Engineering the hydrogen storage properties of the perovskite hydride ZrNiH3 by uniaxial/biaxial strain

In the present work, the bonding length, electronic structure, stability, and dehydrogenation properties of the Perovskite-type ZrNiH₃ hydride, under different uniaxial/biaxial strains are investigated through ab-initio calculations based on the plane-wave pseudo-potential (PW-PP) approach. The findings reveal that the uniaxial/biaxial compressive and tensile strains are responsible for the structural deformation of the ZrNiH₃ crystal structure, and its lattice deformation becomes more significant with decreasing or increasing the strain magnitude. Due to the strain energy contribution, the uniaxial/biaxial strain not only lowers the stability of ZrNiH₃ but also decreases considerably the dehydrogenation enthalpy and decomposition temperature. Precisely, the formation enthalpy and decomposition temperature are reduced from ?67.73 kJ/mol.H₂ and 521 K for non-strained ZrNiH₃ up to ?33.73 kJ/mol.H₂ and 259.5 K under maximal biaxial compression strain of ε = ?6%, and to ?50.99 kJ/mol.H₂ and 392.23 K for the maximal biaxial tensile strain of ε = +6%. The same phenomenon has been also observed for the uniaxial strain, where the formation enthalpy and decomposition temperature are both decreased to ?39.36 kJ/mol.H₂ and 302.78 K for a maximal uniaxial compressive strain of ε = - 12%, and to ?51.86 kJ/mol.H₂ and 399 K under the maximal uniaxial tensile strain of ε = +12%. Moreover, the densities of states analysis suggests that the strain-induced variation in the dehydrogenation and structural properties of ZrNiH₃ are strongly related to the Fermi level value of total densities of states. These ab-initio calculations demonstrate insightful novel approach into the development of Zr-based intermetallic hydrides for hydrogen storage practical applications.     

State of the art advancement in rational design of g-C3N4 photocatalyst for efficient solar fuel transformation,environmental decontamination and future perspectives

Recently, the graphite based heterogeneous photocatalysts has attained tremendous research attention in various environmental applications. Among them, the graphitic carbon nitride (g-C₃N₄) is categorized as a unique solar active particle with its outstanding intrinsic properties i.e., adequate band configuration, excellent light absorptivity and thermo-physical durability, which make it highly useful and reliable for revenue transformation and ecological concerns. Considering the intrinsic potential of g-C₃N₄ in photocatalysis, so far, no report has been done in literature for its extraordinary configuration, morphological characteristics and perspective tuning for said applications. To overcome this research gap, our primary emphasis of this review regarding photocatalysis is to provide layout as well as the advancement of visible-light-fueled materials as highly stabilized and extremely effective ones for pragmatic implementation. Thus, this existing comprehensive assessment conducts a systematic survey over visible light driven non-metal novel g-C₃N₄. The major advancement of this evaluation is the fabrication of well-designed nanosized g-C₃N₄ photocatalysts with unique configurable frameworks and compositions. Furthermore, alternative techniques in order to customize the analogue band configuration and noticeable cultivation such as metal (cation), nonmetal (anion) doping, worthy metal activating, and alloy initiation with certain semiconductors are discussed in detail. In addition to this, g-C₃N₄ photocatalytic functionalities towards photocatalytic hydrogen evolution, CO₂ photoreduction, biological metal ions deterioration as well as bacterial sanitization are also presented and discussed in detail. Therefore, we believe that such a pivotal compact assessment can provide a roadmap in several perspectives on the currently underway obstacles in the innovation of effective g-C₃N₄ catalytic design processes. Moreover, this critical assessment will ultimately serve as a useful supplement in the research area of g-C₃N₄ nanosized photocatalysts and for the researchers working on its key aspects in diverse range of natural, chemistry, engineering and environmental applications.     

Self-assembled cubic-hexagonal perovskite nanocomposite as intermediate-temperature solid oxide fuel cell cathode

Self-assembly is an emerging strategy for preparing composite cathodes with good oxygen electrochemical reduction activity and congenital chemical compatibility for intermediate-temperature solid oxide fuel cell (IT-SOFC). Here we report that a self-assembled BaCo_0.6Zr_0.4O_3-δ (BZC-BC) nanocomposite is prepared through one-pot glycine-nitrate process and exhibits high cathode performance. The BZC-BC nanocomposite is composed of 62 mol% cubic perovskite BaZr_0.82Co_0.18O_3-δ (BZC) as an ionic conductor and 38 mol% hexagonal perovskite BaCo_0.96Zr_0.04O_2.6+δ (12H-BC) as a mixed ionic and electronic conductor. The BZC-BC nanocomposite has the pomegranate-like particles aggregated with a larger number of nanoparticles (50-100 nm) which greatly enlarge the three-phase boundary sites. The BZC-BC nanocomposite exhibits a thermal expansion coefficient of 12.89 × 10⁻⁶ K⁻¹ well-matched with that of Ce_0.8Gd_0.2O_3-δ (12.84 × 10⁻⁶ K⁻¹) electrolyte. The high electro-catalytic activity of BZC-BC nanocomposite cathode for oxygen reduction is reflected by the low polarization resistances of oxygen ions incorporation at cathode/electrolyte interface (0.02823 Ω cm²), oxygen species diffusion (0.03702 Ω cm²) and oxygen adsorptive dissociation (0.07609 Ω cm²) at 700 °C. The single cell with BZC-BC nanocomposite cathode achieves the maximum power density of 1094 mW cm⁻² at 650 °C and shows good stability under 25 h run.     

Effect of strain path change on the through-thickness microstructure during tantalum rolling

High purity tantalum was respectively processed by unidirectional rolling (UR) and clock rolling (CR), and the through-thickness microstructures were investigated by multiple characterization techniques including electron backscatter diffraction (EBSD), Vickers hardness (HV) and X-ray diffraction (XRD). Results show that the through-thickness stored energy distribution in CR specimens is more homogeneous than in UR specimens due to uniform texture distribution. {111} grains possess larger Schmid factors and the corresponding Schmid factor difference ratio than {100} grains, indicating the activation of uniserial slipping in {111} grains, which leads to inhomogeneous deformation and higher stored energy. Besides, X-ray line profile analysis (XLPA) suggests that the stored energy of {111} grains increases successively from the surface to center layer, regardless of strain paths, due to the influence of redundant friction on the surface layers. While the occurrence of multiple slipping in {100} grains leads to homogeneous deformation and lower stored energy.     

Effects of the film thickness and poling electric field on photovoltaic performances of (Pb,La)(Zr,Ti)O3 ferroelectric thin film-based devices

The ferroelectric photovoltaic (FPV) effect obtained in inorganic perovskite ferroelectric materials has received much attention because of its large potential in preparing FPV devices with superior stability, high open-circuit voltage (V_oc) and large short-circuit current density (J_sc). In order to obtain suitable thickness for the ferroelectric thin film as light absorption layer, in which, the sunlight can be fully absorbed and the photo-generated electrons and holes are recombined as few as possible, we prepare Pb_0.93La_0.07(Zr_0.6Ti_0.4)_0.9825O₃ (PLZT) ferroelectric thin films with different layer numbers by the sol-gel method and based on these thin films, obtain FPV devices with FTO/PLZT/Au structure. By measuring photovoltaic properties, it is found that the device with 4 layer-PLZT thin film (~300 nm thickness) exhibits the largest V_oc and J_sc and the photovoltaic effect obviously depends on the value and direction of the poling electric field. When the device is applied a negative poling electric field, both the V_oc and J_sc are significantly higher than those of the device applied the positive poling electric field, due to the depolarization field resulting from the remnant polarization in the same direction with the built-in electric field induced by the Schottky barrier, and the higher the negative poling electric field, the larger the V_oc and J_sc. At a -333 kV/cm poling electric field, the FPV device exhibits the most superior photovoltaic properties with a V_oc of as high as 0.73 V and J_sc of as large as 2.11 μA/cm². This work opens a new way for developing ferroelectric photovoltaic devices with good properties.     

Synthesis,characterization and antifungal property of Ti3C2Tx MXene nanosheets

Although the antibacterial properties of MXene nanosheets containing Ti₃C₂T_x are known, their antifungal properties have not been well studied. Herein, we present for the first time a report on the antifungal properties of Ti₃C₂T_x MXene. The Ti₃C₂T_x MXene was obtained by first exfoliating MAX phase of Ti₃AlC₂ with concentrated hydrofluoric acid, then the Ti₃C₂T_x was intercalated and deliminated by ethanol treatment and ultrasonication process. The delaminated Ti₃C₂T_x MXene nanosheets (d-Ti₃C₂Tx) were characterized using field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray (EDX), X-ray diffraction spectroscopy (XRD), and Raman spectroscopy. It was found that Ti₃C₂T_x MXene was characterized by lamellar structure alternating with layers of Ti, Al and C. The EDX results revealed that the delaminated Ti₃C₂T_x MXene nanosheets were composed of Ti, C, Si, O, F, and a trace amount of Al. The XRD and Raman spectra further indicated the elimination of Al and the formation of two-dimensional Ti₃C₂T_x MXene nanosheets. The antifungal activity of the delaminated Ti₃C₂T_x MXene was determined against Trichoderma reesei using the modified agar disc method. Observation using inverted phase contrastmicroscopy revealed inhibited fungus growth with the absence of hyphae around the discs treated wtih MXene. The surrounding of the control groups without an inclusion of MXene was found with large number of hyphae and spores. In addition, the spores of the fungi treated with the samples containing d-Ti₃C₂T_x MXene nanosheets did not germinate even after 11 days of culture. The results demonstrated disruption to the hemispheric structural formation of fungi colony, inhibition of hyphae growth and cell damage for fungi grown on the d-Ti₃C₂T_x MXene nanosheets. These new findings suggest that d-Ti₃C₂T_x MXene nanosheets developed in this work could be a promising anti-fungi material.     

Comparison of co-current and counter-current flow in a bifunctional reactor containing ammonia synthesis and 2-butanol dehydrogenation to MEK

In this study, a multi-tubular thermally coupled packed bed reactor in which simultaneous production of ammonia and methyl ethyl ketone (MEK) takes place is simulated. The simulation results are presented in two co-current and counter-current flow modes. Based on this new configuration, the released heat from the ammonia synthesis reaction as an extremely exothermic reaction in the inner tube is employed to supply the required heat for the endothermic 2-butanol dehydrogenation reaction in the outer tube. On the other hand, MEK and hydrogen are produced by the dehydrogenation reaction of 2-butanol in the endothermic side, and the produced hydrogen is used to supply a part of the ammonia synthesis feed in the exothermic side. Thus, 30.72% and 31.88% of the required hydrogen for the ammonia synthesis are provided by the dehydrogenation reaction in the co-current and counter-current configurations, respectively. Also, according to the thermal coupling, the required cooler and furnace for the ammonia synthesis and 2-butanol dehydrogenation conventional plants are eliminated, respectively. As a result, operational costs, energy consumption and furnace emissions are considerably decreased. Finally, a sensitivity analysis and optimization are applied to study the effect of the main process parameters variation on the system performance and obtain the minimum hydrogen make-up flow rate, respectively.     

Reactive pulsed laser deposited N–C codoped TiO2 thin films

TiO₂ is a large bandgap chemically stable oxide useful for several applications that involve photo-activated processes, including photocatalysis, photovoltaics, photoelectrolysis, etc. However, the large band gap renders this material not a very efficient absorber of the solar spectrum. Various schemes of cation and anion doping have been utilized that reduce this deficiency to a certain extent. In this paper we present the results of N–C codoping of TiO₂ thin films deposited by a reactive pulsed laser deposition technique. These films were compared for their optical and structural properties with undoped, N doped and C doped TiO₂ films prepared by the same technique. While all samples contained polycrystalline anatase phase, varying N₂ and CH₄ partial pressures resulted in change in TiO₂ lattice parameters due to codoping. X-ray diffraction high-resolution scans show the evidence of C incorporation into TiO₂ lattice by 2θ shift in (101) reflections due to large ionic radius of C. N doping was confirmed by XPS analyses. Direct relationship between oxygen vacancies and doping concentration was established by the deconvolution of XPS peaks. Considerable bandgap reduction occurred that was measured by using UV–vis diffuse reflectance spectroscopy. Results show that reactive pulsed laser deposition is indeed a useful method for the synthesis of codoped TiO₂ thin films as bandgap reduction of ~1.00 eV via N–C codoping was successfully achieved.