Electrode kinetics of Eu3+/Eu2+ reaction by cyclic voltammetry

The cyclic voltammetric behaviour of Eu³⁺/Eu²⁺ couple at hanging mercury drop electrode (HMDE) has been studied in chloride, bromide, iodide, thiocyanate and EDTA supporting electrolytes. The apparent rate constant and transfer coefficient for these systems have been calculated at various voltage scan rates, without using the data for standard or formal potential. The values have been compared with those obtained by earlier workers through other electrochemical methods.     

Double-layer effects on simple electrode reactions II. The effects of specifically adsorbed anions and ion-pairing on the reduction of Eu3+ and Cr3+

The kinetics of the reduction of Eu³⁺ and Cr³⁺ at mercury electrodes have been studied in various mixed perchlorate electrolytes containing iodide, bromide, and p-toluene-sulfonate as adsorbing anions. Specific adsorption data were obtained by means of the constant ionic strength approach due to Hurwitz and Parsons. The rate enhancements observed in the presence of the first two (monatomic) anions were in good agreement with the predictions of the simple Frumkin model only when the experimental, rather than calculated diffuse-layer capacitances were employed in the data analysis. It was demonstrated that the effects of ion-pairing and ligand-bridging of the reactants with the adsorbing anions were negligible under the experimental conditions chosen. From experiments with these systems and also with weakly adsorbing chloride electrolytes it was concluded that ion-pairing did not enhance the electrochemical reactivity of either Eu³⁺ or Cr³⁺. The value of the analyses described in separating various contributions to the catalytic effects of adsorbing anions is emphasized.     

Double-layer effects on simple electrode reactions I. The reduction of Eu3+ and Cr3+ in the absence of specific adsorption of the supporting electrolyte

The kinetics of the reduction of Eu³⁺ and Cr³⁺ at mercury electrodes in various sodium and lanthanum perchlorate supporting electrolytes have been studied over as large a potential range as possible by using both chronocoulometry and d.c. polarography. The objective was to determine the effect of the diffuse double layer upon the reduction rates of these members of the simplest class of electrode reactions in the absence of specific adsorption. Possible additional influences from perchlorate specific adsorption, ion-pairing, and ionic strength-dependent formal potentials, and differences between the site of reaction and the o.H.p. were also considered. The effects of specific adsorption of an uncharged molecule were assessed by noting the changes in the reduction kinetics of Eu³⁺ caused by the adsorption of thiourea.The classical Gouy-Chapman-Stern model of the double layer was found to give an adequate account of the behavior in relatively dilute lanthanum perchlorate solutions, but it failed badly in more concentrated sodium perchlorate media. Better agreement resulted if the statistical theory due to Krylov and Levich was employed but some discrepancies remained. The diffuse-layer properties evaluated here represent a useful basis for comparisons with systems where specific ionic adsorption of components of the supporting electrolyte adds a second component to the electrode surface charge density which determines the diffuse-layer potential.     

吸附在Pt/C催化剂上Eu3+对CO电氧化的促进作用

目前影响质子交换膜燃料电池(PEMFC)迅速发展并商业化的主要问题之一是阳极催化剂抗CO的毒化能力。Pt因其对氢的氧化具有高的催化活性而广泛地用作PEMFC的阳极催化剂，也有人研究将其它金属用于PEMFC阳极催化剂，但催化活性要比Pt低得多。而Pt作PEMFC的阳极催化剂一个问题是痕量的CO，如10-100ppm就可以使Pt催化剂中毒。     

Eu3+ concentration dependent optical properties and energy transfer from host Gd3+ to Eu3+ in GdF3 nanocrystals

By using a hydrothermal method, a series of Eu³⁺ concentration dependent GdF₃ nanocrystals have been synthesized. The crystalline structures of samples are characterized by XRD patterns, the morphology and size of the samples are illustrated by FE-SEM images, and the optical properties of the samples are presented by PL excitation and emission spectra. The energy transfer from host Gd³⁺ to Eu³⁺ is observed in the Eu³⁺ doped GdF₃ nanocrystals. The optical properties of Eu³⁺ and the energy transfer efficiency from host Gd³⁺ to Eu³⁺ are discussed on the basis of the Eu³⁺ concentration dependent integrated PL excitation and emission spectra of Gd³⁺ and Eu³⁺. The discussion on optical properties of Eu³⁺ and the energy transfer from Gd³⁺ to Eu³⁺ is meaningful to design and synthesize Gd³⁺ based compounds.     

A Logic Fluorescent Chemosensor Based on Eu3+ Functionalized Cd-MOFs for Sensing Fe3+ and Cu2+ Synchronously

One of the most critical and yet unsolved issues is the effective monitoring of multiple heavy metal ions in complex systems through their specific function in fluorescence detection. In this work, luminescence-active cadmium base metal-organic frameworks (Cd-MOFs) based on the planar and rigid π-conjugated structure ligand benzo-(1,2;3,4;5,6)-tris (thiophene-2’-carboxylic acid) (H₃BTTC) was chosen. A series of sensing experiments demonstrated that the Cd-MOFs exhibits selective and sensitive response for Fe³⁺ and Eu³⁺ through fluorescence “turn off” and “antenna effect” respectively. In addition, the encapsulation of Eu³⁺ inside the Cd-MOFs (Eu³⁺@Cd-MOFs) led to an excellent probe with dual emission. To this end, a programmable fluorescence platform was developed to detect Fe³⁺ and Cu²⁺, in which the emission peaks of both the ligand and Eu³⁺ are completely quenched by Fe³⁺. The ratiometric detection of Cu²⁺ leads to a decrease in Eu³⁺ emission, while the ligand emission remains stable. To demonstrate the strategy, the fluorescence (Output) of Cd-MOFs, Eu³⁺@Cd-MOFs, and the analytes (Eu³⁺, Fe³⁺, and Cu²⁺, input) achieved elementary Boolean logic operations (OR, NOR, AND) and they constitute a logic fluorescent chemosensor to analyze Fe³⁺ and Cu²⁺ synchronously.     

Electronic excitation energy transfer between Tb3+ and Eu3+ in DMSO

Excitation of Tb³⁺ and Eu³⁺ in DMSO with 487 mμ, which corresponds to the ⁷F₆ → ⁵D₄ transition of Tb³⁺, is accompanied by a reduction in the fluorescence efficiency of Tb³⁺ as [Eu³⁺] increases and by the appearance of a weak emission from Eu³⁺. An average rate constant for both the fluorescence quenching of Tb³⁺ and the energy transfer from Tb³⁺ to Eu³⁺ with subsequent emission from the latter, was found to be (2.2 ± 0.4) × 10³ M^?1 sec^?1.     

Energy Transfer Between Eu3+ Ions and CdS Quantum Dots in Sol-Gel Derived CdS/SiO2 : Eu3+ Gel

We have investigated the energetic correlation between rare-earth ions and semiconductor nanocrystals, using europium ion (Eu³⁺) doped silica (SiO₂) gel with adsorbed cadmium sulfide (CdS) particles. Samples were prepared by a sol-gel technique, in which several methods for the precipitation of CdS colloids were attempted. The fluorescence intensities were compared for different gels, with and without CdS particles. The intrinsic emission lines due to ⁵D₀ ⁷F_J(J = 0–4) transitions of Eu³⁺ were observed, which were enhanced for 24 h-immersed gel (dried at 50°C). From the results on the decay dynamics of fluorescence, we proposed the model that surface-trapped electrons on CdS particles nonradiatively excited 4f electrons in Eu³⁺ ions due to an energy transfer process.     

Separation of strontium from simulated waste in K2SO4/Nitrate medium containing Sr2+, Eu3+, Ce3+, Pd2+, Rh3+, Ru3+, UO 2 2+ , Fe3+, Cr3+, Ni2+, Al3+, Ca2+ and Cs+, by strongly basic anion exchanger

In this work Strontium was separated selectively form, Pd²⁺, Ni²⁺ and Ca³⁺ using anionic resins of Amberlite type IRA-900 and IRA-410 from nitrate medium. The Separation of strontium by strongly basic anion exchangers IRA-410 and IRA-900 from simulated waste containing, Sr²⁺, Eu³⁺, Ce³⁺, Pd²⁺, Rh³⁺, Ru³⁺, VO₂ ²⁺, Fe³⁺, Cr³⁺, Ni²⁺, Al³⁺, Ca²⁺, and Cs⁺, in K₂SO₄/nitrate medium which adsorbed as strontium sulphate complex was achieved through ligand- ligan exchange. The elution of strontium carried out via “loading” the column with a solution of 0.03N EDTA in presence of 0.1N NaNO₃ at pH7 where Sr²⁺ has low K_d value. An inductively Coubled Plasma — Optical Emission Spectrometry (ICP — OES) of ARL type model 3520, was used for elemental analysis.     

Tunable luminescence and energy transfer process between Tb3+ and Eu3+ in GYAG:Bi3+, Tb3+, Eu3+ phosphors

A series of Eu³⁺ ions co-doped (Gd_0.9Y_0.1)₃Al₅O₁₂:Bi³⁺, Tb³⁺ (GYAG) phosphors have been synthesized by means of solvothermal reaction method. The XRD pattern of GYAG phosphor sintered at 1500 °C confirms their garnet phase. The luminescence properties of these phosphors have been explored by analyzing their excitation and emission spectra along with their decay curves. The excitation spectra of the GYAG:Bi³⁺, Tb³⁺, Eu³⁺ phosphors consists of broad bands in the shorter wavelength region due to 4f⁸ → 4f⁷5d¹ transition of Tb³⁺ ions overlapped with 6s² → 6s¹6p¹ (¹S₀ → ³P₁) transition of Bi³⁺ ions and the charge transfer band of Eu³⁺–O^2?. The present phosphors exhibit green and red colors due to ⁵D₄ → ⁷F₅ transition of Tb³⁺ ions and ⁵D₀ → ⁷F₁ transition of Eu³⁺ ions, respectively. The emission was shifted from green to red color by co-doping with Eu³⁺ ions, which indicate that the energy transfer probability from Tb³⁺ to Eu³⁺ ions are dependent strongly on the concentration of Eu³⁺ ions.     

Rare earth complexes chemiluminescence catalyzed by gold nanoparticles for fast sensing of Tb3+ and Eu3+

Developing multiplex sensing technique is of great significance for fast sample analysis. However, the broad emissions of most chemiluminescence(CL) luminophores make the multiplex CL analysis be difficult. In this work, a simple and sensitive CL analytical method has been developed for the simultaneous determination of Tb³⁺and Eu³⁺thanking to their narrow band emission. The technique was based on a mixed CL system of periodate(IO₄^-)-hydrogen peroxide(...     

Effect of Sr2+ doping on the luminescence properties of YVO4:Eu3+,Sr2+ particles prepared by a solvothermal method

Well-dispersed Eu³⁺ and Sr²⁺ co-doped YVO₄ luminescent particles (YVO₄:Eu³⁺,Sr²⁺) on the submicron scale were prepared by a facile solvothermal method at low temperature. The effect of Sr²⁺ doping on the luminescence of YVO₄:Eu³⁺,Sr²⁺ particles was investigated by fixing the Eu³⁺ doping concentration at 7 mol%. It was found that the luminescence intensity of the as-prepared YVO₄:Eu³⁺,Sr²⁺ particles increased with the Sr²⁺ doping concentration x to reach a two-fold enhancement when x = 5 %, and then decreased for higher x. We also investigated the effect of thermal annealing on the luminescence properties of the YVO₄:Eu³⁺ and YVO₄:Eu³⁺,Sr²⁺ particles. A remarkable enhancement in their luminescence properties was observed after annealing at 900 °C in air for 30 min. It was showed that the annealed YVO₄:Eu³⁺,Sr²⁺ particles exhibited a two-fold stronger emission than the annealed YVO₄:Eu³⁺. This work indicates that Sr²⁺ doping is beneficial to the luminescence enhancement for both the as-prepared and annealed YVO₄:Eu³⁺,Sr²⁺ particles.     

Anodic Protection. Theory and Practice in the Prevention of Corrosion.: O.L. Riggs,Jr. and C.E. Locke,Plenum Press,New York, 1981, 284 pp., US$39.50.

The specific adsorption of chloride, bromide, iodide, azide, and thiocyanate has been studied at an electropolished polycrystalline silver-aqueous interface using differential capacitance measurements. For chloride, bromide, and azide, quantitative estimates of the surface concentration of specifically adsorbed anions were obtained from capacitance-potential data in mixed fluoride electrolytes having a constant ionic strength of 0.5. The dependence of the measured capacitance upon the ionic strength of sodium fluoride was also investigated in order to check the behavior of the polycrystalline surface in comparison with the predictions of conventional double-layer models. Estimates of the specifically adsorbed charge densities of chloride, bromide, and thiocyanate anions were also obtained from a “kinetic probe” technique which entailed monitoring the response of the outer-sphere reduction rate of CO(NH₃)₅F²⁺ and Co(NH₃)₆³⁺ to the addition of the appropriate adsorbing anion. At the average potential of zero charge for the polycrystalline silver surface, the standard free energies of adsorption ? Δ₃^o for chloride, bromide, and azide were found to be within ca. 5 kJ mol^?1 of the corresponding quantities obtained at mercury electrodes. However. significantly greater increases in ? Δ₃^o in the sequence Cl^? < N₃^? < Br^? are seen at silver compared to mercury. Electrochemical roughening in chloride media, giving silver surfaces displaying intense surface Raman scattering, yields only minor changes in the surface concentration of specifically adsorbed chloride anions.     

Tuning Mixed‐Valent Eu2+/Eu3+ in Strontium Formate Frameworks for Multichannel Photoluminescence

Cooperative performance of mixed‐valent Eu²⁺/Eu³⁺ in single‐compound phosphors offers significant advantages in color rendering and luminescence efficiency, but their synthesis is challenging because of Eu²⁺ oxidation. Using the tunable nature of the metal‐ion nodes in metal–organic frameworks (MOFs), we present an in situ reduction and crystallization route for preparing MOFs and doping Eu²⁺/Eu³⁺ with a controlled ratio. These materials exhibit rich photoluminescence, including intrinsic‐ and sensitized‐emissions of Eu²⁺ and Eu³⁺, and long‐lived luminescence from charge transfer. Color rendering can be easily achieved by fine‐tuning the valence states of Eu. A linear relation between temperature and the intensity ratio of Eu²⁺/Eu³⁺ emissions provides outstanding properties for applications as self‐calibrated luminescent thermometers with a wide working temperature range. Further incorporation of Tb³⁺ into the MOFs results in white light, utilizing all Eu²⁺,Tb³⁺, and Eu³⁺ emissions in a single crystalline lattice.     

Thermal study in Eu3+-doped boehmite nanofibers and luminescence properties of the corresponding Eu3+:Al2O3

Eu³⁺-doped boehmite nanofiber materials with different Eu³⁺ concentrations were synthesized without any surfactant, and followed by a series of characterizations. It was found that the boehmite nanofibers became coarser with the increase of Eu³⁺ concentration, which resulted in a gradual decrease of their specific surface areas. Moreover, the thermal stability of the boehmite nanofibers was studied by thermogravimetry–differential scanning calorimetry. All materials showed the phase transition from γ-Al₂O₃ to other forms. Yet the transition temperature was increased with the increase of Eu³⁺ concentration. The Eu³⁺-doped boehmite nanofibers with the maximum Eu³⁺ concentrations showed the best thermal stability. Photoluminescence spectra showed that the 2 mol% of doping concentration of Eu³⁺ ions in Eu³⁺:Al₂O₃ nanofiber was optimum.     

The critical concentration for quenching of the Eu3+ luminescence in some Gd3+ : Eu3+ systems

The critical concentration for quenching of the Eu³⁺ luminescence is calculated theoretically for several Gd³⁺ : Eu³⁺ systems. A comparison is made with the experimental values. The results are discussed in terms of energy migration.     

Luminescence behavior of Eu3+ in polytitanasiloxane solution

Polytitanasiloxane solutions containing Eu³⁺ ions have been prepared by the hydrolytic cocondensation of tetraethoxysilane and tetrabutyl titanate. The UV‐vis absorption and the luminescence intensity were both found to increase with the increase of tetrabutyl titanate/tetraethoxysilane (TBT/TEOS) molar ratio. This revealed that the incorporation of TiO₂ can result in the increase of absorption energy of the Ti? O group by near‐UV excitation and in the increase of energy transfer to the metal ion. At the same time, the intensity ratio of ⁵D₀→⁷F₂ to ⁵D₀→⁷F₁ increases as the TBT/TEOS molar ratio increases, indicating the formation of Eu³⁺? O^2?? Ti⁴⁺ bonding. A longer decay time means that the Eu³⁺ ions are better dispersed and less clustered with the increase of TBT/TEOS molar ratio. The results on the luminescence properties of the Eu³⁺ in different media containing ethanol or water suggest that the incorporation of TiO₂ can shield Eu³⁺ ions from the effect of water and ethanol molecules, which leads to an improvement of the Eu³⁺ surroundings. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1357–1363, 2006     

Preparation,Characterization and Luminescence Study of Chitosan Membrane and Powder Forms with Eu3 + and Tb3 +

Chitosan membranes with trivalent lanthanide ion Eu^{3 +} were prepared at a ratio of 3:1 w/w (chitosan:lanthanide). There was no membrane formation at a ratio of 1:1 w/w (chitosan: Eu^{3 +} or Tb^{3 +}); in this case a white solid powder was obtained. Both chitosan compounds were characterized by elemental analysis (CHN), thermal analysis (TG/DTG), scanning electron microscopy (SEM) and luminescence spectroscopy. CHN analysis was performed only for chitosan compounds in powder form, suggesting that these compounds have the general formula QUILn.6H₂O, where QUI = Chitosan and Ln = Eu^{3 +} or Tb^{3 +}. The results of TG/DTG curves for chitosan membranes with Eu^{3 +} ion indicate that the introduction of this metal into the chitosan structure causes gradual degradation in residual carbons, showing lower weight loss in the Eu^{3 +} membranes compared to pure chitosan membrane. Analysis of luminescence demonstrated that chitosan membranes with Eu^{3 +} ion exhibit emission in the visible region, showing emission bands from chitosan and Eu^{3 +} moieties. For chitosan with Eu^{3 +} and Tb^{3 +} ions compounds, in powder form, the analysis of luminescence suggested that chitosan is not transferring energy to the lanthanide ion; however, the chemical region where the lanthanide ion is found breaks the selection rules and favors the emission of these ions.     

Optical Spectroscopy and Excited-State Dynamics of Eu3+-Doped Bismuth Borate Glasses Containing CuO

Bismuth borate glasses containing phosphors and luminescent rare-earths are of interest for applications in light-emitting devices. Herein, the influence of CuO impurities on red-emitting Eu³⁺-doped bismuth borate glasses of the 25Bi₂O₃-15BaO-10Li₂O-50B₂O₃ type was investigated by various spectroscopic methods. The glasses were prepared by the melt-quench technique and characterized by X-ray diffraction (XRD), Fourier transform-infrared (FT-IR) spectroscopy, UV/Vis optical absorption (OA), and photoluminescence (PL) spectroscopy including decay kinetics assessment. The XRD data confirmed the amorphous nature of the glasses whereas FT-IR spectra indicated the basic structural features of trigonal BO₃ units and BO₄ tetrahedra. The OA analysis showed that addition of CuO up to 0.5 mol% results in significant growth of the visible Cu²⁺ absorption band around 715 nm, with slight decrease in the optical band gap energies assessed through Tauc plots. A drastic PL quenching of Eu³⁺ ions emission was evidenced concurring with the detrimental effect of Cu²⁺. The assessment of the Eu³⁺ emission decay curves revealed significant lifetime decrease of the ⁵D₀ emitting state with increasing CuO concentration. An analysis of quenching constants was finally performed comparing results from integrated PL data with the emission decay rates. It is argued that the bismuth borate glass system supports an effective Eu³⁺→Cu²⁺ energy transfer (more so than phosphates) in connection with a strong spectral overlap between Eu³⁺ emission and Cu²⁺ absorption.     

Cyclic voltammetric investigation of Eu<Superscript>3+</Superscript> on a MWCNTs/SDS-modified glassy carbon (GC) electrode

Electrochemical reduction behavior of Eu³⁺ on a multi-walled carbon nanotubes (MWCNTs)/sodium lauryl sulfate (SDS) (MWCNTs/SDS)-modified glassy carbon (GC) electrode was investigated by cyclic voltammetry (CV). Results indicated that the electrochemical reduction process of Eu³⁺ at the MWCNTs/SDS-modified GC electrode is a quasi-reversible and diffusion-controlled process. The value of standard rate constant (k _s) at the MWCNTs/SDS-modified GC electrode was estimated to 1.96 × 10⁻² cm s⁻¹. CV studies showed that the electrochemical response of Eu³⁺ was directly related to the ratio of MWCNTs to SDS, and the tube diameter of MWCNTs had a slight influence on the electrochemical behavior of Eu³⁺, whereas the tube length. of MWCNTs had a strong influence. CVs results also proved that s-MWCNTs (with shorter tube length)-modified GC electrode showed better response to the electrochemical reaction of Eu³⁺.