Structural,electrical and magnetic properties of Co0.5Zn0.5AlxFe2−xO4 (x = 0, 0.2, 0.4, 0.6, 0.8 and 1.0) prepared via sol–gel route

Nanoparticles of Co_0.5Zn_0.5Al_xFe_2?xO₄ (x = 0, 0.2, 0.4, 0.6, 0.8 and 1.0) were synthesized by sol–gel method and the influence of Al³⁺ doping on the properties of Co_0.5Zn_0.5Fe₂O₄ was studied. X-ray diffraction studies revealed the formation of single phase spinel type cubical structure having space group Fd-3m. A decreasing trend of the lattice parameter was observed with increasing Al³⁺ concentration due to the smaller ionic radii of Al³⁺ ion as compared to Fe³⁺ ion. TEM was used to characterize the microstructure of the samples and particle size determination, which exhibited the formation of spherical nanoparticles. The particle size was found to be increases up to ～45 nm after annealing the sample at 1000 °C. Electrical resistivity was found to increase with Al³⁺ doping, attributed to the decrease in the number of Fe²⁺–Fe³⁺ hopping. The activation energy decreased with increasing Al³⁺ ion concentration, indicating the blocking of conduction mechanism between Fe³⁺–Fe²⁺ ions. The value of saturation magnetization decreased, when Fe³⁺ ions were doped with Al³⁺ ions in Co_0.5Zn_0.5Fe₂O₄; however, the coercivity values increased with increasing Al³⁺ ion content.     

In situ monitoring of the adsorption of Co2+ on the surface of Fe3O4 nanoparticles in high-temperature aqueous fluids

Developing an understanding of the reaction processes occurring at the surface⿿fluid interface at the atomic level of nanostructured materials in high-temperature aqueous environments is necessary for establishing general principles of behavior of nanomaterials operating in such extremes. In situ Co K-edge X-ray absorption spectroscopy (XAS) measurements were made on Fe₃O₄ nanoparticles in the presence of Co²⁺ ions in aqueous fluids to 500 °C and approximately 220 MPa. The results from analysis of the in situ EXAFS data, along with SEM-EDX spectra measured from reacted nanoparticles, indicate that adsorption of Co²⁺ ions on the surface of Fe₃O₄ nanoparticles is negligible at temperatures below 200 °C but becomes significant in the 250⿿500 °C temperature range. The low reaction temperature threshold of the Co²⁺ aqua ion with Fe₃O₄ nanoparticles is consistent with a relatively low value of the crystal field stabilization energy (CFSE) of Co²⁺ in octahedral site symmetry in spinels. Modeling of the pre-edge feature of the XANES and analysis of the extended X-ray absorption fine structure (EXAFS) shows that Co²⁺ adsorbs predominantly on octahedral sites of the surface of nanoparticles in aqueous fluids. Structural analyses using EXAFS and high resolution TEM show that the inverse spinel structure is preserved in the Co-incorporated surface atomic layers of the Fe₃O₄ nanoparticles. Our results suggest that the dissolved radioactive isotope ⁶⁰Co in the primary cooling loop of supercritical water-cooled nuclear reactors have a high likelihood of precipitating on the surfaces of spalled ferrite nanomaterial.     

Enhanced in vitro inhibition of MCF-7 and magnetic properties of cobalt incorporated calcium phosphate (HAp and β-TCP) nanoparticles

The Co²⁺ (0.1 M) incorporated hydroxyapatite (HAp) and beta tricalcium phosphate (β-TCP) nanoparticles were synthesized by the microwave assisted technique and sintering of HAp respectively. The samples were thermally treated at temperatures ranging from 200 to 1000°C. The partial substitutions of Co²⁺ at the Ca²⁺ site of HAp were confirmed from the slight shift (～0.2°) in the (002) and (211) XRD peaks. The morphology of the nanoparticles was transformed from nanospheres to twinned particles on thermal treatment. In addition, the particle size of Co-600 was increased (from ～50 nm to ～100 nm) due to the recrystallization process. Further, the thermal treatment enhanced the crystallinity (41.15 to 90.16%), retentivity (M_r) and coercivity (H_c) of the nanoparticles. The cobalt incorporated HAp and β-TCP possessed paramagnetic property. The excellent bioactivity of β-TCP has been confirmed by the mineralization in simulated body fluid (SBF). Compared to HAp, β-TCP possessed better compatibility towards C2C12 cells on cobalt incorporation as evidenced by the in vitro cell viability. Moreover, both HAp and β-TCP have significantly inhibited the growth of MCF-7 on increasing the interaction time (72 h). Hence, the inhibition characteristics of Co²⁺ incorporated calcium phosphate (CaP) towards MCF-7 (without affecting the normal cells) demonstrate its competency as a potential material for cancer therapy over the already existing nanoparticles.     

The Reduction and Oxidation of Co Species in CoZSM-5 Zeolites Studied by IR Spectroscopy

The process of reducing Co ions in zeolite CoZSM-5 by NO, H₂ and CO, as well as of oxidizing them by O₂ was studied by IR spectroscopy with CO as the probe molecule for Co²⁺ and NO as the probe for Co³⁺. Two zeolites of different Co status were used: in the first, Co²⁺ ions were localized mostly in cation exchange positions, and in the second most of the Co²⁺ occurred in the form of CoO and oxide-like clusters. IR studies evidenced that NO reduced some Co³⁺ to Co²⁺ already at room temperature, and also reduced some Co²⁺ to lower oxidation states (probably Co⁺) at 670 and 1070 K. Only Co²⁺ in exchange positions could be reduced with NO. The treatment of zeolite CoZSM-5 with H₂ or with CO at 670 and 1070 K made the reduction of Co³⁺ to Co²⁺ (the contribution of Co³⁺ decreased and the contribution of Co²⁺ increased). IR studies illustrated that the most electron-acceptor Co³⁺ (characterized by a high frequency Co³⁺–NO band) were transformed, by reduction, into the most electron-acceptor Co²⁺ (characterized by a high frequency Co²⁺–CO band). The treatment of zeolite CoZSM-5 with oxygen at 670–1070 K resulted in the oxidation of Co²⁺ to Co³⁺ (the contribution of Co²⁺ decreased while the contribution of Co³⁺ increased).     

Synthesis of Starch-Stabilized Ag Nanoparticles and Hg2+ Recognition in Aqueous Media

The starch-stabilized Ag nanoparticles were successfully synthesized via a reduction approach and characterized with SPR UV/Vis spectroscopy, TEM, and HRTEM. By utilizing the redox reaction between Ag nanoparticles and Hg²⁺, and the resulted decrease in UV/Vis signal, we develop a colorimetric method for detection of Hg²⁺ ion. A linear relationship stands between the absorbance intensity of the Ag nanoparticles and the concentration of Hg²⁺ ion over the range from 10 ppb to 1 ppm at the absorption of 390 nm. The detection limit for Hg²⁺ ions in homogeneous aqueous solutions is estimated to be ~5 ppb. This system shows excellent selectivity for Hg²⁺ over other metal ions including Na⁺, K⁺, Ba²⁺, Mg²⁺, Ca²⁺, Fe³⁺, and Cd²⁺. The results shown herein have potential implications in the development of new colorimetric sensors for easy and selective detection and monitoring of mercuric ions in aqueous solutions.     

XAS and XPS analysis of double magnetic transition,canonical spin glass behavior and magnetoresistance in LaMn1-xCoxO3 (0.1 ≤ x ≤ 0.5) system

Polycrystalline LaMn_1-xCo_xO₃ (0.1≤ x ≤ 0.5) samples were synthesized using conventional ceramic method. Rietveld refined X-ray diffraction pattern revealed the single-phase orthorhombic crystal structure of all the samples with the space group Pbnm. Temperature-dependent magnetic measurements performed in field cooled (FC) and zero field cooled (ZFC) mode at 10² Oe exhibit the onset of double transition in x = 0.3–0.5 compositions. The ordering temperature rises with an increase in Co concentration. FC and ZFC studies show the presence of glassy state below the ordering temperature in all samples; confirmed using a. c. susceptibility measurements. The a. c. susceptibility data are analyzed using power law and the existence of canonical spin glass is revealed. Magnetic hysteresis studies demonstrate the enhanced ferromagnetism amid the presence of unsaturated magnetization with an increase in Co doping. The presence of double transition and spin glass state is attributed to the competing ferromagnetic and anti-ferromagnetic interactions between the Co and Mn ions present in the system. The system also depicts the presence of appreciable value of magnetoresistance ~42% at 8 T magnetic field in x = 0.5 sample. These properties are interpreted through valence and spin states of Mn and Co ions, being confirmed from electronic structure studies using X-ray absorption spectroscopy (XAS) at L_3,2- edges of respective ions along with O K-edge for all samples (0.1≤ x ≤ 0.5). After meticulous analysis and conjoining the results obtained from magnetization and XAS studies, it is found that cobalt is present in high spin Co²⁺ and high/low spin Co³⁺-state. Charge transfer multiplet calculation done at L_3,2 edges of Mn and Co ions confirm the presence of Mn³⁺/Mn⁴⁺ and Co²⁺/Co³⁺ states consistent with XAS results. X-ray photoelectron spectroscopy performed at Mn2p, Co2p, and O1s -edges further substantiate the reasons behind the properties exhibited by the present system.     

Effect of Ni2+ substitution on structural,magnetic, dielectric and optical properties of mixed spinel CoFe2O4 nanoparticles

Nanoparticles of Co_1−xNi_xFe₂O₄ with x=0.0, 0.10, 0.20, 0.30, 0.40 and 0.50 were synthesized by co-precipitation method. The structural analysis reveals the formation of single phase cubic spinel structure with a narrow size distribution between 13–17 nm. Transmission electron microscope images are in agreement with size of nanoparticles calculated from XRD. The field emission scanning electron microscope images confirmed the presence of nano-sized grains with porous morphology. The X-ray photoelectron spectroscopy analysis confirmed the presence of Fe²⁺ ions with Fe³⁺. Room temperature magnetic measurements showed the strong influence of Ni²⁺ doping on saturation magnetization and coercivity. The saturation magnetization decreases from 91 emu/gm to 44 emu/gm for x=0.0–0.50 samples. Lower magnetic moment of Ni²⁺ (2 µ_B) ions in comparison to that of Co²⁺ (3 µ_B) ions is responsible for this reduction. Similarly, overall coercivity decreased from 1010 Oe to 832 Oe for x=0.0–0.50 samples and depends on crystallite size. Cation distribution has been proposed from XRD analysis and magnetization data. Electron spin resonance spectra suggested the dominancy of superexchange interactions in Co_1−xNi_xFe₂O₄ samples. The optical analysis indicates that Co_1−xNi_xFe₂O₄ is an indirect band gap material and band gap increases with increasing Ni²⁺ concentration. Dispersion behavior with increasing frequency is observed for both dielectric constant and loss tangent. The conduction process predominantly takes place through grain boundary volume. Grain boundary resistance increases with Ni²⁺ ion concentration.     

Enhancing piezoelectric properties of Ba0.88Ca0.12Zr0.12Ti0.88O3 lead-free ceramics by doping Co ions

The piezoelectric properties of lead-free Ba_0.88Ca_0.12Zr_0.12Ti_0.88O₃ (BCZT) ceramics were greatly optimized by doping Co ions using a CoO powder. The role of Co²⁺ and Co³⁺ in enhancing the piezoelectric properties and the relationship between the content ratio Co³⁺/Co²⁺ and piezoelectric performance were studied. The X-ray diffraction patterns of all samples indicated that crystalline phases were a BCZT-based single perovskite structure regardless of the Co ion content. The phase transition temperature and lattice distortion degree were related to the Co ion content and the content ratio Co³⁺/Co²⁺ because Co²⁺ resulted in higher oxygen vacancy generation, whereas Co³⁺ induced larger lattice shrinkage. The ceramic containing 0.10 wt% of Co ion showed the best piezoelectric and dielectric performance with the highest piezoelectric constant d₃₃ ~ 490 p.m./V at room temperature and the highest Curie temperature T_c of 110 °C, which increased by 29% and 16%, respectively. In this case, the content ratio Co³⁺/Co²⁺ reached the maximum value of 0.86. The high piezoelectric properties and phase stability of BCZT ceramics by doping Co ions make these ceramics promising piezoelectric materials for practical applications.     

Effects of added metal ions on the interaction of chitin and partially deacetylated chitin with an azo dye carrying hydroxyl groups

The binding of chrome violet, which is a monoazo dye and involves two hydroxyl groups in the o and o′ positions to an azo group, to chintin and partially decetylated chitin, was examined in the presence of metal ions. Zn²⁺ and Cu²⁺ ions do not perceptively influence the binding affinity of chrome voilet to chitin. In contrast, Co²⁺ ion enhances the binding and Ni²⁺ ion suppresses it. In the lower free dye concentrations the dye uptake by partially deceteylated chitin was tremendously enhanced by adding. Co²⁺ ion in the buffer solution of pH 5. The dye uptake by the polymer was considerably increased by the addition of Cu²⁺ ion at pH 5 and became much larger at pH 6. The amount corresponded to that in the presence of Co²⁺ ion. To investigate further the action of added metal ions, a cobalt- or a chrome–complex dye was prepared, and the binding properties for the polymers were compared with those of chrome violet in the presence of Co²⁺ and Cu²⁺ ions. Some possible mechanisms for the enhancement of chrome violet binding by the addition of Co²⁺ and Cu²⁺ ions are described. © 1995 John Wiley & Sons, Inc.     

Carbon-encapsulated magnetic nanoparticles as separable and mobile sorbents of heavy metal ions from aqueous solutions

Carbon-encapsulated magnetic nanoparticles (CEMNPs) are studied as mobile sorbents for removal of heavy metal ions (Cu²⁺, Co²⁺, Cd²⁺) from aqueous solutions. The ion uptakes achieve 95% for cadmium and copper. CEMNPs-based sorbents also have excellent adsorption capacities (between 1.23 and 3.21 mg/g), which are considerably higher than the capacities of activated carbons (between 0.37 and 0.39 mg/g).     

Interaction of heavy metal ions with an ion exchange resin obtained from a natural polyelectrolyte

An ion exchange resin was synthesized by using a natural polyelectrolyte, sodium alginate, and barium ion as a cross-linker reagent. Resin was characterized by TGA and SEM. Equilibrium and kinetic experiments of Pb²⁺, Hg²⁺, Ni²⁺, Co²⁺, Fe²⁺, and Fe³⁺ ions uptake by barium alginate beads were carried out in batch-type experiments under different values of pH. The removal efficiency increases with increasing pH. The uptake of metal ions occurs rapidly in the first hour. Maximum retention capacity was also determined being Fe(II) > Fe(III) > Co(II) > Ni(II) > Pb(II) > Hg(II) in mmol/g dry beads basis. Elution from the loaded resins at maximum capacity was studied by using HCl and HNO₃ as eluents at different concentrations.     

Photo-Ionization of 3d-Ions in Fluoride-Phosphate Glasses

Interaction of radiation with glasses often modifies their properties (e.g., the refractive index). Most noticeable is a loss in transmission. Such phenomena can be exploited in photo-sensitive materials, but have to be avoided in other applications. To improve the understanding of defect generation processes, a systematic comparison of defect formation in (fluoride-)phosphate glasses doped with low concentrations of 3d ions was attempted. Samples doped with 10–5000 ppm of Ti, V, Cr, Mn, Fe, Co, or Ni were irradiated in the UV range by excimer lasers. Defects, which generally form in the levels of several ppm, were characterized by optical and by electron spin resonance spectroscopy. V⁴⁺ was photo-oxidized to the empty valence shell d⁰ ion. Co²⁺, Mn²⁺, and Fe²⁺ were all photo-oxidized to the trivalent state while Ni²⁺ was photo-reduced. The fully oxidized Ti⁴⁺ was also photo-reduced. Cr³⁺ showed photo-disproportionation into Cr²⁺ and Cr⁶⁺. Qualitative and quantitative changes in defect formation rates depend not only on the ion, but also on the radiation parameters, for example, the wavelength of the excimer lasers used (193, 248, 351 nm) or the initial transmission of the glass samples at the chosen laser wavelength. Defect recovery was followed up to 10 years after the irradiation experiments.     

Influence of glass composition on photoluminescence from Ge2+ or Ag nano-cluster in germanate glasses for white light-emitting diodes

Germanium glass has attracted much interest because of its potential application as the optical waveguides and communication devices. In this work, germanium glass was prepared, exhibiting the blue luminescence at the 410 nm from the Ge²⁺. The influence of SiO₂ addition in the germanate glass on the 410 nm luminescence of the Ge²⁺ was observed. The SiO₂ addition promoted the formation of Ge²⁺, which is because the Si⁴⁺ ions can deprive the O²⁻ ions from the Ge⁴⁺ ion caused by the lower optical basicity of Si⁴⁺ ions than Ge⁴⁺ ion. The germanium glasses containing the Ag nano-clusters were prepared using ion-exchange method. The influence of SiO₂ concentration on the size of Ag nano-clusters was observed, which stabilize the size distribution and lead to the miniaturization of Ag nano-clusters. The Ag nano-clusters size dependence of their photoluminescence was observed in germanate glasses, and the tunable photoluminescence of Ag nano-clusters was obtained by controlling the size of Ag nano-clusters. It is noticed that the Ag nano-clusters formed in the germanate glass showed the white light emission characteristic excited at the blue chip, exhibiting the practical application as the blue converted white light-emitting diodes.     

Transport of cobalt(II) through a hollow fiber supported liquid membrane containing di-(2-ethylhexyl) phosphoric acid (D2EHPA) as the carrier

This work presents experimental, modeling and simulation studies for Co²⁺ ion extraction using hollow fiber supported liquid membrane (HFSLM) operated in a recycling mode. Extractant di-(2-ethylhexyl) phosphoric acid (D2EHPA) diluted with kerosene has been used as the membrane phase. The Co²⁺ ion concentration in the aqueous feed phase was varied in the range of 1–3 mM. Also, D2EHPA concentration was varied in the range of 10–30% (v/v). A mass transfer model has been developed considering the complexation and de-complexation reactions to be fast and at equilibrium. Equations for extractant mass balance and counter-ion (H⁺) transport have also been incorporated in the model. Extraction equilibrium constant (K_ex) for cobalt–D2EHPA system has been estimated from equilibration experiments and found to be 3.48 × 10⁻⁶. It was observed that the model results are in good agreement with the experimental data when diffusivity of metal-complex (D_m) through the membrane phase is 1.5 × 10⁻¹⁰ m²/s. Feed phase pH and strip phase acidity had negligible effect on the extraction profiles of Co²⁺ ions. An increase in D2EHPA concentration increased extraction rates of Co²⁺ ions. The membrane phase diffusion step was found to be the controlling resistance to mass transfer.     

Enhanced and Long‐Lived Near‐Infrared Luminescence of Er3+ Ions in Lead Borate Glass‐Ceramics Containing PbWO4 Nanocrystals

Lead tungstate PbWO₄ nanocrystals in transparent lead borate glass‐ceramics containing Er³⁺ ions were fabricated. Luminescence spectra at about 1530 nm due to main ⁴I_13/2–⁴I_15/2 laser transition of Er³⁺ ions were examined for glass samples before and after heat treatment. Near‐infrared luminescence of Er³⁺ ions in glass‐ceramics is enhanced and long‐lived in comparison to precursor glasses. It suggests that the Er³⁺ ions are partially incorporated into PbWO₄ crystalline phase.     

The effects of sintering atmospheres on piezoelectric performances of Co-doped Ba0.88Ca0.12Zr0.12Ti0.88O3 ceramics

This work investigates the effects of content ratio Co³⁺/Co²⁺ on piezoelectric properties of lead-free Ba_0.88Ca_0.12Zr_0.12Ti_0.88O₃ (BCZT) ceramics. For this purpose, 0.10 wt% Co ions using a CoO powder doped BCZT ceramics were sintered under various atmospheres (ranging from pure nitrogen to 100 vol% oxygen concentration) to vary the ratio value Co³⁺/Co²⁺. X-ray photoelectron spectroscopy analysis revealed the coexistence of Co³⁺ and Co²⁺ for oxygen concentration below 40 vol% and the single oxidation state of Co³⁺ for oxygen concentration over 50 vol%. Co²⁺ substitution could induce more oxygen vacancy to accelerate densification and grain growth, whereas Co³⁺ substitution usually leads to larger lattice distortion to generate a stable asymmetric structure. When oxygen concentration was 30 vol% and Co³⁺/Co²⁺ near to 1.0, the respective superiority of Co³⁺ and Co²⁺ is brought into full play, and the ceramic showed the highest piezoelectric constant d₃₃^* ∼ 518 pm/V (380 pm/V for undoped BCZT) and the relatively high Curie temperature T_c ∼ 105°C (95°C for undoped BCZT). This study suggests that optimizing sintering atmosphere might be an effective way to enhance the piezoelectric properties for some composition-modified piezoelectric BCZT ceramics.     

Blue Upconversion Emission in Germanate Glass Co-Doped with Yb3+/Tm3+ Ions

In the paper, the upconversion luminescence of 70GeO₂–30[Ga₂O₃–BaO–Na₂O] glass system co-doped with Yb³⁺/Tm³⁺ ions was investigated. Strong blue emission at 478 nm corresponding to the transition ¹G₄ → ³H₆ in thulium ions was measured under the excitation of 976-nm diode laser. The dependence of the upconversion emission upon the thulium ion concentration was studied to determine the optimal conditions of energy transfer between energy levels of active dopants. The most effective energy transfer Yb³⁺ → Tm³⁺ was obtained in glass co-doped with molar ratio of dopant 0.7 Yb₂O₃/0.07 Tm₂O₃. The increase in thulium concentration more than 0.07 mol% results in the reverse energy transfer from Tm³⁺ → Yb³⁺, which leads to rapid quenching of the luminescence line at the wavelength 478 nm. In germanate glass co-doped with 0.7Yb₂O₃/0.07Tm₂O₃, the longest lifetime of ¹G₄ level equal 278 μs was achieved. The presented results indicate that elaborated germanate glass co-doped with Yb³⁺/Tm³⁺ ions is a promising material that can be used to produce fiber lasers and superluminescent fiber sources generating radiation in the visible spectrum.     

Enhanced luminescence of manganese in singly doped white light zinc phosphate glass

On the basis of a kind of zinc phosphate oxynitride glass matrix with a broadband blue light, a series of manganese single-doped glasses were obtained. A broader red emission with the higher intensity belonging to the Mn²⁺ ion was observed in this glass matrix. The mechanism of the emission from Mn²⁺ ions was clarified through Mn³⁺ as an “energy acquisition probe” to replace complex dynamic luminescence discussion, which was a fit explanation for the differences in luminescence behavior of Mn ions in prepared glasses at different degrees of redox. The research results indicated that the prepared manganese-doped glass was a potential candidate as phosphor-converted white-light-emitting diodes. An encapsulated white-light-emitting diode device based on this glass with 276 nm ultraviolet chip was achieved. It showed the CIE values of (0.33, 0.35), high CRI (Ra = 86), and low color temperature (5228 K).