Heterofullerene C48B12-impregnated MOF-5 and IRMOF-10 for hydrogen storage: A combined DFT and GCMC simulations study

The H₂ storage properties of isoreticular metal-organic framework materials (IRMOFs), MOF-5 and IRMOF-10, impregnated with different numbers and types of heterogeneous C₄₈B₁₂ molecules were investigated using density functional theory and grand canonical Monte Carlo (GCMC) calculations. The excess hydrogen adsorption isotherms of IRMOFs at 77 K within 20 bar indicate that suitable number and type of C₄₈B₁₂ molecules play a crucial role in improving the H₂ storage properties of IRMOFs. Among the studied pure and nC₄₈B₁₂ (n = 1, 2, 4, 8) in Ci symmetry impregnating into MOF-5, at 77 K under 6 bar, MOF-5-4C₄₈B₁₂ with a 3.5 wt% and 29.9 g/L hydrogen storage density, and at 77 K under 12 bar, the pure MOF-5 with a 4.9 wt% and 31.0 g/L hydrogen storage density has the best hydrogen storage properties. Whereas, among the studied pure and nC₄₈B₁₂ (n = 1, 2, 4, 8) in S6 symmetry impregnating into IRMOF-10, IRMOF-10-8C₄₈B₁₂ always shows the best hydrogen storage properties among the pure and C₄₈B₁₂-impregnated IRMOF-10 at 77 K within 20 bar. IRMOF-10-8C₄₈B₁₂ has a 6.0 wt% and 34.6 g/L hydrogen storage density at 77 K under 6 bar, and has a 7.1 wt% and 41.4 g/L hydrogen storage density at 77 K under 12 bar. The confinement effect of IRMOFs on C₄₈B₁₂ molecules, and steric hindrance effect of C₄₈B₁₂ molecules on IRMOFs mainly affects the H₂ uptake capacity by comparing the absolute H₂ molecules in individual IRMOFs units, C₄₈B₁₂ molecules, and IRMOFs-nC₄₈B₁₂ compounds. The absolute hydrogen adsorption profiles show that eight C₄₈B₁₂ molecules impregnating into MOF-5 can exert obvious steric effects for H₂ adsorption. The saturated gravimetric and volumetric H₂ densities of IRMOF-10-8C₄₈B₁₂ higher than those of MOF-5-8C₄₈B₁₂ due to with larger free volume.     

Surface energies in high-entropy carbides with variable carbon stoichiometry

The carbon vacancy in high-entropy carbides (HECs) has a significant impact on their physical and chemical properties, yet relevant studies have still been relatively few. In this study, we investigate the surface energies of HECs with variable carbon vacancies through first-principles calculations. The results show that the surface energy of the (1 0 0) surface of the stoichiometric HECs is significantly lower than that of (1 1 1) surface. With the decrease in carbon stoichiometry, the surface energies of both (1 0 0) and (1 1 1) surfaces increase gradually, which is mainly due to the weakening of covalent bonding and the decrease of metal Hirshfeld-I (HI) charges. However, the surface energy of (1 0 0) surface increases more quickly than that of (1 1 1) surface and will exceed that of (1 1 1) surface when the carbon stoichiometry decreases to a certain extent, which is primarily attributed to the greater decrease rate of metal HI charges of (1 0 0) surface.     

A novel combustion fuel for the synthesis of nanocrystalline ZnAl2O4 particles based on the thermodynamic correlations and their structural and optical studies

ZnAl₂O₄ nanocrystalline particles were prepared using the solution combustion method using a new combustion fuel, Leucine. The prepared samples' structural, microstructural–elemental composition, and optical characteristics were investigated using XRD, SEM-EDS, and UV–Visible spectroscopy. As-synthesized ZnAl₂O₄ nanoparticles are polycrystalline, with no secondary phases, and crystallized in a cubic - spinel structure. The polycrystalline nature of the prepared sample is due to the exothermicity of fuel and oxidizer, which demonstrate that the fuel utilized (Leucine) provided adequate energy for the production of nanoparticles in their as-synthesized form, as supported by adiabatic temperature through thermodynamic calculations. The thermodynamic calculations also include a universal method to estimate the specific heat capacity at constant pressure. Furthermore, even after 2 h of calcination at 600 °C, ZnAl₂O₄ exhibits a single phase with no secondary phases, indicating the material stability and single-phase nature. The crystallinity of ZnAl₂O₄ nanoparticles was observed to increase with increasing annealing temperature. SEM micrographs of as-synthesized samples exhibit the formation of dense particles, voids, and pores in the as-synthesized sample. In addition, tiny aggregates were detected on the surface of more prominent clusters, which reduced as the calcination progressed. In addition, calcined samples exhibit a greater optical reflectance than as-synthesized samples. Tauc's graphs were used to compute the optical energy bandgap. The calculated energy band gap is redshifted to that of the bulk material. The bandgap energy decreases upon calcination, suggesting that the prepared materials have a larger crystallite size or more crystallinity. Correlations were found between the T_ad, and the structural and optical properties of the prepared samples. The findings suggest that Leucine could be used as a novel combustion fuel to produce crystalline ZnAl₂O₄ nanoparticles in their as-synthesis form.     

Transition metal atoms anchored on nitrogen-doped α-arsenene as efficient electrocatalysts for nitrogen electroreduction reaction

Electrocatalytic reduction of N₂ to NH₃ under ambient conditions, inspired by biological nitrogen fixation, is a new approach to address the current energy shortage crisis. As a result, developing efficient and low-cost catalysts is critical. The catalytic activity, catalytic mechanism, and selectivity of α-arsenene (α-Ars) catalysts anchored with various transition metal atoms and doped with different numbers of N atom were investigated for N₂ reduction reaction (NRR) in this paper. Results reveal that compared with WN₃-α-Ars which is coordinated with three N atoms, asym-WN₂As-α-Ars that coordinated with two N atoms not only exhibits high catalytic activity (U_L = ?0.36 V), but can also successfully suppress the hydrogen evolution reaction (HER). It is manifested that reducing the number of coordination atoms can promote the selectivity of the transition metal (TM) loaded N-doped arsenene catalysts. Furthermore, activity origin analyses show both the charge on 1N–NH and φ form volcano-type relationship with the limiting potential. The active center of the catalyst, which acts as the charge transporter and has the moderate ability to retrieve charges, is the most efficient in NRR. Overall, this research creates high performance NRR catalysts by varying the number of coordinating N atoms, which provides a novel idea for the development of new NRR catalysts.     

Lithiation MXene Derivative Skeletons for Wide-Temperature Lithium Metal Anodes

Lithium (Li) metal, as an appealing candidate for the next-generation of high-energy-density batteries, is plagued by its safety issue mainly caused by uncontrolled dendrite growth and infinite volume expansion. Developing new materials that can improve the performance of Li-metal anode is one of the urgent tasks. Herein, a new MXene derivative containing pure rutile TiO₂ and N-doped carbon prepared by heat-treating MXene under a mixing gas, exhibiting high chemical activity in molten Li, is reported. The lithiation MXene derivative with a hybrid of LiTiO₂-Li₃N-C and Li offers outstanding electrochemical properties. The symmetrical cell assembling lithiation MXene derivative hybrid anode exhibits an ultra-long cycle lifespan of 2000 h with an overpotential of ≈30 mV at 1 mA cm⁻², which overwhelms Li-based anodes reported so far. Additionally, long-term operations of 34, 350, and 500 h at 10 mA cm⁻² can be achieved in symmetrical cells at temperatures of −10, 25, and 50 °C, respectively. Both experimental tests and density functional theory calculations confirm that the LiTiO₂-Li₃N-C skeleton serves as a promising host for Li infusion by alleviating volume variation. Simultaneously, the superlithiophilic interphase of Li₃N guides Li deposition along the LiTiO₂-Li₃N-C skeleton to avoid dendrite growth.     

Theoretical investigation of intrinsic point defects and the oxygen migration behavior in rare earth hafnates

In this work, the composition-dependent point defect types and formation energies of RE₂Hf₂O₇ (RE = La, Ce, Pr, Nd, Pm, Sm, Eu and Gd) as well as the oxygen diffusion behavior are systematically investigated by first-principles calculations. The possible defect reactions and dominant defect complexes under stoichiometric and non-stoichiometric conditions are revealed. It is found that O Frenkel pairs are the predominant defect in stoichiometric pyrochlore hafnates. Hf-RE cation anti-site defects, accompanied by RE vacancies and/or oxygen interstitials, are stable in the non-stoichiometric case of HfO₂ excess. On the other hand, RE-Hf anti-site defects together with oxygen vacancies and/or RE interstitials are preferable in the case of RE₂O₃ excess. The energy barriers for the migration along the V_O48f - V_O48f pathway of pyrochlore hafnates were calculated to be between 0.81 eV and 0.89 eV. Based on these results, a defect engineering strategy is proposed and the pyrochlore hafnates investigated here are predicted to exhibit potential oxygen ionic conductivity.     

Elastic Properties and Stacking Fault Energies of Borides,Carbides and Nitrides from First-Principles Calculations

Owing to the excellent elastic properties and chemical stability, binary metal or light element borides, carbides and nitrides have been extensively applied as hard and low-compressible materials. Researchers are searching for harder materials all the time. Recently, the successful fabrication of nano-twinned cubic BN(Tian et al. Nature 493:385–388, 2013) and diamond(Huang et al. Nature 510:250–253, 2014) exhibiting superior properties than their twin-free counterparts allows an efficient way to be harder. From this point of view, the borides, carbides and nitrides may be stronger by introducing twins, whose formation tendency can be measured using stacking fault energies(SFEs). The lower the SFEs, the easier the formation of twins. In the present study, by means of first-principles calculations, we first calculated the fundamental elastic constants of forty-two borides, seventeen carbides and thirty-one nitrides, and their moduli, elastic anisotropy factors and bonding characters were accordingly derived. Then, the SFEs of the {111} 112 glide system of twenty-seven compounds with the space group F43 m or Fm3m were calculated. Based on the obtained elastic properties and SFEs, we find that(1) light element compounds usually exhibit superior elastic properties over the metal borides, carbides or nitrides;(2) the 5 d transitionmetal compounds(ReB_2, WB, OsC, RuC, WC, OsN_2, TaN and WN) possess comparable bulk modulus( B) with that of cBN( B = 363 GPa);(3) twins may form in ZrB, HfN, PtN, VN and ZrN, since their SFEs are lower or slightly higher than that of diamond(SFE = 277 mJ/m~2). Our work can be used as a valuable database to compare these compounds.     

Single transition metal atom catalysts on Ti2CN2 for efficient CO2 reduction reaction

Electrochemical CO₂ reduction reaction (CO₂RR) is an efficient way in the utilization of CO₂. In this work, single transition-metal (TM) atom (TM = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn) anchored on two-dimensional (2D) Ti₂CN₂ are designed for CO₂RR using density-functional-theory (DFT) calculation. We show that Ti₂CN₂ serves as an excellent substrate to support single atom catalysts (SACs), compared to Ti₂CO₂ and Ti₂CF₂. We find that the Sc, Ti and V supported on Ti₂CN₂ show high catalytic activities to produce CO with a low overpotential of 0.37, 0.27, and 0.23 eV, respectively. Differently, the Mn and Fe on Ti₂CN₂ are catalytically active for the production of HCOOH with a low overpotential of 0.32 and 0.43 eV, respectively. We further show that the negatively charged TM-Ti₂CN₂ can capture and activate CO₂ more effectively, and the catalytic activity and selectivity can be significantly tuned by injecting extra electrons.     

Mechanistic study of the effect of Ca–Sn co-doping on the microwave dielectric properties and magnetic properties of YIG

To investigate the crystal structure, electrical properties, and magnetic properties of Ca–Sn co-doped Y_3-xCa_xFe_5-xSn_xO₁₂ (x = 0.00–0.25 in steps of 0.05), solid-state reaction experiments, first principles calculations, and complex crystal bonding theoretical calculations were performed. The relative permittivity (ε_r) is strongly correlated with the average bond ionicity when Ca²⁺ is added. Furthermore, appropriate Sn⁴⁺ substitution significantly lowers the dielectric loss (tanδ_ε) associated with the lattice energy. The right amount of Ca–Sn co-doping can change the saturation magnetization (4πM_S) and improve the microscopic morphology of YIG, lowering the ferromagnetic resonance linewidth (ΔH) of YIG. The optimized microwave dielectric and magnetic properties are as follows: ε_r = 14.7, tanδ_ε = 4.15 × 10^?4, 4πM_S = 1680 G, and ΔH = 53 Oe for Y_2.8Ca_0.2Fe_4.8Sn_0.2O₁₂ sintered for 6 h at 1425 °C. Based on this material, a simple 3D model of a strip-line circulator with an insertion loss of less than 0.3 dB at each port and isolation greater than 20 dB in the 10–12 GHz range was developed, indicating the potential of the material for microwave high-frequency components such as circulators.