Building Fe atom–cluster composite sites using a site occupation strategy to boost electrochemical oxygen reduction

The high-temperature pyrolysis process for preparing M–N–C single-atom catalyst usually results in high heterogeneity in product structure concurrently contains multiscale metal phases from single atoms(SAs),atomic clusters to nanoparticles.Therefore,understanding the interactions among these components,especially the synergistic effects between single atomic sites and cluster sites,is crucial for improving the oxygen reduction reaction(ORR)activity of M–N–C catalysts.Accordingly,herein,we constructed a model catalyst composed of both atomically dispersed FeN4 SA sites and adjacent Fe clusters through a site occupation strategy.We found that the Fe clusters can optimize the adsorption strength of oxygen reduction intermediates on FeN4 SA sites by introducing electron-withdrawing–OH ligands and decreasing the d-band center of the Fe center.The as-developed catalyst exhibits encouraging ORR activity with halfwave potentials(E1/2)of 0.831 and 0.905 V in acidic and alkaline media,respectively.Moreover,the catalyst also represents excellent durability exceeding that of Fe–N–C SA catalyst.The practical application of Fe(Cd)–CNx catalyst is further validated by its superior activity and stability in a metalair battery device.Our work exhibits the great potential of synergistic effects between multiphase metal species for improvements of singleatom site catalysts.

A first-principles study of site occupancy and interfacial energetics of an H-doped TiAl-Ti_3 Al alloy

We investigate the site occupancy and the interfacial energetics of TiAl-Ti3Al binary-phase system with H using a first-principles method. H energetically prefers to occupy the Ti-rich octahedral interstitial site because H prefers to bond with Ti rather than with Al. The occupancy tendency of H in the binary phase TiAl-Ti3Al alloy from high to low is α2-Ti3Al to γ/α2 interface and 7-TiAl, because the decrease of the Ti local concentration is in the same order. We demonstrate that H can largely affect the mechanical properties of the TiAl-Ti3Al system. On the one hand, H at the interface reduces the interface energy with the H2 molecule as a reference, implying the TiAl/Ti3Al interface is stabilized. On the other hand, the ratio between the cleavage energy and the unstable stacking fault energy decreases after H-doping, indicating H will reduce the ductility of the TiAl/Ti3Al interface. Consequently, the mechanical property variation of TiA1 alloy due to the presence of H not only depends on the amount of TiAl/Ti3Al interfaces but also is related to the H concentration in the alloy.

Effects of hydrogen in a vanadium grain boundary:From site occupancy to mechanical properties

We have investigated site occupancy and mechanical properties of a vanadium (V) Σ 5(310)/[001] grain boundary (GB) with hydrogen (H) using a first-principles method. The segregation energy is calculated to be 0.29 eV for the energetically favora- ble V GB interstitial site, indicating that H energetically prefers to segregate into the V GB. We demonstrate that H can largely affect the mechanical properties of the V GB. The tensile strength and the Griffith fracture energy are reduced by approximately 13% (to 18.42 GPa) and 10% (to 1.74 J/m2) because of H segregation in comparison with that of the clean V GB, respectively. Our total energy calculations show that H acts as an embrittler to the V GB based on the Rice-Wang model. The atomic configurations and charge transfer analysis show that the segregated H weakens the surrounding interfacial V-V bonds, leading to the V GB mechanical properties degradation.

Axial electron channeling statistical method of site occupancy determination

Multibeams dynamical theory of electron diffraction has been used to calculate the fast electron thickness-integrated probability density on Ti and Al sites in the γ-TiAl phase as a function of the incident electron beam orientation along \[100\], \[110\] and \[011\] zone axes, with the effect of absorption considered. Both of the calculation and experiments show that there are big differences in electron channeling effect for different zone axes or the same axis but with different orientations, so we should choose proper zone axis and suitable incident beam tilting angles when using the axial electron channeling statistical method to determine the site occupancies of impurities. It is suggested to calculate the channeling effect map before the experiments.

Fe^(2+)SITE OCCUPANCY IN CUMMINGTONITEGRUNERITE AND ESTIMATION OF EQUILIBRIUM TEMPERATURE

One of the important applications of M?ssbauer effect in mineralogy is the measurement of cation site occupancy in minerals. The combination of M?ssbauer effect and infrared Spectrum will be a more effective method for Fe and Mg order-disorder measurement of amphibole. Some results of studies on cummingtonite-grunerite by this method

Quantitative calculation on atomic site occupation during precipitation of Ni_3(Al_(1-x)Fe_x) by microscopic phase-field study

Microscopic phase-field method was used to simulate the site occupation of a series of alloys with a stoichiometric composition of Ni75Al25?xFex (x=0, 5?10) aged at 1273 K. With the change of Fe content, quantitative calculations were made on each atomic site occupation probability (SOP) in L12-Ni3 (Al1?xFex), so as to find out the dynamic response law. The result of the study shows that, with the increase of Fe content, the Fe atom preferentially occupies the B sites (corner sites of FCC) with its SOP value being increased gradually, and the SOP of the Al atom on the B sites is greatly decreased. Meanwhile, AlNi and FeNi anti-sites form in the precipitation of L12 phase. Moreover, with the increase of Fe content, the formation of AlNi and FeNi anti-sites becomes much easier. In addition, it has been found that the instantaneous dynamic evolution of the atomic SOP is completed at the early stage of the growth of L12 phases.

Composition and temperature dependences of site occupation for Al,Cr,W, and Nb in MoSi_2

The composition and temperature dependences of site occupation for Al, Cr, W, and Nb in MSi2 are investigated by using a thermodynamics model and first principles calculations. A simple parameter measuring the substitution energy difference between Si and Mo sites reflects the nature of site occupancy. At 0 K, these elements prefer Si sites in Mo-rich and Mo sites in Si-rich, and show no site preference in stoichiometric MoSi2. At elevated temperature, the site occupation behaviors show strong dependence on both composition and temperature. Some calculated results have been certified in previous experiments.

Mechanism of Ag and Al on improving the glass forming ability of CuZr-based alloys

By a mean field theoretical computation,the equilibrium distributions of additional Ag and Al in the crystalline phase of CuZr-based alloys were determined to occupy the two sublattices of the B2 structure randomly.With the molecular dynamics technique,the effects of Ag and Al on the enthalpy difference（ΔH） between the supercooled melt and the crystalline phase were evaluated.The improved glass forming ability of Cu45Zr45Al10 and Cu45Zr45Ag10 can be attributed to their remarkably smaller ΔH than that of CuZr.The calculated diffusion coefficients are more sensitive to the atomic weight of the component atoms than to their interaction strength.As the component atom with the largest mass,the additional Ag increases the viscosity of the supercooled melt significantly and the experimentally stronger glass formation ability of Cu45Zr45Ag10 than Cu45Zr45Al10 can be well understood.

First-principles calculations of LaNi_(5-x)Sn_xH_y intermetallics and intermediate phase

The crystal and electronic structures of LaNi4.75Sn0.25 intermetallics and LaNi4.5Sn0.5Hy （y=2.0, 2.5） intermediate phase have been investigated by the fullpotential linearized augmented plane wave （FP-LAPW） method. Hydrogen occupation sites in LaNi4.5Sn0.5Hy have been determined based on Westlake＇s criterions： （1） the minimum hole radiuS is 0.04 nm; （2） the minimum H-H distance is 0.21 nm; as well as geometry optimizations and internal coordinates optimizations. We find that hydrogen atoms prefer to occupy the 12n＊, 6m, 12o, 6m＊ sites in LaNi4.5Sn0.5H2.0 and the 6m＊, 4h, 6m, 12o, 12n＊ sites in LaNi4.5Sn0.5H2.5. The specific coordinates of hydrogen atoms in LaNi4.5Sn0.5Hy are also determined. The results show that hydrogen atoms tend to keep away from tin atoms. The maximum hydrogen content decreases compared with LaNi5. The interactions between Sn and Ni with H play a dominate role in the stability of LaNi4.5Sn0.5-H system. Lattice expansion and increment of Fermi energy EF show that both Sn and H atoms decrease structural stability of these alloys.

SUBSTITUTION BEHAVIOR OF ALLOYING ELEMENTS IN INTERMETALLIC COMPOUND，TiAl

A method based on electronic structure calculation is proposed to predict the substitution behavior of elements in ordered intermetallics. The electronic structure of 20 alloying elements in TiAl is calculated using the DV-Xα cluster method The bond orders between alloying elements and surrounding atoms, Bo_Ti,Bo_Al, are used as parameters. Two lines on the Bo_Ti-Bo_Al diagram separate the elements into three groups. The elements located outside of the two lines substitute either Ti or Al atom regardless of the composition of TiAl. The substitution behavior of elements between the two lines will be affected by the Ti/Al ratio and the amount of alloying elements added Substituting sequence in multi-element alloy is discussed The prediction based on this method agrees well with the experimental results.

CRYSTAL STRUCTURE OF Y_2(Fe_(0.95)Al_(0.05))_(14)B

The site occupancies in permanent magnetic alloy Y_2(Fe_(0.95)Al_(0.05))_(14)B has been studied by means of neutron diffraction.The results from profile refinement show that Al enters the tetragonal structure of Nd_2Fe_(14)B and occupies the 4c and 8j_2 sites of the space group P4_2/mnm preferably.The relation between the site occupancies and the magnetic proper- ties is discussed preliminarily.

Multi-site occupancies and dependent photoluminescence of Ca_(9)Mg_(1.5)(PO_(4))_(7):Eu^(2+) phosphors:A bifunctional platform for optical thermometer and plant growth lighting

Herein,we demonstrate an optical thermometer based on single Eu^(2+)doped Ca_(9)Mg_(1.5)(PO_4)_7 phosphors,which were prepared by traditional solid-state reaction technique under a reduction atmosphere.Considerations on the bond length obtained by the crystal structure refinement and the dependent photoluminescence performances allow to assign the two distinct emission bands to Eu^(2+)ions occupied Cal-Ca3 and Mg2 sites.Moreover,the blue and red emitting bands perfectly match with the photosynthetic action spectrum,which can enhance the indoor plant photosynthesis.The optimal doping content of Eu^(2+)ions in this Ca_(9)Mg_(1.5)(PO_(4))_(7)system is 3 mol%.The corresponding concentration quenching effect is verified as dipole-dipole interaction with the critical distance of 3.315 nm.Furthermore,by exploiting the fluorescence intensity technique,the optical thermal resistance properties of Ca_(9)Mg_(1.5)(PO_4)_7:Eu^(2+)are identified based on the temperature dependent emission spectra in a range of 303-523 K.In detail,the maximum absolute and relative sensitivity S_(a)and S_(r)of Ca_9Mg_(1.5)(PO_(4))_(7):Eu^(2+)thermometer are as high as 0.637%/K and 0.3155 K^(-1),respectively.Consequently,the Eu^(2+)doped Ca_(9)Mg_(1.5)(PO_(4))_(7)phosphors establish a bifunctional platfo rm for both optical the rmometer and plant growth lighting via multi-site occupancies.

Luminescence Properties of Ce^(3+) in KMF_3(M=Mg,Ca,Sr,Ba) Hosts with Perovskite Structure

KMF 3(M=Mg, Ca, Sr, Ba) compounds were synthesized by solid state reaction under argon atmosphere. Their structures were determined by X ray diffraction. It belongs to cubic system with perovskite structure. The excitation and emission spectra of KMF 3∶Ce 3+ were measured. According to the characteristics of spectral structures, the occupation site of Ce 3+ is discussed.

First-principles study of multiple-site substitutions of alloying elements in Ni-based single crystal superalloys

The development of Ni-based single crystal superalloys relies heavily on the composition design with the addition of critical alloying elements,e.g.,Re and Ru.Understanding the role of alloying effects require to know the configurations of the alloying element distribution betweenγ-Ni andγ′-Ni3Al phases and among various non-equivalent sites.This work employed firstprinciples density functional theory calculations to study the preference of phase and site occupancy of 11 alloying elements including Al and transition metal elements:3d (Ti,Cr,Co,Ni),4d (Mo,Ru),and 5d (Hf,Ta,W,Re) in Ni and Ni3Al.We calculated the substitution energies of 1298 triple-site doping configurations including 286 Ni Ni Ni site doping of Ni,726 Al Ni Ni site doping,and 286 Ni Ni Ni site doping of Ni3Al with alloying elements Ni,Co,Ru,Cr,Re,Mo,W,Al,Ti,Ta,and Hf.In the dual-site and triple-site doping of Ni and Ni3Al,all studied alloying elements preferred to occupy Ni phase rather than Ni3Al phase.We found that the most stable defect complexes often contained the favorable substitutions of Al,Ti,Ta,and Hf for the Ni sites that stabilized the alloying elements doping at the other one or two nearest neighbor sites.The co-substitutions of various alloying elements at multiple sites are critical to understanding the strengthening mechanism of alloying elements in Ni-based single crystal superalloys.

Site occupancies of iron in saimaite and chevkinite

Saimaite is a new Zr-Ti silicate mineral. In this note X-ray and electron probe analyses for saimaite were carried out, and the chemical formula of saimaite was calculated. In addition, the Mossbauer effects of saimaite and chevkinite were investigated. Site occupancies

Revealing the role of site occupation in phase stability,magnetic and electronic properties of Ni-Mn-In alloys by ab initio approach

The effects of site occupation on the phase stability,martensitic transformation,and the magnetic and electronic properties of a full series of Ni-Mn-In alloys are theoretically studied by using the ab initio calculations.Results indicate that the excess atoms of the rich component directly take the sublattices of the deficient components of the Ni2Mn_(1+x)In_(1-x),Ni2-xMn_(1+x)In,and Ni_(2+x)Mn_(1-x)In alloys.Nevertheless,the mixed and indirect site occupations may coexist in the Ni_(2+x)Mn In_(1-x)system.The relevant magnetic configurations of the austenite for the four alloy systems have also been determined.The results show that,except for the austenite in the Ni2-xMn_(1+x)In alloys,which tend to be ferrimagnetic,the other alloys all present ferromagnetic austenite.Thus,the site occupation and associated magnetic states are the crucial influencing factors of the phase stability,martensitic transformation,and the total magnetic moment.The electronic structure of the austenite phase also shows that the covalent bonding plays an important role in the phase stability.The key finding of this work is both Ni2Mn_(1+x)In_(1-x)and Ni_(2+x)Mn In_(1-x)alloys serve as the potential shape memory alloys.

Site occupation and energy transfer in full color emitting phosphor Ba2Ca(BO3)2:Ce3+(K+),Eu^(2+),Mn2+

White light-emitting diodes(WLEDs)fabricated by single-phase full color emitting phosphor are an emerging solution for health lighting.The crystallographic site occupation of activators in a proper host lattice is crucial for sophisticated design of such phosphor.Here,we report a high quality white lightemitting phosphor Ba_(2)Ca(BO_(3))_(2):Ce^(3+)(K^(+)),Eu^(2+),Mn^(2+)with spectral distribution covering whole visible region.Blue light emission originates from Ce3+ions occupying preferentially Ba^(2+)site by controlling synthesis conditions.Green and red lights are obtained from Eu^(2+)occupying Ba2+(and Ca)site and Mn2+occupying Casite,respectively.In this triple-doped phosphor,strong red emission with a low concentration of Mn2+is realized by the efficient energy transfer from Ce3+and Euto Mn.Furthermore,high quality white light is accomplished by properly tuning the relative doping amount of Ce^(3+)(K^(+))/Eu^(2+)/Mn^(2+)based on efficient simultaneous energy transfer.The results indicate that Ba_(2)Ca(BO_(3))_(2):Ce^(3+)(K^(+)),Eu^(2+),Mn^(2+)is a promising white light-emitting phosphor in WLEDs application.

Effects of Alloying Elements Ti, Cr, Al, and Hf on β-Nb_5Si_3 from First-principles Calculations

The energy, lattice parameters, electronic structures, and elastic constants of the intermetallic compound β-Nb5Si3 alloyed by Ti, Cr, Al, and Hf elements are investigated using first-principles methods based on plane-wave pseudopotential theory. From the impurity forma- tion energy calculated, it is found that Ti, Cr, and Hf prefer to occupy the NbI, NbI, and NbII site, respectively, and that Al decreases the stability of β-Nb5Si3. Ti and Cr atoms reduce the c/a ratio of crystal lattices and Hf atom transf...

Explore the Possibility of Forming fcc High Entropy Alloys in Equal-Atomic Systems CoFeMnNiM and CoFeMnNiSmM

The multi-principal high-entropy alloys (HEAs) are promising new alloys.However,it is a challenge to screen out the suitable composition from the diverse combinations.Referring to the prototype AuCu 3 with AB 3-L1 2 structure,where it becomes a face-centered cubic (fcc) structure if element A and B are the same element,the site occupying tendencies of the elements and thermodynamic functions are predicted by using the sublattice model supported with first-principles total energy calculations.By considering the Gibbs energy of formation and the configurational entropy,the fcc HEAs in available literatures are examined,and the results of the quinary system with equal-atomic composition CoFeMnNiM and the hexbasic system with equal-atomic composition CoFeMnNiSmM are reported,respectively,where the element M is selected from the rest of the periodical table.When M=Cr,Zn,Ru,Rh,Pd,Re,Os,Ir,or Pt in the quinary systems CoFeMnNiM and when M=Ru,Pd,or Pt in the hexbasic systems CoFeMnNiSmM,respectively,the alloys are recommended to be potential fcc HEAs.The new approach opens a new way to mine the rich ores of HEAs.

Synthesis and characterization of oriented linked LiFePO4 nanoparticles with fast electron and ion transport for high-power lithium-ion batteries

LiFePO4 nanoparticles with different morphologies and sizes were synthesized via a solvothermal method using environmentally benign and low-cost glycerol as the surfactant. The morphology, size, and structure of the particles were found to relate closely to the concentration of glycerol. Oriented linked LiFePO4 nanorods along mostly non-[010] were obtained with the proper concentration of glycerol. The nanorods showed good electronic and ionic conductivities, resulting in superior rate capability and cycling performance. This performance was attributed to the oriented linkages along mostly non-[010], the small particle size along [010], and the occupation of Li at Fe sites. Initial discharge capacities of 162.4 mA.h.g-1 at 0.1 C and 102.1 mA.h.g-1 at 30 C were achieved, with capacity retentions after 500 cycles at 5 and 20 C of 99.5% and 93.2%, respectively. At the rate of 40 C, the solid-solution phase transition dominated during lithiation and delithiation of all samples.