Extraction of cadmium from solutions containing various heavy metal ions by Amberlite LA-2

In present study, selective extraction of cadmium from acidic leach solutions, containing various heavy metal ions, by emulsion liquid membrane (ELM) is studied. For this reason, the zinc plant copper cake was leached with sulfuric acid and main acidic leach solution containing Zn(II), Cu(II), Fe(II), Cd(II), Co(II) and Ni(II) ions was obtained. After Zn(II), Cu(II), Fe(II) and Cd(II) ions in the acidic leach solution were separated, the important parameters influencing the extent of cadmium extraction were investigated and optimum conditions were determined. Cadmium extraction was influenced by number of parameters like initial metal ion concentration, mixing speed, phase ratio, extractant concentration, surfactant concentration, the stripping solution type and concentration, and the feed solution acid concentration. The optimum values of parameter above mentioned were used and cadmium in the acidic leach solution containing 650 mg Cd/L, 365 mg Co/L, 535 mg Ni/L, and 1260 mg Zn/L was almost completely extracted within 10 min. The results showed that it is possible to extract 99% of cadmium after 10 min contact time by using ELM from aqueous solutions, containing Fe(II), Al(III), Cu(II), Zn(II), Pb(II), Co(II) and Ni(II) ions, at the optimum operating conditions.     

NO SCR with propane and propene on Co-based alumina catalysts prepared by co-precipitation

Homogeneous dispersions and small size of deposited high-content cobalt on alumina were achieved by the co-precipitation method and were well maintained on the cobalt-based binary alumina catalysts with Zn, Ag, Fe, Cu or Ni as modifiers. The component and concentration of deposited cobalt species were characterized by UV–vis, EDX and XPS spectra and found to be greatly related to the Co loading, calcination temperatures and the type of additive metals. The optimal Co loading of 8 wt% and calcination temperatures of 800 °C were demonstrated. With respect to the single cobalt-based alumina catalyst, the surface concentration of Co²⁺ on the binary catalysts with addition of Fe, Cu, Ag or Ni was all reduced and accompanying with part conversion of Co²⁺ to Co₃O₄ on the Fe and Ni-modified catalysts. A slight enhanced surface Co²⁺ concentration was only achieved on the Zn-promoted catalyst. It was also demonstrated that for the case of Cu and Fe the additive metals themselves participated in the activation of propene. The octahedral and tetrahedral Co²⁺ ions were suggested as the common active sites. A maximum deNOx activity of 96% was observed on the 8Co4ZnA800 catalyst at the reaction temperatures of 450 °C, and the catalytic performance on the cobalt-based binary alumina catalysts can be described as fellows: CoZn > CoAg, CoNi > Co Cu > CoFe. Based on the in situ DRIFT spectra, different reaction intermediates R–ONO and –NCO besides –NO₂ were formed on the 8Co4ZnA800 and 8Co4FeA800 samples, respectively, demonstrating their dissimilar reaction mechanisms.     

Cation distribution and magnetic analysis of wideband microwave absorptive CoxNi1−xFe2O4 ferrites

Co_xNi_1−xFe₂O₄ ferrites (x=0, 0.2, 0.4, 0.4, 0.6, 0.8 and 1) were prepared by a sol-gel auto-combustion method. The samples were structurally characterized by X-ray diffractometry (XRD), field emission scanning electron microscopy (FE-SEM), energy dispersive X-ray analysis (EDX), and Fourier transform infrared spectroscopy (FTIR). The XRD patterns confirmed single phase formation of spinel structure. Cation distribution estimated from XRD data suggested the mixed spinel structure of ferrite. The EDX analysis was in good agreement with the nominal composition. The results of FTIR analysis indicated that the functional groups of Co-Ni spinel ferrite were formed during the combustion process. According to FE-SEM micrographs, by addition of cobalt ion the average particle size of substituted nickel ferrite was gradually became smaller from 450 nm to 280 nm. Magnetic measurement using vibrating sample magnetometer (VSM) showed an increase in saturation magnetization and coercivity by Co²⁺ substitution in nickel ferrite. For Co_0.8Ni_0.2Fe₂O₄ sample, M_s and H_c reaches as high as 93 emu/g and 420 Oe, respectively. The reflection loss properties of the nanocomposites were investigated in the frequency range of 8–12 GHz, using vector network analyzer (VNA). Cobalt substitution could enhance reflection loss of NiFe₂O₄ ferrite. The maximum reflection loss value of the Co²⁺ substituted Ni ferrite was ~ −26 dB (i.e. over 99% absorption) at 9.7 GHz with bandwidth of 4 GHz (RL<– 10 dB) through the entire frequency range of X-band.     

Structure and catalytic performance of Pt-promoted alumina-supported cobalt catalysts under realistic conditions of Fischer–Tropsch synthesis

The structure of alumina-supported cobalt catalysts promoted with platinum and their catalytic performance in Fischer–Tropsch synthesis were investigated under realistic reaction conditions (P = 20 bar, T = 493 K) using in situ time-resolved X-ray diffraction with simultaneous analysis of reaction products. The catalysts were prepared via incipient wetness impregnation and characterized by a wide range of ex situ techniques. Direct in situ measurements were indicative of considerable versatility of alumina-supported cobalt catalysts during Fischer–Tropsch synthesis. Cobalt sintering occurred at the first hours of the reaction and resulted in a significant drop of the catalytic activity. In addition to sintering, partially oxidized catalysts containing smaller cobalt particles (mean particle size <5 nm) were slowly reducing during Fischer–Tropsch reaction. Treatment of cobalt catalysts in pure carbon monoxide led to selective transformation of cobalt metallic phases to Co₂C cobalt carbide. Cobalt carbidization followed by hydrogenation selectively led to cobalt hcp metallic phase, which seems to be more active in Fischer–Tropsch synthesis than cobalt fcc phase. Cobalt oxidation by water was not significant in the catalysts with metal particles larger than 5 nm even at high water concentrations.     

Conductivity of Co and Ni doped lanthanum-gallate synthesized by citrate sol–gel method

Solid solutions of Sr and Mg doped lanthanum-gallate (LSGM) with addition of 3 and 5 at% of cobalt and nickel at the B-site in ABO₃ perovskite structure were obtained using citrate sol–gel method. The synthesized powders were calcined at 900 °C and then finally sintered at 1450 °C for only 2 h, which resulted in approximately 95% density. Impedance spectroscopy was utilized for electrical characterization in the temperature range 200–600 °C. The activation energies calculated from impedance spectra for bulk and grain boundary conductivities were decreased by the addition of transition metals (Co and Ni) and subsequently the conductivity was increased. Two different regions were clearly distinguished in the plots ln(σT) vs. 10,000/T for grain boundary conductivities, indicating changes in the mechanism of charge transport with the temperature. It is concluded that addition of cobalt above 5 at% in the LSGM prepared by citrate sol–gel method does not enhance the electrolytic properties of LSGM. XRD results suggested possible coexistence of two perovskite crystalline phases in nickel doped samples. However, it is still more favorable for use in IT-SOFC applications than cobalt since it has less influence on the electrolytic domain of LSGM.     

Carbon nanotube growth at 420 °C using nickel/carbon composite thin films as catalyst supports

Nickel/carbon composite (Ni/C) thin films were used as catalyst supports for the growth of vertically aligned multiwalled carbon nanotubes (MWCNTs) at temperature as low as 420 °C. Nickel nanoparticles embedded within the carbon matrix of Ni/C films have served as catalysts for the synthesis of nanotubes by PECVD using acetylene/ammonia plasma. Two different nickel contents (40 at.% and 60 at.%) in the films were used. Analysis indicated a diffusion of nickel atoms in the form of nanoparticles to the film surface upon annealing. This diffusion depends on both annealing temperature and nickel concentration in the films and affects the MWCNT growth at low temperature. The MWCNT synthesis was tested at growth temperature ranging between 335 and 520 °C. The growth of MWCNTs at 420 °C was only achieved by using Ni/C films with a high nickel content (60 at.%). These MWCNTs did not present considerable loss in their growth rate and structural quality compared to MWCNTs grown on classical substrates (Ni catalysts deposited on TiN), at higher temperature (520–600 °C). The results suggest that carbon saturation at the surface and subsurface of nickel catalysts of the Ni/C films is responsible for the improvement of MWCNT growth at low temperature.     

Effective hydrolysis of sodium borohydride driven by self-supported cobalt oxide nanorod array for on-demand hydrogen generation

Hydrogen storage, distribution and controlled release are of important concerns for hydrogen based economy. Sodium borohydride (NaBH₄) is one of the mostly studied chemical hydrides used for hydrogen storage and generation. However, it requires efficient catalysts to accelerate its dehydrogenation for controllable hydrogen production. In this paper, we demonstrate that the dehydrogenation of NaBH₄ in alkaline solutions can be driven by self-supported cobalt oxide nanorod array on Ti sheet (Co₃O₄ NA/Ti). Such Co₃O₄ NA/Ti shows high catalytic performance with a maximum hydrogen generation rate of 1940 mL/min/g_Co3O4 and an activation energy of 59.84 kJ/mol under ambient condition. Moreover, this catalyst exhibits no mass or activity loss even after 5 cycles with an obvious advantage of easy separation from the fuel solution. This development offers us a cost-effective and recyclable catalytic material toward hydrolytic hydrogen production for applications.     

A two-dimensional metal-organic framework composed of paddle-wheel cobalt clusters with permanent porosity

A cobalt(II)-organic framework, [Co₂(TPEC)(DMA)₂]·(DMA)₃ (1) (H₂TPEC = 1,1,2,2-tetra(4-(4-carboxyl-phenyl)benzenyl)ethene; DMA = N,N′’-dimethylacetamide), was synthesized and characterized by single crystal diffraction analysis. The structure shows a two-dimensional (2D) sheet composed of paddle-wheel Co₂(COO)₄ clusters linking TPEC ligands. The permanent porosity was established for the activated phase and gas sorption isotherms acquired.     

The synthesis,cyclic voltammetry and spectroelectrochemical studies of Co(II) phthalocyanines tetra-substituted at the α and β positions with phenylthio groups

Non-peripherally substituted cobalt 1,(4)-(tetraphenylthiophthalocyaninato) and peripherally substituted cobalt 2,(3)-(tetraphenylthiophthalocyaninato) complexes were synthesized. Redox processes were observed at E_1/2 = ?1.44 V (I), ?0.39 V (II), +0.37 V (III), +0.78 V (IV) and 1.15 V (V) for the non-peripherally substituted and at E_1/2 = ?1.42 V (I), ?0.57, ?0.39 V (II), +0.27 V (III), +0.79 V (IV) and +1.10 V (V) for the peripherally substituted complexes, respectively. The couples were assigned to Co^IPc^?2/Co^IPc^?3 (I), Co^IIPc^?2/Co^IPc^?2 (II), Co^IIIPc^?2/Co^IIPc^?2 (III), and Co^IIIPc^?1/Co^IIIPc^?2 (IV) using spectroelectrochemistry. The last process (V) could not be ascertained by spectroelectrochemistry but is associated with ring oxidation. Upon reduction or oxidation, the Q band of the non-peripherally substituted complex became less red shifted compared to that of its peripherally substituted counterpart.     

Tunable ceria–zirconia support for nickel–cobalt catalyst in the enhancement of methane dry reforming with carbon dioxide

Ceria–zirconia mixed oxides (CeZr) were glycol-thermally synthesised as nano-crystalline supports with tunable ratios for the anchoring of nickel–cobalt (Ni–Co) catalyst to enhance methane dry reforming (MDR) reaction with carbon dioxide. High conversion of methane (90%) and carbon dioxide (92%), good output (H₂ = 32%; CO = 44%), and selectivity and stability of syngas prove the effectiveness of the catalyst deposited on this support. 80:20 for Ce:Zr was identified as the optimal ratio to attain active and stable catalytic performance in MDR, with a low coking content of 0.47 wt.%.     

Solvothermal in situ synthesis of (Schiff-base)-containing dinuclear cobalt compound

A new dinuclear cobalt compound, namely Co₂(L)(H₂O)Cl₂ (1, H₂L = N,N′-o-phenylenebis(salicylide-neimine) was obtained by one-pot solvothermal self-assembly of CoCl₂, 1,2-phenylenediamine, and salicylaldehyde in C₂H₅OH. The magnetic studies suggest weak antiferromagnetic behavior and the magnetic data were interpreted by means of a dinuclear cobalt model with the parameters of g = 2.12, J = ?1.25 cm^?1, θ = ?3.12 K.     

Electrodeposition and characterization of ordered mesoporous cobalt hydroxide films on different substrates for supercapacitors

Novel ordered mesoporous cobalt hydroxide films have been successfully electrodeposited on different substrates, i.e., foamed nickel mesh and titanium plate, from cobalt nitrate dissolved in the aqueous domains of the hexagonal lyotropic liquid crystalline phase of Brij 56. Field emission scanning electron microscope (FESEM) and transmission electron microscopy (TEM) studies present that the as-deposited films have an interlaced nanosheet-like surface morphology and possess a regular nanostructure with hexagonal arrays of pores of nanometer dimension and extended periodicity. Various electrochemical test results show that the films on both substrates exhibit excellent electrochemical capacitive behavior due to the special ordered mesoporous nanostructure. Furthermore, it is obvious that the ordered mesoporous cobalt hydroxide film on foamed Ni mesh has much higher specific capacitance (maximum: 2646 F g^?1) than that of the film on Ti plate (maximum: 1018 F g^?1), which is mainly because that the foamed Ni mesh substrate with much larger surface area than Ti plate could enhance the utilization and the capacitance of Co(OH)₂ film greatly.     

Easy synthesis of ordered mesoporous carbon containing nickel nanoparticles by a low temperature hydrothermal method

Ordered mesoporous carbons (OMCs) with embedded metallic nickel (Ni) nanoparticles have been directly synthesized by a simple and low temperature (50 °C) hydrothermal method. The synthesis involved the use of a triblock copolymer Pluronic F127 as the mesostructure directing agent, resorcinol (R) and formaldehyde (F) as carbon precursors, and Ni(NO₃)₂·6H₂O as nickel source. It consisted in the self-assembly of F127, Ni²⁺ salt and RF polymer in an acidic medium and further carbonization, where the Ni²⁺ was captured by the network of F127/RF and further reduced into metallic Ni nanoparticles. The resultant Ni/carbon materials were characterised by X-ray diffraction, thermogravimetric analysis, transmission electron microscopy and nitrogen sorption. Ni/carbon materials with a highly ordered mesostructure were obtained using equal moles of resorcinol and formaldehyde molar ratio (R/F = 1/1), whereas an excess amount of formaldehyde (R/F = 1/2) was found to not form an ordered carbon structure. The results showed that nickel particles, with sizes of ∼10–50 nm, were homogeneously dispersed in the carbon matrices, while the pore mesostructure remained intact. The homogeneous Ni/carbon composites synthesized by this easy hydrothermal route have been demonstrated to be effective molecular adsorbents for magnetic separation.     

β-cyclodextrin as inverse phase transfer catalyst on the electrocatalytic hydrogenation of organic compounds in water

The optimum conditions for the electrocatalytic hydrogenation (ECH) of benzaldehyde in water, using a nickel sacrificial anode (SA) (referred to as ECH-SA) and β-cyclodextrin (β-CyD) as inverse phase transfer catalyst (IPTC) were determined. Four parameters were investigated: the morphology of the nickel deposited on the cathode matrix (Cu, Fe, Ni or Fe/Ni alloy (64:36)) during a pre-electrolysis, the size of the CyD cavity, the concentration of β-CyD, the supporting electrolyte concentration and the current density applied. The results showed that a Ni matrix together with ultrasound pre-electrolysis treatment allowed a nanostructured nickel deposit on the cathode surface. Under the best electrolysis conditions (2.8 mmol dm^?3 of β-CyD, 1.0 mol dm^?3 of NH₄Cl and a current density of 330 mA dm^?2), the yield of benzyl alcohol (99%) was 27% higher than that obtained under the same conditions but in the absence of β-CyD. Taking into account the hydrophobic character of the β-CyD, the best conditions of the ECH-SA method were applied to the hydrogenation of a variety of organic substrates. Excellent yields and current efficiencies were obtained with arylbenzaldehydes and acetophenone. ECH-SA of styrene gave moderate yield and current efficiency, and the hydrogenation of a terminal non-conjugated olefin (safrole) was not efficient.     

Investigation of the hydrogenation reactivity of some organic substrates using an electrocatalytic method

The hydrogenation reactivity of some classes of organic substrates (α,β-unsaturated ketones, benzaldehydes and acetophenones) was investigated using an electrocatalytic method (undivided cell, nickel sacrificial anode and water/methanol solvent). During the process a nickel deposit is produced on the cathode surface, at the same time that hydrogen is generated by water reduction. Nickel deposit morphologies (catalyst surface) were investigated, taking into account different cathode matrix materials (Cu, Ni, Fe, Fe/Ni (alloy 64:36)). The electrocatalytic method was evaluated by electrochemical efficiency of the hydrogenation process ((hydrogenation theoretical charge/experimental charge) × product yield). It was observed that Ni deposit/Ni cathode matrix ensemble exhibits slightly better catalytic activity, likely due the nanostructure of the nickel deposit. Moreover, the reactivity order determined through the electrochemical efficiencies (α,β-unsaturated ketones > benzaldehydes > acetophenones) is the same as that found in the literature.     

Selective transport of cobalt (II) from ammoniacal solutions containing cobalt (II) and nickel (II) by emulsion liquid membranes using 8-hydroxyquinoline

The selective transport of cobalt (II) from ammoniacal solutions containing nickel (II) and cobalt (II) by emulsion liquid membranes (ELMs) using 8-hydroxyquinoline (8-HQ) as extractant has been presented. Membrane solution consists of a diluent (kerosene), a surfactant (ECA 4360J), and an extractant (8-HQ). Very dilute sulphuric solution buffered at pH 5.0 has been used as a stripping solution. The ammoniacal feed solution pH was adjusted to 9.0 with hydrochloric acid. The important variables governing the permeation of cobalt (II) have been studied. These variables are membrane composition, pH of the feed solution, cobalt (II) and nickel (II) concentrations of the feed solution, stirring speed, surfactant concentration, extractant concentration, complexing agent concentration and pH of the stripping solution, and phase ratio. After the optimum conditions had been determined, it was possible to selectively transport 95.0% of cobalt (II) from ammoniacal feed solution containing Co²⁺ and Ni²⁺ ions. The separation factors of cobalt (II) with respect to nickel (II), based on initial feed concentration, have experimentally found to be of as high as 31 for equimolar Co(II)–Ni(II) feed solution.     

A stable peroxo- and hydroxido-bridged dinuclear cobalt(III) ethylenediammine 2,4-dinitrophenolate complex

A simple synthesis of a stable (μ-peroxo)(μ-hydroxido)bis[bis(ethylenediammine)cobalt(III)]2,4-dinitrophenolate trihydrate a dinuclear complex having peroxo-unit, Co^3 + ions along with 2,4-dinitrophenolate anion which is generated by reactions of Co^2 + with air is described. The Co^3 + complex interacts with catechol under mild acid conditions.     

Hydrogenation of carbon monoxide to methane over mesoporous nickel-M-alumina (M = Fe,Ni, Co,Ce, and La) xerogel catalysts

Mesoporous nickel(30 wt%)-M(10 wt%)-alumina xerogel (30Ni10MAX) catalysts with different second metal (M = Fe, Ni, Co, Ce, and La) were prepared by a single-step sol–gel method for use in the methane production from carbon monoxide and hydrogen. In the methanation reaction, yield for CH₄ decreased in the order of 30Ni10FeAX > 30Ni10NiAX > 30Ni10CoAX > 30Ni10CeAX > 30Ni10LaAX. Experimental results revealed that CO dissociation energy of the catalyst and H₂ adsorption ability of the catalyst played a key role in determining the catalytic performance of 30Ni10MAX catalyst in the methanation reaction. Optimal CO dissociation energy of the catalyst and large H₂ adsorption ability of the catalyst were favorable for methane production. Among the catalysts tested, 30Ni10FeAX catalyst with the most optimal CO dissociation energy and the largest H₂ adsorption ability exhibited the best catalytic performance in terms of conversion of CO and yield for CH₄ in the methanation reaction. The enhanced catalytic performance of 30Ni10FeAX was also due to a formation of nickel–iron alloy and a facile reduction.     

Effect of carbonization temperature on the nickel crystallite size of a Ni/C catalyst for catalytic hydrothermal gasification of organic compounds

A carbon based nickel (Ni) catalyst was prepared by ion exchanging Ni ions with the ion exchangeable sites in an ion exchange resin followed by carbonization of the resin. Effect of carbonization parameters such as temperature and time on nickel crystallite size and dispersion were studied. Samples were prepared at 500, 600, 700 and 800 °C to investigate the effect of carbonization temperature. The XRD pattern and TEM images of the catalysts showed that Ni particles become bigger in size as carbonization temperature increases. No effect of carbonization time on particle size was observed. The catalytic hydrothermal gasification (CHTG) experiments with 0.2% TOC organic water at 350 °C, 20 MPa, and 50 h⁻¹ liquid hourly space velocity (LHSV) showed that the conversion or activity decreased as particle size increased, from 99% for Ni500 (3.3 nm) to 25% for Ni800 (21.5 nm). The extended time experiments showed that the conversion or activity was stable for both Ni500 and Ni700 for 50 h run time. The XRD and TEM patterns of the two catalysts after 50 h gasification run showed that Ni500 with smaller particle size shows slightly higher sintering rate than Ni700 with bigger particles.     

Modification of a hydrophobic-ligand-containing porous sheet using tri-n-octylphosphine oxide,and its adsorption/elution of bismuth ions

A neutral extractant, tri-n-octylphosphine oxide (TOPO), was used to chemically modify a porous sheet, with a final density of 1.0 mmol/g. First, glycidyl methacrylate (GMA) was graft-polymerized onto a porous polyethylene sheet with an average pore diameter, porosity, and thickness of 1.2 μm, 75%, and 2.0 mm, respectively. Second, an octadecane thiol group was introduced into the poly-GMA graft chain. Third, TOPO was deposited on the graft chain via a hydrophobic interaction. Bismuth chloride solution (BiCl₃ in 0.15 M HNO₃) was forced through the pores of the TOPO-modified porous sheet. The equilibrium binding capacity for bismuth was 0.19 mmol/g. Bismuth ions bound to TOPO were quantitatively eluted with 11 M HNO₃.