Paper & Patents

Striking an optimal balance between the hydrogen storage properties and cost, while identifying a viable material capable of storing hydrogen under ambient conditions, remains a persistent challenge in the present era. AB2-type laves phase alloys have garnered significant interest due to their hydrogen storage capabilities. This work employs a strategy of utilizing inexpensive Ti to occupy either Ni or Al sites, to form Ti-rich alloys, with the aim of enhancing the hydrogen storage properties of Ti–Ni–Al alloys. We used the first-principles approach to systematically explore the structural, electronic, and hydrogen storage properties of Ti-rich ternary Laves-phase alloys. Accordingly, we investigated two Ti-rich alloys for their hydrogen storage capabilities: one with a fixed Al-composition, Ti5Ni3Al4, and the other with a fixed Ni-composition, Ti5Ni4Al3. Our investigation shows that the A2B2 tetrahedral site is the energetically stable site for the hydrogen absorption of these alloys. Specifically, Ti-rich, with fixed Ni-concentration (Ti5Ni4Al3), exhibits a higher hydrogen weight percentage than the fixed Al-concentration (Ti5Ni3Al4). Furthermore, we have included the release temperatures corresponding to the hydrogen concentration. With enhanced kinetics in Ti5Ni4Al3, we conclude that the release temperatures are within the working temperature range for fuel cell applications. Additionally, we have used a thermodynamical model to explore the pressure–composition–temperature (PCT) curves for AB2 type laves phase systems and provided a comparative analysis for the compounds under study. This study offers valuable insights for the development of cost-effective, Ti–Ni–Al hydrogen storage alloys with better hydrogen storage properties.

Half-metallic ferromagnets, conducting for one spin channel while insulating for the other, are highly desirable for spintronic applications due to 100 % spin polarization around the Fermi level. Cobalt-based half-metallic Heusler compounds have attracted enormous attention due to their large spin polarization and a high magnetic transition temperature. In the present study, we report the experimental and theoretical investigation of crystal structure and anomalous Hall effect (AHE) in half-metallic ferromagnet Co2VAl. The structural investigation of high-resolution synchrotron x-ray diffraction data reveals 10 % antisite disorder between V and Al atoms within the L21 ordered crystal structure. The scaling analysis of anomalous Hall data shows that the AHE in our system is mainly driven by the Berry curvature in the momentum space. The magnitude of experimental intrinsic anomalous Hall conductivity (AHC) due to the momentum space Berry curvature is about 44.67 ± 0.02 S/cm at 5 K, which is less than the theoretically calculated AHC for the ordered structure. Our theoretical calculations suggest that the lower AHC obtained for the present system is due to the reduced Berry curvature in the disordered case with negligible impact on half-metallicity of the system.

Accurate band gap prediction in semiconductors is crucial for materials science and semiconductor technology advancements. This paper extends the Perdew–Burke–Ernzerhof (PBE) functional for a wide range of semiconductors, tackling the exchange and correlation enhancement factor complexities within density functional theory (DFT). Our customized functionals offer a clearer and more realistic alternative to DFT+U methods, which demand large negative U values for elements like sulfur (S), selenium (Se), and phosphorus (P). Moreover, these functionals are more cost-effective than GW or Heyd–Scuseria–Ernzerhof (HSE) hybrid functional methods, therefore, significantly facilitating the way for unified workflows in analyzing electronic structure, dielectric constants, effective masses, and further transport and elastic properties, allowing for seamless calculations across various properties. We point out that such development could be helpful in the creation of comprehensive databases of band gap and dielectric properties of the materials without expensive calculations. Furthermore, for the semiconductors studied, we show that these customized functionals and the strongly constrained and appropriately normed semilocal density functional (SCAN) perform similarly in terms of the band gap.

Recent developments in the magnetization dynamics in spin textures, particularly skyrmions, offer promising new directions for magnetic storage technologies and spintronics. Skyrmions, characterized by their topological protection and efficient mobility at low current density, are increasingly recognized for their potential applications in next-generation logic and memory devices. This study investigates the dynamics of skyrmion magnetization, focusing on the manipulation of their topological states as a basis for bitwise data storage through a modified Landau–Lifshitz–Gilbert equation (LLG). We introduce spin-polarized electrons from a topological ferromagnet that induce an electric dipole moment that interacts with the electric gauge field within the skyrmion domain. This interaction creates an effective magnetic field that results in a torque that can dynamically change the topological state of the skyrmion. In particular, we show that these torques can selectively destroy and create skyrmions, effectively writing and erasing bits, highlighting the potential of using controlled electron injection for robust and scalable skyrmion-based data storage solutions.

MAX phase is a family of ceramic compounds, typically known for their metallic properties. However, we show here that some of them may be narrow bandgap semiconductors. Using a series of first-principles calculations, we have investigated the electronic structures of 861 dynamically stable MAX phases. Notably, Sc2SC, Y2SC, Y2SeC, Sc3AuC2, and Y3AuC2 have been identified as semiconductors with band gaps ranging from 0.2 to 0.5 eV. Furthermore, we have assessed the thermodynamic stability of these systems by generating ternary phase diagrams utilizing evolutionary algorithm techniques. Their dynamic stabilities are confirmed by phonon calculations. Additionally, we have explored the potential thermoelectric efficiencies of these materials by combining Boltzmann transport theory with first-principles calculations. The relaxation times are estimated using scattering theory. The zT coefficients for the aforementioned systems fall within the range of 0.5 to 2.5 at temperatures spanning from 300 to 700 K, indicating their suitability for high-temperature thermoelectric applications.

Magnetization dynamics in magnetic materials are well described by the modified semiclassical Landau-Lifshitz-Gilbert equation, which includes the magnetic damping ˆ𝜶 and the magnetic moment of inertia ̂I, both usually being tensors, as key parameters. Both parameters are material specific and physically represent the timescales of damping of precession and nutation in magnetization dynamics. ˆ𝜶 and ̂I can be calculated quantum mechanically within the framework of the torque-torque correlation model. The quantities required for the calculation are torque matrix elements, the real and imaginary parts of the Green's function, and its derivatives. Here, we calculate these parameters for the elemental magnets such as Fe, Co, and Ni in an ab initio framework using density functional theory and Wannier functions. We also propose a method to calculate the torque matrix elements within the Wannier framework. We demonstrate the effectiveness of the method by comparing it with the experiments and previous ab initio and empirical studies and show its potential to improve our understanding of spin dynamics and to facilitate the design of spintronic devices.

Employing density functional theory, we delved into the comprehensive pathways for methane oxidation on the Pd single atom supported with CeO2(111) encompassing sequential methane dehydrogenation, O2 dissociation, and oxidation processes. The introduction of a Pd atom into CeO2(111) led to a reduction in the barrier for CH4 dissociation to 0.50 eV. The methane dehydrogenation proceeded through a series of reactions: CH4 → CH3 → CH2 → CH → C, with all dehydrogenation steps being exothermic except the CH3 → CH2 step. The O2 dissociation reaction (O2 → O* + O*) is thermodynamically exothermic, with a dissociation barrier of 2.12 eV over Pd@CeO2. Subsequently, the generation of CO2 via the C* + O* and CO* + O* reactions is characterized by thermodynamically exothermic processes, with reaction energies of −1.20 and −1.01 eV, respectively. On the other hand, water production occurs through O* + H (an exothermic reaction) and OH* + H (an endothermic reaction) with reaction energies of −0.80 and +0.64 eV, respectively. These findings offer valuable insights into the potential pathways for single-atom catalysis involving transition metals supported on CeO2(111) in methane oxidation for industrial application.

Slow kinetics related to oxygen evolution reactions (OERs) are currently the main obstacle in developing effective and extremely stable oxygen electrocatalysts for alkaline water electrolysis cells. Catalysts based on spinel-structured cobalt ferrites (CoFe2O4), which have remarkable catalytic activity and quick kinetics, are highly promising OER electrocatalysts. Here, sulfur-doped cobalt ferrites nanoarrays on iron foam (S-CoFe2O4/IF) are made using an effective and simple technique based on anion–exchange reactions in order to create effective OER catalysts. These S-CoFe2O4/IF catalysts demonstrate exceptional OER activity via a topotactical transformation, wherein their Co oxide undergoes continuous cyclic voltammetry scanning to evolve into active Co oxyhydroxide (CoOOH) nanoplates while the Fe stays stable within the Fe–O component. This sulfidation, as evidenced by its electronic density of states, can induce surface reconstruction, leading to the formation of active CoOOH under OER conditions by elevating the O 2p energy level as a result of cation substitution. When sulfidation is applied to the spinel-structured CoFe2O4/IF, the total catalytic activity is greatly increased. This leads to a smaller Tafel slope and overpotential (42 mV dec−1 and 286 mV) at 0.1 A cm−2 than when CoFe2O4/IF is used as the catalyst (51 mV dec−1 and 304 mV). The relationship between activity and structure in spinel structures is explained by this work.

Electronic transport in monolayer MoS2 is significantly constrained by several extrinsic factors despite showing good prospects as a transistor channel material. Our paper aims to unveil the underlying mechanisms of the electrical and magneto-transport in monolayer MoS2. In order to quantitatively interpret the magneto-transport behavior of monolayer MoS2 on different substrate materials, identify the underlying bottlenecks, and provide guidelines for subsequent improvements, we present a deep analysis of the magneto-transport properties in the diffusive limit. Our calculations are performed on suspended monolayer MoS2 and MoS2 on different substrate materials taking into account remote impurity and the intrinsic and extrinsic phonon scattering mechanisms. We calculate the crucial transport parameters such as the Hall mobility, the conductivity tensor elements, the Hall factor, and the magnetoresistance over a wide range of temperatures, carrier concentrations, and magnetic fields. The Hall factor being a key quantity for calculating the carrier concentration and drift mobility, we show that for suspended monolayer MoS2 at room temperature, the Hall factor value is around 1.43 for magnetic fields ranging from 0.001 to 1 Tesla, which deviates significantly from the usual value of unity. In contrast, the Hall factor for various substrates approaches the ideal value of unity and remains stable in response to the magnetic field and temperature. We also show that the MoS2 over an Al2O3 substrate is a good choice for the Hall effect detector. Moreover, the magnetoresistance increases with an increase in magnetic field strength for smaller magnetic fields before reaching saturation at higher magnetic fields. The presented theoretical model quantitatively captures the scaling of mobility and various magnetoresistance coefficients with temperature, carrier densities, and magnetic fields.

Janus MXenes, a new category of two-dimensional (2D) materials, show promising potential for advances in optoelectronics, spintronics, and nanoelectronics. Our theoretical investigations not only provide interesting insights but also highlight the promise of Janus MCrCT2 (M = Ti, Mo; T = O, F, OH) MXenes for future spintronic applications and highlight the need for their synthesis. Electronic structure analysis shows different metallic and semimetallic properties: MoCrCF2 exhibits metallic property, TiCrC(OH)2 and MoCrCO2 exhibit near semimetallicity with spin polarization values of 61 and 86%, respectively, while TiCrCO2 and TiCrCF2 are completely half-metallic with 100% spin polarization at the Fermi level. All studied Janus MXenes exhibit intrinsic ferromagnetism, which is mainly attributed to the chromium (Cr) atoms, as shown by the spin density difference plots. Among them, the TiCrCO2 monolayer stands out with the highest exchange constant and ferromagnetic transition temperature (Tc). Notably, the O-terminated Janus MXenes exhibit weak perpendicular magnetic anisotropy, in contrast to the in-plane anisotropy observed for F and OH-terminated MXenes, making them particularly interesting for future spintronic applications, which we further demonstrate with micromagnetic simulation which reveal distinct current-induced switching behaviors in these Janus MXenes with different surface terminations.