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1.
The ultrasonic parameters, the optical parameters along with the IR spectroscopy and magnetic susceptibility studies have been employed to explore the role of Gd2O3 in the structure of the glasses xGd2O3–60B2O3–10MoO3–(30-x)Bi2O3, with 0 ≤ x ≤ 7 mol %. IR analysis indicates that Gd2O3 is preferentially incorporated into the borate network-forming BO4 units. It is assumed that Bi2O3 and MoO3 enter the structure as modifiers in the form of BiO6 and MoO6 only. The compositional dependence of the mechanical and the optical parameters are interpreted in terms of the transformation of the structural units BO3 into BO4, the increase in the number of bridging oxygen atoms, and the substitution of high bond strength Gd–O, in the place of low bond strength Bi–O bond. The results of the magnetic susceptibility reveal the paramagnetic behavior as described by the Curie-Weiss law and indicating the presence of weak antiferromagnetic exchange interactions between Gd3+ ions. The magnetic entropy change of the glasses was determined according to the temperature and magnetic field dependence of magnetization. 相似文献
2.
Analysis of Dopant Atom Distribution and Quantification of Oxygen Vacancies on Individual Gd‐Doped CeO2 Nanocrystals
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Dr. Daniel G. Stroppa Prof. Cleocir J. Dalmaschio Dr. Lothar Houben Dr. Juri Barthel Prof. Luciano A. Montoro Prof. Edson R. Leite Dr. Antonio J. Ramirez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(21):6288-6293
This work reports the analysis of the distribution of Gd atoms and the quantification of O vacancies applied to individual CeO2 and Gd‐doped CeO2 nanocrystals by electron energy‐loss spectroscopy. The concentration of O vacancies measured on the undoped system (6.3±2.6 %) matches the expected value given the typical Ce3+ content previously reported for CeO2 nanoparticles. The doped nanoparticles have an uneven distribution of dopant atoms and an atypical amount of O vacant sites (37.7±4.1 %). The measured decrease of the O content induced by Gd doping cannot be explained solely by the charge balance including Ce3+ and Gd3+ ions. 相似文献
3.
《Chemical physics》2006,322(3):477-484
XAFS experiments at the Mn and Sr K-edges were carried out in order to investigate the short-range arrangement of Mn and Sr sites on La1−xSrxMnO3±δ highly doped perovskites (x = 0, 0.2, 0.4 and 0.6). The Mn K-edge EXAFS spectra show a static Jahn–Teller distortion of the MnO6 for x = 0 and 0.2, which is drastically reduced as x increases. The distortion of perovskite, characterized by the Mn–O–Mn tilt angle, progressively decreases with increasing Sr contents. Sr K-edge results indicated a decrease on the Sr–Mn coordination number upon Sr doping. Based on this and TPD results, a charge compensating mechanism is proposed suggesting a partial Mn oxidation and formation of Mn defect vacancies due to the introduction of Sr. 相似文献
4.
Optical absorption and EPR spectroscopic studies were carried on (30 ? x)Li2O–xK2O–10CdO–59B2O3–1Fe2O3 (x = 0–30) glass system to understand the effect of progressive doping of Li+ ion with K+ ion. Optical absorption results show typical spectra of Fe3+ ions and the various optical parameters such as, optical band gap, Urbach energy, oxide ion polarizability, optical basicity and interaction parameter were evaluated from the experimental data. The observed optical band gap and Urbach energy values show large deviation from the linearity where as the other parameters show small deviation from the linearity with the progressive substitution of Li+ ions with K+ ions. The observed EPR spectra are representative of Fe3+ ion in octahedral and axial fields in the glass network. The number of paramagnetic centers and paramagnetic susceptibility values were evaluated at different resonance lines for all the specimens and these parameters show non-additive nature with the progressive substitution of Li+ ions with K+ ions in the glass network. This is first ever observation of mixed alkali effect (MAE) in EPR and optical parameters of mixed alkali borate glasses. 相似文献
5.
Realizing the ubiquitous presence of rare-earth orthoborates in various applications involving their optical properties, the current investigation is directed towards the exploration of epoxide mediated rapid synthesis to make YBO3. Highly crystalline orthoborate with disordered vaterite structure resulted on calcining xerogel from the reaction of yttrium chloride, boric acid and propylene oxide at 900 °C as verified from diffraction, vibration spectroscopic and microscopic techniques. Following this approach, orthoborate containing 50 mol% of Y and Gd was obtained and characterized. Dissolution limit of Ce3+ in Y0.50Gd0.50BO3 has been determined. Cerium doping resulted in the reduction in the optical band gap of these samples and appended photocatalytic ability in terms of degradation of aqueous rhodamine-6G (Rh-6G) dye solution. The intensity of 4f → 5d transition of Ce3+ increased monotonously with increase in cerium content. The role of distortion on the blue emission from Ce3+ and photocatalytic properties of these samples were comprehended by characterizing Li+, Ca2+ and Al3+-doped samples (up to 10 mol%) for yttrium. The distortion of Y0.50?xMxGd0.45Ce0.05BO3 lattice decreased in the order, RCa2+ > RY3+ > RLi+ > RAl3+, with the emission intensity (5d → 4f transitions) from Ce3+ increasing in the reverse order. Optical band gap was found to decrease for the Li+, Ca2+ and Al3+ doped samples as compared to undoped one. These doped samples retained their catalytic ability as verified from their use in the photo degradation of rhodamine-B (Rh-B) dye. An insight in to possible mechanism operative in the present photo catalytic degradation experiments has been attempted by carrying out trapping experiments. 相似文献
6.
Transparent glasses, melt quenching derived, containing 10RO·20Bi2O3·(70 ? x)B2O3·xTiO2 [R = Ca, Sr] with x = 0, 0.5, 1.0 wt% were characterized by X-ray powder diffraction. Physical and spectroscopic properties viz., density, absorption, emission, electron paramagnetic resonance (EPR) and FTIR were investigated. The absorption band around 823 nm in pure glass samples is attributed to the electronic transition of 3P0 to 3P2 of Bi+ radicals. A small absorption hump centered around 609 nm is found in all doped glasses due to 2T2g to 2Eg transition of octahedral Ti3+ ions. The emission results revealed that all the samples exhibit a broad emission band covering entire visible-light range, with λex = 360 nm, centered 470–520 nm corresponds to electronic transition of 3P1 to 1S0 of Bi3+ ions, therefore the present materials can be potentially used as tunable or full-color display systems. And a strong emission around 706 nm with λex = 514 nm due to transition of 2P3/2 to 2P1/2 of Bi2+ ions. In SrO mixed glasses Ti4+ ions effect the environment of Bi3+ ion symmetry units from C2 to C3i. A small EPR signal (at room temperature) is observed in titanium doped glasses due to Ti3+ ions. In both the series with increase of TiO2 concentration BO4 units are gradually converted into BO3 units and new cross linkages are formed, like B–O–Ti, Bi–O–Ti at the expense of B–O–B bonds. 相似文献
7.
A. Zalga Z. Moravec J. Pinkas A. Kareiva 《Journal of Thermal Analysis and Calorimetry》2011,105(1):3-11
The preparation and characterization of the M′–M′′–O nitrate–tartrate (M′ = Ca, Ba, Gd and M′ = W, Mo) precursor gels synthesized
by simple, inexpensive, and environmentally benign aqueous sol–gel method is reported. The obtained gels were studied by thermal
(TG/DSC) analysis. TG/DSC measurements revealed the possible decomposition pathway of synthesized M′–M′′–O nitrate–tartrate
gels. For the synthesis of different metal tungstates and molybdates, the precursor gels were calcined at different temperatures
(650, 800, and 900 °C). According to the X-ray diffraction (XRD) analysis data, the crystalline compounds CaMo1-x
W
x
O4 doped with Ce3+ ions, BaMo1-x
W
x
O4 doped with Eu3+ ions and Gd2Mo3O12 were obtained from nitrate–tartrate gels annealed at 650–900 °C temperatures. The XRD data confirmed that the fully crystalline
single-phase powellite, scheelite, or Gd2(MoO4)3 structures were formed already at 650 °C. Therefore, the suggested sol–gel method based on the complexation of metal ions
with tartaric acid is suitable for the preparation of mixed tungstates–molybdates at relatively low temperature in comparison
with solid-state synthesis. 相似文献
8.
Partial substitution of cations and anions in perovskite-type materials is a powerful way to tune the desired properties. The systematic variation of the cations size, the partial exchange of O2− for N3− and their effect on the size of the optical band gap and the thermal stability was investigated here. The anionic substitution resulted in the formation of the orthorhombic perovskite-type oxynitrides Mg0.25Ca0.65Y0.1Ti(O,N)3, Ca1-xYxZr(O,N)3, and Sr1–xLaxZr(O,N)3. A two-step synthesis protocol was applied: i) (nano-crystalline) oxide precursors were synthesized by a Pechini method followed by ii) ammonolysis in flowing NH3 at T = 773 K (Ti) and T = 1273 K (Zr), respectively. High-temperature synthesis of such oxide precursors by solid–state reaction generally resulted in phase separation of the different A-site cations. Changes of the crystal structures were investigated by Rietveld refinements of the powder XRD data, thermal stability by DSC/TG measurements in oxygen atmosphere, oxygen and nitrogen contents by O/N analysis using hot gas extraction technique, and optical band gaps by photoluminescence spectroscopy. By moving from Mg0.25Ca0.65Y0.1Ti(O,N)3 via Ca1–xYxZr(O,N)3 to Sr1–xLaxZr(O,N)3, the degree of tilting of the octahedral network is reduced, as observed by an increase in the B–X–B angles caused by the simultaneously increasing effective ionic radius of the A-site cation(s). In general, increasing substitution levels on the A-site (Y3+ and La3+) are accompanied by an enhanced replacement of O2− by N3−. In all three systems, this anionic substitution resulted in a reduction of the optical band gap by approximately 1 eV (Ti) and up to 2.1 eV (Zr) compared to the respective oxides. For Mg0.25Ca0.65Y0.1Ti(O,N)3 an optical band gap of 2.2 eV was observed, appropriate for a solar water splitting photocatalyst. The Zr-based oxynitrides required a by a factor of 2 higher nitrogen contents to significantly reduce the optical band gap and the measured values of 2.9 eV–3.2 eV are larger compared to the Ti-based oxynitride. Bulk thermal stability was revealed up to T = 881 K. In general, the thermal stability decreased with increasing substitution levels due to an increasing deviation from the ideal anionic composition as demonstrated by O/N analysis. 相似文献
9.
C. Aydın Sh. A. Mansour Z. A. Alahmed F. Yakuphanoglu 《Journal of Sol-Gel Science and Technology》2012,62(3):397-403
Pure and boron (B) doped iron oxide (Fe2O3) nanostructured thin films were prepared by sol–gel spin coating method. The effects of B (0.1, 0.2, 0.5 and 1 %) content
on the crystallinity and morphological properties of Fe2O3 films were investigated by X-ray diffractometer and atomic force microscopy. X-ray diffraction patterns revealed that the
Fe2O3 films have a rhombohedral crystalline phase of α-Fe2O3 phase (hematite) with nanostructure and their crystallite size (D) is changed from 27 ± 2 to 45 ± 5 nm with B dopant content.
The minimum crystallite size value of 27 ± 2 nm was obtained for 0.2 % B doped Fe2O3 film. Carrying out UV–VIS absorption study for both doped and undoped films at room temperature, it was realized that allowed
optical transitions may be direct or indirect transitions. The direct and indirect energy gap values for pure Fe2O3 were obtained to be 2.07 and 1.95 eV, respectively. The optical band gap value of the films was changed with 0.1 % B doping
to reach 1.86 eV for direct band gap and 1.66 eV in case of indirect band gap. 相似文献
10.
The luminescence properties of 2%Er3+/15%Yb3+ doped LnP0.5V0.5O4 (LnPVO4) (Ln = Y, Gd, La) phosphors, synthesized via the traditional citric-assisted Sol gel method, are studied under light excitations of 980 nm and 325 nm to generate the 2H11/2/4S3/2–4I15/2 transitions via up- and downshifting mechanisms, respectively. The phase purity of the samples was characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). We present herein a comparative study of the spectral and temperature sensing properties of LnPVO4: Er3+/Yb3+ (Ln = Y, Gd, La) phosphors. The crystal field effects on the up-shifting luminescence and on the thermometric parameters are investigated by the substitution of Er3+ ions on Y3+, Gd3+ or La3+ sites in the YPVO4, GdPVO4 and LaPVO4 hosts respectively. Fluorescence intensity ratio (FIR) technique was used to study the temperature sensing behavior of the phosphors. This study showed that downshifting emission gives the highest thermal sensitivities and the greatest thermal resolution compared to downshifting emission. These outcomes indicate that these materials are preferred for use in the luminescence temperature sensing in a down-conversion process to provide the greatest performance. 相似文献
11.
A solid-solution of cerium-substituted alkaline earth scandium silicate phosphors, (Ba1−xSrx)9Sc2Si6O24:Ce3+,Li+ (x = 0, 0.25, 0.50, 0.75, 1), have been prepared by solid-state reaction. The structures, characterized using synchrotron X-ray powder diffraction, show the solid-solution closely follows Vegard's law. The substitution of Sr for Ba results in a decrease of the alkaline earth–oxygen bond distances by more than 0.1 Å at all three crystallographic sites, leading to changes in optical properties. The room temperature photoluminescent measurements show the structure has three excitation peaks corresponding to Ce3+ occupying the three independent alkaline earth sites. The emission of (Ba1−xSrx)9Sc2Si6O24:Ce3+,Li+ is red-shifted from the near-UV (λmax = 384 nm) for x = 0 to blue (λmax = 402 nm) for x = 1. The red-shifted photoluminescent quantum yield also increases when Sr is substituted for Ba in these compounds. 相似文献
12.
《Arabian Journal of Chemistry》2020,13(1):474-480
In this paper, luminescence properties of orthovanadates, Y1−x−yGdxVO4:ySm3+ (where x = 0.05–0.50, y = 0.01–0.05), and the energy transfer mechanism from VO43− to Sm3+ via Gd3+ ions were investigated in detail. X-ray diffraction (XRD) analysis confirmed the crystalline phase for synthesized nanophosphor in a tetragonal structure with I41/amd space group. The average crystallite size estimated from XRD was ∼28 nm. Field-emission scanning electron microscopy coupled with energy dispersive X-ray analysis revealed oval shaped morphology and composition of the nanophosphor, respectively. From high-resolution transmission electron microscopy observations, the particle sizes were found to be in the range 10–80 nm. The photoluminescence studies of Y0.77Gd0.20VO4:0.03Sm3+ nanophosphor under 311 nm excitation exhibits dominant emission peak at 598 nm corresponding to 4G5/2 → 6H7/2 transition. The energy transfer occurs from VO43− to Sm3+ via Gd3+ ions was confirmed by applying Dexter and Reisfeld’s theory and Inokuti-Hirayama model. Moreover, the energy transfer efficiencies and probabilities were calculated from the decay curves. Furthermore, Commission Internationale de l’Eclairage (CIE) color coordinate (0.59, 0.37) has been observed to be in the orange-red (598 nm) region for Y0.77Gd0.20VO4:0.03Sm3+ nanophosphor. These results perfectly established the suitability of these nanophosphors in improving the efficiency of silicon solar cells, light emitting diodes, semiconductor photophysics, and nanodevices. 相似文献
13.
Herein, we synthesized molybdenum oxide quantum dots using bovine serum albumin as a ligand (BSA-MoOx QDs) via a simple method. The synthesized fluorescent BSA-MoOx QDs were stable, and blue fluorescence was noticed upon exposure to UV lamp at 365 nm. When excited at 320 nm, BSA-MoOx QDs showed an emission peak at 406 nm. Atomic force microscopic images demonstrated that the thickness of BSA layer on the surface of MoOx QDs is 3.9 ± 1.6 nm. The as-synthesized BSA-MoOx QDs acted as a sensor for the detection of digoxin, La3+, and epinephrine via fluorescence OFF-ON-OFF mechanisms, exhibiting linear ranges of 1–25, 0.125–5, and 0.5–10 μM with lower detection limits of 9.74, 23.08, and 4.58 nM for digoxin, La3+, and epinephrine, respectively. This method was successfully demonstrated to be an effective analytical platform for measuring digoxin and epinephrine in pharmaceutical and biofluid samples. 相似文献
14.
Zhang Ruo-Hua Wang Hong-Mei Liao Dai-Zheng Chen Jing-Tang Wang Hong-Gen Yao Xing-Kan 《中国化学》1996,14(6):506-515
The crystal structure of [Gd2(μ-L)3(H2O)2]1.5(NO3)1.5 (OH)5H2O (where L is union of N, N-Diisonicotinoyl-2-hydroxy-5-methyl-isophthalaldehyde dihydrazone) has been determined by X-ray diffraction method. The complex crystallizes in the monoclinic system, space group P21/c with a=1.6654(3), b=1.6904(3), c=2.8039(6) nm, β=91.30(3), final R factor is 6.3%. The structure consists of [Gd2(μ-L)3(H2O)2]3+ cation, one and a half nitrate and 1.5 hydroxyl anions and five water molecules. Within dinuclear cation, Gd(III)—Gd(III) is bridged by oxygen and nitrogen atoms of the three ligands, resulting in Gd? Gd distance of 0.36353(2) nm. Gd(III) exhibits a distorted 1333 stack coordination environment. Magnetic susceptibility measurements in the temperature range 300–4 K revealed the occurrence of weak antiferromagnetic exchange interaction between two Gd(III) ions with a J value of—0.22, and g of 1.93. 相似文献
15.
Correlation of crystal structure with electric field gradient (EFG) in the fluorite- and pyrochlore-type compounds in the Gd2O3-ZrO2 system GdxZr1−xO2−x/2 with 0.18?x?0.62 were investigated by 155Gd Mössbauer spectroscopy, powder X-ray diffraction and point-charge model (PCM) calculation. An intermediate ordered pyrochlore phase forms for 0.45?x?0.55, sandwiched with a disordered fluorite phase for 0.18?x<0.45 and 0.55<x?0.62. Some 155Gd Mössbauer parameters, especially the quadrupole coupling constant (e2qQ), were found to exhibit a characteristic maximum around the ideal-pyrochlore Gd2Zr2O7 (x=0.50) composition. The validity of the proposed pyrochlore-based structural model was examined by comparing the experimental values of EFG at the Gd sites with those calculated by the PCM calculations. 相似文献
16.
V. V. Bakovets L. N. Trushnikova P. E. Plyusnin I. V. Korolkov I. P. Dolgovesova T. D. Pivovarova S. A. Savintseva 《Russian Journal of General Chemistry》2013,83(10):1808-1814
The process of dehydration of Gd(OH)3·nH2O obtained by the sol-gel method from a solution of Gd(NO3)3, to Gd2O3 in the temperature range of 50–700°C was explored. The hydrogel and Gd2O3 structurization is shown to depend on the additives (AF-12 and 2-propanol). The final average particle size of Gd2O3 after annealing at 700°C is 20±2 nm, depending on the conditions of the synthesis. The resulting oxide particles are larger than the particles of yttrium oxide Y2O3 (17±2) obtained under the same conditions of the process due to the higher basicity of gadolinium and its higher coordination number with respect to the OH groups. This promotes the formation of crystalline phases of Gd(OH)3 at lower temperature, 50–250°C, while maintaining a favorable structural short-range order in passing through an amorphous state to a crystalline Gd2O3. 相似文献
17.
Yuzuki Eda Tomoyo Manaka Takao Hanawa Peng Chen Maki Ashida Kazuhiko Noda 《Surface and interface analysis : SIA》2022,54(8):892-898
Titanium (Ti) is always covered by thin passive films. Thus, valence band (VB) spectra, obtained using X-ray photoelectron spectroscopy (XPS), are superpositions of the VB spectra of passive films and that of the metallic Ti substrate. In this study, to obtain the VB spectra only of passive films, angular resolution (for eliminating the substrate Ti contribution) and argon ion sputtering (for removing passive films) were used along with XPS. The passive film on Ti was determined to consist of a very thin TiO2layer with small amounts of Ti2O3, TiO, hydroxyl groups, and water with a thickness of 5.9 nm. The VB spectra of Ti were deconvoluted into four peak components: a peak at ~1 eV, attributed to the Ti metal substrate; a broad peak in the 3–10 eV range, mainly attributed to O 2p (~6 eV) and O 2p-Ti 3d hybridized states (~8 eV), owing to the π (non-bonding) and σ (bonding) orbitals in the passive oxide film; and a peak at ~13 eV, attributed to the 3σ orbital of O 2p as OH−or H2O. The VB region spectrum between approximately 3 and 14 eV from Ti is originating from the passive film on Ti. In particular, characterization of VB spectrum obtained with a takeoff angle of less than 24° is effective to obtain VB spectrum only from the passive film on Ti. The property as n-type semiconductor of the passive film on Ti is probably higher than that of rutile TiO2ceramics. 相似文献
18.
In this study, lithium yttrium borate (LYBO) phosphor was doped with various concentrations of trivalent dysprosium ions. To produce these phosphors, the raw materials were sintered. The phase conformation, crystallinity, grain size, and overall morphology of the synthesized phosphors were studied with X-ray diffraction and scanning electron microscopy. The optimized LYBO phosphor, i.e., the LYBO phosphor that exhibited the highest X-ray- and ultraviolet (UV)-induced photoluminescent intensities, had a Dy3+ concentration of 4 mol%. Photoluminescence analysis showed that this phosphor could be easily excited with near-UV light (300–400 nm). The dominant photoluminescence bands were found in the blue (480 nm) and yellow (577 nm) regions of the visible spectrum. The light yield of the X-ray-induced luminescence of the optimized Li6Y(BO3)3:Dy3+ was found to be 66% of that of the commercially available X-ray imaging material, Gd2O2S:Tb3+ (GOS). The chromaticity coordinates of the Li6Y(BO3)3:Dy3+ phosphor were x = 0.34 and y = 0.32, which agree well with achromatic white (x = 0.33, y = 0.33). The results of this study show that the synthesized Li6Y(BO3)3:Dy3+ phosphor could be used as X-ray imaging material. 相似文献
19.
《Electrochemistry communications》2007,9(2):245-248
A new type of lithium ion conducting solid electrolyte based on a cubic rare earth oxide was developed by co-doping LiNO3 and KNO3 into a (Gd1−xNdx)2O3 solid, which possesses large interstitial open spaces within the structure. Among the samples prepared, 0.6(Gd0.4Nd0.6)2O3–0.16LiNO3–0.24KNO3 exhibits the highest lithium ion conductivity of 8.05 × 10−2 and 1.35 × 10−3 S cm−1 at 400 and 100 °C, respectively, which is comparable to that of the LISICON materials. Pure Li+ ion conduction was successfully demonstrated by the dc electrolysis method. 相似文献
20.
Synthesis,properties and mechanism of photodegradation of core–shell structured upconversion luminescent NaYF4:Yb3+,Er3+@BiOCl
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Shiyu Zhou Qiyan Zhang Deqiang Zhao Wenjuan Zong Zihong Fan Yaofang Sun Xuan Xu 《应用有机金属化学》2018,32(4)
Microspherical bismuth oxychloride (BiOCl) can only utilize ultraviolet (UV) light to promote photocatalytic reactions. To overcome this limitation, a uniform and thin BiOCl nanosheet was synthesized with a particle size of about 200 nm. As results of UV–visible diffuse reflectance spectroscopy showed, the band gap of this nanostructure was reduced to 2.78 eV, indicating that the BiOCl nanosheet could absorb and utilize visible light. Furthermore, the upconversion material NaYF4 doped with rare earth ions Yb3+ and Er3+ emitted visible light at 410 nm following excitation with near‐infrared (NIR) light (980 nm), which could be utilized by BiOCl to produce a photocatalytic reaction. To produce a high‐efficiency photocatalyst (NaYF4:Yb3+,Er3+@BiOCl), BiOCl‐loaded NaYF4:Yb3+,Er3+ was successfully synthesized via a simple two‐step hydrothermal method. The as‐synthesized material was confirmed using X‐ray diffraction, scanning electron microscopy, X‐ray photoelectron spectroscopy as well as other characterizations. The removal ratio of methylene blue by NaYF4:Yb3+,Er3+@BiOCl was much higher than that of BiOCl alone. Recycling experiments verified the stability of NaYF4:Yb3+,Er3+@BiOCl, which demonstrated excellent adsorption, strong visible‐light absorption and high electron–hole separation efficiency. Such properties are expected to be useful in practical applications, and a further understanding of the NIR‐light‐responsive photocatalytic mechanism of this new catalytic material would be conducive to improving its structural design and function. 相似文献