Search

As a non-metallic organic semiconductor, graphitic carbon nitride (g-C3N4) has received much attention due to its unique physicochemical properties. However, the photocatalytic activity of this semiconductor faces challenges due to factors such as low electronic conductivity and limited active sites provided on its surface. The morphology and structure of g-C3N4, including macro/micro morphology, crystal structure and electronic structure can affect its catalytic activity. Non-metallic heteroatom doping is considered as an effective method to tune the optical, electronic and other physicochemical properties of g-C3N4. Here, we synthesized non-metal-doped highly crystalline g-C3N4 by one-pot calcination method, which enhanced the photocatalytic activity of g-C3N4 such as mesoporous nature, reduced band gap, wide-range photousability, improved charge carrier recombination, and the electrical conductivity was improved. Hence, the use of low-power white-LED-light illumination (λ ≥ 420 nm) and ultrasound (US) irradiation synergistically engendered the Methylene Blue (MB) mineralization efficiency elevated to 100% within 120 min by following the pseudo-first-order mechanism under the following condition (i.e., pH 11, 0.75 g L−1 of O-doped g-C3N4 and S-doped g-C3N4, 20 mg L−1 MB, 0.25 ml s−1 O2, and spontaneous raising temperature). In addition, the rapid removal of MB by sonophotocatalysis was 4 times higher than that of primary photocatalysis. And radical scavenging experiments showed that the maximum distribution of active species corresponds to superoxide radical O 2 · - . More importantly, the sonophotocatalytic degradation ability of O-doped g-C3N4 and S-doped g-C3N4 was remarkably sustained even after the sixth consecutive run. [ABSTRACT FROM AUTHOR]

A possible fabrication of photoluminescent fluoride nanoparticles NaYF4 doped with rare-earth ions employing high-energy ball milling is demonstrated. The melt-grown bulk cubic crystal Na0.40Y0.480Yb0.108Er0.012F2.2 and composite Na0.55Y0.360Yb0.081Er0.009F2.10 comprising hexagonal β-NaYF4 modification were used as raw materials. The samples were analyzed using X-ray diffraction analysis, differential scanning calorimetry, transmission electron microscopy, and optical spectroscopy after the milling. Pure single-phase NaYF4 was not obtained even after 14 hours of mechanochemical treatment of individual components. However, high-energy ball milling of the crystals in the presence of oleic acid as a surfactant for 16 hours allowed production of single-phase β-NaYF4:Yb,Er nanoparticles with an average size of 20–30 nm. The milled β-NaYF4:Yb,Er nanoparticles demonstrate intense green fluorescence upon excitation at λ = 980 nm and can potentially be used in biomedicine and nanophotonics. The optimized methodology of high-energy milling has great potential for scalable and reproducible production of β-NaYF4 nanoparticles for industrial and scientific applications. High-temperature X-ray diffraction confirmed the phase transformation of melt-grown α-NaYF4 crystals into the hexagonal β-modification both during mechanical (4 hours) and thermal treatment in the 653–823 K range. The long duration of the process precludes the possibilities of large scale preparation of the cubic α-NaYF4 by mechanical milling. [ABSTRACT FROM AUTHOR]

Crystals based on alkaline earth metal difluorides are widely used optical materials. In this study, in order to expand the range of optical matrices, multicomponent Pb1−x−yCdxSryF2 (0.27 < x < 0.55, 0.06 < y < 0.18) solid solution crystals with a fluorite structure (sp. gr. Fm-3m) were grown from melt using the vertical directional crystallization technique for the first time. The densities and refractive indices of the grown crystals vary depending on the quantitative content components (x and y) in the ranges of 6.6039(5)–7.5232(5) g/cm3 and 1.6403–1.7084, respectively. The optical transmission and electrochemical impedance spectra were studied. The homogenous composition regions of non-cellular crystallization of this ternary solid solution at a crystallization rate of 6 mm/h and an interface temperature gradient of 80 deg/cm were experimentally determined as 0.30 < x < 0.35, 0 < y < 0.6. These grown crystalline materials may be of interest as high-density highly refractive cubic isomorphic hosts and low-temperature ionic conductors (~2 × 10−5 S/cm at room temperature) for various applications. [ABSTRACT FROM AUTHOR]

Multiphase fluoride polycrystalline eutectics pRF3 × qMF2 forming in the MF2–RF3 (M = Ca, Sr, Ba; R = La–Nd) binary systems were synthesized by the directional crystallization technique from a melt. The phase composition, morphology, and temperature dependences of fluorine ionic conductivity in fabricated composites were studied in detail. The pRF3 × qMF2 (p and q are the mole percentages of components) eutectic composites consist of both extremely saturated fluorite-type structure M1−xRxF2+x solid solutions and the tysonite-type R1−yMyF3−y ones. Microsized growth blocks with a fine lamellar structure are typical for synthesized composites. The thinnest (from 3 μm) and longest lamellae are observed in the 68LaF3 × 32BaF2 composition. The ionic conductivity values of pRF3 × qMF2 composites are determined by the phase composition, practically do not depend on their morphological features, and reach 10−3–10−2 S/cm at 500 K (with an ion transport activation enthalpy of about 0.5–0.6 eV). Crystallized eutectics are superior to any single-phase M1−xRxF2+x solid solutions and ball-milling R1−yMyF3−y nanoceramics in terms of ion-conducting properties. These fluoride materials represent an alternative to widely applied tysonite-type ceramic composites in various electrochemical devices and require further in-depth studies. [ABSTRACT FROM AUTHOR]

We report on hybrid nanocomposite scaffolds on the base of cross-linked hyaluronic acid derivative with embedded upconversion nanoparticles (UCNPs). The unique photoluminescence properties of specially designed hydrophilic UCNPs enable visualization of hydrogel using NIR irradiation. Formation of scaffold structure can be produced by means of 3D printing or direct laser writing. For the first time, we present visualization of nanohybrid scaffolds in live small animal aiming to demonstrate new possibilities of their luminescent remote control for tissue engineering.

The optical and magneto-optical characteristics of KTb3F10 crystals in the transition region of 5D4 → 7F6 4f8 configurations of the Tb3+ ion at temperatures of 90 and 300 K were studied. The schemes of the optical transitions in the KTb3F10 crystals were constructed, and the energies of most of the Stark sublevels of the ground 7F6 and excited 5D4 multiplets of the Tb3+ ion split by the C4v symmetry crystal environment were determined. The presence of three- and two-doublet states in the energy spectra of the Tb3+ion multiplets 7F6 and 5D4, respectively, was established, which is in good agreement with theoretical predictions. The use of the wavefunctions of the Stark sublevels of multiplets split by a tetragonal crystal field and combining in the studied optical transition made it possible to explain some of the magnetic and magneto-optical features observed in the KTb3F10 single crystals. [ABSTRACT FROM AUTHOR]

The temperature dependences of the ionic electrical conductivity of fluorite-type (sp. gr. F m 3 ‾ m , Z = 8) KDy3F10 and KHo3F10 single crystals grown by the Bridgman technique have been studied by impedance spectroscopy for the first time. The correlation between the conductometric and structural characteristics of KR3F10 (R = Tb, Dy, Ho, Y) crystal family from the point of view of the observed size effect in the ionic conductivity is discussed. With decrease in the unit-cell volume V1F per fluorine atom in a series of crystals with R = Tb, Dy, Ho and Y, the activation energy Eσ of ion transfer decreases from 1.57 to 1.16 eV respectively and the fluorine-ion conductivity value increases from 3.0 × 10−5 to 4.4 × 10−4 S cm at 773 K, i.e. the nature of the conductivity change is linearly antibatic. This phenomenon can be useful for developing approaches and search strategies for new ionic conductors. [ABSTRACT FROM AUTHOR]

This paper investigates the Faraday effect and absorption and luminescence spectra of single-crystal TbF3 measured at 90 K and 300 K. The optical-quality single-phase TbF3 crystals (structural type β-YF3) were grown by the Bridgman technique. Faraday rotation angles were measured at remagnetization along the [100] crystallographic axis. Low temperature optical measurements were carried out along the [100] axis. "Quasi-doublet" sublevels with energy at 0 cm-1, 65 cm-1, and 190 cm-1, and also a singlet sublevel with energy at 114 cm-1 located in the ground 7F6 multiplet were determined from the low temperature luminescence spectra. The Van-Vleck behavior of the magnetic susceptibility χb can be satisfactorily explained by the magnetic mixing of wave functions belonging to the ground and first excited "quasi-doublet" sublevels at 0 and 65 cm-1, respectively. Analysis of the oscillation dependences of the rotation angle showed that the value of the natural birefringence (Δn ≈ 0.0186) remains nearly constant within the wavelength and temperature ranges under investigation. As the temperature decreases, we find significant increases in the oscillation amplitude of the rotation angle and in the Verdet constant V. The spectral dependences V(χ) are linear throughout the temperature range. The magnetooptical activity of TbF3 can be explained by means of the spin- and parity-allowed electric-dipole 4f → 5d transitions in the Tb3+ ions. [ABSTRACT FROM AUTHOR]

BaY2F8 nanoparticles (NPs), doped with Yb3+ and Er3+ ions, were successfully produced by high-energy ball-milling. High-quality monoclinic single crystals (sp. gr. C2/m, a = 0.6969(3), b = 1.0502(1), c = 0.4254(1) nm, β = 99.676°) grown from the melt by the Bridgman technique were used as raw materials. The prepared nanocrystals were comprehensively studied by X-ray diffraction analysis, transmission electron microscopy, and optical spectroscopy. The fabrication possibility of single-phase irregular shaped Ba(Y0.964Yb0.030Er0.006)2F8 NPs in the size range of 20–100 nm with a milling duration of 10 h at 600 rpm is demonstrated. Ba(Y0.964Yb0.030Er0.006)2F8 NPs show intense luminescence by both up- (λ = 540 and 650 nm) and down-conversion (λ = 1540 nm) mechanisms upon IR excitation (λ = 980 nm). A qualitative comparison of the spectroscopic characteristics of the produced Ba(Y0.964Yb0.030Er0.006)2F8 NPs with the initial bulk crystal and the widely used up-conversion β-Na1.5(Y1.17Yb0.3Er0.03)F6 NPs is presented. Experimental data offer great opportunities of the Ba(Y0.964Yb0.030Er0.006)2F8 NPs applications in nanophotonics and biotechnology. High-energy ball-milling has potential as a versatile method for the scalable production of fluoride nanoparticles. [ABSTRACT FROM AUTHOR]

Bulk c-oriented CeF3 single crystals (sp. gr. P 3 ¯ c 1 ) were grown successfully by the vertical Bridgman technique in a fluorinating atmosphere. A description of the crystal growth procedure and the solution of the difficulties during the growth process are presented in detail. The anisotropy of the mechanical, thermal and electrophysical properties were studied for the first time. The maximum values of the thermal conductivity coefficient (α = 2.51 ± 0.12 W·m−1·K−1) and the ionic conductivity (σdc = 2.7 × 10−6 S/cm) at room temperature are observed in the [0001] direction for the CeF3 crystals. The Vickers (HV) and Berkovich (HB) microhardnesses for the (0001) , (10 1 ¯ 0) and (11 2 ¯ 0) crystallographic planes were investigated. The HB values were higher than the HV ones and decreased from 3.8 to 2.9 GPa with an increase in the load in the range of 0.5–0.98 N for the hardest (0001) plane. The { 11 2 ¯ 0 } , { 10 1 ¯ 0 } and { 0001 } cleavage planes were observed during the indentation process of the CeF3 crystals. The variability of Young's, the shear modules and Poisson's ratio were analyzed. A significant correlation between the shapes of the Vickers indentation patterns with Young's modulus anisotropy was found. The relationship between the anisotropy of the studied properties and the features of the CeF3 trigonal crystal structure is discussed. [ABSTRACT FROM AUTHOR]

The concentration series of nonstoichiometric crystals Ca1–xYxF2+x (x = 0.01–0.14) was obtained from a melt by directional crystallization to refine the composition of the temperature maximum on the melting curves. A precision (±9 × 10−5 Å) determination of lattice parameters of the Ca1–xYxF2+x crystals with the structure of fluorite (sp. gr. Fm-3m) was performed, and a linear equation of their concentration dependence was calculated: a(x) = 5.46385(5) + 0.1999(4) x. The distribution of yttrium along the crystals Ca1–xYxF2+x, the content of which is determined by the precision lattice parameters, is studied. The congruently melting composition x = 0.105(5) of the Ca1–xYxF2+x phase is refined by the method of directional crystallization. [ABSTRACT FROM AUTHOR]

A series of nonstoichiometric La1–yBayF3–y (0 ≤ y ≤ 0.12) single crystals with a tysonite-type structure (sp. gr. P-3c1) was grown from the melt by the directional crystallization method in a fluorinating atmosphere, and some physical properties were characterized. The concentration dependence of electrical conductivity σdc(y) La1–yBayF3–y crystals was studied. The composition of the ionic conductivity maximum for this solid electrolyte was refined. It was confirmed that the maximum conductivity σmax = 8.5 × 10–5 S/cm (295 K) was observed at the composition ymax = 0.05 ± 0.01. Analysis of the electrophysical data for the group of tysonite-type solid electrolytes R1–yMyF3–y (M = Ca, Sr, Ba, Eu2+ and R = La, Ce, Pr, Nd) showed that the compositions of the maxima of their conductivity were close and amount to y = 0.03−0.05. This fact indicates a weak influence of the size effect (ionic radii R3+ and M2+) on the value of ymax for R1–yMyF3–y solid electrolytes. [ABSTRACT FROM AUTHOR]

The defect structure of Ba0.69La0.31F2.31 single crystals in as-grown state and after annealing at 1173 K for 336 h was studied by X-ray diffraction analysis. Both crystals belong to the CaF2 structure type (sp. gr. F m 3 ¯ m ). They have vacancies in the main anion motif and interstitial fluorine anions in Wyckoff positions 48i and 4b. Relaxation (static displacement of some main anions to Wyckoff position 32f) is observed in the annealed crystal. It was established that annealing leads to a change in the type of displacement of the main anions in Wyckoff positions 8c from dynamic to static. Displacement of La3+ cations to Wyckoff position 32f is observed in both crystals. A model of the defect structure of Ba0.69La0.31F2.31 is proposed, according to which interstitial fluorine anions and La3+ cations are aggregated into [Ba14−nLanF64+n] clusters with the cuboctahedral anionic core formed by interstitial fluorine anions in Wyckoff positions 48i. Ba2+ cations are located in the cluster in the centers of the faces, and the La3+ cations are shifted by 0.24 Å from the vertices of the cluster along the three-fold axis towards the center of the cluster. The study establishes the relationship between the defect structure of crystals and their structurally sensitive properties, and to develop approaches to their management. [ABSTRACT FROM AUTHOR]

Cubic KR3F10 (R = Y, Tb) single crystals have been successfully grown using the Bridgman technique. Growth of crystals of this type is complicated due to the hygroscopicity of potassium fluoride and melt overheating. The solution to the problem of oxygen-incorporated impurities has been demonstrated through the utilization of potassium hydrofluoride as a precursor. In this study, the crystal quality, structure features, and optical, thermal and electrophysical properties of KR3F10 were examined. Data on the temperature dependences of conductivity properties of KTb3F10 crystals were obtained for the first time. These crystals indicated thermal conductivity equal to 1.54 ± 0.05 Wm−1K−1 at room temperature caused by strong phonon scattering in the Tb-based crystal lattice. Ionic conductivities of KY3F10 and KTb3F10 single crystals were 4.9 × 10−8 and 1.2 × 10−10 S/cm at 500 K, respectively, and the observed difference was determined by the activation enthalpy of F− ion migration. Comparison of the physical properties of the grown KR3F10 crystals with the closest crystalline analog from the family of Na0.5−xR0.5+xF2+2x (R = Tb, Y) cubic solid solutions is reported. [ABSTRACT FROM AUTHOR]