted much attention because they are considered as potential superhard materials and have more abundant crystal structures compared with traditional superhard materials.So far,however,no superhard materials have been found in TMBs.A large number of structures and potential new properties in TMBs are induced by the various hybridization ways of boron atoms and the high valence electrons of transition metals,which provide many possibilities for its application.And most TMBs have layered structures,which make TMBs have the potential to be a two-dimensional(2D)material.The 2D materials have novel properties,but the research on 2D TMBs is still nearly blank.In this paper,the research progress of TMBs is summarized involving structure,mechanical properties,and multifunctional properties.The strong covalent bonds of boron atoms in TMBs can form one-dimensional,twodimensional,and three-dimensional substructures,and the multiple electron transfer between transition metal and boron leads to a variety of chemical bonds in TMBs,which are the keys to obtain high hardness and multifunctional properties of TMBs.Further research on the multifunctional properties of TMBs,such as superconductors,catalysts,and high hardness ferromagnetic materials,is of great significance to the discovery of new multifunctional hard materials.展开更多
Using the evolutionary methodology for crystal structure prediction,we have predicted the orthorhombic Cmcm and Pnma phases for ScB_(4).The earlier proposed Cr B_(4)^(-),Fe B_(4)^(-),Mn B_(4)^(-),and Re P_(4)^(-)type ...Using the evolutionary methodology for crystal structure prediction,we have predicted the orthorhombic Cmcm and Pnma phases for ScB_(4).The earlier proposed Cr B_(4)^(-),Fe B_(4)^(-),Mn B_(4)^(-),and Re P_(4)^(-)type structures for ScB_(4)are excluded.It is first discovered that the Cmcm phase transforms to the Pnma phase at about 18 GPa.Moreover,both phases are dynamically and mechanically stable.The large bulk modulus,shear modulus,and Young's modulus of the two phases make it an optimistic low compressible material.Moreover,the strong covalent bonding nature of ScB_(4)is confirmed by the ELF analysis.The strong covalent bonding contributes greatly to its stability.展开更多
In this paper, density functional computations have been applied to the structural, elastic and electronic properties of ternary transition metal diborides Re0.5Ir0.5B2, Re0.5Tc0.5B2, Os0.5W0.5B2 and Os0.5Ru0.5B2 in h...In this paper, density functional computations have been applied to the structural, elastic and electronic properties of ternary transition metal diborides Re0.5Ir0.5B2, Re0.5Tc0.5B2, Os0.5W0.5B2 and Os0.5Ru0.5B2 in hexagonal （P63/mmc） and orthorhombic （Pmmn） structures with both local density approximation and generalized gradient approximation. LDA gives smaller lattice parameters and larger elastic moduli than GGA. Both results show that the hexagonal ones are more stable than orthorhombic ones except Os0.5Ru0.5B2. Moreover, the hexagonal structure has superior elastic property than orthorhombic one. Generally speaking, the calculated elastic moduli of Re0.5Ir0.5B2 and Os0.5Ru0.5B2 are smaller than those values of Re0.5Tc0.5B2 and Os0.5W0.5B2 within the same structure because of the filling of antibonding states. The relativistic effects result in weaker bonds of Tc-B （Ru-B） than those of Re-B （Os-B）. All the diborides are ultra-incompressible. Re0.5Tc0.5B2 has the largest shear modulus and it is a promising superhard diboride like Os0.5W0.5B2. The elastic properties are in high correlation with the bond strength. The shear moduli are more sensitive than the bulk moduli to the bond strength.展开更多
基金financially supported by the National Natural Science Foundation of China(No.21878063)Key Program of Shandong Provincial Natural Science Foundation(No.ZR2020KB011)+2 种基金Taishan Scholars Program of Shandong Province(No.tsqn201909119)financial support from the Flemish Government through the Moonshot cSBO project P2C(HBC.2019.0108)through long-term structural funding(Methusalem CASAS2,Meth/15/04)。
文摘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.
基金supported by the National Natural Science Foundation of China(Grant Nos.12104127 and 22131006)the Doctoral Starting Up Foundation of Hebei Normal University for Nationalities(Grant No.DR2020001)+1 种基金the Clean Energy(Carbon Peaking and Carbon Neutrality)Industry Research Institute of Chengde(Grant No.202205B090)the Natural Science Foundation of Shandong Province(Grant No.ZR2020QA060)。
文摘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.
基金financial support for the XRPD experiments (proposals nr. 20200101 and 20210215)supported by the U.S. National Science Foundation through Grant CMMI-1902069
文摘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.
基金Project(2010JK404) supported by the Education Committee Natural Science Foundation of Shaanxi Province,ChinaProjects(ZK0918,ZK0915) supported by the Baoji University of Arts and Sciences Key Research,China
文摘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.
基金supported by the National Natural Science Foundation of China(52025013,51622102)Ministry of Science and Technology of China MOST(2018YFB1502101)+1 种基金the 111 Project(B12015)the Fundamental Research Funds for the Central Universities.
文摘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.
基金Iran National Science Foundation(INSF)for supporting the research under project No.95841122.
文摘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.
文摘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.
基金financially supported by the National Natural Science Foundation of China (Nos. 51725401, 51904030, and 21935006)
文摘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.
文摘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.
文摘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.
文摘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.
基金Project(07JJ3102)supported by the Natural Science Foundation of Hunan Province,ChinaProject(k0902132-11)supported by the Changsha Municipal Science and Technology,China
文摘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.
基金supported by National Natural Science Foundation of China(No.59975054).
文摘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.
基金financially supported by“The Scientific and Technological Research Council of Turkey(TUBITAK)”with the project title of“Synthesis of Refractory Metal Borides via Three Different Production Methods from Solid,Liquid and Gas Raw Materials for Various Application Areas,Sintering,Characterization,Comparison of Process and Final Products”and with the project number of 112M470
文摘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.
文摘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.
基金supported by the National Natural Science Foundation of China(Grant No.11804031)the Scientific Research Project of Education Department of Hubei Province,China(Grant No.Q20191301)+1 种基金Youth Science Foundation of Jiangxi Province,China(Grant No.20171BAB211009)Henan Province Key Research and Development and Promotion of Special Scientific and Technological Research Project(Grant No.222102320283)。
文摘The recent discovery of the novel boron-framework in boron-rich metal borides with complex structures and intriguing features under high pressure has stimulated the search into the unique boron-network in the metal monoborides or boron-deficient metal borides at high pressure.Herein,based on the particle swarm optimization algorithm combined with first-principles calculations,we thoroughly explored the structural evolution and properties of TiB up to 200 GPa.This material undergoes a pressure-induced phase transition of Pnma→Cmcm→Pmmm.Besides of two known phases Pnma and Cmcm,an unexpected orthorhombic Pmmm structure was predicted to be energetically favored in the pressure range of 110.88–200 GPa.Intriguingly,the B covalent network eventually evolved from a one-dimensional zigzag chain in Pnma-TiB and Cmcm-TiB to a graphene-like B-sheet in Pmmm-TiB.On the basis of the microscopic hardness model,the calculated hardness(H_(v))values of Pnma at 1 atm,Cmcm at 100 GPa,and Pmmm at 140 GPa are 36.81 GPa,25.17 GPa,and15.36 GPa,respectively.Remarkably,analyses of the density of states,electron localization function and the crystal orbital Hamilton population(COHP)exhibit that the bonding nature in the three TiB structures can be considered as a combination of the B–B and Ti–B covalent interactions.Moreover,the high hardness and excellent mechanical properties of the three Ti B polymorphs can be ascribed to the strong B–B and Ti–B covalent bonds.
基金supported by the National Natural Science Foundation of China(No.51825401).
文摘To strengthen the face-centered-cubic(FCC)type CoCrFeNi high-entropy alloy(HEA)by in-situ reinforced phase,(CoCrFeNi)_(100-x)(NbB_(2))_(x)(x=0,2,4,6,8,at.%)alloys were prepared.Phase constitution,microstructure,tensile mechanical properties of the alloys were studied,and the mechanisms were discussed.Results show that the microstructure of all the reinforced alloys consists of the matrix FCC phase,Laves phase,and(Cr_(3)Fe)B_(x) phase.The eutectic structure and(Cr_(3)Fe)B_(x) phases are formed in the interdendritic region,and the eutectic structure is composed of Laves and FCC phases.When x increases from 0 to 8,i.e.,with increase of Nb and B elements,the volume fraction of Laves and(Cr_(3)Fe)B_(x) phases increases gradually from 0 to 5.84%and 8.3%,respectively.Tensile testing results show that the ultimate strength of the alloys increases gradually from 409 MPa to 658 MPa,while the fracture strain decreases from 75%to 1.6%.Fracture analysis shows that the crack originates from the(Cr_(3)Fe)B_(x) phase.The CoCrFeNi alloys are mainly strengthened by the second phase(Laves phase and boride phase).
基金supported by the National Key Research and Development Program of China(Grant Nos.2016YFA0401503 and 2018YFA0305700)the National Natural Science Foundation of China(Grant No.11575288)+1 种基金the Strategic Priority Research Program and Key Research Program of Frontier Sciences of the Chinese Academy of Sciences(Grant Nos.XDB33000000,XDB25000000,and QYZDBSSW-SLH013)the Youth Innovation Promotion Association of the Chinese Academy of Sciences(Grant No.Y202003)。
文摘In recent years,transition metal borides(TMBs)have attracted much attention because they are considered as potential superhard materials and have more abundant crystal structures compared with traditional superhard materials.So far,however,no superhard materials have been found in TMBs.A large number of structures and potential new properties in TMBs are induced by the various hybridization ways of boron atoms and the high valence electrons of transition metals,which provide many possibilities for its application.And most TMBs have layered structures,which make TMBs have the potential to be a two-dimensional(2D)material.The 2D materials have novel properties,but the research on 2D TMBs is still nearly blank.In this paper,the research progress of TMBs is summarized involving structure,mechanical properties,and multifunctional properties.The strong covalent bonds of boron atoms in TMBs can form one-dimensional,twodimensional,and three-dimensional substructures,and the multiple electron transfer between transition metal and boron leads to a variety of chemical bonds in TMBs,which are the keys to obtain high hardness and multifunctional properties of TMBs.Further research on the multifunctional properties of TMBs,such as superconductors,catalysts,and high hardness ferromagnetic materials,is of great significance to the discovery of new multifunctional hard materials.
基金the Young Scientists Fund of the National Natural Science Foundation of China(Grant Nos.11704170 and 61705097)the Natural Science Foundation of Shandong Province,China(Grant Nos.ZR2016AP02 and ZR2016EMP01)。
文摘Using the evolutionary methodology for crystal structure prediction,we have predicted the orthorhombic Cmcm and Pnma phases for ScB_(4).The earlier proposed Cr B_(4)^(-),Fe B_(4)^(-),Mn B_(4)^(-),and Re P_(4)^(-)type structures for ScB_(4)are excluded.It is first discovered that the Cmcm phase transforms to the Pnma phase at about 18 GPa.Moreover,both phases are dynamically and mechanically stable.The large bulk modulus,shear modulus,and Young's modulus of the two phases make it an optimistic low compressible material.Moreover,the strong covalent bonding nature of ScB_(4)is confirmed by the ELF analysis.The strong covalent bonding contributes greatly to its stability.
基金supported by the National Natural Science Foundation of China (No. 20973174)973 Project (2007CB805307)
文摘In this paper, density functional computations have been applied to the structural, elastic and electronic properties of ternary transition metal diborides Re0.5Ir0.5B2, Re0.5Tc0.5B2, Os0.5W0.5B2 and Os0.5Ru0.5B2 in hexagonal （P63/mmc） and orthorhombic （Pmmn） structures with both local density approximation and generalized gradient approximation. LDA gives smaller lattice parameters and larger elastic moduli than GGA. Both results show that the hexagonal ones are more stable than orthorhombic ones except Os0.5Ru0.5B2. Moreover, the hexagonal structure has superior elastic property than orthorhombic one. Generally speaking, the calculated elastic moduli of Re0.5Ir0.5B2 and Os0.5Ru0.5B2 are smaller than those values of Re0.5Tc0.5B2 and Os0.5W0.5B2 within the same structure because of the filling of antibonding states. The relativistic effects result in weaker bonds of Tc-B （Ru-B） than those of Re-B （Os-B）. All the diborides are ultra-incompressible. Re0.5Tc0.5B2 has the largest shear modulus and it is a promising superhard diboride like Os0.5W0.5B2. The elastic properties are in high correlation with the bond strength. The shear moduli are more sensitive than the bulk moduli to the bond strength.
