Enhancement of H2 adsorption on a boron-doped carbon system for hydrogen storage

We study the adsorption of the molecular hydrogen on boron-doped polypyrrole ((–C₄BH₃)_n) using first-principles density functional calculations. We find that the binding energy of H₂ molecules is slightly reduced to 0.39 eV/H₂ from 0.51 eV/H₂ as the number of adsorbed H₂ molecules increases. This is in sharp contrast to the case of boron-doped fullerenes where the binding energy is drastically reduced as the number of adsorbed H₂ molecules increases. We find that the enhancement of H₂ adsorption is due to a local charge transfer by H₂ adsorption in the B-doped polypyrrole as opposed to a delocalized charge transfer in the B-doped fullerenes. Our finding shows that B-doped carbon systems could be utilized for room temperature hydrogen storage.     

Evidence of sustained ferroelectricity in glycine sodium nitrate single crystal

The nonlinear optical single crystals of glycine sodium nitrate were grown by the slow evaporation method. XRD confirmed monoclinic structure. Thermal stability and melting point (225 °C) were investigated. The dielectric behaviour of the crystals in the frequency range 20 Hz–2 MHz at different temperatures is reported in which a ferroelectric to paraelectric phase transition at T_c = 56 °C is observed. The activation energies of GSN were found to be 3.615 eV, 0.593 eV and 0.0733 eV in three temperature regions of conductivity plot due to a hopping conduction mechanism. The crystal has shown high piezoelectric charge coefficient (d₃₃) of 16 pC/N which is nearly double of observed value for γ-glycine single crystal. The spontaneous polarization P_s at room temperature was found to be 1.489 μC/cm² at applied maximum field of 26 kV/cm (1.194 μC/cm² at 12 kV/cm) and the pyroelectric coefficient was determined to be 400 μC/m²/°C. High value of squareness parameter (1.93) makes the GSN crystal suitable for switching applications. Detailed investigations of Ferro-/Piezoelectricity were observed for the first time in glycine sodium nitrate crystals which was found to preserve the ferroelectricity even after applying an electric field much higher than the saturation electric field (12–26 kV/cm). Application of GSN crystals as sensor, high power switch gears and storage memories has been established.     

Hydrogen adsorption and storage of Ca-decorated graphene with topological defects: A first-principles study

As a candidate for hydrogen storage medium, geometric stability and hydrogen capacity of Ca-decorated graphene with topological defects are investigated using the first-principle based on density functional theory (DFT), specifically for the experimentally realizable single carbon vacancy (SV), 585 double carbon vacancy (585 DCV) and 555–777 double carbon vacancy (555–777 DCV) defects. It is found that Ca atom can be stabilized on above defective graphenes since Ca׳s binding energy on vacancy defect is much larger than its cohesive energy. Up to six H₂ molecules can stably bind to a Ca atom on defective graphene with the average adsorption energies of 0.17–0.39 eV/H₂. The hybridization of the Ca-3d orbitals with H₂-σorbitals and the electrostatic interaction between the Ca cation and the induced H₂ dipole both contribute to the H₂ molecules binding. Double-side Ca-decorated graphene with 585 DCV and 555–777 DCV defects can theoretically reach a gravimetric capacity of 5.2 wt% hydrogen, indicating that Ca-decorated defective graphene can be used as a promising material for high density hydrogen storage.     

Phase transitions and dielectric properties of (1 − x)KNbO3 − xK0.5Bi0.5TiO3 ceramics synthesized by a stirred hydrothermal process

Dielectric ceramic materials (1 − x) KNbO₃ − xK_0.5Bi_0.5TiO₃ (0 ≤ x ≤ 0.3) have been successfully synthesized via a stirred (dynamic) hydrothermal method. The microstructure, relative density and dielectric properties were studied as a function of KBT doping. The structure of the solid solutions changed from orthorhombic (x = 0; 0.05) to tetragonal (x = 0.1; x = 0.3) at room temperature. The morphotropic phase limit was obtained at x = 0.075 where we have noted the coexistence of the orthorhombic and tetragonal structures. The mean value of the measured dielectric permittivity ε_r was 700 and dielectric loss tanδ was about 0.06 at room temperature. The dielectric properties of the studied ceramics, from 80 to 450 K, depend not only on their microstructure but also on their relative density. A relaxation behavior was observed for the tanδ curves at temperature below 150 K. The activation energy (E_a) of this phenomenon increases from 0.15 to 0.34 eV with the increase of KBT amount. The conductivity σ_ac remains constant at about 10⁻⁶ S m⁻¹.     

Hydrogen storage of beryllium adsorbed on graphene doping with boron: First-principles calculations

Based on density-functional theory, we find that B-doped graphene significantly enhances the Be adsorption energy and prevent Be atoms from clustering. The complex of Be adsorbed on B-doped graphene can serve as a high-capacity hydrogen storage medium: the hydrogen storage capacity (HSC) can reach up to 15.1 wt% with average adsorption energy ?0.298 eV/H₂ for double-sided adsorption. It has exceeded the target specified by US Department of Energy with HSC of 9 wt% and a binding energy of ?0.2 to ?0.6 eV/H₂ at near-ambient conditions. By analyzing the projected electronic density of states of the adsorbed system, we show that the high HSC is due to the change of electron distribution of H₂ molecules and a graphene system decorated with B and Be atoms.     

Structural,vibrational study and superprotonic behavior of a new mixed dipotassium hydrogenselenate dihydrogenphosphate K2(HSeO4)1.5(H2PO4)0.5

Ongoing studies of the KHSeO₄–KH₂PO₄ system aiming at developing novel proton conducting solids resulted in the new compound K₂(HSeO₄)_1.5(H₂PO₄)_0.5 (dipotassium hydrogenselenate dihydrogenphosphate). The crystals were prepared by a slow evaporation of an aqueous solution at room temperature. The structural properties of the crystals were characterized by single-crystal X-ray analysis: K₂(HSeO₄)_1.5(H₂PO₄)_0.5 (denoted KHSeP) crystallizes in the space group P 1¯ with the lattice parameters: a = 7.417(3) Å, b = 7.668(2) Å, c = 7.744(5) Å, α = 71.59(3)°, β = 87.71(4)° and γ = 86.04(6)°. This structure is characterized by HSeO₄⁻ and disordered (H_xSe/P)O₄⁻ tetrahedra connected to dimers via hydrogen bridges. These dimers are linked and stabilized by additional hydrogen bonds (O–H–O) and hydrogen bridges (O–H…O) to build chains of dimers which are parallel to the [0, 1, 0] direction at the position x = 0.5.The differential scanning calorimetry diagram showed two anomalies at 493 and 563 K. These transitions were also characterized by optical birefringence, impedance and modulus spectroscopy techniques. The conductivity relaxation parameters of the proton conductors in this compound were determined in a wide temperature range. The transport properties in this material are assumed to be due to H⁺ protons hopping mechanism.     

Enhanced magnetocaloric effect in Eu-doped La0.7Ca0.3MnO3 compounds

Orthorhombic La_0.7-xEu_xCa_0.3MnO₃ samples (x = 0.04–0.12) with apparent density of ρ = 3.9–4.1 g/cm³ prepared by solid-state reactions have been studied. The analysis of temperature-dependent magnetization for an applied field H = 500 Oe indicated a decrease of the Curie temperature (T_C) from about 225 K for x = 0.04 through 189 K for x = 0.08–146 K for x = 0.12. The magnetocaloric (MC) study upon analyzing M(H, T) data has revealed that the magnetic entropy change around T_C reaches the maximum (|ΔS_max|), which is dependent on both x and H. For an applied field interval of ΔH = 60 kOe, |ΔS_max| values are about 5.88, 4.93, and 4.71 J/kg⋅K for x = 0.04, 0.08, and 0.12, respectively. Though |ΔS_max| decreases with increasing x, relative cooling power (RCP) increases remarkably from 383 J/kg for x = 0.04 to about 428 J/kg for x = 0.08 and 0.12. This is related to the widening of the ferromagnetic-paramagnetic transition region when x increases. Particularly, if combining two compounds with x = 0.04 and 0.08 (or 0.12) as refrigerant blocks for MC applications, a cooling device can work in a large temperature range of 145–270 K, corresponding to RCP ≈ 640 J/kg for H = 60 kOe. M(H) analyses around T_C have proved x = 0.04 exhibiting the mixture of first- and second-order phase transitions while x = 0.08 and 0.12 exhibit a second-order nature. The obtained results show potential applications of Eu-doped La_0.7Ca_0.3MnO₃ materials for magnetic refrigeration below room temperature.     

钇覆盖Si@Al12团簇的贮氢性能

利用密度泛函理论系统地研究了Y_mSi@Al₁₂ (m=1—3)团簇及其贮氢性质. 结果表明, 在所研究的尺度范围内, 钇原子未在Si@Al₁₂团簇上团聚; 每个钇原子按18电子规则吸附氢分子, 其中Y₃Si@Al₁₂团簇可以吸附16个完整氢分子, 贮氢质量分数为5.0 %, 平均吸附能处于0.324—0.527 eV之间, 较为理想的吸附能说明在室温条件下吸氢和脱氢是可行的.     

Synthesis,crystal structure,spectroscopic characterization and optical properties of bis(4-acetylanilinium) tetrachlorocobalt (II)

The chemical preparation, crystal structure, spectroscopic investigations and optical features are given for a novel organic–inorganic hybrid material [C₈H₁₀NO]₂CoCl₄.The compound is crystallized in the orthorhombic space group Cmca, with the following unit cell parameters: a=19.461(2) Å, b=15.523(2) Å, c=13.7436(15) Å, and Z=8. The atomic arrangement shows an alternation of organic and inorganic layers along the b-axis. The cohesion between these entities is performed by N–H…Cl and N–H…O hydrogen bonds and π–π stacking interactions.Infrared and Raman spectra at room temperature are recorded in the 4000−400 and 4000−0 cm⁻¹ frequency regions, respectively and analyzed on the basis of literature data. This study confirms the presence of the organic cation [C₈H₁₀NO]⁺ and of the [CoCl₄]²⁻ anion. UV–vis spectroscopy results showed the indirect transition with band gap energy 2.98 eV.     

Luminescence response of CsI:Na to electron pulse irradiation

This paper investigates the influence of activator concentration and temperature on the scintillation process in CsI:Na crystal which was excited by a pulsed electron beam (E_ex = 0.25 MeV, t_1/2 = 15 ns, W = 0.003…0.16 J/cm²) at temperature within 77–300 K. It has been established that the transition of Na-bound two halide exciton from singlet state causes 3 eV emission of CsI:Na. The capturing of V_k by Na⁺ ion determines the scintillation pulse shape. Thermal liberation of V_k from V_kA centers results in an inertial rise of the emission pulse in lightly activated CsI:Na and in a mono-exponential decay of the emission pulse in heavily activated CsI:Na. The value of thermal dissociation energy of V_kA centers is 0.24 ± 0.01 eV, which was obtained from the temperature dependences of the emission decay time constant for CsI:2.8∙10⁻³%Na and of the rise time constant for CsI:2.0∙10⁻⁴%Na.     

Magnetic characterisation and hydrogen absorption characteristics of Pr3(Fe,Ti)29Hx

An interstitial Pr₃(Fe,Ti)₂₉ hydride was synthesised by gas-phase hydrogenation on Pr₃(Fe,Ti)₂₉ powder using H₂. The reaction kinetics between Pr₃(Fe,Ti)₂₉ and H₂ gases was studied in a constant-volume reactor. The sample starts to rapidly absorb hydrogen, interstitially, at about 533 K. Absorption passes through a maximum at about 598 K (1.6 H/f.u) and then interstitial hydrogen desorption takes place up to the temperature of 673 K. By cooling to room temperature, the sample absorbs more hydrogen, interstitially, reaching the value of 3.6 H/f.u. By remaining at room temperature, the sample absorbs even more hydrogen reaching the value of 5.2 H/f.u. The lattice expansion observed is 2.1% and the Curie temperature, T_C, increased from 392 to 518 K. The hydride exhibits saturation magnetisation, M_S, of 145.4 and 157.5 Am²/kg at room temperature (RT) and at 5 K, respectively, anisotropy field, H_A, of 2.1 T (RT) and 4.5 T (5 K) and average hyperfine field, H_eff, of 23.3 T (RT). The magnetic anisotropy of Pr₃(Fe,Ti)₂₉ hydride is the same as that of the parent compounds, easy-cone-like, changing only in the cone angle (from 34° to 26°).     

Giant magneto-caloric effect around room temperature at moderate low field variation in La0.7(Ca1−xSrx)0.3MnO3 perovskites

Among the perovskite manganites, a series of La_1?xCa_xMnO₃ has the largest magneto-caloric effect (MCE) (|ΔS_m|_max=3.2–6.7 J/kg K at ΔH=13.5 kOe), but the Curie temperatures, T_C, are quite low (165–270 K). The system of LaSrMnO₃ has quite high T_C but its MCE is not so large. The manganites La_0.7(Ca_1?xSr_x)_0.3MnO₃ (x=0, 0.05, 0.10, 0.15, 0.20, 0.25) have been prepared by solid state reaction technique with an expectation of large MCE at room temperature region. The samples are of single phase with orthorhombic structure. The lattice parameters as well as the volume of unit cell are continuously increased with the increase of x due to large Sr²⁺ ions substituted for smaller Ca²⁺ ions. The field-cooled (FC) and zero-field-cooled (ZFC) thermomagnetic measurements at low field and low temperatures indicate that there is a spin-glass like (or cluster glass) state occurred. The Curie temperature T_C increases continuously from 258 K (for x=0) to 293 K (for x=0.25). A large MCE of 5 J/kg K has been observed around 293 K at the magnetic field change ΔH=13.5 kOe for the sample x=0.25. The studied samples can be considered as giant magneto-caloric materials, which is an excellent candidate for magnetic refrigeration at room temperature region.     

Fullerene-like Si60C60 nanocage: Hydrogen storage capacity

For investigating the hydrogen storage capacity of the Si₆₀C₆₀ nanocage, we have performed first principle density functional theory calculations with van der waals corrections. According to the force and energy minimization of the complex structures of nH₂@Si₆₀C₆₀, we have found that the systems with n = 1 to 70 are energetically favorable. We also found that the most stable nH₂@Si₆₀C₆₀ system is related to the systems with n close to 50 which make it possible to reach 4.2 wt% of hydrogen storage. Although it is found that the nH₂@Si₆₀C₆₀ system remains stable up to n = 70 and 5.8 wt%. The NPT molecular dynamic investigation at different pressures (0–30 atm) and also different temperatures (300–1800 K) were carried out on the optimized stable system with maximum capacity of encapsulating H₂ molecules (70H₂@Si₆₀C₆₀).     

Improved critical current density in Zn doped YBCO single crystals

Magnetic measurements were made using pure YBCO and Zn doped YBa₂(Cu_1?xZn_x)₃O_7?σ. Single crystals with Zn concentration of 0.5%, 1.5%, 3.0% and 4.3%. The magnetic hysteresis loops for these samples were measured in the temperature range 0.1 ? T/T_c ? 0.96 under magnetic fields of 5 T using SQUID. It was found that the critical current density J_c increased for low Zn content samples up to 3% Zn concentration compared to pure YBCO sample and decreased for the higher Zn content samples. These values varied consistently when compared at magnetic fields of 1 T and 3 T. Moreover Zn doped samples showed significant values of J_c in the temperature range of 0.7–0.9T_c, close to critical temperature compared to pure YBCO sample. The irreversibility field H_irr was also enhanced in this temperature range showing consistent decrease with increase of Zn concentration. The peak field H_p above H_c1 and irreversibility field H_irr, both show power law dependence of the form H = m₁(1 ? T/T_c)^m2 in the temperature range of 0.75–0.96T_c. The values of parameter m₂ increased from 1.44 to 1.95 for the samples up to 3% Zn content and decreased to 1.37 for higher Zn contents. The ratio H_irr/H_p was found to be 3–4 for the lower Zn content samples and was 7–8 for the sample with high Zn content indicating more disorder for higher Zn content samples. The region between peak field H_p and irreversibility field H_irr was broadened with the increase of Zn concentration. The strong effect of Zn substitution in modifying behavior of these samples even at elevated temperatures is possibly due to the changes in the anisotropy of our samples with the increase of Zn concentration and also due to the locally induced changes in magnetic moments by Zn substitution.     

Physical properties of the delafossite LaCuO2

High-quality LaCuO₂, elaborated by solid-state reaction in sealed tube, crystallizes in the delafossite structure. The thermal analysis under reducing atmosphere (H₂/N₂: 1/9) revealed a stoichiometric composition LaCuO_2.00. The oxide is a direct band-gap semiconductor with a forbidden band of 2.77 eV. The magnetic susceptibility follows a Curie-Weiss law from which a Cu²⁺ concentration of 1% has been determined. The oxygen insertion in the layered crystal lattice induces p-type conductivity. The electrical conduction occurs predominantly by small polaron hopping between mixed valences Cu^+/2+ with an activation energy of 0.28 eV and a hole mobility (μ_300 K=3.5×10⁻⁷ cm² V⁻¹ s⁻¹), thermally activated. Most holes are trapped in surface-polaron states upon gap excitation. The photoelectrochemical study, reported for the first time, confirms the p-type conduction. The flat band potential (V_fb=0.15 V_SCE) and the hole density (N_A=5.8×10¹⁷ cm⁻³) were determined, respectively, by extrapolating the curve C⁻² versus the potential to their intersection with C⁻²=0 and from the slope of the linear part in the Mott-Schottky plot. The valence band is made up of Cu-3d orbital, positioned at 4.9 eV below vacuum. An energy band diagram has been established predicting the possibility of the oxide to be used as hydrogen photocathode.     

Generation of H− ions in a low-pressure xenon-hydrogen discharge. I

A theory of a low-pressure discharge in a xenon-molecular hydrogen mixture is developed. It is shown that, in such a discharge, at an interelectrode distance of L = 1 cm and a total plasma pressure of p ₀ ～ 1 Torr, the density of negative hydrogen ions produced via the dissociative attachment of thermal electrons to vibrationally excited molecules H₂ can reach a value as high as N_H ^? ≥ 10¹² cm^?3. According to calculations, the electron temperature in discharge operating regimes under study attains T _e ≈ 1?2 eV, which corresponds to the maximum of the e-v exchange rate constant of H₂ molecules. This ensures a relatively high rate of vibrational pumping of H₂ molecules in the discharge.     

Optical charge transfer absorption in proton injected tungsten oxide thin films analyzed with spectroscopic ellipsometry

Tungsten oxide thin films with protons injected during deposition (H_xWO₃) were prepared using reactive direct-current magnetron sputtering in a mixture of argon, oxygen, and hydrogen gases. The concentration of injected protons, given by the x-values in H_xWO₃, was evaluated by electrochemically ejecting protons from the films. The complex dielectric functions (? = ?₁ + i?₂) of the films were estimated by analyzing the experimental spectra of Ψ and Δ measured with spectroscopic ellipsometry using the model composed of a homogeneous tungsten bronze layer with an additional surface roughness layer. As a result of this analysis, the imaginary part of the dielectric function ?₂, which represents optical absorption, was composed of two Lorentz oscillator terms whose peak positions were about 1.0 eV (L₁) and 1.6 eV (L₂). The two terms with L₁ and L₂ are assumed using the modified site-saturation model to be due to optical charge transition between W⁶⁺ and W⁵⁺ sites, and between W⁶⁺ and W⁴⁺ sites, respectively.     

DFT(B3LYP/LanL2DZ), non-linear optical and electrical studies of a new hybrid compound: [C6H10(NH3)2]CoCl4·H2O

A new organic-inorganic material [C₆H₁₀(NH₃)₂]CoCl₄·H₂O was reported. The title compound was synthesized at room temperature by slow evaporation and then characterized by a single X-ray diffraction, spectroscopic measurements, thermal analysis and dielectric technique. It crystallizes in the non-centrosymmetric space group Pna2₁ with the following unit cell parameters: a=12.5328(1) Å, b=9.0908(1) Å, c=11.7440(1) and α=β=γ=90°. The structure can be described by the alternation of two different cationic-anionic layers. It consists of isolated H₂O, isolated [CoCl₄]²⁻ tetrahedral anions and diammoniumcyclohexane [C₆H₁₀(NH₃)₂]²⁺ cations, which are connected via N–H…Cl, N–H…O and O–H…N hydrogen bonds. The Hirshfeld surface analysis was conducted to investigate intermolecular interactions and associated 2D fingerprint plots, revealing the relative contribution of these interactions in the crystal structure quantitatively. Theoretical calculations were performed using DFT/B3LYP/LanL2DZ method for studying the molecular structure and vibrational spectra and especially to examine the non-linear optical behavior of the compound. Solid state ¹³C NMR spectrum shows three signals correspond to three different carbon environments. Thermal analysis discloses a phase transition at the temperature 315 K and the evaporation of water molecule at 327 K. A detailed dielectric study was reported and shows a good agreement with thermal measurements.     

Optoelectronic properties of Cu1−xPtxFeO2 (0 ≤ x ≤ 0.05) delafossite for p-type transparent conducting oxide

The samples of Cu_1−xPt_xFeO₂ (0 ≤ x ≤ 0.05) delafossite have been synthesized by solid-state reaction method to investigate their optical and electrical properties. The properties of electrical resistivity and Seebeck coefficient were measured in the high temperature ranging from 300 to 960 K, and the Hall effect and the optical properties were measured at room temperature. The obtained results of Seebeck showed the samples are p-type conductor. The optical properties at room temperature exhibited the samples are transparent visible light material with optical direct gap 3.45 eV. The low electrical resistivity, hole mobility and carrier density at room temperature displayed value ranging from 0.29 to 0.08 Ω cm, 1.8 to 8.6 cm²/V s and 1.56 × 10¹⁸ to 4.04 × 10¹⁹ cm⁻³, respectively. The temperature range for transparent visible light is below 820 K because the direct energy gap contains value above 3.1 eV. Consequently, the Cu_1−xPt_xFeO₂ delafossite enhance performance for materials of p-type transparent conducting oxide (TCO) with low electrical resistivity.