Removal of lead from aqueous solutions by using the natural and Fe(III)-modified zeolite

In the present study, the sorption of lead by the natural and Fe(III)-modified zeolite (clinoptilolite) is described. The characterization of the natural zeolite-rich rock and the Fe(III)-modified form was performed by chemical analysis, point of the zero charge (pH_pzc), X-ray powder diffraction, applying the Rietveld/RIR method for the quantitative phase analysis, and scanning electron microscopy. The effects of sorbents dose and the initial lead concentrations on its sorption by two sorbents were investigated. For both sorbents, it was determined that at lower initial concentrations of lead, ion exchange of inorganic cations in zeolites with lead, together with uptake of hydrogen dominated, while at higher initial lead concentrations beside these processes, chemisorption of lead occurred. Significantly higher sorption of lead was achieved with Fe(III)-modified zeolite. From sorption isotherms, maximum sorbed amounts of lead, under the applied experimental conditions, were 66 mg/g for the natural and 133 mg/g for Fe(III)-modified zeolite. The best fit of experimental data was achieved with the Freundlich model (R² ≥ 0.94).     

Kinetics and thermodynamics of Pb(II) adsorption onto modified spent grain from aqueous solutions

Spent grain, a main by-product of the brewing industry, is available in large quantities, but its main application has been limited to animal feeding. Nevertheless, in this study, spent grain modified with 1 M NaCl solution as a novel adsorbent has been used for the adsorption of Pb(II) in aqueous solutions. Isotherms, kinetics and thermodynamics of Pb(II) adsorption onto modified spent grain were studied. The equilibrium data were well fitted with Langmuir, Freundlich and Dubinin-Radushkevick (D-R) isotherm models. The kinetics of Pb(II) adsorption followed pseudo-second-order model, using the rate constants of pseudo-second-order model, the activation energy (E_a) of Pb(II) adsorption was determined as 12.33 kJ mol⁻¹ according to the Arrhenius equation. Various thermodynamic parameters such as ΔG^ads, ΔH^ads and ΔS^ads were also calculated. Thermodynamic results indicate that Pb(II) adsorption onto modified spent grain is a spontaneous and endothermic process. Therefore, it can be concluded that modified spent grain as a new effective adsorbent has potential for Pb(II) removal from aqueous solutions.     

The growth of carbon nanotubes on montmorillonite and zeolite (clinoptilolite)

Synthesis of carbon nanotubes described in the present work is based on activation of methane in a hot filament CVD reactor and subsequent creation of nanostructures on a catalyst pre-treated polished surface of silicon. An essential step of the synthesis is the use of natural minerals as catalysts. We have studied the catalyst parameters, the way of its application and the amount of Fe³⁺ cations on the surface of aluminosilicates on the quality of the grown nanotube layers. The growth of carbon nanotubes catalyzed by montmorillonite and zeolite (clinoptilolite) was confirmed by scanning electron microscopy and Raman spectroscopy.     

Adsorption and solid phase extraction of 8-hydroxyquinoline from aqueous solutions by using natural bentonite

The nitrogen-heterocyclic compound 8-hydroxyquinoline (8HQ) is one of the components of coal tar and has a wide variety of uses in industry. Because of its toxicity for aquatic organisms and harmful effects for human health, the removal of 8HQ from aqueous solutions by adsorption onto natural bentonite was investigated in the present work. The experimental results show that the optimum pH value of 2.5 is favourable for the 8HQ adsorption. The experimental data were fitted well with the pseudo-second-order kinetic and Langmuir adsorption isotherm models at all studied temperatures. The maximum adsorption capacity obtained from the Langmuir isotherm model at 20 °C was 120.6 mg g⁻¹. The calculated thermodynamic results such as ΔG° (−24.3 kJ mol⁻¹) and ΔH° (−9.56 kJ mol⁻¹) indicate that the adsorption process is spontaneous and exothermic in nature. Solid phase extraction of 8HQ was also performed. The X-ray diffractometry (XRD), Fourier Transform Infrared (FTIR) and thermogravimetric (TG) analyses were carried out in order to confirm the 8HQ adsorption onto bentonite. According to the obtained results, natural bentonite can be a reusable and effective adsorbent for the removal of 8HQ.     

Electron paramagnetic relaxation in aqueous solutions of manganese (II) ions

The processes of the electron paramagnetic relaxation, molecular motions and structural changes in aqueous solutions of manganese nitrate have been investigated by direct measurement of spin-lattice (T ₁) and spin-spin (T ₂) relaxation times for a wide range of concentrations, temperatures and viscosities. T ₁ and T ₂ were measured by a non-resonance absorption method.

It was discovered that some structural regions exist at the different concentrations of Mn(II) ions in solution. So, the structure of highly concentrated solutions may be considered as one of the corresponding crystallohydrate. The structural microinhomogeneities were observed also in the intermediate concentration range at definite temperatures. It is shown that the relaxation mechanism proposed by Bloembergen and Morgan is not effective in the concentration range studied by us.

The analysis of relaxation times and E.P.R. spectra has shown the formation of ‘liquid microphases’ at the freezing point of the solution. Such microphases can exist at temperatures a few tenths of a degree below the solvent freezing point, and its composition considerably differs from the initial solution.

The correlation times for intramolecular and intermolecular electron relaxation mechanisms are evaluated and their nature is discussed.     

Surface effect of natural zeolite (clinoptilolite) on the photocatalytic activity of TiO2

The surface interaction between TiO₂ and natural zeolite, clinoptilolite, has been investigated by means of transmission electron microscope (TEM), atom force microscope (AFM), X-ray diffractometer (XRD), diffuse reflectance infrared Fourier transform (DRIFT) and far Fourier transform infrared ray (FTIR) spectroscopy. And the photocatalytic degradation (PCD) rate of methyl orange (MO), a model of recalcitrant azo dye, in aqueous system has been measured to compare the photocatalytic activities of different photocatalysts. A model has been carried out to explain the incorporation between TiO₂ particles and natural zeolite. The results show that the TiO₂ particles loaded on zeolite are 50 nm or so, smaller than the pure one, and combine with zeolite via chemical force. Since the reserved adsorption ability and the existence of electron trapper, the TiO₂-zeolite performed more efficient at low initial concentration and in the later period of PCD process, as compared with pure TiO₂ nanopowders.     

含硫磷酸钙纳米颗粒的制备及对铅离子的高效选择性去除

用一种简易共沉淀法制备了非晶含硫磷酸钙（SCP）材料,实现硫原子原位引入磷酸钙纳米颗粒中,并研究了其对Pb（II）的吸附特性和机理。与羟基磷灰石相比,SCP对Pb（II）的去除性能显著增强,在10 min内能快速将20 ppm的Pb（II）溶液降低至饮用水标准下。由Langmuir吸附等温线模型计算可知,SCP对Pb（II）的最大饱和吸附量高达1720.57 mg/g,这个数值远远超过以往所报道的绝大部分吸附剂材料。在竞争离子Ni（II）,Co（II）,Zn（II）和Cd（II）共存的条件下,SCP还表现出对Pb（II）的选择性去除。研究表明,SCP对Pb（II）超高的去除效率和优异的亲和力归因于其可通过溶解沉淀和离子交换反应在其表面形成棒状的羟基磷酸铅晶体,以及形成沉淀物硫化铅。SCP以其对Pb（II）快速、高效和优异选择性成为在实际铅污染治理中的理想材料.     

Luminescence behavior of tetraaza macrocylic nickel (II) complexes and non-linear Stern-Volmer quenching

Macrocylic dicarbinolamine nickel (II) complexes with diimine moiety in their ligand exhibited luminescence, when irradiated at their charge transfer band. The Stern-Volmer (S-V) plots of one of the complexes in DMF medium exhibited positive curvature, when FeC1₃ was used as a quencher, while the same complex showed negative curvature when nitrobenzene was used as a quencher. The mechanism for the luminescence quenching of the macrocyclic complex has also been discussed.     

Dendrimer-conjugated magnetic nanoparticles for removal of zinc (II) from aqueous solutions

Dendrimers are novel nanostructure materials that possess a unique three-dimensional molecular configuration. They have high adsorption capacities of heavy metals. Dendrimer-conjugated magnetic nanoparticles (Gn-MNPs) combining the superior adsorbent of dendrimers with magnetic nanoparticles (MNPs) have been developed for effective removal and recovery of Zn(II). In this study, the Gn-MNPs were synthesized, characterized, and examined as reusable adsorbents of Zn(II). Characterization conducted by transmission electron microscopy (TEM), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and elemental analysis revealed that dendrimers were successfully coated onto the surface of MNPs made of magnetite (Fe₃O₄). The pH effect studies indicate the Zn(II) adsorption with Gn-MNPs is a function of pH. The adsorption efficiency increases with increasing pH. At pH less than 3, Zn(II) is readily desorbed. Hence, the Gn-MNPs can be regenerated using the diluted HCl aqueous solution (0.1 M) where Zn(II) can be recovered in a concentrated form. It was found that the Gn-MNPs underwent 10 consecutive adsorption–desorption processes still retained the original removal capacity of Zn(II). The adsorption data were fitted well with both Langmuir and Freundlich isotherms. The maximum adsorption capacity determined by the Langmuir model is 24.3 mg/g at pH 7 and 25°C. A synergistic effect between the complexation reaction and the electrostatic interaction may account for the overall performance of Gn-MNPs.     

Study on the preparation of a novel hybrid system nickel oxide-modified AgNPs/CNFs

The nanomaterial is very popular in recent years. In this article, a new hybrid system by nickel oxide-modified Ag NPs/CNFs has been successfully produced by combining the electrospinning technique and calcination. Different proportions of nickel nitrate were mixed into the solution and the influence on the morphological structure of Ag nanoparticles was investigated, and then composite nanofibers were investigated, which indicated that Ag nanoparticles and NiO nanoparticles were uniform in size and dispersed homogeneously in the carbon nanofibers by different characterizations.     

High‐accuracy X‐ray absorption spectra from mM solutions of nickel (II) complexes with multiple solutions using transmission XAS

A new approach is introduced for determining X‐ray absorption spectroscopy (XAS) spectra on absolute and relative scales using multiple solutions with different concentrations by the characterization and correction of experimental systematics. This hybrid technique is a development of standard X‐ray absorption fine structure (XAFS) along the lines of the high‐accuracy X‐ray extended range technique (XERT) but with applicability to solutions, dilute systems and cold cell environments. This methodology has been applied to determining absolute XAS of bis(N‐n‐propyl‐salicylaldiminato) nickel(II) and bis(N‐i‐propyl‐salicylaldiminato) nickel(II) complexes with square planar and tetrahedral structures in 15 mM and 1.5 mM dilute solutions. It is demonstrated that transmission XAS from dilute systems can provide excellent X‐ray absorption near‐edge structure (XANES) and XAFS spectra, and that transmission measurements can provide accurate measurement of subtle differences including coordination geometries. For the first time, (transmission) XAS of the isomers have been determined from low‐concentration solutions on an absolute scale with a 1–5% accuracy, and with relative precision of 0.1% to 0.2% in the active XANES and XAFS regions after inclusion of systematic corrections.     

2,6-双[N-(1′,1′-二甲基-2′-羟基)甲酰胺]吡啶及镍(Ⅱ)配合物的合成与光谱学研究

合成并表征了有机配体2,6-双[N-(1′,1′-二甲基-2′-羟基)甲酰胺]吡啶(L)及其镍(Ⅱ)配合物,采用元素分析确定目标配合物组成为C15H21N3O4Ni.H2O,通过对比分析的方法讨论了配位前后游离配体L和镍(Ⅱ)配合物的核磁共振氢谱、核磁共振碳谱、红外吸收光谱和紫外-可见吸收光谱的谱学性质,进而推断出镍(Ⅱ)配合物的结构。结果表明,配体2,6-双[N-(1′,1′-二甲基-2′-羟基)甲酰胺]吡啶以2个酰胺负离子N和1个吡啶环N原子为配位原子,与中心金属离子Ni(Ⅱ)通过三齿形式配位;配合物中Ni(Ⅱ)采取dsp2杂化轨道方式与配位原子构成配位键,中心金属Ni(Ⅱ)的配位数为4,1个Ni(Ⅱ)与1个三齿配体L和1个水分子配位,形成平面正方形构型的低自旋镍(Ⅱ)配合物。     

The effect of temperature on the preparation of electrochromic nickel oxide by an electroless method

The advantages of nickel oxide as an electrochromic material are due to its good contrast of transmittance and its suitable use as a secondary electrochrome. Compared to other methods of depositing eletrochromic nickel oxide, coating nickel oxide by electroless is simple and easy to scale-up for industrial application. This study presents the preparation of nickel oxide film on an ITO substrate by an electroless method and oxidizing it with heat treatment. The influence of oxidizing temperature in heat treatment procedures is notable. The morphology of the film was analyzed by a scanning electron microscope (SEM) and X-ray diffraction (XRD). Heat temperature at 380 °C obtained optimal of electrochromic properties. The transmittance difference (ΔT) of the film at 630 nm was maintained at 69%, and the amount of transferred charge during cyclic voltammetry was approximately 0.8 mC/cm² after 1000 cycles of redox, which was operated between −1.5 and +1.5 V potential step. The degradation of the film was decreased by increasing the oxidizing temperature. The evidences showed electrochromic abilities of nickel oxide were affected by heat-treatment procedures. All these analyses provided a novel method for preparing the electrochromic nickel oxide in a low-cost way.     

Adsorption of Zn(II) and Cd(II) ions onto magnesium and activated carbon composite in aqueous solution

Magnesium and coconuts shell activated carbon composite was prepared to selectively remove heavy metals ions in aqueous solution. Zinc(II) and cadmium(II) ions were used to clarify the adsorption capacity of the composite in comparison with no magnesium containing activated carbon. Influence of the initial heavy metal concentration, time course and solution temperature on the adsorption amounts were examined for the two adsorbents, and surface chemistry of the adsorbents was also characterized using Boehm titration. The magnesium composite adsorbed greater amount of Zn(II) and Cd(II) ions than the no magnesium counterpart. The adsorption amount of Cd(II) was not influenced with rise in solution temperature for the composite, whereas decrease in adsorption was observed for the counterpart. The loaded magnesium was estimated to be combined with carbon surface via oxygen bridge. Cadmium(II) was adsorbed onto the composite surface by ion exchange process with releasing equivalent amount of Mg(II) from the carbon surface, while Zn(II) would adsorb onto the composite by not only the ion exchange, but also the electrostatic interaction with the Cπ electrons on the graphite surface from the experimental results.     

Removal of rhodamine B from aqueous solutions using vanadium pentoxide/titanium butyl oxide hybrid xerogels

A stable and insoluble V_2O_5·n H_2O/tetra-n-butyl titanate(TBO) hybrid xerogel was synthesized by the sol–gel method. This novel material proved to be an efficient absorbent with an absorption capacity of 179 mg·g~(-1)for Rhodamine B(Rh B) in water due to its unique layered structure, which can effectively accommodate Rh B molecules between its layers as demonstrated by XRD and FTIR spectroscopic analyses.     

Ultrasound-assisted fabrication of a novel nickel(II)-bis-pyrazolyl borate two-nuclear discrete nano-structured coordination compound

Ultrasound was used to synthesize nano-structures of [Ni(bpzB)₂]₂(1), a new two-nuclear discrete-coordination compound of divalent nickel with bis-pyrazolyl borate(bpzB). The nanostructure was characterized by scanning electron microscopy, X-ray powder diffraction, infrared, and elemental analysis. The single-crystal X-ray data show that the coordination number of Ni(II) ions is four (Ni1N₄ and Ni2N₄) with square planar geometry. The supramolecular features in these complexes are guided and controlled by weak directional intermolecular interactions. The discrete molecules interact with each other through labile interactions, creating a 3D supramolecular framework.     

Synthesis of hybrid nanostructures composed of copper ions and poly(p-phenylenediamine) in aqueous solutions

A new kind of hybrid nanoparticles composed of copper ions and poly(p-phenylenediamine) has been synthesized in aqueous solution at room temperature. The nanoparticles have been characterized and studied by TEM, AFM, XPS, and UV spectroscopy. The synthesized nanoparticles are prone to connect with each other and form large nanoclusters. The diameters of the nanoparticles are 46 ± 26 nm. It is believed that a porous network structure exists inside the nanoparticles. The UV absorption spectra of the nanoparticles are sensed with pH and can be reversibly changed according to the pH level. This phenomenon of the nanoparticles has some potential applications. Nanosheets and branched rods composed of copper ions and poly(p-phenylenediamine) have also been obtained by using different ratios of copper ions and p-phenylenediamine as the initial reactant.     

Removal of heavy metals from aqueous solutions using Fe3O4, ZnO, and CuO nanoparticles

This study investigated the removal of Cd²⁺, Cu²⁺, Ni²⁺, and Pb²⁺ from aqueous solutions with novel nanoparticle sorbents (Fe₃O₄, ZnO, and CuO) using a range of experimental approaches, including, pH, competing ions, sorbent masses, contact time, scanning electron microscopy, transmission electron microscopy, and X-ray diffraction. The images showed that Fe₃O₄, ZnO, and CuO particles had mean diameters of about 50?nm (spheroid), 25?nm (rod shape), and 75?nm (spheroid), respectively. Tests were performed under batch conditions to determine the adsorption rate and uptake at equilibrium from single and multiple component solutions. The maximum uptake values (sum of four metals) in multiple component solutions were 360.6, 114.5, and 73.0?mg?g^?1, for ZnO, CuO, and Fe₃O₄, respectively. Based on the average metal removal by the three nanoparticles, the following order was determined for single component solutions: Cd²⁺?>?Pb²⁺?>?Cu²⁺?>?Ni²⁺, while the following order was determined in multiple component solutions: Pb²⁺?>?Cu²⁺?>?Cd²⁺?>?Ni²⁺. Sorption equilibrium isotherms could be described using the Freundlich model in some cases, whereas other isotherms did not follow this model. Furthermore, a pseudo-second order kinetic model was found to correctly describe the experimental data for all nanoparticles. Scanning electron microscopy, energy dispersive X-ray before and after metal sorption, and soil solution saturation indices showed that the main mechanism of sorption for Cd²⁺ and Pb²⁺ was adsorption, whereas both Cu²⁺ and Ni²⁺ sorption were due to adsorption and precipitation. These nanoparticles have potential for use as efficient sorbents for the removal of heavy metals from aqueous solutions and ZnO nanoparticles were identified as the most promising sorbent due to their high metal uptake.