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Register a new userTuning the hydrogen desorption of Mg(BH$_4$)$_2$ through Zn alloying
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We study the effect of Zn alloying on the hydrogen desorption properties of Mg(BH$_4$)$_2$ using $it{ab initio}$ simulations. In particular, we investigate formation/reaction enthalpies/entropies for a number of compounds and reactions at a wide range of temperatures and Zn concentrations in Mg$_{1-x}$Zn$_x$(BH$_4$)$_2$. Our results show that the thermodynamic stability of the resulting material can be significantly lowered through Zn alloying. We find that e.g. the solid solution Mg$_{2/3}$Zn$_{1/3}$(BH$_4$)$_2$ has a reaction enthalpy for the complete hydrogen desorption of only 25.3 kJ/mol H$_2$$-$a lowering of 15 kJ/mol H$_2$ compared to the pure phase and a corresponding lowering in critical temperature of 123 K. In addition, we find that the enthalpy of mixing is rather small and show that the decrease in reaction enthalpy with Zn concentration is approximately linear.
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Experiments of Electron Spin Resonance (ESR) were performed on Co$% ^{2+}$ substituting Zn$^{2+}$ or Mg$^{2+}$ in powder samples of Zn$_2$(OH)PO$_4$ and Mg$_2$(OH)AsO$_4$. The observed resonances are described with a theoretical model that considers the departures from the two perfect structures. It is shown that the resonance in the penta-coordinated complex is allowed, and the crystal fields that would describe the resonance of the Co$^{2+}$ in the two environments are calculated. The small intensity of the resonance in the penta-coordinated complex is explained assuming that this site is much less populated than the octahedral one; this assumption was verified by a molecular calculation of the energies of the two environments, with both Co and Zn as central ions in Zn$_2$(OH)PO$_4$.
Aluminum borohydride (Al(BH$_4$)$_3$) is an example of a promising hydrogen storage material with exceptional hydrogen densities by weight and volume and a low hydrogen desorption temperature. But, unfortunately, its production of diborane (B$_2$H$_6$) gases upon heating to release the hydrogen restricts its practical use. To elucidate this issue, we investigate the properties of a number of metal borohydrides with the same problem and find that the electronegativity of the metal cation is not the best descriptor of diborane production. We show that, instead, the closely related formation enthalpy is a better descriptor and we find that diborane production is an exponential function thereof. We conclude that diborane production is sufficiently suppressed for formation enthalpies of $-$80 kJ/mol BH$_4$ or lower, providing specific design guidelines to tune existing metal borohydrides or synthesize new ones. We then use first-principles methods to study the effects of Sc alloying in Al(BH$_4$)$_3$. Our results for the thermodynamic properties of the Al$_{1-x}$Sc$_x$(BH$_4$)$_3$ alloy clearly show the stabilizing effect of Sc alloying and thus the suppression of diborane production. We conclude that stabilizing Al(BH$_4$)$_3$ and similar borohydrides via alloying or other means is a promising route to suppress diborane production and thus develop viable hydrogen storage materials.
The Mg-Zn and Al-Zn binary alloys have been investigated theoretically under static isotropic pressure. The stable phases of these binaries on both initially hexagonal-close-packed (HCP) and face-centered-cubic (FCC) lattices have been determined by utilizing an iterative approach that uses a configurational cluster expansion method, Monte Carlo search algorithm, and density functional theory (DFT) calculations. Based on 64-atom models, it is shown that the most stable phases of the Mg-Zn binary alloy under ambient condition are $rm MgZn_3$, $rm Mg_{19}Zn_{45}$, $rm MgZn$, and $rm Mg_{34}Zn_{30}$ for the HCP, and $rm MgZn_3$ and $rm MgZn$ for the FCC lattice, whereas the Al-Zn binary is energetically unfavorable throughout the entire composition range for both the HCP and FCC lattices under all conditions. By applying an isotropic pressure in the HCP lattice, $rm Mg_{19}Zn_{45}$ turns into an unstable phase at P$approx$$10$~GPa, a new stable phase $rm Mg_{3}Zn$ appears at P$gtrsim$$20$~GPa, and $rm Mg_{34}Zn_{30}$ becomes unstable for P$gtrsim$$30$~GPa. For FCC lattice, the $rm Mg_{3}Zn$ phase weakly touches the convex hull at P$gtrsim$$20$~GPa while the other stable phases remain intact up to $approx$$120$~GPa. Furthermore, making use of the obtained DFT results, bulk modulus has been computed for several compositions up to pressure values of the order of $approx$$120$~GPa. The findings suggest that one can switch between $rm Mg$-rich and $rm Zn$-rich early-stage clusters simply by applying external pressure. $rm Zn$-rich alloys and precipitates are more favorable in terms of stiffness and stability against external deformation.
We report temperature dependent measurements of ambient pressure specific heat, magnetic susceptibility, anisotropic resistivity and thermal expansion as well as in-plane resistivity under pressure up to 20.8 kbar on single crystals of EuAg$_4$As$_2$. Based on thermal expansion and in-plane electrical transport measurements at ambient pressure this compound has two, first order, structural transitions in 80 - 120 K temperature range. Ambient pressure specific heat, magnetization and thermal expansion measurements show a cascade of up to seven transitions between 8 and 16 K associated with the ordering of the Eu$^{2+}$ moments. In-plane electrical transport is able to detect more prominent of these transitions: at 15.5, 9.9, and 8.7 K as well as a weak feature at 11.8 K at ambient pressure. Pressure dependent electrical transport data show that the magnetic transitions shift to higher temperatures under pressure, as does the upper structural transition, whereas the lower structural transition is suppressed and ultimately vanishes. A jump in resistivity, associated with the upper structural transition, decreases under pressure with an extrapolated disappearance (or a change of sign) by 30-35 kbar. In the 10 - 15 kbar range a kink in the pressure dependence of the upper structural transition temperature as well as the high and low temperature in-plane resistivities suggest that a change in the electronic structure may occur in this pressure range. The results are compared with the literature data for SrAg$_4$As$_2$.
The two-dimensional (2D) C3N has emerged as a material with promising applications in high performance device owing to its intrinsic bandgap and tunable electronic properties. Although there are several reports about the bandgap tuning of C3N via stacking or forming nanoribbon, bandgap modulation of bilayer C3N nanoribbons (C3NNRs) with various edge structures is still far from well understood. Here, based on extensive first-principles calculations, we demonstrated the effective bandgap engineering of C3N by cutting it into hydrogen passivated C3NNRs and stacking them into bilayer heterostructures. It was found that armchair (AC) C3NNRs with three types of edge structures are all semiconductors, while only zigzag (ZZ) C3NNRs with edges composed of both C and N atoms (ZZ-CN/CN) are semiconductors. The bandgaps of all semiconducting C3NNRs are larger than that of C3N nanosheet. More interestingly, AC-C3NNRs with CN/CN edges (AC-CN/CN) possess direct bandgap while ZZ-CN/CN have indirect bandgap. Compared with the monolayer C3NNR, the bandgaps of bilayer C3NNRs can be greatly modulated via different stacking orders and edge structures, varying from 0.43 eV for ZZ-CN/CN with AB-stacking to 0.04 eV for AC-CN/CN with AA-stacking. Particularly, transition from direct to indirect bandgap was observed in the bilayer AC-CN/CN heterostructure with AA-stacking, and the indirect-to-direct transition was found in the bilayer ZZ-CN/CN with AB-stacking. This work provides insights into the effective bandgap engineering of C3N and offers a new opportunity for its applications in nano-electronics and optoelectronic devices.
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