Insight into the performance of novel kaolinite-cellulose/cobalt oxide nanocomposite as green adsorbent for liquid phase abatement of heavy metal ions: Modelling and mechanism

A cost-efficient kaolinite-cellulose/cobalt oxide green nanocomposite (Kao-Cel/Co₃O₄ NC) was successfully synthesized, and utilized as a promising material for removing Pb²⁺ and Cd²⁺ from aqueous solution. The fabricated nanocomposite has been characterized by Fourier transform infrared spectroscopy, X-ray diffraction, scanning electron microscopy-energy dispersive X-ray, high-resolution transmission electron microscopy, and Brunauer-Emmett-Teller analysis. The batch methodology was exploited for optimization of process parameters and the optimized conditions were found to be adsorbent dosage (2.0 g/L), extraction time (50 min), initial concentration (60 mg/L), and initial solution pH (6). Kao-Cel/Co₃O₄ NC displayed excellent adsorption properties and achieved maximum saturation capacity (Q_m) of 293.68 mg Pb²⁺/g and 267.85 mg Cd²⁺/g, with an equilibration time of 50 min at 323 K. The Langmuir model best expressed the isotherm data recommending the adsorption onto energetically homogeneous NC surface, while the compatibility of kinetics data with pseudo-second-order model revealed the dependency of adsorption rate on adsorption capacity, and probable involvement of chemisorption in the rate-controlling step. Electrostatic interaction and ion exchange mechanism were responsible for the uptake of Pb²⁺ and Cd²⁺ by Kao-Cel/Co₃O₄ NC as demonstrated by Fourier transform infrared spectroscopy and pH studies. Thermodynamic parameters confirmed the physical, spontaneous, and endothermic sequestration processes. Real water investigation specified that the present adsorbent could be effectively used for liquid phase decontamination of Pb²⁺ and Cd²⁺. The nanocomposite exhibited high reusability, which could be utilized efficiently for five runs with sustainable results. In summary, this study portrayed the present nanocomposite as an emerging material for the adsorption of heavy metal ions particularly Pb²⁺ and Cd²⁺.     

Optimized solid phase extraction based on diethyldithiocarbamate-coated Fe3O4 magnetic nanoparticles followed by ICP-OES for determination of Cd(II) and Ni(II) in rice and water samples

In the present study, application of Fe₃O₄ magnetic nanoparticles (MNPs) coated with diethyldithiocarbamate as a solid-phase sorbent for extraction of trace amounts of cadmium (Cd²⁺) and nickel (Ni²⁺) ions by the aid of ultrasound was investigated. The analytes were determined by inductively coupled plasma-optical emission spectroscopy. Fe₃O₄ MNPs were prepared by solvothermal method and characterized with dynamic light scattering, scanning electron microscope and X-ray diffraction. Response surface methodology was used for optimization of the extraction process and modeling the data. The optimal conditions obtained were as follows: chelating agent, 1.2 g L^?1; pH, 6.13; sonication time, 13 min and Fe₃O₄ MNPs, 10.3 mg. The calibration curves were linear over the concentration range of 1–1,000 μg L^?1 for Cd²⁺ and 2.5–1,000 for Ni²⁺ with the determination coefficients (R ²) of 0.9997 and 0.9995, respectively. The limits of detection were 0.27 μg L^?1 for Cd²⁺ and 0.76 μg L^?1 for Ni²⁺. The relative standard deviations (n = 7, C = 200 μg L^?1) for determination of Cd²⁺ and Ni²⁺ were 2.0 and 2.7 %, respectively. The relative recoveries of the analytes from tap, river and lagoon waters and rice samples at the spiking level of 10 μg L^?1 were obtained in the range of 95–105 %.     

Solubility of cadmium in lead tellurides

The solubility of cadmium in PbTe was determined using microhardness and hydrostatic density measurements and by electron microscopy and electron probe microanalysis. All these methods indicate that the existence region of Pb_{1 − x} Cd _x Te solid solutions (ss) extends to x = 0.08 at 670°C. As the cadmium concentration of the solid solution increases, microhardness shifts up, whereas density shifts down.     

Synthesis of Co2+-doped Fe2O3 photocatalyst for degradation of pararosaniline dye

In this paper, x (=2, 5, 7 and 10mol%) Co²⁺-doped Fe₂O₃ (xCo:Fe₂O₃) nanoparticles with enhanced photocatalytic activity have been reported. xCo:Fe₂O₃ nanoparticles were successfully prepared by co-precipitation followed thermal decomposition method. The structural, optical and morphological properties of the prepared samples were studied by X-ray diffraction (XRD), Fourier transform infrared (FT-IR), X-ray photoelectron spectroscopy (XPS), diffuse reflectance (DR) UV–visible absorption spectroscopy, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The obtained results revealed that Co²⁺ ions were well doped within the lattices of Fe₂O₃. Also, Co²⁺ ions suppress the formation of the most stable α- Fe₂O₃ and stabilize less stable γ-Fe₂O₃ at 450 °C. The photocatalytic activity of xCo:Fe₂O₃ was examined by using pararosaniline (PR) dye. It was found that photocatalytic degradation of PR depends on dopant concentration (Co²⁺ ions). Relatively, the highest photocatalytic activity was observed for 5%Co:Fe₂O₃ nanoparticles. The plausible photocatalytic degradation pathway of PR at xCo:Fe₂O₃ surface has also been proposed.     

Electrochemical Sensing of Mercury over Cadmium and Lead Cations by the Redox-Active Polyazacycloalkane Ligand 1,1″: 1′,1′′′-Bis[ethane-1,2-diylbis(iminomethylene)]bis[ferrocene]

The coordination behaviour of the redox-active polyazacycloalkane L¹ against the toxic heavy-metal ions Cd²⁺, Pb²⁺, and Hg²⁺ was studied in THF/H₂O 70 : 30 (containing 0.1 mol⋅dm⁻³ of (Bu₄N)ClO₄). The crystal and molecular structure of the cadmium complex [Cd(L¹)(NO₃)₂] ( 1 ) was determined by X-ray single-crystal analysis. The cadmium ion is in a 4+2 surrounding with the ligand L¹ acting as tetradentate and the apical positions occupied by the O-atoms of the nitrate anions. An electrochemical study reveals that L¹ shows a selective electrochemical response against Hg²⁺ over Cd²⁺ and Pb²⁺.     

Thermal Dissociation of CdO and CdFe2O4

Knudsen effusion mass spectrometry has been applied to two identical alumina cells inside a revolving molybdenum cylinder. The one cell was filled with cadmium ferrite and the other with cadmium oxide, and the ionic current intensities of Cd⁺ and O₂⁺ were measured above both samples. The ratio between the intensities above the ferrite and above the oxide was found to be approx. 0.6, for both Cd⁺ and O₂⁺. From this ratio and from calorimetric data the Gibbs energy of the reaction CdO + Fe₂O₃ → CdFe₂O₄ could be derived. The endothermic ferrite is stable above 677 K. Its normal enthalpy, H°₂₉₈ is - 1 065 kJ/mol, and its normal entropy, S°₂₉₈ is 168 J/K mol. The non-stoichiometry of CdO is discussed.     

Crystal structure,DNA-binding,and fluorescence properties of cadmium(II) complex with N-(2-acetic acid)salicyloyl hydrazone and imidazole

A novel cadmium(II) complex with N-(2-acetic acid)salicyloyl hydrazone (C₉H₈N₂O₄, H₃L) and imidazole (Im) was prepared and characterized. The crystal structures of ligand H₃L and cadmium(II) complex were determined by X-ray single-crystal diffractometry. The complex consists of three binuclear neutral unattached units. One of Cd²⁺ is six-coordinated by the carboxylic O atom, acylic O atom, and azomethinic N atom of one ligand H₃L (HL²⁻ form), carboxylic O atom from the other ligand H₃L by the μ₂-bridging form and N atoms from two imidazoles, but the other five Cd²⁺ ions all are seven-coordinated more than an O atom from coordinated water molecule compared with six-coordinated Cd²⁺. HL²⁻ acts as tridentate ligand forming two stable five-numbered rings and sharing one side in the keto form for each ligand, and the carboxyl groups of two HL²⁻ ligands are coordinated via the μ₂-bridging form. The coordination polyhedron around Cd²⁺ was described as a octahedron or pentagonal bipyramidal. The inter- and intramolecular hydrogen bonds resulted in a three- dimensional network and provided extrastability for the structure. The complex exhibits good fluorescence properties. The complex was also searched for the interaction with CT-DNA by electronic absorption titration and emission titration. The results show that the complex is bound to calf thymus DNA mainly by intercalation.     

Ionic liquid-based hydrothermal synthesis of Lu2O3 and Lu2O3:Eu3+ microcrysals

Uniform and well-defined Lu₂O₃ and Lu₂O₃:Eu³⁺ microarchitectures have been successfully synthesized via a green and facile ionic liquid-based hydrothermal method followed by a subsequent calcination process. Novel 3D micro-rodbundles and 1D microrods of Lu₂O₃ and Lu₂O₃:Eu³⁺ were controllably obtained through this method. X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy and photoluminescence spectra were used to characterize the micromaterials. The proposed formation mechanisms have been investigated on the basis of a series of SEM studies of the products obtained at different hydrothermal durations. The results indicated that hydrothermal temperature and the ionic liquid-tetrabutylammonium hydroxide were two key factors for the formation as well as the morphology control of the Lu₂O₃ and Lu₂O₃:Eu³⁺ microarchitectures.     

Luminescent core–shell Fe3O4@Gd2O3:Er3+, Li+ composite particles with enhanced optical properties

Bifunctional magneto-optical nanocomposites with Fe₃O₄ nanoparticles as a core and erbium and lithium codoped gadolinium (Gd₂O₃:Er³⁺, Li⁺) as the shell were synthesized successfully using a simple urea homogeneous precipitation method. The fabricated Fe₃O₄@Gd₂O₃:Er³⁺, Li⁺ particles were characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, photoluminescence spectroscopy and quantum design vibrating sample magnetometry. The upconversion emission intensity was enhanced significantly comparing to that without Li⁺ ions. These bifunctional composites are expected to be potentially applied for drug delivery, cell separation and bioimaging.     

Photochemical synthesis of cadmium sulfide nanoparticles

The formation of cadmium sulfide nanoparticles upon UV irradiation of aqueous solutions of cadmium thiosulfates was established on the basis of spectroscopic and macroscopic data. The yield and size of the cadmium sulfide nanoparticles depend on the ratio of cadmium to thiosulfate ions in solution, the concentration of the solution, and the irradiation duration. The cadmium sulfide nanoparticles with a diameter of 4 nm were obtained by the photolysis of solutions with a concentration of 10⁻³ mol L⁻¹ at the ratio S₂O₃ ²⁻: Cd²⁺ = 2: 1.     

Cadmium determination based on silver nanoparticles modified with 1,13-bis(8-quinolyl)-1,4,7,10,13-pentaoxatridecane

We propose a simple, fast and sensitive colorimetric method for the determination of Cd²⁺ using 1,13-bis(8-quinolyl)-1,4,7,10,13-pentaoxatridecane modified silver nanoparticles. The addition of Cd²⁺ causes the aggregation of AgNPs, while other ions do not have such effect. As a result, the color of the solution changes from yellow to red which can be detected using naked eye or by UV–Vis spectroscopy. The aggregation of the AgNPs is confirmed by UV–Vis and transmission electron microscopy. Limit of detection is found to be 0.016 µM for Cd²⁺ ions. A linear calibration plot is correlated to the concentration of cadmium ion in the 0.5–6.0 μM range with the naked-eye detection limit of 2.0 µM. The method was successfully applied to determine Cd²⁺ in water and urine samples and gave recoveries that ranged from 93.3 to 98.6%.     

Fabrication and Characterization of Carbon Nanotube‐Hydroxyapatite Nanocomposite: Application to Anodic Stripping Voltammetric Determination of Cadmium

A novel chemically modified electrode for stripping determination of cadmium is presented in this paper, based on carbon nanotube‐hydroxyapatite (CNT‐HAP) nanocomposite, which can be prepared by an easy and effective one‐step sonication. The newly synthesized nanocomposite was characterized with FTIR, TEM, and electrochemical methods. Due to the combination of the strong absorption ability of HAP and excellent electroanalytical properties of CNTs, the GC/CNT‐HAP electrode has been successfully used for determination of Cd²⁺ by anodic stripping voltammetry with a linear range of 20 nM–3 μM. The sensitivity and detection limit are 25.6 μA/μM and 4 nM, respectively. The practical application of the proposed electrode has been carried out for the determination of trace levels of Cd²⁺ in real water samples.     

纳米羟基磷灰石纳米管的一种简便制备方法及其对溶液中重金属离子的吸附

采用简便的方法合成了20~40 nm长、56 m^2·g^-1的比表面积的羟基磷灰石纳米管(HAP)。然后用制备的HAP纳米管在水溶液中同时吸附Pb^2+、Cd^2+、Cu^2+、Co^2+、Ni^2+、Zn^2+和Hg^2+,其具有高的吸附能力,并能实现快速去除。此外,制备的HAP纳米管对7种重金属离子的脱附率均小于1%,表现出较强的稳定性。实验数据采用Langmuir等温线模型和Freundlich等温线模型进行分析。2个方程的应用结果表明,吸附平衡最适合Langmuir模型,单层饱和吸附能力为958.28 mg·g^-1,具有较好的吸附性能。通过能量色散X射线光谱(EDS)和X射线衍射(XRD)图进一步研究了吸附机理,结果表明,当溶液中Pb^2+离子数量足够时,吸附机理为Pb取代了HAP中的Ca,形成了更稳定的Pb5(PO4)3(OH)。上述实验研究预测了利用HAP纳米管处理含铅废水在环境污染治理中的可行性。     

Phase equilibria in the Nb<Subscript>2</Subscript>O<Subscript>5</Subscript>–CdO system and the thermal stability of Cd<Subscript>2</Subscript>Nb<Subscript>2</Subscript>O<Subscript>7</Subscript> and CdNb<Subscript>2</Subscript>O<Subscript>6</Subscript>

Phase equilibria were studied in the Nb₂O₅–CdO system in the Nb₂O₅-rich region including CdNb₂O₆ and Cd₂Nb₂O₇. It was determined that CdNb₂O₆ and Cd₂Nb₂O₇ in air are stable to 1150 and 1120°C, respectively, and that, above these temperatures, there is solid-phase decomposition of niobates with CdO release in the gas phase. Along with the cadmium oxide evaporation, the Cd₂Nb₂O₇ decomposition is accompanied by the formation of cadmium metaniobate CdNb₂O₆ and the CdNb₂O₆ decomposition results in the formation of niobium oxide Nb₂O₅. No thermal events were observed in the differential thermal analysis curve for a 1: 1 CdNb₂O₆–Cd₂Nb₂O₇ mixture heated to 1100°C in air, which suggests that there are neither phase transformations in cadmium niobates, nor a eutectic within this temperature and concentration ranges. A study of the morphology of compacted samples of niobates determined specific conditions for producing dense composite ceramics, a mixture of niobates, that is suitable for using as a dielectric material.     

Synthesis and Structure of Transition-Metal-Containing Tungstomolybdosilic Polyoxometalates and their Catalytic Performance in Oxidation of Cyclohexene with Hydrogen Peroxide

A series of title complexes with the general molecular formula, K₄H₂[SiW₇Mo₄Me(H₂O)O₃₉]·xH₂O (denoted as MeW₇; Me = Mn²⁺, Co²⁺, Ni²⁺, Cu²⁺, Zn²⁺, Cd²⁺), were synthesized. IR spectra, electronic spectra, XPS spectra and thermal analyses were systematically recorded. The crystal structure of MnW₇, determined from single-crystal X-ray diffraction at 293?K, belongs to the tetragonal system, space group P4/mnc, Z = 2, a = 1.4105(5) and c = 1.2476(7)?nm. These samples were investigated for the oxidation of cyclohexene with H₂O₂, and showed more activity than their corresponding parent compounds.     

A two‐dimensional CdII coordination polymer based on naphthalenediimide: synthesis,crystal structure and photochromic properties

Naphthalenediimides, a class of organic dyes with an expanded π‐electron‐deficient plane, have attracted considerable interest because of their photoinduced electron transfer from neutral organic moieties to stable anionic radicals. This makes them excellent candidates for organic linkers in the construction of photochromic coordination polymers. Such a photochromic two‐dimensional coordination polymer has been prepared using N,N′‐bis(pyridin‐4‐ylmethyl)naphthalene‐1,8:4,5‐bis(dicarboximide) (DPMNI). In crystallization tubes, upon slow diffusion of an MeOH solution of cadmium perchlorate into a CHCl₃ solution of DPMNI, the complex poly[[bis[μ₂‐2,7‐bis(pyridin‐4‐ylmethyl)benzo[imn][3,8]phenanthroline‐1,3,6,8(2H,7H)‐tetrone‐κ²N:N′]bis(perchlorato‐κO)cadmium(II)] chloroform tetrasolvate], {[Cd(C₂₆H₁₆N₄O₄)₂(ClO₄)₂]·4CHCl₃}_n, (I), was obtained. The asymmetric unit contains one Cd²⁺ cation, two DPMNI ligands, two coordinated ClO₄⁻ anions and four CHCl₃ solvent molecules. Each Cd²⁺ cation is interconnected by four DPMNI linkers to generate a neutral two‐dimensional naphthalenediimide coordination network with all the ClO₄⁻ anions above or below this plane. Strong interlaminar anion–π interactions between the coordinated ClO₄⁻ anions and the imide rings of an adjacent layer lead to a three‐dimensional supramolecular structure. Compound (I) exhibits reversible photochromic behaviour and photocontrolled tunable luminescence properties, which may originate from the photoinduced electron‐transfer generation of radicals in the DPMNI ligand.     

Ni2+ supported on hydroxyapatite-core-shell γ-Fe2O3 nanoparticles: a novel,highly efficient and reusable lewis acid catalyst for the regioselective azidolysis of epoxides in water

In this research, Ni²⁺ supported on hydroxyapatite-core-shell magnetic γ-Fe₂O₃ nanoparticles (γ-Fe₂O₃@HAp-Ni²⁺) as a novel, efficient, reusable and heterogeneous catalyst was reported. In this protocol, we used this catalyst for the ring opening of epoxide with sodium azide in water. The catalyst can be readily isolated using an external magnet and no obvious loss of activity was observed when the catalyst was reused in seven consecutive runs. The mean size and the surface morphology of the nanoparticles were characterized by transmission electron microscopy, scanning electron microscope, vibrating sample magnetometry, X-ray powder diffraction and Fourier transform infrared techniques.     

Solubilities of zinc oxide and cadmium oxide in CsI melt at 700°C

The solubility products of ZnO (pL = 10.0 ± 0.5) and CdO (pL = 6.8 ± 0.2) in CsI melt at 700°C are determined by potentiometric titration with the use of a Pt(O₂)|ZrO₂(Y₂O₃) membrane oxygen electrode. In the Zn-Cd family, metal oxide solubilities grow with increasing metal cation radius. The solubilities in an iodide melt are much lower than in a chloride melt due to a higher basicity of the former; for the Cd²⁺ cation, the difference between solubilities in these melts is lower owing to the formation of Cd²⁺-I⁻ (soft acid-soft base) complexes.     

Effect of thermal transformations of constituent polyhedra of the crystal structure on the properties of Cd2V2O7

Analysis of variations in the linear and angular parameters of constituent polyhedra of the cadmium pyrovanadate Cd₂V₂O₇ structure, namely, VO₄ tetrahedra and CdO₆ octahedra, as calculated from the results of in situ high-temperature X-ray diffraction experiments in the range from 25 to 900°C, showed that, in the range from 600 to 720°C, the thermal expansion coefficient (tec) of CdO₆ polyhedra is near zero, whereas VO₄ tetrahedra increase in volume, although less strongly than in other temperature ranges. A structural interpretation is given to anomalous temperature dependences of cadmium ion emission and electrical conductivity on the basis of different thermal behavior patterns of the constituent polyhedra of the Cd₂V₂O₇ structure.     

Synthesis,crystal structure and magnetic properties of a new tri‐nuclear iron (II,III) complex,a precursor for the preparation of superparamagnetic Fe3O4 nanoparticles applicable in the removal of Cd2+

This study reports the structural and spectroscopic characterization of a novel metal organic compound formulated as [Fe (bpy)₃] [Fe (dipic)₂]₂.7H₂O ( 1 ) (dipic = pyridine‐2,6‐dicarboxylate and bpy = 2,2^′‐bipyridine). 1 was investigated by elemental analysis, FT‐IR spectroscopy, powder X‐ray diffraction and single crystal X‐ray diffraction (SC‐XRD), which revealed a triclinic structure of expected composition. Thermal degradation of 1 was also investigated. Complex 1 was used as a precursor to prepare superparamagnetic nanoparticles of Fe₃O₄ by thermal analysis. The obtained Fe₃O₄ was characterized by Fourier transformed infrared spectroscopy (FT‐IR), powder X‐ray diffraction (XRD) and scanning electron microscopy (SEM). Fe₃O₄ nanoparticles were used as a nano‐adsorbent to remove Cd²⁺ from water at room temperature. The results showed that this nano‐adsorbent is effective in removing Cd²⁺ from contaminated water sources, and that the maximal effectivity of adsorption occurs at pH = 6. Magnetic measurements of complex 1 and Fe₃O₄ nanoparticles at room temperature revealed paramagnetic and superparamagnetic behavior, respectively.