Ternary Borides Research Articles

Crystallization of CoWB ternary boride in nickel-based metallic glass

The crystallization kinetics of CoWB ternary boride were investigated through non-isothermal differential scanning calorimetry experiments, using a Ni-based metallic glass precursor as the starting material. The effects of isothermal heat treatment temperature on the phase evolutions were also systematically studied. The results showed that the melt crystallization and glass crystallization behaviors of the alloy differ from each other. The continuous heating transformation diagram plotted from non-isothermal analyses is consistent with the results of isothermal heat treatments. A broad ternary boride precipitation zone was demonstrated, involving the gradual precipitation of CoWB crystals. Avrami exponent values for the early crystallization stage showed that the crystallization mechanism of CoWB is governed by the interface-controlled three-dimensional growth mechanism, and nucleation rate is high. As the crystallization progresses, a diffusion-controlled growth occurs and the nucleation rate decreases. This study offers insights into the heat treatment of CoWB-reinforced nickel matrix nanocomposites, benefiting future research and industrial production processes.

Accelerated Exploration of Empty Material Compositional Space: Mg-Fe-B Ternary Metal Borides.

Borides are a family of materials with valuable properties for various applications. Their diverse structures and compositions, yet disparity in the constituent chemical elements for the known compounds, give elemental substitutions for prototypes great potential for material discovery. To explore uncharted material compositional space, we develop a workflow that joins high-throughput crystal structure prediction and automated diffraction pattern matching to discover new compounds with significant prediction and synthesis hurdles. Utilizing the workflow, we explore the empty Mg-Fe-B ternary compositional space, previously uncharted largely due to the immiscibility of Mg and Fe, as a paradigm. A total of 275 ternary boride prototypes are classified, using which we predict 23 (158) stable and metastable ternary phases within 50 (200) meV/atom above the convex hull. We identify Gd2(FeB)7-type Mg2Fe7B7 and ZrCo3B2-type MgFe3B2 to match previously unsolved experimental powder X-ray diffraction (PXRD) patterns. The discovered Mg2Fe7B7 and related channeled structures feature mismatched Mg and (FeB) sublattice periods, for which we conduct structural analyses with respect to the PXRD. They are predicted to exhibit exceptionally fast superionic transport of Mg and outstanding electrochemical performance, which serve as post-Li-ion battery candidate electrode materials. This result opens a new avenue for borides' potential applications as electrode materials and fast ionic conductors. This work also portrays the map and landscape of ternary metal borides with similar chemical environments. With high efficiency, the prototype- and PXRD-assisted crystal structure prediction workflow opens a new avenue for exploring various material compositional spaces across the periodic table.

Predicting potential hard materials in Nb[sbnd]B ternary boride: First-principles calculations

To identify potential superhard materials, we conducted a comprehensive theoretical investigation of the thermodynamic and kinetic stability, mechanical properties, electronic structure, Debye temperatures and melting point of sixteen ternary transition metal borides NbTMBx (x = 1, 2, 4 and TM = Ti, V, Fe, Co, Ni, Zr, Ru, Hf, W, Os) using first-principles methods. Our findings indicate that, with the exception of NbFeB, NbRuB, and NbWB, all other borides exhibit both thermodynamic and kinetic stability. Notably, NbTiB4, NbVB4, NbZrB4 and NbHfB4 demonstrate superior hardness and enhanced resistance to deformation, with NbTiB4 showing an impressive hardness value of 40.84 GPa, positioning it as a promising candidate for superhard materials. Both NbVB4 and NbTiB4 have very high Debye temperatures and melting points and can be used in high temperature environments. We further explored the mechanical properties of NbTiB4 at elevated temperatures by employing a combination of first-principles and quasi-static methods. Our analysis reveals that the elastic constants and moduli of NbTiB4 decrease with increasing temperature. Additionally, bonding analysis indicates that all NbB ternary borides exhibit hybridization involving metallic, ionic, and covalent interactions, resulting in the formation of exceptionally strong covalent bonds between boron atoms.

Influence of laser remelting on the microstructure and properties of Mo2FeB2 ternary boride coatings prepared by laser cladding

This study investigated the impact of laser remelting on the microstructure and properties of Mo₂FeB₂ coatings on AISI 1045 steel substrate. Different laser remelting powers were applied to pre-deposited Mo₂FeB₂ coatings. The cross-sectional morphology, phase composition, microstructure, microhardness, residual stress, fracture toughness, and wear resistance of the coatings were systematically analyzed. Compared to the untreated coatings, the remelted coatings exhibited reduced height and significantly refined microstructure. The primary phase observed in the coating was Mo₂FeB₂, accompanied with minor phases such as Cr₃C₂. Optimal microhardness (1209.4 HV0.5), fracture toughness (14.5 MPa·m1/2), and wear rate (5.4× 10−5 mm3/N·m) were achieved at a remelt power of 1200 W. Additionally, the residual stress in the coatings decreased with increasing power, reaching a minimum of 268 MPa at 1500 W. The wear mechanism transitioned from adhesive wear to abrasive wear with increasing remelting power. These findings highlight the beneficial effects of laser remelting in enhancing the performance of Mo₂FeB₂ coatings for industrial applications.

Intermetallic Compounds Mo2 TMB2 (TM: Fe, Co, Ni) for Hydrogen Evolution Reaction

Due to rising energy demand, renewable energy sources integrated processes have gained great interest in the recent years. Water electrolysis powered with renewable energy have potential to contribute to the development of sustainable hydrogen economy enormously. Despite the fact that “green” hydrogen is produced in the water electrolyzers with eco-friendly product O2, the excess energy input still hinders this technology to replace the fossil fuel-based technologies. Even with tremendous attempts and considerable contribution to the electrocatalyst development/optimization/improvement over last decades, there is a continued massive endeavor on the way of noble-metal based catalyst replacement for oxygen evolution reaction (OER) as well as for hydrogen evolution reaction (HER). From this point of view, transition metal-containing intermetallic compounds with well-defined electronic and crystal structures, are considered as promising electrocatalysts or precursors for them [1, 3]. Up to now, Mo-Ni and Mo-B systems have been explored for the hydrogen evolution reaction, and noticeable HER activities have been demonstrated for the binary compounds in these systems [4-6].The chemical behavior of ternary borides Mo2FeB2, Mo2CoB2 and Mo2NiB2 under hydrogen evolution (HER) reactions is investigated. Material synthesis and electrode manufacturing include the arc melting of elements in 2:1:2 atomic ratio, homogenization annealing at 1300-1400 °C and densification of grinded powder into cylindrically shaped electrodes via spark plasma sintering (SPS). The electrochemical measurements are carried out in 1M KOH and ambient conditions. Electrocatalytic activity and stability are monitored with cyclic voltammetry (CV) and 2-hour chronopotentiometry (CP) measurements performed at reducing current density of 10 mA cm-2, which are considered as conditions of standard benchmarking HER experiment. Furthermore, long-term stability of HER activity at elevated reducing current densities such as 50, 100, 200 mA cm-2 are essential to prove the preserved catalytic performance under harsh reaction conditions. For the comprehensive pre- and post-characterization of the electrode materials, bulk and surface-sensitive techniques are utilized.The pristine Mo2FeB2, Mo2CoB2 and Mo2NiB2 in HER region outperform their constituent TM components and indeed, their HER activity is close to that of the state-of-art Pt catalyst (Figure). During short-term CP experiment, Mo2NiB2 and Mo2FeB2 show continuing activation during the measurement, whereas Mo2CoB2 maintained its stability. Energy dispersive X-ray analysis (EDXS) of electrochemically treated areas indicate an enrichment in Fe, Co and Ni due to the noticeable leaching of Mo into electrolyte. Also, chemical analysis via ICP-OES reveals only Mo among all three constituent elements in the exploited electrolyte solution.As a conclusion, Mo2 TMB2 intermetallic compounds show outstanding HER activity and its stability over 2h of CP with respect to corresponding reference materials. Long-term chronopotentiometry in alkaline media were carried out and will be extensively presented. Figure. HER activity of Mo2 TMB2 (TM: Fe, Co, Ni) with respect to elemental references Fe, Co, Ni and state-of-art Pt. Inlets: Backscattered secondary electron images after 2h CP, including energy dispersive X-ray (EDXS) analysis results.

Synthesis, Characterization, and Magnetocaloric Properties of the Ternary Boride Fe2AlB2 for Caloric Applications.

The ternary transition metal boride Fe2AlB2 is a unique ferromagnetic "MAB" phase that demonstrates a sizable magnetocaloric effect near room temperature-a feature that renders this material suitable for magnetic heat pump devices (MHP), a promising alternative to conventional vapor compression technology. Here, we provide a comprehensive review of the material properties of Fe2AlB2 (magnetofunctional response, transport properties, and mechanical stability) and discuss alloy synthesis from the perspective of shaping these materials as porous active magnetic regenerators in MHPs. Salient aspects of the coupled magnetic and structural phase transitions are critically assessed to elucidate the fundamental origin of the functional response. The goal is to provide insight into strategies to tune the magnetofunctional response via elemental substitution and microstructure optimization. Finally, outstanding challenges that reduce the commercial viability of Fe2AlB2 are discussed, and opportunities for further developments in this field are identified.

Synthesis and radiation damage tolerance of Mo0.75W0.25AlB solid solution for nuclear fusion reactor applications

MAB phases (M = transition metal, A = aluminium (Al), B = boron (B)), a new family of nano-laminated ternary transition metal borides with an excellent combination of functional and structural properties, are currently being investigated as potential radiation shielding materials in nuclear fusion reactors. Here, we report the fabrication of a solid solution MAB phase Mo0.75W0.25AlB (Mo - molybdenum, W - tungsten), in the form of dense and high purity pellets, synthesised for the first time using a reactive hot-pressing method. The shielding and irradiation damage properties of the material were also evaluated. Monte Carlo N-Particle (MCNP) calculations showed that W doping in the MoAlB phase is likely to enhance the shielding capacity against neutrons and gamma rays of different energies. The experimental damage tolerance of Mo0.75W0.25AlB to silicon ion (Si+) irradiation indicated that this solid solution compound has a high resistance to crack formation and other radiation damage effects compared to that of pure MoAlB. Thermal annealing of the amorphous Mo0.75W0.25AlB layer formed by irradiation showed that the damaged structure easily recrystallizes at high temperatures, completely returning to the virgin state. The results show that this solid solution should be considered as a promising candidate material for radiation shielding components.

Study on the Infrared and Raman spectra of Ti3AlB2, Zr3AlB2, Hf3AlB2, and Ta3AlB2 by first-principles calculations

In this paper, the crystal geometry, electronic structure, lattice vibration, Infrared and Raman spectra of ternary layered borides M3AlB2 (M = Ti, Zr, Hf, Ta) are studied by using first principles calculation method based on the density functional theory. The electronic structure of M3AlB2 indicates that they are all electrical conductors, and the d orbitals of Ti, Zr, Hf, and Ta occupy most of the bottom of the conduction band and most of the top of the valence band. Al and B have lower contributions near their Fermi level. The lightweight and stronger chemical bonds of atom B are important factors that correspond to higher levels of peak positions in the Infrared and Raman spectra. However, the vibration frequencies, phonon density of states, and peak positions of Infrared and Raman spectra are significantly lower because of heavier masses and weaker chemical bonds for M and Al atoms. And, there are 6 Infrared active modes A2u and E1u, and 7 Raman active modes, namely A1g, E2g, and E1g corresponding to different vibration frequencies in M3AlB2. Furthermore, the Infrared and Raman spectra of M3AlB2 were obtained respectively, which intuitively provided a reliable Infrared and Raman vibration position and intensity theoretical basis for the experimental study.

Unveiling a Family of Dimerized Quantum Magnets, Conventional Antiferromagnets, and Nonmagnets in Ternary Metal Borides.

Dimerized quantum magnets are exotic crystalline materials where Bose-Einstein condensation of magnetic excitations can happen. However, known dimerized quantum magnets are limited to only a few oxides and halides. Here, we unveil 9 dimerized quantum magnets and 11 conventional antiferromagnets in ternary metal borides MTB4 (M = Sc, Y, La, Ce, Lu, Mg, Ca, and Al; T = V, Cr, Mn, Fe, Co, and Ni), where T atoms are arranged in structural dimers. Quantum magnetism in these compounds is dominated by strong antiferromagnetic (AFM) interactions between Cr (Cr and Mn for M = Mg and Ca) atoms within the dimers, with much weaker interactions between the dimers. These systems are proposed to be close to a quantum critical point between a disordered singlet spin-dimer phase, with a spin gap, and the ordered conventional Néel AFM phase. They greatly enrich the materials inventory that allows investigations of the spin-gap phase. Conventional antiferromagnetism in these compounds is dominated by ferromagnetic Mn (Fe for M = Mg and Ca) interactions within the dimers. The predicted stable and nonmagnetic (NM) YFeB4 phase is synthesized and characterized, providing a scarce candidate to study Fe dimers and Fe ladders in borides. The identified quantum, conventional, and NM systems provide a platform with abundant possibilities to tune the magnetic exchange coupling by doping and study the unconventional quantum phase transition and conventional magnetic transitions. This work opens new avenues for studying novel magnetism in borides arising from spin dimers and establishes a theoretical workflow for future searches for dimerized quantum magnets in other families of materials.

Crystal Structure, Microhardness and Thermal Expansion of Ternary TaIr2B2 Boride

Crystal Structure, Microhardness and Thermal Expansion of Ternary TaIr2B2 Boride

High-Throughput Screening for Boride Superconductors.

A high-throughput screening using density functional calculations is performed to search for stable boride superconductors from the existing materials database. The workflow employs the fast frozen-phonon method as the descriptor to evaluate the superconducting properties quickly. Twenty-three stable candidates were identified during the screening. The superconductivity was obtained earlier experimentally or computationally for almost all found binary compounds. Previous studies on ternary borides are very limited. Our extensive search among ternary systems confirmed superconductivity in known systems and found several new compounds. Among these discovered superconducting ternary borides, TaMo2B2 shows the highest superconducting temperature of ∼12 K. Most predicted compounds were synthesized previously; therefore, our predictions can be examined experimentally. Our work also demonstrates that the boride systems can have diverse structural motifs that lead to superconductivity.

Mechanical effects of Cr and V substitutions in AlFe2B2 by first-principles calculations

MAB phase AlFe2B2 has attracted a lot of attention as a ternary transition metal boride with layered structure due to its near-room temperature magneto-caloric effect (MCE), composed of earth-abundant elements and other properties. In this work the electronic structure, chemical bonding characteristics, mechanical stability, elastic properties, and elastic anisotropy of AlFe2B2-based compounds (borides) have been investigated using first-principles calculations based on density functional theory (DFT). The substitution effect of transition metals (TM) Cr and V in AlFe(2-x)TMxB2 (x = 0–1), (TM = Cr, V) compounds have been investigated. It was determined that all the elements added instead of the removed Fe element in the borides increased the mechanical properties such as hardness, brittleness, and isotropy. Moreover, it has been observed that hardness, brittleness, and isotropy increase with the increasing amount of the fourth alloying element. In AlFe(2-x)TMxB2, it has been observed that for x = 0.25 and 0.5 values, V causes an increase in stiffness more than Cr; however, for x = 1, while the increase in Cr continues to have an effect, a reverse trend is observed for V. Additionally, it has been observed that an increase in isotropy is significantly more influenced by Cr than by V. Among borides, it has been determined that AlFeCrB2 exhibits the highest elastic moduli (bulk, shear, and Young's modulus), hardness, and isotropy.

Nontrivial Topological Phases in Ternary Borides M2XB2 (M=W, Mo; X=Co, Ni)

The nontrivial band topologies protected by certain symmetries have attracted significant interest in condensed matter physics. The discoveries of nontrivial topological phases in real materials provide a series of archetype materials to further explore the topological physics. Ternary borides M2XB2 (M = W, Mo; X = Co, Ni) have been widely investigated as the wear-resistant and high-hardness materials. Based on first-principles calculations, we find the nontrivial topological properties in these materials. Taking W2NiB2 as an example, this material shows the nodal line semimetal state in the absence of spin-orbit coupling. Two types of nodal lines appear near the Fermi level simultaneously. One is protected by the combined space-inversion and time-reversal symmetry, and the other is by the mirror symmetry. Part of these two-type nodal lines form nodal chains. When spin-orbit coupling is included, these nodal lines are fully gapped and the system becomes a strong topological insulator with nontrivial Z 2 index (1;000). Our calculations demonstrate that a nontrivial spin-momentum locked surface Dirac cone appears on the (1¯10) surface. We also find that other isostructural ternary borides Mo2NiB2, Mo2CoB2, and W2CoB2 possess similar topological band structures. Therefore, our work not only enriches the understanding of band topology for ternary borides, but also lays the foundation for the further study of topological phases manipulation and potential spintronic applications in realistic materials.

Synthesis and characterization of a remarkable ternary boride: Mo2NiB2

In this communication, we report the synthesis of predominantly single phase Mo2NiB2 by pressureless reactive sintering. XRD analysis showed the samples were ≥95% pure. Both computational and experimental results showed the structure and space group to be orthorhombic and 71: Immm, respectively. Computational results showed Mo2NiB2 has superior mechanical properties as compared to ternary borides like MoAlB, WAlB and Cr2AlB2. As a representative example, the bulk modulus of Mo2NiB2 is 299.5 GPa, outperforming the range of 209.2–228.2 GPa observed in MAB phases. With experimental hardness of 12.0 ± 1.48 GPa and compressive strength of 2469.5 ± 84.6 MPa, Mo2NiB2 outperformed ternary borides like MoAlB, Fe2AlB2 and Mn2AlB2. Magnetic measurements by vibrating sample magnetometer showed Mo2NiB2 to be diamagnetic with minor ferromagnetism which was attributed to residual Ni in the samples.

Low temperature controllable synthesis of transition metal and rare earth borides mediated by molten salt

Transition meal and rare earth borides have been subjected to extensive investigations because of their unique structures, superior properties and diverse applications. Conventional methods for their syntheses suffer from various drawbacks. So several alternative approaches have been explored. Among them, the so-called ‘molten salt synthesis (MSS)’ technique has proved promising. Over the past 10–15 years, it has been used to prepare a range of transition metal and rare earth borides. In this paper, the main results from these studies are reviewed. Initially, the relevant background on metal borides and their conventional synthesis methods are introduced, followed by the main principles/mechanisms of MSS. The following three sections provide an overview of the main work on MSS of binary and ternary borides, boride solid solutions, and boride-based composite powders. Then, two newly modified MSS approaches are presented. Finally, the main issues covered in this paper are summarised, and future prospects considered.

Crystal structure, microhardness and thermal expansion of ternary TaIr2B2 boride

The ternary TaIr2B2 boride was prepared by the reaction between iridium and TaB2 powders. It was shown that a choice in favor of any crystal structure of TaIr2B2 boride using only X-ray powder diffraction analysis and single-crystal XRD is rather difficult to make. The DFT calculations were carried out to predict the energetically preferred crystal structure of TaIr2B2. The 11B solid-state NMR spectrum of TaIr2B2 was recorded for the first time. A combination of diffraction and spectroscopic methods, as well as theoretical calculations, allowed us to make clear choice in favor of the triclinic space group P-1 for the crystal structure of TaIr2B2. The Vickers microhardness value for TaIr2B2 was found to be 17.9 ± 2.3 GPa, and the ternary TaIr2B2 boride can be considered a hard material. Therefore, the family of hard ternary boride phases got a new member. The coefficients of thermal expansion of TaIr2B2 measured by in situ high-temperature XRD analysis are independent of temperature along the a and b axes, but the CTE along the c axis deviates noticeably at elevated temperatures. The findings for the new ternary TaIr2B2 boride are of interest for the rational design of complex structural materials containing Ta–Ir–B-based components and prediction of their high-temperature behavior. Further research into this ternary boride as well as other iridium-containing ternary borides will provide a tool to solve the problems faced by high-temperature materials science.

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.

Soft Chemistry of Hard Materials: Low-Temperature Pathways to Bulk and Nanostructured Layered Metal Borides.

Conspectus"Synthesis by design" is often considered to be the primary goal of chemists who make molecules and materials. Synthetic chemists usually have in mind a target they want to make, and they want to be able to design a pathway that can get them to that target as quickly and efficiently as possible. Chemists who synthesize refractory solids, which have melting points above 1000 °C and are often chemically inert at these high temperatures, have access to only a small number of synthetic strategies due to the need to overcome solid-state diffusion, which is the rate-limiting step in such reactions. The use of extremely high temperatures to facilitate diffusion among two or more refractory solids, which precedes any chemical reaction that must occur, generally drives the system to form only the product that is the most thermodynamically stable-the global minimum on an energy landscape-for a certain combination of elements. When trying to target a different product in the same system, one generally cannot rely on thermally driven reactions. Lower-temperature reactions that side step this diffusion limitation can succeed where high temperatures fail by providing access to local minima on an energy landscape. These local minima represent metastable phases that are primed for synthesis, but only if an appropriate pathway and set of reactions can be identified. It is therefore important to develop and understand low-temperature, or "soft", chemical reactions in "hard" refractory systems. These reactions allow us to apply the retrosynthetic framework that molecular chemists rely on to systems where chemists have not previously had such control over reactions, reactivities, and metastable product formation.In this Account, we discuss the development of soft chemical reactions of hard materials in the context of a class of layered, refractory metal borides that are precursors to an emerging family of two-dimensional nanomaterials. Layered ternary metal boride phases such as MoAlB have layers of metal borides, which are chemically unreactive, interleaved with layers of aluminum, which are reactive. Some of the interlayer aluminum can be deintercalated at room temperature in dilute aqueous sodium hydroxide, transforming stable MoAlB into destabilized MoAl1-xB. Mild thermal treatment of submicrometer grains of this destabilized MoAl1-xB sample allows it to traverse the energy landscape and crystallize as Mo2AlB2, a metastable compound. Further thermal treatment transforms Mo2AlB2 into a Mo2AlB2-alumina nanolaminate and ultimately mesoporous MoB, all through continued traversing of the energy landscape using mild chemical and thermal treatments. Similar topochemical manipulations, which maintain structure but change composition, are emerging for other MAB phases and are opening the door to new types of metastable compounds and nanostructured materials in traditionally refractory systems.

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.

Prediction of Van Hove singularity systems in ternary borides

A computational search for stable structures among both α and β phases of ternary ATB4 borides (A = Mg, Ca, Sr, Ba, Al, Ga, and Zn, T is 3d or 4d transition elements) has been performed. We found that α-ATB4 compounds with A = Mg, Ca, Al, and T = V, Cr, Mn, Fe, Ni, and Co form a family of structurally stable or almost stable materials. These systems are metallic in non-magnetic states and characterized by the formation of the localized molecular-like state of 3d transition metal atom dimers, which leads to the appearance of numerous Van Hove singularities in the electronic spectrum. The closeness of such singularities to the Fermi level can be easily tuned by electron doping. For the atoms in the middle of the 3d row (Cr, Mn, and Fe), these singularities led to magnetic instabilities and magnetic ground states with a weakly metallic or semiconducting nature. Such states appear as non-trivial coexistence of the different spin ladders formed by magnetic dimers of 3d elements. These magnetic states can be characterized as an analog of the spin glass state. Experimental attempts to produce MgFeB4 and associated challenges are discussed, and promising directions for further synthetic studies are formulated.