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Journal of Alloys and Compounds
Elsevier Science S.A.
Journal of Alloys and Compounds

Elsevier Science S.A.

0925-8388

Journal of Alloys and Compounds/Journal Journal of Alloys and CompoundsSCIISTPEI
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    First-principles calculation on effects of oxygen vacancy on α-MnO2 and β-MnO2 during oxygen reduction reaction for rechargeable metal-air batteries

    Rittiruam M.Buapin P.Saelee T.Khajondetchairit P....
    7页
    查看更多>>摘要:? 2022 Elsevier B.V.MnO2 is widely applied as oxygen reduction reaction (ORR) electrocatalysts in different metal-air batteries (MABs). Enhancing the ORR activity of MnO2-based catalysts is necessary for improving the performance of MABs. Defect-engineering of catalyst materials is a key approach for enabling the high performance of ORR. Here, the defect-engineering of α-MnO2 (211) and β-MnO2 (110) by oxygen vacancy (OV) is investigated using the first-principles density functional theory calculation. The geometric structure, adsorption, electronic conductivity, and oxygen reduction reaction (ORR) activity are studied. As a result, the OV induces the geometric structure that the Mn–Mn and Mn–O distances are closer when the catalysts lose the oxygen atom(s) on the top-layer surfaces. The presence of OV not only enhances the adsorption energy of *OOH, *O, and *OH, but also increases the electronic conductivity analyzed via the electron transfer. The Bader charge analysis demonstrates that the Mn(IV) can be altered to Mn(III) by the electron accumulation from OV. The volcano plot of ORR overpotential indicates that having the excess OV concentration on MnO2 surfaces cannot enhance the ORR activity. The excellent activity is yielded by 12.50 % OV α-(211) and 66.66 % OV β-(110) with the ORR overpotential of 0.31 V and 0.60 V, respectively. The results demonstrate that Ov is an essential parameter defining the existence of Mn(III) and Mn(IV) on the surface of MnO2-based catalysts. The optimal ratio of Mn(IV):Mn(III) is in challenge developing the α-MnO2 and β-MnO2 electrocatalyst cathode for metal-air batteries. This study provides a guideline for developing the potential cathode catalyst for MABs, used for harvesting energy.

    Heterogeneous cobalt-iron phosphide nanosheets formed by in situ phosphating of hydroxide for efficient overall water splitting

    Yang Y.Kong C.Zhou Q.Yang J....
    13页
    查看更多>>摘要:? 2022 Elsevier B.V.Transition metal phosphides (TMPs) have emerged as one of the most promising electrocatalysts toward water decomposition because of exceptional catalytic properties and abundant reserves. Herein, we successfully construct an unique CoP3/Fe2P nanosheet catalyst grown on Ni foam (CoP3/Fe2P@NF NSs) via a successive solvothermal-phosphating strategy for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). It should be emphasized that abundant heterointerfaces and lots of nanopores are formed by in-situ phosphating CoFe layered double hydroxides (CoFe-LDHs) precursor. Specifically, the redistribution of electrons at heterogeneous interfaces provides more active sites for reactant molecules or intermediates, and abundant nanopores on the nanosheets facilitate escape of resulting gas, thus releasing active sites in time. Density functional theory (DFT) calculation also proves that CoP3-Fe2P heterointerfaces can further optimize hydrogen adsorption energy (ΔGH*) to effectively reduce free energy barrier. Thus, the CoP3/Fe2P@NF-2 catalyst presents extraordinary electrocatalytic performance towards HER and OER with overpotentials of 81 mV and 236 mV at 10 mA cm?2. As an encouraging result, it provides a low voltage of 1.53 V at 20 mA cm?2 and satisfactory cycling stabilization of over 28 h, comparable to most reported catalysts. This work affords a promising approach for synthesis of binary and above transition metal phosphides.

    Mass stopping power and nuclear shielding behavior of lead borate glasses: Influence of gamma irradiation on physical properties

    Sallam O.I.Ezz-Eldin F.M.Madbouly A.M.
    14页
    查看更多>>摘要:? 2022 Elsevier B.V.Four glassy systems with dissimilar PbO ratios were synthesized by the melting method. Raman scattering was used to study the chemical bonds inside the glass structures and follow the chemical changes occurring inside their networks after using the glasses in a radiation field. The glass samples are based on several tetrahedral and triangular groups where in BO3 is predominant. The energy gap of each sample was calculated from two different equations extracted from absorption and transmission measurements as ETauc and ETrans, respectively. Also, chemical durability has been studied to show the stability of these glasses against acidic environmental effect and followed by SEM images. Our findings showed that radiation effect on the prepared samples did not cause significant variations of structural and optical characteristics, however, increasing PbO concentrations resulting in enhancement of several radiation attenuation competencies. This study presented a comprehensive study of the radiation shielding properties of lead borate glass by assessing the effectiveness of proton, electron, neutron, and gamma shielding. Mass stopping power (ψp) and projected range (PR) values were calculated for proton particles (H1) using SRIM Monte Carlo simulation code and its subroutine TRIM, which predicts the radiation damage and atomic displacements per atom (dpa), while the ESTAR program was used to calculate ψe and the continuous slowing down approximation (CSDA) range for electrons. Furthermore; the findings estimate the excess lifetime cancer risk% for radiation workers behind the glass shields. Also, the glass with the lowest PbO content has the highest ΣR value, whereas the sample with the highest PbO content has the highest MAC value of gamma rays.

    Exploration of concentration-reliant optical and luminescence aspects of Sm3+: B2O3-Gd2O3-Li2O-Na2O-LiF glasses for color displays and visible lasers utilization

    Lee D.-E.Yoon J.Park T.Lakshminarayana G....
    17页
    查看更多>>摘要:? 2022 Elsevier B.V.In this work, for seven compositions of 0.1–2.0 mol% Sm3+-doped transparent borate-rich glasses (prepared utilizing a quick and facile melt-quenching process), optical and visible fluorescence traits combined with luminescence decay patterns have been inspected and analyzed thoroughly. By X-ray diffraction, the amorphous phase has been clarified. Absorption spectra displayed distinctive peaks of Sm3+ ion in ultraviolet, visible, and infrared spectral regions. Relying on absorption and fluorescence spectra, for all Sm3+: glasses, J-O (Judd-Ofelt) analysis has been conducted to compute J-O parameters Ωλ (λ = 2, 4, 6) from experimental oscillator strengths, and using such parameters, radiative aspects like transition probabilities, branching ratios, and radiative decay times of 4G5/2 metastable state to 6H11/2, 6H9/2, 6H7/2, and 6H5/2 levels have been estimated. Ω2 reduced continually as Sm2O3 content increased from 0.1–2.0 mol%, hinting at improved symmetry and ionicity between Sm3+ ions and related ligands. Four luminescence bands centered at 565 nm, 602 nm, 648 nm, and 710 nm ascribed to transitions from 4G5/2 →6H5/2, 6H7/2, 6H9/2, and 6H11/2 levels sequentially are obtained under intense λexci. = 401 nm. In all emission peaks, the reddish-orange one (602 nm) is identified to be very intense in all glasses. All fluorescence bands’ intensity increased up to 0.5 mol% Sm3+ doping level and above 0.5 mol% doping content, intensity reduced regularly owing to the concentration quenching effect caused by the ET (energy transfer) via CR (cross-relaxation) channels among Sm3+ ions. CIE (Commission Internationale de l′éclairage) coordinates, CCT (correlated color temperature), dominant wavelength, and color purity have been derived from emission spectra of all investigated samples, and derived CIE (x, y) and CCT values are located in the CIE plot's reddish-orange light region, signifying such glasses potential for color displays and orange light-emitting diodes. As CCT< 3200 K, all samples could be categorized as “warm” light sources. Further, 4G5/2 level decay profiles exhibited single and double exponential characters at lower (0.1 and 0. 25 mol% Sm3+) and higher (? 0.25 mol% Sm3+) doping contents accordingly for deducing τexp (experimental decay time). Here τexp of 4G5/2 state (λexci. = 401 nm, λemi. = 602 nm) gradually decreased with an increase in Sm3+ content from 0.1 m to 2.0 mol%. Non-exponential decay curves are well fitted to the Inokuti–Hirayama model for S = 6, implying that the ET process is of dipole-dipole nature for Sm-Sm ions. Later, effective bandwidth, stimulated emission cross-section, gain bandwidth, and optical gain have been calculated for all Sm3+ ion fluorescence transitions in studied glasses. In all samples, possessing lesser CR rates and higher quantum efficiency, 0.1 mol% Sm3+: glass could be opted for producing effective visible lasing action upon violet excitation.

    FeCo nanoalloys encapsulated in N-doped carbon nanofibers as a trifunctional catalyst for rechargeable Zn-air batteries and overall water electrolysis

    Yang W.Guo J.Ma J.Wu N....
    7页
    查看更多>>摘要:? 2022 Elsevier B.V.Developing low-cost, high-efficiency and durable trifunctional electrocatalysts for enhancing the speed of oxygen reduction, oxygen evolution and hydrogen evolution reactions (ORR, OER and HER) is critical for expanding the industrial production and the commercial application of rechargeable Zn-air batteries and water electrolysis, but it still exists as a tremendous challenge. Herein, FeCo nanoalloys embedded into N-doped carbon nanofibers was prepared as a superior trifunctional catalyst for ORR, OER and HER by a universal and facile method. Under the synergistic effect of FeCo nanoalloys and N-doped carbon nanofibers, the Fe, Co/N-C catalyst exhibits half-wave potential of 0.86 V for ORR, and overpotentials of 388 mV and 249 mV at 10 mA·cm?2 for OER and HER, respectively. What's more, the Zn-air battery based on Fe, Co/N-C catalyst displayed a considerable open-circuit voltage of 1.5 V and a continuous cycle life span of 210 h. Moreover, this catalyst was also used as the sole catalyst in overall water splitting to show excellent performance. This work provides an effective way to design efficient and durable multifunctional electrocatalysts, which will facilitate the development of high-performance multifunctional catalysts and their application in renewable energy applications.

    Embedding anatase TiO2 nanoparticles into holely carbon nanofibers for high-performance sodium/lithium ion batteries

    Yao M.Li L.Yao T.Wang H....
    10页
    查看更多>>摘要:? 2022 Elsevier B.V.Titanium dioxide (TiO2) has been considered as a promising anode material for alkaline ion batteries (AIBs), yet the low electrical conductivity and sluggish reaction kinetics have restricted its practical applications, while rational structure design can significantly overcome these drawbacks. Herein, we report a one-step fabrication of ultrafine anatase TiO2 nanoparticles within holely carbon nanofibers (denoted as A-TiO2 @HCNFs) via a facile electrospinning method and subsequent annealing treatment. The chemical reaction between TEOS (Si(OC2H5)4) and PVDF ((CH2CF2)n) in the precursor induces the generation of numerous holes (via 4HF + SiO2 = SiF4↑+ 2 H2O) during the carbonization process by annealing in Ar at 800 °C, leading to the formation of holely structure and the suppression of the anatase-to-rutile phase transformation. When employed as anode materials for AIBs, the A-TiO2 @HCNFs exhibit a high sodium storage capacity of 206.8 mAh g?1 at 1.0 A g?1 after 500 cycles and a superior rate performance of 188.4 mAh g?1 at 5.0 A g?1, and a lithium storage capacity is 354.0/233.9 mAh g?1 at 0.2/1.0 A g?1 after 100/500 cycles with an excellent rate performance of 145.6 mAh g?1 at 5.0 A g?1. The superior electrochemical performance is related to the unique structure with integration of ultrafine anatase TiO2 nanoparticles and holely carbon nanofibers, which bring many advantages including improved electrical conductivity, sufficient reaction sites and robust structure stability.

    High performance and exchange coupling in magnetization reversal of sintered (Nd,Dy)-Fe-B magnets

    Li Z.-B.Zhang Z.Fu Y.-Z.Wei L....
    5页
    查看更多>>摘要:? 2022 Elsevier B.V.Improving the coercivity in sintered Nd-Fe-B magnets would sacrifice the remanence and the energy product. In this work it develops a method of preparing the composite (Nd,Dy)-Fe-B magnets to enhance the coercivity with a slighter decrease of remanence. The high performance (Nd,Dy)-Fe-B magnets were prepared via adding Dy-Fe-B into Nd-Fe-B powders in blending, followed by compacting and sintering. The addition of Dy-Fe-B powders gave rise to the enhancement of coercivity in the sintered magnets. The investigation of thermal activation indicates that the fluctuation field in thermal activation doesn't obey the law of increasing with the coercivity. The grains of Dy-Fe-B crystal phase coexist in (Nd,Dy)-Fe-B magnets, which could increase the domain wall size by exchange coupling and decrease the fluctuation field in magnetization reversal. Some of Dy atoms diffuse into the grain outer-layer of Nd2Fe14B crystal phase, the grain boundary structure is probably optimized, the anisotropy increases at grain shell, and so the domain wall size would be reduced, leading to an increase of the fluctuation field. Though their effects of the exchange coupling and the anisotropy increasing are opposite on the changes of the domain wall size and fluctuation field, they are beneficial to improve the nucleation field in magnetization reversal, and the coercivity increases significantly in the sintered magnets. Since Dy-Fe-B powders mainly evolve into the main phase of RE2Fe14B crystal instead of the intergranular phase, the mass fraction of ferromagnetic phase doesn't decrease evidently. Owing to the exchange coupling effect, the core-shell morphology of grains and the no remarkable increase in the amount of intergranular phase, the high performance with high energy product of 46.6 MGOe and high coercivity of 20.5 kOe could be obtained in the sintered (Nd,Dy)-Fe-B composite magnets.

    Study of the role of P doping on microstructure and magnetic properties of Nd2Fe14B/α-Fe nanocomposite magnets

    Li H.Zhang H.Xia A.Fu K....
    6页
    查看更多>>摘要:? 2022 Elsevier B.V.In the present work, the Nd9Fe85B6?xPx (x = 0–0.3) magnets were prepared via melt rapid quenching method. The P addition greatly improved the microstructure and magnetic properties. The study shows that the P addition increased the nucleation resistance of α-Fe, and hindered the precipitation of the α-Fe phase. The distribution of P in the Nd9Fe85B5.9P0.1 permanent alloys was characterized by the three-dimensional atom probe (3DAP) technique. Experimental results demonstrated that the P element is mainly concentrated at the grain boundary, inhibiting the growth of soft and hard magnetic crystals. The maximum energy product (BH)max of 20.0 MGOe and coercivity Hci of 6.34 kOe were obtained with the P content at x = 0.1, these values were larger than those of Nd9Fe85B6 alloys, with (BH)max = 17.7 MGOe and Hci = 5.61 kOe. The improvements of magnetic properties originate from the enhanced domain-wall-pinning strength and exchange coupling between the soft and hard phases.

    Atomic-scale and optical investigation of nanostructured Er disilicates in silica

    Guehairia S.Demoulin R.Pareige P.Talbot E....
    8页
    查看更多>>摘要:? 2022 Elsevier B.V.The optical and structural properties of Er-doped Silicon oxide based thin films elaborated by RF magnetron sputtering were investigated as a function of annealing treatment. Atom Probe Tomography and Transmission electron microscopy were used to analyze the position of rare-earth ions as well as the phase separation occurring in the layer in order to provide a complete picture of the nanostructure. The emission properties of Er3+ ions were investigated using cathodoluminescence (CL) spectroscopy. The high doping level of Er ions in silicon oxide matrix leads to a phase decomposition of pure SiO2 and Er2Si2O7 phases with a nanostructure which is influenced by the annealing treatment. It results on different emission intensities in ultraviolet or infrared ranges. The relationship between the nanostructuration observed and the optical properties is discussed in regards of annealing treatment.

    Carbon spheres prepared by amino acid-catalyzed resorcinol-formaldehyde polymerization for supercapacitors

    Chen A.Yao H.Zhang J.Du J....
    8页
    查看更多>>摘要:? 2022 Elsevier B.V.Carbon spheres (CS) have been widely used in supercapacitor due to their uniform structure and high surface area. The final properties of CS are affected by both the synthesis conditions and the preparation of precursors. Herein, a simple and green method to catalyze resorcinol/formaldehyde polymerization with catalysis of amino acids was proposed. As the reaction progressed, the amino acid molecules were consumed through the interaction with resorcinol, indicating that it can successfully catalyze the resin polymerization. The L-arginine catalyzed CS shows favorable characteristics for electrochemical energy storage, such as high specific surface area (416 m2 g?1) and high pore volumes (0.24 cm3 g?1). As the electrode material of supercapacitors, it has high specific capacitance of 235 F g?1 at 1 A g?1, excellent rate performance and long-term stability in 6 M KOH As an electrode material, after 10,000 cycles of testing, it can still retain 97.46 % of the initial capacity.