A first report of the complexes of 5,11,17,23-tetra-tert-butyl-25,27-diethoxycarboxymethoxy-26,28-dihydroxycalix[4]arene with Mn(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II)

Totally six dinuclear complexes of Mn(II), Fe(III), Co(II), Ni(II), Cu(II) and Zn(II) of calix[4]arene derivatized with two pendants possessing terminal –COOH functions at two of its alternate phenolic –OH groups were synthesized for the first time and were well characterized.     

Decomposition of nitrous oxide over the catalysts derived from hydrotalcite-like compounds

Catalytic decomposition of nitrous oxide into nitrogen and oxygen has been carried out on ‘in situ' thermally calcined hydrotalcites of general formula M(II)–M(III)-CHT where M(II)=Mg, Co, Ni, Cu or Zn and M(III)=Al, Fe or Cr having different M(II)/M(III) atomic ratios. The reaction was performed in a recirculatory static reactor at 50 Torr (133.3 Pa) initial pressure of N₂O in the temperature range 423–773 K. Among the catalysts screened, Ni and Co containing catalysts with Al as the trivalent cation showed good activity (even at 423 K) wherein 50% and 100% conversion was achieved at 463 K and 523 K, respectively. Results on effect of composition for Co–Al system indicated that the activity increased with increase in the active metal ion concentration (Co²⁺), with closer dependence on the surface concentration (as determined by XPS). The observed activity pattern is explained on the basis of redox property and electronic effects. These materials were further evaluated under flow conditions (at Air Products and Chemicals, USA) simulating the industrial process streams (10% N₂O, 2% H₂O, 2% O₂ and balance N₂ and GHSV=18,500). Among the non-precious metal ions investigated, cobalt-based catalysts offered comparable activity similar to metal-exchanged zeolites for removing N₂O from combustion and Nylon-6,6 processes.     

Electrodeposition of Ni, Fe and Ni–Fe alloys on a 316 stainless steel surface in a fluorborate bath

Electrodeposition processes of Ni, Fe and Ni–Fe alloys on 316 stainless steel surfaces in fluorborate baths were studied using conventional electrochemical techniques and atomic force microscopy. The results showed that these processes occurred under mass transfer control, associated with nucleation and growth process. Cathodic current–time transients indicated that the nucleation and growth of Ni–Fe alloy was different from that of the single metal (Ni or Fe). For one, two nucleation and growth processes occurred during Ni–Fe alloy codeposition. Also, there was a nucleation and growth process of Ni–Fe alloy on Ni–Fe clusters, due to a change of the Ni–Fe alloy composition and phase. Homogeneous Ni–Fe alloy deposits could be obtained by pulse potential plating. AFM images of Ni, Fe and Ni–Fe deposits prepared by pulse potential plating revealed the following results: (1) the growth rate of Ni nuclei was faster in parallel than in perpendicular to the 316 electrode surface; (2) for Fe nuclei, the preferential growth direction was perpendicular to the 316 electrode surface; and (3) for Ni–Fe nuclei, there was no preferential growth direction and uniformly hemispherical Ni–Fe clusters were obtained.     

Surface microstructure and corrosion resistance of electrodeposited ternary Zn–Ni–Co alloy

The electroplating of ternary Zn–Ni–Co alloy, the influence of cobalt codeposition on crystal orientation, surface topography and corrosion resistance were investigated and contrasted with the characteristics of Zn–Ni electrodeposits. It was found that the Zn–Ni–Co alloy showed better corrosion resistance, in 3% sodium chloride, in comparison with Zn–Ni alloy electroplated under similar conditions. The best corrosion resistance was observed for ternary deposits having 11.24% Ni and 6.52% Co. The crystal orientation and surface topography were characterized by means of X-ray diffraction analysis and scanning electron microscopy, respectively.     

EXAFS and FTIR characterization of tetrarhodium carbonyl clusters attached on tris-(hydroxymethyl)phosphine grafted silica catalytically active for olefin hydroformylation

A series of perovskites of the formula Ca_1–x Sr _x Ti_1–y M _y O_3–, M=Fe, Co, Cr or Ni,x = 0–1,y = 0–0.6, has been synthesized by a modified sol-gel method using citrate. Several of these materials were proved to be stable under operating conditions in reducing atmospheres of air and hydrocarbons. An outline of the synthesis procedure is given, together with the results of XRD, SEM, BET, TG, DTA and IR characterization before and after catalytic testing. The solubility of Ni and Cr in this perovskite was very limited, and the solubility of Co decreased abruptly above 1173 K. The solubility range of Ca and Sr on alkaline earth sites is 100%.     

New carbon composites containing ultrafine metal particles. 2. Synthesis by pyrolisis of pitch-organometallic blends

Air-stable new carbon composites containing uniformly dispersed ultrafine Fe, Co, Ni, Ru, Pd, Rh, or Ag particles were obtained by thermal degradation of coal pitches mixed homogeneously with 1–10% of poly(vinyl ferrocene), cobaltocene, nickelocene, (acenaphthylene) Ru₃(CO)₇, PdCl₂(COD), RhCp(COD), and AgC₆H₄CH₂NMe₂, respectively, at 400–1200°C in Ar. Carbonization yields are 45–55% and the size of metal particles varied from 5 to 65 nm depending upon the treatment temperature and identity of the metal. The carbon composites containing Fe particles showed high Vicat hardness and good electrical conductivity. Pd- and Rh-dispersed materials exhibited good catalysis in hydrogenation of 1-hexene. The composite containing ultrafine Ag particles showed excellent bacteriostatic activity forEscherichia coli, Pseudomonas aeruginosa, andBatchillus subtilis.     

Dissolution kinetics of dehydroxylated nickeliferous goethite from limonitic lateritic nickel ore

The dissolution kinetics in 2 M H₂SO₄ of variously dehydroxylated nickeliferous goethites was investigated for five oxide-type lateritic nickel deposits. Goethite was the main constituent with minor amounts of quartz, talc, kaolinite and Mn oxides. Dissolution of Fe from heated materials followed the Kabai equation. There was a 9–34-fold increase in the Kabai dissolution rate constant (k) for samples heated at 340–400 °C due to both the increased surface area (1.5–2.6 fold) and higher density of structural defects (5–10 fold) in the variously dehydroxylated products. The presence of structural Al and Cr in goethite appears to reduce dissolution rate possibly through the greater M³⁺–OH, O bond strength relative to Fe³⁺, Ni²⁺–OH, O. Nickel showed congruent dissolution with Fe indicating that Ni was uniformly incorporated in the goethite structure. Pre-heating goethite to 600–800 °C for 30 min resulted in incongruent dissolution of Fe and Ni. It is postulated that some Ni is ejected from the neo-formed hematite structure and resides on the crystal surface or in voids. These results may contribute to the development of more efficient procedures for Ni extraction including heap leaching of lateritic nickel ores.     

镍造锍熔炼过程及伴生元素行为的计算机模型

借助于多相多成份系统平衡计算，开发了硫化镍矿造锍熔炼过程的数学模型，对卡尔古利镍闪速炉的实际生产操作进行了模拟，并将预测结果与实际生产数据进行了比较，吻合得较好．热力学计算表明：在镍熔炼过程中，Ｎｉ，Ｃｏ，Ｃｕ，Ｆｅ，Ｓ，Ｏ等在冰镍、渣相和气相中的分配取决于操作条件和热力学量，如熔炼温度、炉料成份、风矿比、富氧浓度及各组份在体系各相中的活度系数．     

Effects of anode materials in the electroforming of iron-nickel alloy foil

The effects of soluble and insoluble anodes upon the composition and mechanical properties of iron-nickel alloy foil of thickness about 0.1 mm have been studied. The soluble materials include stainless steels, main constituents 17.5–19% Cr, 9–11% Ni or 16–18% Cr, 0.5% Ni, and iron-nickel alloys of composition 60% Fe, 40% Ni or 30% Fe, 70% Ni. The performance of these materials is compared with graphite, an insoluble anode. The presence of chromium as a constituent in soluble anodes has an adverse effect on the electroforming process: the current efficiency of metal deposition is reduced, as is the working current density for the production of foil of acceptable quality and with satisfactory mechanical properties. The nickel content of the alloy foil can be increased, and the quality of the foil improved, by using iron-nickel anodes which are free of chromium.     

Platinum-based Alloys as oxygen–reduction Catalysts for Solid–Polymer–Electrolyte Direct Methanol Fuel Cells

Electrocatalytic activities of various carbon-supported platinum-based binary, namely, Pt–Co/C, Pt–Cr/C and Pt–Ni/C, and ternary, namely, Pt–Co–Cr/C and Pt–Co–Ni/C, alloy catalysts towards oxygen reduction in solid–polymer–electrolyte direct methanol fuel cells were investigated at 70°C and 90°C both at ambient and 2bar oxygen pressures. It was found that Pt–Co/C exhibits superior activity relative to Pt/C and other alloy catalysts.     

Removal of heavy metals and neutralisation of acid mine drainage with un-activated attapulgite

Unactivated attapulgite was characterised and utilised as an adsorbent for the removal of heavy metal and neutralisation of acid mine drainage (AMD) from a gold mine. Adsorption experiments were carried out by agitation of a fixed amount of attapulgite with a fixed volume of AMD in a thermostatic shaker for varying times. Attapulgite showed that it can neutralise acid mine drainage as the pH after 4 h was 7.11. The results showed that metal ion removal after 4 h was 100% for Cu(II) and Fe(II), 93% for Co(II), 95% for Ni(II) and 66% for Mn(II) using a 10% (w/v) attapulgite loading. The experimental data best fit the Langmuir Isotherm with maximum adsorption capacities for Cu(II), Co(II), Mn(II), Fe(II) and Ni(II) being 0.0053, 0.0044, 0.0019, 0.01, and 0.0053 mg/g, respectively. The adsorption process fitted well the pseudo first order kinetics for Co(II) and Cu(II) and pseudo second order for Ni(II), Mn(II) and Fe(II). Thermodynamic data show that Cu(II), Co(II), Fe(II) and Ni(II) adsorption was thermodynamically spontaneous whilst Mn(II) was not thermodynamically spontaneous. The process is endothermic for Cu(II), Co(II), Mn(II), and Ni(II) and exothermic for Fe(II). Spent attapulgite (attapulgite that has already been used to remove metals) could be reused twice without regeneration.     

A comparative study of different leaching processes for the extraction of Cu,Ni and Co from a complex matte

The extraction behaviors of Cu, Ni and Co from a complex matte under different leaching conditions have been discussed. The synthetic Cu-Ni-Co-Fe-S matte was prepared by melting the pure metals. The matte contained 24.95% Cu, 35.05% Ni, 4.05% Co, 11.45% Fe, 24.5% S, similar composition as is expected to be obtained by reduction smelting of the Pacific Ocean nodules followed by sulphidisation of the alloy. The different phases identified are CuFeS₂, CuS₂, (FeNi)₉S₈, (FeNi)S₂, Ni₉S₈, Ni₃S₂, (CoFeNi)₉S₈ and Co metal. The merits and demerits of each process of dissolution i.e., H₂SO₄/oxygen pressure leaching, atmospheric FeCl₃ leaching, NH₄OH/(NH₄)₂SO₄ pressure leaching are discussed in detail. Out of the three, the H₂SO₄/oxygen pressure leaching process is found to be the most suitable with more than 99% metal extraction efficiency within 1 h of leaching time. From the X-ray diffraction analysis, the different undissolved phases corresponding to different leaching processes have been identified. The metal extraction efficiency decreased in case of atmospheric FeCl₃ leaching and NH₄OH/(NH₄)₂SO₄ pressure leaching processes due to the formation of product layer such as elemental sulfur and goethite, respectively.     

Electrochemical reduction of carbon dioxide in methanol at ambient temperature and pressure

The electrochemical reduction of carbon dioxide was studied in methanol-based supporting electrolytes on various metal electrodes at ambient temperature and pressure. The ionophore of the catholyte was benzalkonium chloride, [RN(CH3)2CH2C6H5]⁺Cl^–, where R=C8–C18, the chain length being distributed around C14. A divided H-type cell was used, the supporting electrolytes were 10–2moldm–3 benzalkonium chloride in double distilled methanol (catholyte) and a 10–1moldm–3 aqueous KHCO3 solution (anolyte). Nine different, high purity (>99.5%) metal electrodes were used: Ti, Fe, Co, Ni, Pt, Ag, Au, Zn and Sn. Carbon monoxide, methane and ethane were the main organic products. Silver, Au, Zn and Sn cathodes allowed for the best faradaic yields of CO production, the maximum amount of CO (71%, 185 mmol) being formed on the Ag electrode. Methane evolved on each of the nine tested electrodes, with current yields in the range from 0.2 to 3.0%. Ethane and ethylene were produced on the nickel electrode, with low faradaic efficiencies, 0.5 and 0.3%, respectively. No dimerization products were detected. This research can contribute to large-scale manufacturing of useful organic products from a readily available and cheap raw material: CO2-saturated methanol from industrial absorbers (the Rectisol process).     

Heavy metals adsorption on some iminodiacetate chelating resins as a function of the adsorption parameters

The adsorption properties of some novel chelating resins (CRs) bearing iminodiacetate groups for removal of heavy metal ions like: Cu(II), Co(II) and Ni(II) from aqueous solutions comparative with the commercial resin Amberlite IRC-748 have been studied in this work by a batch equilibrium technique. Quantitative analysis for adsorption was conducted using UV–vis spectroscopy to investigate the kinetics, adsorption isotherm and thermodynamics of the removal process considering equilibration time, pH, metal ion concentration and temperature as controlling parameters. The metal adsorption capacities, at pH 5, were in the order Cu(II) > Ni(II) > Co(II), for both the CR with 10 wt.% DVB (CR-10) and the commercial resin Amberlite IRC-748. The adsorption capacities on CR-10 were higher for Ni(II) and Co(II) ions, but lower for Cu(II) ions compared with Amberlite IRC-748. Both Freundlich and Langmuir isotherms well fitted on the adsorption results of Cu(II), Ni(II) and Co(II) ions on all iminodiacetate resins.     

The effect of graphitization catalyst on the structure and porosity of SiC derived carbons

A number of carbide-derived carbon (CDC) samples were synthesized through the reaction between α-SiC and gaseous chlorine at temperatures 900, 1000 and 1100 °C and by varying the amount of catalyst. The chlorides of Co(II), Ni(II) and Fe(III) were used as catalytic additives in a range of concentration of 0.1–5 wt%. The structural differences of the obtained carbons were studied by low-temperature nitrogen adsorption, X-ray diffraction and Raman spectroscopy. Results showed that porosity, specific surface area and graphitization degree of the CDC materials is a function of chlorination temperature and catalyst concentration, which agrees with previous results. It was shown that the catalytic graphitization only weakly influences the L_a value of the crystallites, which according to the Raman scattering is 4–5 nm in both the highly disordered SiC derived carbons and in fully graphitic carbons made from SiC containing 15 wt% of surface-contacted Co–Ni–Fe catalyst. The surface area of the CDC materials can be controlled in the range of 300–1350 m² g⁻¹, depending on the amount of catalysts used.     

Improving Lining Resistance Using High-Magnesia Fluxes in the Converter Steelmaking Process

Tests carried out at the Severstal Joint-Stock Co. and Magnitogorskii Iron-and-Steel Works JSC showed that a lime-magnesia flux containing 30 – 35% MgO used in the converter steelmaking process produced a favorable effect on the refractory lining resistance. Compositions for high-magnesia granules (50 – 65% MgO) were developed, their properties characterized, and the rate of solution in the slag melt was determined. Using these granules in the converter process makes it possible to increase the service life of periclase-carbon refractories for converter linings.     

Effect of EDTA on hydrotreating activity of CoMo/γ-Al2O3 catalyst

γ-Al₂O₃ supported Co (0–4.5 wt%) Mo (9.0 wt%) sulfide catalysts were prepared in the presence and the absence of ethylenediaminetetraacetic acid (EDTA). The hydrodenitrogenation (HDN) activity of these catalysts was studied in the model reaction of 2,6-dimethylaniline (DMA) at 300 °C under 4 MPa. The CoMo/Al₂O₃ catalysts prepared with the EDTA showed higher HDN of DMA than those prepared without EDTA. The maximum of 36% increase in rate constant of HDN of DMA was observed over the catalyst with 3% Co prepared using EDTA. The FT-IR spectroscopy of adsorbed CO on CoMo catalysts showed that EDTA addition promoted the formation of catalytically active “CoMoS” phase as evidenced from increases in intensity of band at 2070 cm⁻¹, which is maximum for 3% Co loaded catalysts. The HDN and hydrodesulfurization (HDS) activity of 3% Co loaded catalyst prepared using EDTA was tested and compared with those catalyst prepared without EDTA in a trickle bed reactor using heavy gas oil derived from Athabasca bitumen in the temperature range 370–400 °C and 8.8 MPa. Improved HDN and HDS conversion of heavy gas oil was obtained for the catalyst prepared with EDTA.     

The role of vacancies in the hydrogen storage properties of Prussian blue analogues

The porosity and hydrogen storage properties of the dehydrated Prussian blue type solids Ga[Co(CN)₆], Fe₄[Fe(CN)₆]₃, M₂[Fe(CN)₆] (M = Mn, Co, Ni, Cu), and Co₃[Co(CN)₅]₂ are reported and compared to those of M₃[Co(CN)₆]₂ (M = Mn, Fe, Co, Ni, Cu, Zn). Nitrogen sorption measurements suggest partial framework collapse for M₂[Fe(CN)₆] (M = Co, Ni) and Co₃[Co(CN)₅]₂, and complete collapse for Mn₂[Fe(CN)₆]. Hydrogen sorption isotherms measured at 77 K reveal a correlation between uptake capacity and the concentration of framework vacancies, with Langmuir–Freundlich fits predicting saturation values of 1.4 wt.% for Ga[Co(CN)₆], 1.6 wt.% for Fe₄[Fe(CN)₆]₃, 2.1 wt.% for Cu₃[Co(CN)₆]₂, and 2.3 wt.% for Cu₂[Fe(CN)₆]. Enthalpies of H₂ adsorption were calculated from isotherms measured at 77 and 87 K. Importantly, the values obtained for compounds with framework vacancies are not significantly greater than for the fully-occupied framework of Ga[Co(CN)₆] (6.3–6.9 kJ/mol). This suggests that the exposed metal coordination sites in these materials do not dominate the hydrogen binding interaction.     

Adsorptive removal of trace NO from a CO2 stream over transition-metal-oxide-modified HZSM-5

This study investigates the adsorption performance of a number of absorbents prepared by incipient wetness impregnation of 3.85 wt% Fe, Co, Ni, Mn, Co and Ce oxides on HZSM-5 for the removal of trace NO (150–200 ppm) from a CO₂ stream to produce food-grade CO₂. The adsorbents were characterized using X-ray diffraction, X-ray fluorescence, and N₂ adsorption with their performances evaluated in a fixed-bed flow system. The investigations revealed NO removal of better than 0.1 ppm from the CO₂ stream. The breakthrough capacities of the adsorbents for NO removal in the presence of O₂ were found to significantly increase. The converse was observed in the case of NO adsorption selectivity. Co/HZSM-5(25) was found to be the best adsorbent under all the conditions tested producing CO₂ purities of better than 99.9999%. This is significantly higher than for Fe–Mn mixed oxides, claimed to be the best NO adsorbent reported in the literature for CO₂ purification.     

Effect of heat treatment on electroless ternary nickel–cobalt–phosphorus alloy

Ternary Ni–Co–P and binary Ni–P alloy coatings were deposited on mild steel panels from an alkaline bath in the presence and absence of cobalt sulfate using an electroless process. The effects of heat treatment on surface topography and crystal orientation of Ni–Co(11.17%)–P(3.49%) alloy coatings were studied in contrast to that of Ni–P ones. It was found that the as plated Ni–Co–P alloy is a supersaturated solid solution of P and Co dissolved in a microcrystalline Ni matrix with 111 preferred direction. Heat treatment induces structural changes. The formation of Ni₃P phase precipitates and recrystallization of nickel occur when the sample is treated at > 400 °C for one hour. It is observed that the Ni diffraction lines of treated Ni–Co–P alloy at > 400 °C are shifted to lower angles as compared to those of treated Ni–P or as plated Ni–Co–P alloys. The surface topography of Ni–Co–P alloy also changes with heat treatment temperature. The surface topography and crystal orientation were characterized by means of scanning electron microscopy and X-ray diffraction, respectively. The hardness and corrosion resistance, in 5 wt % NaCl solution, of heat treated Ni–Co–P samples were studied.