1H NMR Study of Zeolite Water Structure and Broensted Acid Centers in Chabazite

The disordered structure of absorbed water in a highly porous zeolite chabazite Ca₂[Al₄Si₈O₂₄]·nH₂O (2 ≤ n ≤ 12.8) is studied from motionally narrowed ¹H nuclear magnetic resonance spectra at room temperature. Concentration phase transitions were observed at n ≈ 8.3 and n ≈ 10.2. The transitions are accompanied by displacement of Ca²⁺ ions and variation of the Broensted acid centers at inner surface of zeolite pores.     

Cooperativity of tetrel bonds tuned by substituent effects

Substituent effects on cooperativity between N···X and C···X interactions are studied in the 4-Z-Py···XH₃(NC)···XH₃(NC) complexes, where X = C, Si; Z = H, F, OH, CH₃, NH₂, F, NC, CN, NO₂ and Py = pyridine. All N···X and C···X binding distances in the ternary complexes are always shorter than those in the corresponding binary complex. This indicates that the formation of the N···X interaction strengthens C···X bond in these complexes and vice versa. Our results reveal that the strength of N···X and C···X interactions in the ternary complexes considerably depends on the nature of X and Z substituents. For a given aromatic system, the shortening of N···X and C···X distances is more important for SiH₃(NC) complexes than CH₃(NC) counterparts. The mechanism of cooperative effects in the ternary complexes is unveiled by electrostatic potential analyses and natural bond theory.     

Visible-light photocatalysis of nitrogen-doped TiO2 nanoparticulate films prepared by low-energy ion implantation

Nitrogen-doped TiO₂ (N-TiO₂) films were prepared by low-energy implantation of nitrogen ions into pulsed laser deposited anatase TiO₂ films. The anatase phase of the films was not changed by the implantation with very low energy of 200 eV. XPS measurements revealed that the implanted nitrogen species were mainly interstitial ones. The nitrogen concentration was increased with increasing ion flux which could be controlled by adjusting the gas flow rate of the ion source. All the produced N-TiO₂ films exhibited visible-light photocatalytic activities in degradation of methylene blue in aqueous solutions, indicating that interstitial nitrogen could also be responsible for the photocatalysis in visible region. Higher visible-light photocatalytic efficiency was achieved with higher implanted nitrogen concentration.     

Evolution of structural,magnetic and magnetocaloric properties in Sn-doped manganites La0.57Nd0.1Sr0.33Mn1−x Sn x O3 (x = 0.05–0.3)

Structural and magnetic properties of manganites series La_0.57Nd_0.1Sr_0.33Mn_1?x Sn _x O₃ with (0.05 ≤ x ≤ 0.30) have been investigated, and the critical exponents and magnetocaloric effect are studied around the room temperature, to shed light on Sn substitution influence. A solid-state reaction method was used in the preparation. A structural study using Rietveld refinement of XRD patterns indicates rhombohedral structure with R \( \overline{3} \) c space group for (0.05 ≤ x ≤ 0.20) and shows the existence of a secondary phase attributed to the neodymium tin oxide (Nd₂Sn₂O₇) pyrochlore for x = 0.3. The variation of the magnetization (M) vs. temperature (T), under an applied magnetic field of 0.05 T, reveals a ferromagnetic–paramagnetic transition at the Curie temperature T _C. In addition, it was discovered that increasing the tin content leads to a reduction in magnetization and a lowering of T _C from 282 K (x = 0.05) to 158 K (x = 0.20) with increasing Sn substitution. The samples exhibit the characteristics of spin/cluster-glass state which is evident from (zero-field-cooled and field-cooled) magnetization vs. temperature curves. Indeed, the thermal evolution of magnetization in the ferromagnetic phase at low temperature varies as T ^3/2, in accordance with Bloch’s law. The spin-stiffness constant D obtained from the Bloch constant was determined. A large magnetocaloric effect has been observed in both samples (x = 0.05 and x = 0.10): the maximum entropy change, \( \left| {\varDelta S_{\text{M} }^{\text{peak}} } \right| \) , reaches the highest value of 3.22 J/kg K under a magnetic field change of 5 T with a RCP value of 56 J/kg for x = 0.10 composition. This opens an interesting opportunity to this compound to compete with materials which work as magnetic refrigerants near room temperature. Besides, we show that the samples follow the conventional behavior of a second-order ferromagnetic transition. This was possible by investigating the critical behavior at the transition region by adopting the modified Arrott plot method. The values of the critical exponents (β, γ, δ and n) are determined and they are between those predicted by the three-dimensional Heisenberg model.     

Synthesis and Optical Properties of Novel Red-Emitting PbNb<Subscript>2</Subscript>O<Subscript>6</Subscript>: Eu<Superscript>3+</Superscript> Phosphors

Undoped and PbNb₂O_6:Eu³⁺ (1.0 ≤ x ≤ 6.0 mol%) phosphors were synthesized at 1100 °C for 3.5 h by the conventional solid state reaction method. Synthesized PbNb₂O₆:Eu³⁺ phosphors were characterized by X-ray diffraction (XRD), Scanning electron microscopy (SEM), Energy dispersive spectroscopy (EDS) and Photoluminescence (PL) analyses. The PL spectra showed series of excitation peaks between 350 and 430 nm due to the 4f–4f transitions of Eu³⁺. For 395.0 nm excitation, emission spectra of Eu³⁺ doped samples were observed at 591 nm (orange) and 614 nm (red) due to the ⁵D₀ → ⁷F₁ transitions and ⁵D₀ → ⁷F₂ transitions, respectively. PL analysis results also showed that the emission intensity increased by increasing Eu³⁺ ion content. No concentration quenching effect was observed. The CIE chromaticity color coordinates (x,y) of the PbNb₂O₆:Eu³⁺ phosphors were found to be in the red region of the chromaticity diagram.     

Assessing the subsequent effect of nitrogen released from tobacco-waste on maize crop using a 15N isotope technique

The investigation of the residual effect of nitrogen (N) released from tobacco-waste (TW) using isotope techniques will provide valuable data for sustainable organic farming. For this aim, a pot experiment was conducted using the ¹⁵N isotope technique. The experiment was based on a completely randomised design with four replications and was conducted on a calcareous ustochrepts soil. TW at levels of 0, 10, 20, 30 and 40 t ha^?1 and N fertiliser as (NH₄)₂SO₄ at levels of 0, 20, 40, 60 and 80 kg N ha^?1 were used for the Bezostaja-1 wheat variety. Concerning mineral N fertilisation with 20 and 80 kg N ha^?1, additional treatments with ¹⁵N-labelled (NH₄)₂SO₂ (10 at.% exc.) have been applied. Following harvesting wheat plants, the Pioneer 3377 maize variety was used to see the residual effect of TW. After harvesting, dry matter yields were recorded and total N concentrations were determined. ¹⁵N determinations and calculations were also made for ¹⁵N treatments separately. TW had a significant residual effect on the growth of corn plant under the pot condition. Increasing rates of TW significantly increased the dry matter yield of corn plant following wheat from 3.31 t ha^?1 (at control) to 7.89 t ha^?1 (at the TW treatment of 40 t ha^?1). The ¹⁵N values derived from the ¹⁵N fertiliser decreased with increasing TW application. The average values of N derived from N fertiliser (Ndff) varied from 2.14 to 3.09% at the rates of 20 and 80 kg N ha^?1, respectively. However, N derived from TW (Ndftw) significantly increased from 16.93 to 24.59% (at 20 kg N ha^?1), and it also increased from 23.06 to 28.15% (at 80 kg N ha^?1) with increasing TW applications from 20 to 40 t ha^?1, respectively.     

Effects of γ rays irradiation on structure and property of TiO2 thin films

TiO₂ thin films were deposited on a glass substrate by the radio frequency magnetron sputtering method, and annealed for 2 h at temperatures of 550°C. Then, ⁶⁰Co γ rays with different doses were used to irradiate the resulting TiO₂ thin films. The surface features of films before and after irradiation were observed by scanning electron microscope (SEM). Simultaneously, the crystal structure and optical properties of films before and after irradiation were studied by X-ray diffraction (XRD), UV–VIS transmission spectrum and Photoluminescence (PL) spectrum, respectively. The SEM analysis shows that the film is smooth with tiny particles on the film surface, and non-crystallization trend was clear after irradiated with γ rays. The XRD results indicated that the structure of the film at the room temperature mainly exists in the form of amorphous and mixed crystal at a sputtering power of 200 W, and non-crystallinity was more obvious after irradiation. Obvious difference can be found for the transmissibility of the irradiated and pre irradiation TiO₂ films by the UV-VIS spectra. The color becomes light yellow, and the new absorption edge also appeared at about 430 nm. PL spectra and photocatalysis experiments indicate that the photocatalysis degradation rate of the TiO₂ films on methylthionine chloride solution irradiated with the maximum dose can be increased to 90%.     

Effects in 94 GHz Orientation-Selected PELDOR on a Rigid Pair of Radicals with Non-Collinear Axes

For aromatic organic radicals, pulsed electron-electron double resonance (PELDOR) experiments at high magnetic fields provide information not only about the distance between the paramagnetic species but also about their relative orientation. However, the three-dimensional biradical structure is encoded in a complex pattern of orientation-selected PELDOR traces and the execution of the experiment is generally aggravated by constraints posed by the available hardware and the intrinsically low modulation depth observed. We present a 94 GHz PELDOR experiment performed with a commercial spectrometer and probe heads that permit separation of pump and detection frequencies up to 150 MHz. The setup is employed to examine the orientation selections on a general case of rigid biradicals with non-collinear g axes. The interacting radicals, a tyrosyl radical (Y₁₂₂·) located in the β2 subunit and an 3-aminotyrosyl radical (NH₂Y₇₃₁·) located in the α2 subunit, are generated by Escherichia coli ribonucleotide reductase with a 3-aminotyrosine (NH₂Y) site specifically incorporated into α2 in the presence of cytidine 5′-diphosphate and adenosine 5′-triphosphate. The experimental designs as well as some characteristic features of the observed modulation pattern are discussed.     

Influence of the surface on the quantum P.E.M. effect in InP

The photoelectromagnetic effect of InP is studied in quantizing magnetic fields at 4·2 K in an energy range 1·4–1·5 eV for linearly polarized light. Depending on the sample surface condition two types of spectral oscillations may appear, those associated with interband transitions between Landau levels or the LO phonon type usually seen in photoconductivity. An analysis of the spectral oscillations gives: E₀ = 1·423±0·001 eV; Δ₀ = 0·102±0·006 eV; hω_L = 0·036 eV.     

27Al Magic Angle Spinning Nuclear Magnetic Resonance Study of Al1−x Cr x K(SO4)2·12H2O (x = 0, 0.07, and 0.2)

The physical properties of Al_1?x Cr _x K(SO₄)₂·12H₂O (x = 0, 0.07, and 0.2) were studied as a function of temperature using magic angle spinning nuclear magnetic resonance for ²⁷Al. On the basis of the physical properties of pure AlK(SO₄)₂·12H₂O, the effects of partially replacing Al³⁺ with Cr³⁺ ions were examined. Molecular motion changed with the concentration of Cr³⁺ ions. The relaxation process near 320 K was found to undergo molecular motion as described by the Bloembergen–Purcell–Pound theory. The activation energies, phase transition temperatures, and spin–lattice relaxation times in the rotating frame T _1ρ changed with the concentration of paramagnetic ions.     

EPR study of the illumination effect on properties of paramagnetic centers in nitrogen-doped TiO<Subscript>2</Subscript> active in visible light photocatalysis

An electron paramagnetic resonance study of nitrogen-doped TiO₂ samples has been carried out in the dark and under illumination with light at different wavelengths. N^· and NO^· paramagnetic species were detected in the samples and their dynamics under illumination of TiO₂ was investigated. Photosensitivity of the nitrogen-doped TiO₂ and its photocatalytic activity under visible-light irradiation increases through the creation of additional levels in the band gap of TiO₂ caused by doping.     

Bi-MOFs with two different morphologies promoting degradation of organic dye under simultaneous photo-irradiation and ultrasound vibration treatment

For the first time, piezocatalysis activity has been observed in bismuth-based MOFs (ultrasound vibration treatment) with two different morphologies, namely FCAU-17 (flakes) and CAU-17 (rods). CAU-17 and FCAU-17 were synthesized by solvothermal and ultrasonic methods, respectively, with the same organic ligand (1,3,5-benzenetricarboxylic acid) and metal salt (Bi(NO₃)₃·5H₂O). Among these, the apparent rate constant k of CAU-17 in piezo-photocatalysis is 3.9 × 10⁻² min⁻¹, which is ∼3.9 and ∼ 1.5 times of those in photocatalysis and piezocatalysis, respectively. CAU-17 showed much high piezo-photocatalytic activity during degradation of RhB. Efficiently coupling between piezocatalysis and photocatalysis has been realized in rod-like CAU-17 (ultrasound vibration treatment). Our results provide a new strategy to improve catalytic performance of Bi MOFs through an efficient synergistic piezo-photocatalysis approach for environmental remediation.     

Impurity photoconductivity in epitaxial layers of gallium arsenide

Impurity photoconductivity spectra in the range 0.5–1.5 eV are studied in epitaxial layers of n-GaAs grown on substrates of semiconductive GaAs withρ > 10⁶ Ω·cm in the system Ga-AsCl₃ -H₂. The effect of uncontrolled acceptor impurities on the impurity photoconductivity spectrum is evaluated.     

Structure and magnetostriction of Tb0.4Nd0.6(Fe0.8Co0.2) x alloys

Structural, magnetic and magnetostrictive properties of Tb_0.4Nd_0.6(Fe_0.8Co_0.2) _x (1.50 ≤ x ≤ 1.90) alloys have been investigated by means of X-ray diffraction (XRD), a vibrating sample magnetometer and a standard strain technique. XRD analysis shows the presence of single Laves phase with a cubic MgCu₂-type structure for the high Nd content alloy around the composition of x = 1.80, which tends to be formed by curing at relatively low annealing temperature. The easy direction of magnetization at room temperature is observed toward <111> axis, accompanied by a rhombohedral distortion with a large spontaneous magnetostriction λ₁₁₁. An optimized effect on the linear anisotropic magnetostriction, 360 ppm at 3 kOe, was observed for the high Nd content Tb_0.4Nd_0.6(Fe_0.8Co_0.2)_1.80 alloy, which can be attributed to its single Laves phase, the large λ₁₁₁ (~1,520 ppm) of the MgCu₂-type (Tb,Nd)(Fe,Co)₂ phase and the good soft magnetic behaviors.     

Low temperature photoconductivity in electron - irradiated p-type Si

The photoconductivity spectra of p-type silicon irradiated at ～15 °K with 1.2 MeV electrons were studied in the wavelength range from 1.2 to 5.5 μ at temperatures from 23 to 80 °K. The 3.9 μ photoconductivity band appears immediately after irradiation in all crystals already at low temperatures, giving further evidence that it is due to the divacancy formed directly during irradiation by electrons. Three main annealing stages of the photoconductivity have been observed; (a) below 160 °K, (b) 160–250 °K, and (c) 280–360 °K. A radiation-induced deep level at E_v , +(0.12±0.02 eV disappears upon annealing at stage b. The annealing behavior of the spectra depends strongly on the measuring temperature. The dependence of the spectra on chopper speed was also investigated.     

Network analysis of the Íslendinga sögur – the Sagas of Icelanders

It is well-known that cooperative properties such as magnetic ordering can depend on the samples’ dimensions (Ds) in a qualitative way. However, there have been no samples with well-defined non-integer Ds. The dimension of a given sample has been always discussed on the anisotropy of the electronic/crystal/magnetic structures, which has no definition suitable for quantitative discussion on dimensions vs. properties. On the other hand a particular type of porous samples, i.e. fractal bodies, can have well-defined non-integer Ds dependent exclusively on the geometrical feature of structures, and physical properties of such materials remains unexplored. This paper reports on magnetic ordering in samples covering 2.5 ≤ D ≤ 3, in addition to a way of precise control of the fractal dimensions of given samples simply by wax (alkylketene dimer). The results show that the magnetic ordering temperatures, i.e. Néel temperatures (T _N s), of CoO depend on D, and rapidly enhance immediately below D = 3. This means that one can control or enhance the critical temperature simply by tuning D with keeping the remaining magnetic properties unchanged.     

Solid state synthesis of nonstoichiometric Bi<Subscript>2</Subscript>WO<Subscript>6</Subscript>/Bi<Subscript>2</Subscript>O<Subscript>3</Subscript> composites as visible-light photocatalyst

Nonstoichiometric Bi₂WO₆ photocatalyst with the composition of Bi_2?+?x WO_6?+?1.5x (?0.25 ≤ x ≤ 1) wa synthesized by a facile solid state reaction method. The products were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and UV-vis absorption spectrum. The Bi_2.5WO_6.75 photocatalyst showed excellent visible-light-driven photocatalytic performance; nearly 100 % of RhB (10 ppm, pH?=?3?~?4) was decomposed within 25 min, which demonstrated that nonstoichiometric semiconductors could be an efficient visible-light-driven photocatalyst.     

Substitution effects on the bulk and surface properties of (Li,Ni)Mn<Subscript>2</Subscript>O<Subscript>4</Subscript>

Manganese oxides of spinel structure, LiMn₂O₄, Li_1-x Ni _x Mn₂O₄ (0.25 ≤ x≤ 0.75), and NiMn₂O₄, were studied by EDS, XRD, SEM, magnetic (M-H, M-T), and XPS measurements. The samples were synthesized by an ultrasound-assisted sol-gel method. EDS analysis showed good agreement with the formulations of the oxides. XRD and Rietveld refinement of X-ray data indicate that all samples crystallize in the Fd3m space group characteristic of the cubic spinel structure. The a-cell parameter ranges from a = 8.2276 Å (x = 0) to a = 8.3980 Å (x = 1). SEM results showed particle agglomerates ranging in size from 2.3 μm (x = 0) down to 0.8 μm (x = 1). Hysteresis magnetization vs. applied field curves in the 5–300K range was recorded. ZFC-FC measurements indicate the presence of two magnetic paramagnetic-ferrimagnetic transitions. The experimental Curie constant was found to vary from 5 to 7.1 cm³ K mol^?1 for the range of compositions studied (0 ≤ x ≤ 1). XPS studies of these oxides revealed the presence of Ni²⁺, Mn³⁺, and Mn⁴⁺. The experimental Ni/Mn atomic ratios obtained by XPS were in good agreement with the nominal values. A linear relationship of the average oxidation state of Mn with Ni content was observed. The oxide’s cation distributions as a function of Ni content from x = 0 ?Li⁺[Mn³⁺Mn⁴⁺]O₄ to x = 1 \( {\mathrm{Ni}}_{0.35}^{2+}{\mathrm{Mn}}_{0.65}^{3+}\left[{\mathrm{Ni}}_{0.65}^{2+}\right.\left.{\mathrm{Mn}}_{1.35}^{3+}\right]{\mathrm{O}}_4 \) were proposed.     

Zero field splittings of Gd3+IN Nd2(SO4)3 · 8H2O and Sm2(SO4)3 · 8H2O crystals at 273 K

The electron paramagnetic resonance (EPR) of Nd₂(SO₄)₃ · 8H₂O and Sm₂(SO₄)₃ · 8H₂O doped with Gd³⁺ has been carried out at 273 K and the spin-Hamiltonian parameters are deduced. The zero field splittings have been computed and compared with those observed directly by Bogle and Symmons. It is found that the discrepancy in the zero field splittings. between computed and directly observed values falls within the range of linewidths of directly observed values.