Transition Metal Borides Research Articles

First-principles study of multifunctional Mn2B3 materials with high hardness and ferromagnetism.

Transition metal boride TM2B3 is widely studied in the field of physics and materials science. However, Mn2B3 has not been found in Mn-B systems so far. Mn2B3 undergoes phase transitions from Cmcm (0-28 GPa) to C2/m (28-80 GPa) and finally to C2/c (80-200 GPa) under pressure. Among these stable phases, Cmcm- and C2/m-Mn2B3s comprise six-membered boron rings and C2/c-Mn2B3 has wavy boron chains. They all have good mechanical properties and can become potential multifunctional materials. The strong B-B covalent bonding is mainly responsible for the structural stability and hardness. Comparison of the hardness of the five TM2B3s with different bonding strengths of TM-B and B-B bonds reveals a nonlinear change in the hardness. According to the Stoner model, these structures possess ferromagnetism, and the corresponding magnetic moments are almost the same as those of GGA and GGA + U (U = 3.9 eV, J = 1 eV).

Exploring the potential of MB2 MBene family as promising anodes for Li-ion batteries.

In recent years, finding high-performance energy storage materials has become a major challenge for Li-ion batteries. B-based two-dimensional materials have become the focus of attention because of their abundant reserves and non-toxic characteristics. A series of two-dimensional transition metal borides (MBenes) are reported and their electrochemical properties as anode materials for Li-ion batteries are investigated by density functional theory (DFT) calculations. The surface of MB2 possesses medium adsorption strength and diffusion energy barrier for Li atoms, which are conducive to the insertion and extraction of Li-ions during the charge/discharge process of Li-ion batteries. Herein, we explore the potential of MB2 (M = Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Fe, Co, Ni, Cu and Zn) as the anode material for LIBs. Excitingly, the Li atom can be stably adsorbed on the surface of MB2 (M = Sc, Ti, V, Nb, Mo, W) monolayers, and the theoretical capacity of the MB2 monolayer is high (521.77-1610.20 mA h g-1). The average open circuit voltage range is within 0.10-1.00 V (vs. Li/Li+). The relationship between the p-band center of the B atom and the adsorption energy of Li on the surface of MB2 is also investigated. Furthermore, it is found that the charge transfer of Li atom and metallic center in the most stable position is strongly related to the corresponding value of diffusion energy barrier. These results confirm that MB2 monolayers are promising 2D anode materials for Li-ion batteries, demonstrating the application prospects of B-based 2D materials.

Boosted Li₂CO₃ reversible conversion utilizing Cu-doped TiB MBene/graphene for Li-CO₂ batteries

Two-dimensional transition metal borides (MBenes), particularly TiB, hold promise as electrocatalysts for CO₂-related reactions. However, their bifunctional catalytic performance for reversible Li₂CO₃ conversion in Li-CO₂ batteries remains inferior to that...

Discovery of superconductivity in technetium borides at moderate pressures.

Advances in theoretical calculations have boosted the search for high-temperature superconductors, such as sulfur hydrides and rare-earth polyhydrides. However, the required extremely high pressures for stabilizing these superconductors has handicapped further implementation. Based upon thorough structural searches, we identified a series of unprecedented superconducting technetium borides at moderate pressures, including TcB (P63/mmc) with a superconducting transition temperature of Tc = 20.2 K at ambient pressure and TcB2 (P6/mmm) with Tc = 23.1 K at 20 GPa. Superconductivity in these technetium borides mainly originates from the coupling between the low-frequency vibrations of technetium atoms and the dominant technetium-4d electrons at the Fermi level. Our work therefore presents a fresh group in the family of superconducting borides, whose diversified crystal structures suggest rich possibilities in the discovery of other superconducting transition-metal borides.

Recent advances and key challenges of the emerging MBenes from synthesis to applications

AbstractTwo‐dimensional (2D) transition metal borides (MBenes) as an analog to 2D transition metal carbides/nitrides (MXenes) have been considered promising platform materials for exploring their physical and chemical properties, due to their tunable composition, excellent stability, and good conductivity. Lots of theoretical studies have predicted possible mechanical, magnetic, and catalytic properties of MBenes, which inspired their research in energy storage and conversion applications. However, a detailed review focusing on the synthesis of high‐quality MBene nanosheets and their energy‐related applications is not available. In this review, MBene with different structures and the latest developments in synthesizing high‐quality MBene nanosheets from top‐down exfoliation and down‐top chemical vapor deposition are first summarized. Then, the basic properties of MBene are investigated, including mechanical properties, metallicity, and magnetism. Next, their key applications such as hydrogen production, ammonia production, and energy storage are elaborately discussed. Finally, the future perspectives and key challenges of MBenes's synthesis and applications are briefly provided.

Ternary Lithium Nickel Boride with 1D Rapid-Ion-Diffusion Channels as an Anode for Use in Lithium-Ion Batteries.

Anode materials with high-rate performances and good electrochemical stabilities are urgently required for the grid-scale application of lithium-ion batteries (LIBs). Theoretically, transition metal borides are desirable candidates because of their appropriate working potentials and good conductivities. However, the reported metal borides exhibit poor performances owing to their lack of favorable Li+ storage sites and poor structural stabilities during long-term charging/discharging. In this work, a ternary alkali metal boride, Li1.2Ni2.5B2, which displays a high Li+ storage capacity and remarkable electrochemical stability and an excellent rate performance is studied. In contrast to conventional transition metal borides, the introduction of Li atoms facilitates the formation of 1D Ni/B-based honeycomb channels during synthesis. This Ni/B framework successfully sustains the strain during Li+ intercalation and deintercalation, and thus, the optimized Li1.2Ni2.5B2 anode exhibits an excellent cycle stability over 500 charge/discharge cycles. This electrode also exhibits superior reversible capacities of 350, 183, and 80mAhg-1 at 0.1, 1, and 5Ag-1, respectively, indicating the considerable potential of the 1D Ni/B framework as a commercially available fast-charging LIB anode.

Electronic Structure and Chemical Bonding of the First-, Second-, and Third-Row-Transition-Metal Monoborides: The Formation of Quadruple Bonds in RhB, RuB, and TcB.

Boron presents an important role in chemistry, biology, and materials science. Diatomic transition-metal borides (MBs) are the building blocks of many complexes and materials, and they present unique electronic structures with interesting and peculiar properties and a variety of bonding schemes which are analyzed here. In the first part of this paper, we present a review on the available experimental and theoretical studies on the first-row-transition-metal borides, i.e., ScB, TiB, VB, CrB, MnB, FeB, CoB, NiB, CuB, and ZnB; the second-row-transition-metal borides, i.e., YB, ZrB, NbB, MoB, TcB, RuB, RhB, PdB, AgB, and CdB; and the third-row-transition-metal borides, i.e., LaB, HfB, TaB, WB, ReB, OsB, IrB, PtB, AuB, and HgB. Consequently, in the second part, the second- and third-row MBs are studied via DFT calculations using the B3LYP, TPSSh, and MN15 functionals and, in some cases, via multi-reference methods, MRCISD+Q, in conjunction with the aug-cc-pVQZ-PPM/aug-cc-pVQZB basis sets. Specifically, bond distances, dissociation energies, frequencies, dipole moments, and natural NPA charges are reported. Comparisons between MB molecules along the three rows are presented, and their differences and similarities are analyzed. The bonding of the diatomic borides is also described; it is found that, apart from RhB(X1Σ+), which was just recently found to form quadruple bonds, RuB(X2Δ) and TcB(X3Σ-) also form quadruple σ2σ2π2π2 bonds in their X states. Moreover, to fill the gap existing in the current literature, here, we calculate the TcB molecule.

Applications, prospects and challenges of metal borides in lithium sulfur batteries

Although the lithium-sulfur (Li-S) battery has a theoretical capacity of up to 1675 mA h g−1, its practical application is limited owing to some problems, such as the shuttle effect of soluble lithium polysulfides (LiPSs) and the growth of Li dendrites. It has been verified that some transition metal compounds exhibit strong polarity, good chemical adsorption and high electrocatalytic activities, which are beneficial for the rapid conversion of intermediate product in order to effectively inhibit the “shuttle effect”. Remarkably, being different from other metal compounds, it is a significant characteristic that both metal and boron atoms of transition metal borides (TMBs) can bind to LiPSs, which have shown great potential in recent years. Here, for the first time, almost all existing studies on TMBs employed in Li-S cells are comprehensively summarized. We firstly clarify special structures and electronic features of metal borides to show their great potential, and then existing strategies to improve the electrochemical properties of TMBs are summarized and discussed in the focus sections, such as carbon-matrix construction, morphology control, heteroatomic doping, heterostructure formation, phase engineering, preparation techniques. Finally, the remaining challenges and perspectives are proposed to point out a direction for realizing high-energy and long-life Li-S batteries.

Two-Dimensional Transition Metal Boride TMB12 (TM = V, Cr, Mn, and Fe) Monolayers: Robust Antiferromagnetic Semiconductors with Large Magnetic Anisotropy.

Currently, two-dimensional (2D) materials with intrinsic antiferromagnetism have stimulated research interest due to their insensitivity to external magnetic fields and absence of stray fields. Here, we predict a family of stable transition metal (TM) borides, TMB12 (TM = V, Cr, Mn, Fe) monolayers, by combining TM atoms and B12 icosahedra based on first-principles calculations. Our results show that the four TMB12 monolayers have stable antiferromagnetic (AFM) ground states with large magnetic anisotropic energy. Among them, three TMB12 (TM=V, Cr, Mn) monolayers display an in-plane easy magnetization axis, while the FeB12 monolayer has an out-of-plane easy magnetization axis. Among them, the CrB12 and the FeB12 monolayers are AFM semiconductors with band gaps of 0.13 eV and 0.35 eV, respectively. In particular, the AFM FeB12 monolayer is a spin-polarized AFM material with a Néel temperature of 125 K. Moreover, the electronic and magnetic properties of the CrB12 and the FeB12 monolayers can be modulated by imposing external biaxial strains. Our findings show that the TMB12 monolayers are candidates for designing 2D AFM materials, with potential applications in electronic devices.

Cobalt-based transition metal boride electrocatalysts for alkaline water oxidation reactions

Cobalt-based transition metal boride electrocatalysts for alkaline water oxidation reactions

A Review of Transition Metal Boride, Carbide, Pnictide, and Chalcogenide Water Oxidation Electrocatalysts.

Transition metal borides, carbides, pnictides, and chalcogenides (X-ides) have emerged as a class of materials for the oxygen evolution reaction (OER). Because of their high earth abundance, electrical conductivity, and OER performance, these electrocatalysts have the potential to enable the practical application of green energy conversion and storage. Under OER potentials, X-ide electrocatalysts demonstrate various degrees of oxidation resistance due to their differences in chemical composition, crystal structure, and morphology. Depending on their resistance to oxidation, these catalysts will fall into one of three post-OER electrocatalyst categories: fully oxidized oxide/(oxy)hydroxide material, partially oxidized core@shell structure, and unoxidized material. In the past ten years (from 2013 to 2022), over 890 peer-reviewed research papers have focused on X-ide OER electrocatalysts. Previous review papers have provided limited conclusions and have omitted the significance of "catalytically active sites/species/phases" in X-ide OER electrocatalysts. In this review, a comprehensive summary of (i) experimental parameters (e.g., substrates, electrocatalyst loading amounts, geometric overpotentials, Tafel slopes, etc.) and (ii) electrochemical stability tests and post-analyses in X-ide OER electrocatalyst publications from 2013 to 2022 is provided. Both mono and polyanion X-ides are discussed and classified with respect to their material transformation during the OER. Special analytical techniques employed to study X-ide reconstruction are also evaluated. Additionally, future challenges and questions yet to be answered are provided in each section. This review aims to provide researchers with a toolkit to approach X-ide OER electrocatalyst research and to showcase necessary avenues for future investigation.

Effects of bias voltage on the structure, mechanical properties and tribological properties of TaBx films at elevated temperatures

Transition metal boride (TMBx) show the potential application as protective films at extreme environment due to their high hardness, but their low toughness limits reliability. In order to achieve both excellent mechanical and high wear resistances of the films, the microstructure of TaBx films deposited by magnetron sputtering were regulated by varing the substrate bias voltages. With the increase of the higher bias voltage, the B content of TaBx films decreases and the crystallinity of the TaBx films is enhanced. Meanwhile, the microstructure of TaBx films transforms from fibrous to dense columnar and then to granular structure with the increase of the bias voltage. The hardness and elastic modulue decrease then increase when the substrate bias voltage increases from 0 V to −240 V. The films exhibit a super high hardness of 86.07 GPa at the bias voltage increases of −180 V. The dislocation motion inhibited by the lattice defects lead to the super high hardness and a mild fracture toughness (KIC = 1.20 MPa m1/2) . For the high hardness and relatively moderate fracture toughness, the TaBx film deposited at a bias voltage of −180 V show a lower wear rate (∼1.86 × 10−6, ∼5.22 × 10−6 mm3/Nm) at room temperature and 600 °C. Meanwhile, the hardness (77.5GPa) and thermal stability of −180 V films were mantained after annealing.

Dandelion-like ZIF-67 supported ternary transition metal borides as efficient hydrolysis catalysts for KBH4

The development of high-efficient and low-cost catalysts is crucial for promoting KBH4 hydrolysis to produce hydrogen. Herein, ZIF-67 supported cobalt-molybdenum-nickel based boride (Co–Mo–Ni–B/ZIF-67) nanocomposites with dandelion-like morphology were designed as catalysts of KBH4 hydrolysis reaction and were synthesized via the chemical reduction process. Moreover, the element ratio and the loading amount of Co–Mo–Ni–B were optimized, and effects of KBH4 concentration, KOH concentration, and reaction temperature on catalytic performances were studied. As expected, ZIF-67 substrate avoids the agglomeration of amorphous Co–Mo–Ni–B, and the synergy between ZIF-67 and uniformly dispersed Co–Mo–Ni–B active substances accelerates hydrogen generation rate. As a result, the maximum hydrogen generation rate of 17400 mL min−1 g−1 is achieved with the optimized KOH concentration of 10% and KBH4 concentration of 6% at the reaction temperature of 30 °C. In addition, Co–Mo–Ni–B/ZIF-67 exhibits moderate durability performance with a cyclic retention rate of 51.9 % after five cycles. This dandelion-like structure design provides an idea for the development of efficient catalyst for hydrolysis of borohydrides.

Low-temperature synthesis and mechanical performance analysis of single-phase high-entropy (Ti,Cr,V,Nb,Ta)B1.9 ceramics

The structural stability of non-stoichiometric TiB1.5 was assessed using first principles calculations, followed by synthesis through the mechanical alloying method. Subsequently, TiB1.5 was combined with other transition metal borides to fabricate high-entropy ceramics (HEB1.9) consisting of multi-component transition metal borides (Ti, Cr, V, Nb, Ta)B1.9 via spark plasma sintering (SPS). The sintered bodies were prepared at various temperatures ranging from 1700 °C to 1900 °C and were subjected to characterization. Simulation results indicate that TiB1.5 exhibits a negative formation energy, signifying its stability. Experimental findings reveal that at relatively low sintering temperatures, the combined influence of temperature and pressure facilitates the diffusion of several other compounds into the TiB1.5 phase, resulting in the synthesis of a single-phase high-entropy diboride ceramic (HEDC) at 1700 °C. As the sintering temperature increases, the Vickers hardness and flexural strength of the sintered body initially increase and subsequently decrease, a trend influenced by both porosity and grain size. Concurrently, fracture toughness exhibits a pattern of decreasing, increasing, and then decreasing again. At a temperature of 1850 °C, the single-phase HEDC demonstrates peak values in Vickers hardness (23.28 GPa), fracture toughness (5.33 MPa m1/2), and flexural strength (681.39 MPa).

Excitonic effects on the optical spectra of TiB2 nanosheets

Two-dimensional (2D) transition metal borides, have recently attracted tremendous interest and become an emerging class of 2D materials due to their intriguing properties. We report systematic investigation of stability, electronic properties and optical activity of 2D-TiB2 nanosheets using first-principles calculations. By combining elastic and phonon-dispersion calculations, we substantiated the mechanical and dynamic stability of 2D-TiB2 nanosheets. Our results of elastic calculations reveal that addition of an extra layer destroys the auxetic behaviour of monolayer (ML) 2D-TiB2 with significant reduction in the brittleness. Further, based on the spin-polarised electronic structure calculations, we find that a low-dimensional metallic state of ML can be achieved by tuning the distance between the titanium and boron layers. The calculations clearly reveal that metallic nature does not destroys the auxetic behaviour of ML. Subsequently, we investigated the optical response of 2D-TiB2 nanosheets (ML and bilayer (BL)) at the level of density functional theory and many-body perturbation theory. The results obtained by solving Bethe–Salpeter equation (GW+BSE formalism) shows that excitonic effects causes a slight blue-shift in the absorption spectra of the nanosheets with ML being optically active with sharp peaks in infrared (IR) and ultraviolet (UV) regions while BL shows the reduced optical activity across wide range of photon energies spanning the near-IR to UV region. In addition, electronic polarisability of the nanosheet decreases with addition of another layer in ML 2D-TiB2. Further investigation of transition probabilities clearly indicates that the response of ML at Dirac point is tunable by spin–orbital coupling effects which makes these nanosheets promising for spintronic applications. The BL exhibits distinct electronic, and optical properties compared to ML. Our study unravels the structural, elastic, electronic, and optical properties of 2D-TiB2 nanosheets and suggests them as promising candidate for variety of optoelectronic and spintronic applications.

Phytic acid-derivative Co2B-CoPOx coralloidal structure with delicate boron vacancy for enhanced hydrogen generation from sodium borohydride

Application of transition metal boride (TMB) catalysts towards hydrolysis of NaBH4 holds great significance to help relieve the energy crisis. Herein, we present a facile and versatile metal-organic framework (MOF) assisted strategy to prepare Co2B-CoPOx with massive boron vacancies by introducing phytic acid (PA) cross-linked Co complexes that are acquired from reaction of PA and ZIF-67 into cobalt boride. The PA etching effectively breaks down the structure of ZIF-67 to create more vacancies, favoring the maximal exposure of active sites and elevation of catalytic activity. Experimental results demonstrate a drastic electronic interaction between Co and the dopant phosphorous (P), thereby the robustly electronegative P induces electron redistribution around the metal species, which facilitates the dissociation of B-H bond and the adsorption of H2O molecules. The vacancy-rich Co2B-CoPOx catalyst exhibits scalable performance, characterized by a high hydrogen generation rate (HGR) of 7716.7 mL min−1 g−1 and a low activation energy (Ea) of 44.9 kJ/mol, rivaling state-of-the-art catalysts. This work provides valuable insights for the development of advanced catalysts through P doping and boron vacancy engineering and the design of efficient and sustainable energy conversion systems.

Ultrasmall nickel boride nanoparticles supported on reduced graphene oxide as a high-performance catalyst for hydrazine electrooxidation

The direct hydrazine fuel cell is an attractive power generation technology for automotive applications. However, existing anode electrocatalysts generally suffer from low stability and problematic selectivity towards the non-Faradaic hydrazine (N2H4) decomposition. Herein, we report the fabrication of reduced graphene oxide (rGO)-supported nickel boride (Ni2B) nanocatalyst with a narrow size distribution around 1.5 nm by an ice-melting controlled NaBH4 reduction of Ni salt and graphene oxide. The chemical combination of Ni with B improves the intrinsic activity for N2H4 electrooxidation while suppressing the non-Faradaic N2H4 decomposition concurrently. Furthermore, Ni2B/rGO exhibits excellent stability with 91.4 % activity retention after 3000 cycles and a potential increment of only 13 mV after 50 h of constant-current measurement at 100 mA cm–2. Such stable performance is unprecedented for HzOR electrocatalysts. Our study presents the prospect of transition metal borides as high-performance HzOR electrocatalysts and may encourage further studies to explore their electrocatalytic applications.

Metastable phase formation in europium hexaboride on compression to 187 GPa

Transition-metal and rare-earth borides are of considerable interest due to their electronic, mechanical, and magnetic properties as well as their structural stability under extreme conditions. Here, we report on a series of high-pressure Raman and x-ray diffraction experiments on the cubic rare-earth hexaboride EuB6 to an ultrahigh pressure of 187 GPa in a diamond anvil cell. In EuB6, divalent europium ions occupy the corners of the cubic structure, which encloses a rigid boron-bonded cage. So far, no structural phase transitions have been reported, while the nanoindentation studies indicate amorphization in nanoscale shear bands during plastic deformation. Our x-ray diffraction studies have revealed that the ambient cubic phase of EuB6 shows broadening and splitting of diffraction peaks starting at 72 GPa and the broadening continuing to 187 GPa. The high-pressure phase is recovered on decompression, and the Raman spectroscopy of the recovered sample from 187 GPa shows a downward frequency shift and broadening of T2g, Eg, and A1g modes of boron octahedron. The density functional theory simulations of EuB6 at 100 GPa have identified five possible lowest energy crystal structures. The experimental x-ray diffraction data at high pressures is compared with the theoretical predictions and the role of structural distortions induced by shear stresses is also discussed.

Synthesis and Thermal Oxidation Resistance of Boron-Rich Boron-Carbide Material.

A boron-rich boron-carbide material (B4+δC) was synthesized by spark plasma sintering of a ball-milled mixture of high-purity boron powder and graphitic carbon at a pressure of 7 MPa and a temperature of 1930 °C. This high-pressure, high-temperature synthesized material was recovered and characterized by X-ray diffraction, X-ray photoelectron spectroscopy, Raman spectroscopy, Vickers hardness measurements, and thermal oxidation studies. The X-ray diffraction studies revealed a single-phase rhombohedral structure (space group R-3m) with lattice parameters in hexagonal representation as a = 5.609 ± 0.007 Å and c = 12.082 ± 0.02 Å. The experimental lattice parameters result in a value of δ = 0.55, or the composition of the synthesized compound as B4.55C. The high-resolution scans of boron binding energy reveal the existence of a B-C bond at 188.5 eV. Raman spectroscopy reveals the existence of a 386 cm-1 vibrational mode representative of C-B-B linear chain formation due to excess boron in the lattice. The measured Vickers microhardness at a load of 200 gf shows a high hardness value of 33.8 ± 2.3 GPa. Thermal gravimetric studies on B4.55C were conducted at a temperature of 1300 °C in a compressed dry air environment, and its behavior is compared to other high-temperature ceramic materials such as high-entropy transition metal boride. The high neutron absorption cross section, high melting point, high mechanical strength, and thermal oxidation resistance make this material ideal for applications in extreme environments.

Transition Metal Borides for All-in-One Radiation Shielding.

All-in-one radiation shielding is an emerging concept in developing new-generation radiation protection materials since various forms of ionizing radiation, such as neutrons and gamma rays, can occur simultaneously. In this study, we examine the ability of transition metal borides to attenuate both photon and particle radiation. Specifically, fourteen different transition metal borides (including inner transition metal borides) are selected for examination based on their thermodynamic stabilities, molecular weights, and neutron capture cross-sections of the elements they contain. Radiation shielding characteristics of the transition metal borides are computationally investigated using Phy-X/PSD, EpiXS and NGCal software. The gamma-ray shielding capabilities of the transition metal borides are evaluated in terms of the mass attenuation coefficient (μm), the linear attenuation coefficient (µ), the effective atomic number (Zeff), the half-value layer (HVL), the tenth-value layer (TVL), and the mean free path (MFP). The mass and linear attenuation factors are identified for thermal and fast neutrons at energies of 0.025 eV and 4 MeV, respectively. Moreover, the fast neutron removal cross-sections (∑R) of the transition metal borides are calculated to assess their neutron shielding abilities. The results revealed that borides of transition metals with a high atomic number, such as Re, W, and Ta, possess outstanding gamma shielding performance. At 4 MeV photon energy, the half-value layers of ReB2 and WB2 compounds were found as 1.38 cm and 1.43 cm, respectively. Most notably, these HVL values are lower than the HVL value of toxic Pb (1.45 cm at 4 MeV), which is one of the conventional radiation shielding materials. On the other hand, SmB6 and DyB6 demonstrated exceptional neutron attenuation for thermal and fast neutrons due to the high neutron capture cross-sections of Sm, Dy, and B. The outcomes of this study reveal that transition metal borides can be suitable candidates for shielding against mixed neutron and gamma radiation.