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.     

Impact of precursor preparation on density of gadolinium iron garnets synthesized via reactive sintering

Gadolinium iron garnet was obtained from two different precursors, homogenized in isopropyl alcohol and in an aqueous environment with a fixed pH. In the first case, it was a mixture of goethite (FeO(OH)) and gadolinium oxide (Gd₂O₃); in the second, a mixture of GdIP (GdFeO₃) and α-Fe₂O₃. Conditions of homogenization in the aqueous environment were selected based on the zeta (ξ) potential measurements as the function of pH. DSC measurements of the output powder mixtures allowed the identification of the effects observed during the temperature rise. In the case of the material obtained from a mixture of goethite (FeO(OH)) and gadolinium oxide, with the increasing temperature, we observe three effects, the first of which corresponds to the phase transformation of goethite into α-Fe₂O₃, the second corresponds to the reaction of gadolinium iron perovskite (GdIP) formation, and the third to the reaction in which a gadolinium iron garnet (GdIG) is formed. However, in the case of heat treatment of the mixture of GdIP and α-Fe₂O₃, we only observe the effect responsible for a solid state reaction leading to the formation of gadolinium iron garnet. Dilatometric measurements allowed to determine the changes in linear dimensions at various stages of reaction sintering. The resulting materials were sintered at temperatures of 1200, 1300, and 1400 °C. In the case of the material obtained from a mixture of perovskite and iron (III) oxide, already at the temperature of 1300 °C, a density has been obtained at around 95% of the theoretical density, and the temperature of 1400 °C allowed achieving a density of 97% of the theoretical density. Whereas, for the material obtained from a mixture of goethite (FeO(OH)) and gadolinium oxide, a density above 95% of theoretical density was achieved only at 1400 °C.     

Reforming methanol to electricity in a high temperature PEM fuel cell

In this paper we demonstrate for the first time a compact power unit, where a methanol reforming catalyst is incorporated into the anode of a PEMFC. The proposed internal reforming methanol fuel cell (IRMFC) mainly comprises: (i) a H₃PO₄-imbibed polymer electrolyte based on aromatic polyethers bearing pyridine units, able to operate at 200 °C and (ii) a 200 °C active and with zero CO emissions Cu–Mn–O methanol reforming catalyst supported on copper foam. Methanol is being reformed inside the anode compartment of the fuel cell at 200 °C producing H₂, which is readily oxidized at the anode to produce electricity. The IRMFC showed promising electrochemical behavior and no signs of performance degradation for more than 72 h.     

Solely μ1,1-azido-bridged heterometallic compound

Solely end-on azide-bridged bimetallic Cu(II)–Mn(III) tetranuclear compound [Mn(salophen)(H₂O)]₂[Cu₂(N₃)₆]·4H₂O shows strong ferromagnetic coupling, giving rise to a ground spin state of S = 5.     

Effect of ethyleneglycol addition on the properties of P-doped NiMo/Al2O3 HDS catalysts: Part I. Materials preparation and characterization

Phosphorous-doped NiMo/Al₂O₃ hydrodesulfurization (HDS) catalysts (nominal Mo, Ni and P loadings of 12, 3, and 1.6 wt%, respectively) were prepared using ethyleneglycol (EG) as additive. The organic agent was diluted in aqueous impregnating solutions obtained by MoO₃ digestion in presence of H₃PO₄, followed by 2NiCO₃·3Ni(OH)₂·4H₂O addition. EG/Ni molar ratio was varied (1, 2.5 and 7) to determine the influence of this parameter on the surface and structural properties of synthesized materials. As determined by temperature-programmed reduction, ethyleneglycol addition during impregnation resulted in decreased interaction between deposited phases (Mo and Ni) and the alumina carrier. Dispersion and sulfidability (as observed by X-ray photoelectron microscopy) of molybdenum and nickel showed opposite trends when incremental amounts of the organic were added during catalysts preparation. Meanwhile Mo sulfidation was progressively decreased by augmenting EG concentration in the impregnating solution, more dispersed sulfidic nickel was evidenced in materials synthesized at higher EG/Ni ratios. Also, enhanced formation of the so-called “NiMoS phase” was registered by increasing the amount of added ethyleneglycol during simultaneous Ni–Mo–P–EG deposition over the alumina carrier. That fact was reflected in enhanced activity in liquid-phase dibenzothiophene HDS (batch reactor, T = 320 °C, P = 70 kg/cm²) and straight-run gas oil desulfurization (steady-state flow reactor), the latter test carried out at conditions similar to those used in industrial hydrotreaters for the production of ultra-low sulfur diesel (T = 350 °C, P = 70 kg/cm², LHSV = 1.5 h⁻¹ and H₂/oil = 2500 ft³/bbl).     

The phenol steam reforming reaction towards H2 production on natural calcite

The steam reforming of phenol towards H₂ production was studied in the 650–800 °C range over a natural pre-calcined (air, 850 °C) calcite material. The effects of reaction temperature, water, hydrogen, and carbon dioxide feed concentrations, and gas hourly space velocity (GHSV, h⁻¹) were investigated. The increase of reaction temperature in the 650–800 °C range and water feed concentration in the 40–50 vol% range were found to be beneficial for catalyst activity and H₂-yield. A similar result was also obtained in the case of decreasing the GHSV from 85,000 to 30,000 h⁻¹. The effect of concentration of carbon dioxide and hydrogen in the phenol/water feed stream was found to significantly decrease the rate of phenol steam reforming reaction. The latter was probed to be related to the reduction in the rate of water dissociation as evidenced by the significant decrease in the concentration of adsorbed bicarbonate and OH species on the surface of CaO according to in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS)-CO₂ adsorption experiments in the presence of water and hydrogen in the feed stream. Details of the CO₂ adsorption on the CaO surface at different reaction temperatures and gas atmospheres using in situ DRIFTS and transient isothermal adsorption experiments with mass spectrometry were obtained. Bridged, bicarbonate and unidentate carbonate species were formed under CO₂/H₂O/He gas mixtures at 600 °C with the latter being the most populated. A substantial decrease in the surface concentration of bicarbonate and OH species was observed when the CaO surface was exposed to CO₂/H₂O/H₂/He gas mixtures at 600 °C, result that probes for the inhibiting effect of H₂ on the phenol steam reforming activity. Phenol steam reforming reaction followed by isothermal oxygen titration allowed the measurement of accumulated “carbonaceous” species formed during phenol steam reforming as a function of reaction temperature and short time on stream. An increase in the amount of “carbonaceous” species with reaction time (650–800 °C range) was evidenced, in particular at 800 °C (4.7 vs. 6.7 mg C/g solid after 5 and 20 min on stream, respectively).     

Solvothermal synthesis of 1D and 2D cobalt(II) and nickel(II) coordination polymers with 2,5-dihydroxy-p-benzenediacetic acid

1D cobalt(II) and nickel(II) coordination polymers {[Co(dba)(H₂O)₄] · H₂O}_n (1) and {[Ni(dba)(H₂O)₄] · H₂O}_n (2) (H₂dba = 2,5-dihydroxy-p-benzenediacetic acid) were synthesized under low temperature solvothermal condition. When 4,4′-bipyridine (bpy) was introduced to the synthetic systems of 1 and 2, respectively, two novel 2D coordination polymers {[Co(dba)(bpy)] · 0.5H₂O}_n (3) and [Ni(dba)(bpy)(H₂O)₂]_n (4) with different structures were obtained. All of the compounds were characterized by elemental analysis, FT-IR, UV–Vis spectra and single crystal X-ray diffraction.     

Ferrite process of electroplating sludge and enrichment of copper by hydrothermal reaction

In this paper, ferrite process of electroplating sludge and enrichment of copper by hydrothermal reaction was investigated. By the hydrothermal treatment, Zn, Ni, Cu, Cr-bearing electroplating sludge can be transformed into high value-added Ni–Zn–Cr ferrite by adding iron source (FeCl₃·6H₂O) and precipitator. The most optimum reaction conditions were explored: 1.57 g/g dry sludge as the dosage of FeCl₃·6H₂O, pH 8.5 of the slurry adjusted by ammonia, 4 h as the reaction time, and 200 °C as the reaction temperature. Under these conditions, the purer Ni–Zn–Cr ferrite could be prepared, and Cu was extracted to the range from 76 wt% to nearly 84 wt%, when ammonia was selected as the precipitator. Leaching toxicity of heavy metals from Ni–Zn–Cr ferrite prepared with additional iron source and precipitator, was much lower than the regulated limit of Toxicity Characteristic Leaching Procedure (TCLP), indicating that Ni–Zn–Cr ferrite synthesized hydrothermally from electroplating sludge had a better chemical stability. Therefore, the ferrite process by hydrothermal reaction is a feasible method with respect to the reuse and self-purification of electroplating sludge.     

Heterogeneously Pd/C catalysed procedure for the vinylation of aryl bromides

Heterogeneous Pd/C catalyst was applied to the Suzuki–Miyaura vinylation of various aryl and heteroaryl halides under aerobic and mild reaction conditions [1.0 mmol aryl halide, 1.5 mmol potassium vinyltrifluoroborate, 3.0 mmol K₃PO₄·H₂O, 0.1 mol% Pd/C_(EVO), 1 mL NMP, 100 °C, 24 h]. Useful isolated yields (57–73%) were achieved. In some cases, the catalytic system should be tuned to face the reactivity of the aryl halides: while 0.1 mol% Pd/C is sufficient for almost all aryl bromides, 1.0 mol% Pd/C was used for free phenols.The heterogeneous catalyst was proved to be stable upon several catalytic cycles; however, the results showed that this was dependent on addition of the base. Hot-filtration experiment indicates that the activity was mainly due to leached Pd-species, indicating that the Pd/C catalyst acts as a palladium reservoir.     

Two novel Zn(II) coordination polymers based on trigonal ligand: 4′-(4-pyridyl)-3,2′:6′,3″-terpyridine

Two novel Zn(II) coordination polymers, [Zn₅(pytpy)₈(fum)₄(H₂O)₄(OH)₂]_n · n(CH₃OH) · 2n(H₂O) (1) and [Zn₃(pytpy)₄ (btc)₂]_n · 2n(H₂O) (2) (pytpy = 4′-(4-pyridyl)-3,2′:6′,3″-terpyridine, H₂fum = fumaric acid, H₃btc = 1,3,5-benzenetricarboxylic acid) have been hydrothermally synthesized and structurally characterized. Complex 1 is a 2D layer structure, which is constructed from linear pentanuclear Zn(II) subunits interconnected via bidentate-bridging pytpy ligands and tridentate-bridging fum²⁻ anions. Complex 2 is a 3D network structure, μ₂-pytpy ligands link the layers based on the heart-like hexanuclear subunits to form the 3D network. Both complexes show strong fluorescence emission upon excitation at 310 nm in solid state. Additionally, these two complexes possess great thermal stabilities, especially for 2, the framework is stable up to 350 °C.     

Uptake of heavy metal ions from aqueous solution using Mg–Al layered double hydroxides intercalated with citrate, malate, and tartrate

Mg–Al layered double hydroxide (Mg–Al LDH) was modified with organic acid anions using a coprecipitation technique, and the uptake of heavy metal ions from aqueous solution by the Mg–Al LDH was studied. Citrate·Mg–Al LDH, malate·Mg–Al LDH, or tartrate·Mg–Al LDH, which had citrate³⁻ (C₆H₅O₇³⁻), malate²⁻ (C₄H₄O₅²⁻), or tartrate²⁻ (C₄H₄O₆²⁻) anions intercalated in the interlayer, was prepared by dropwise addition of a mixed aqueous solution of Mg(NO₃)₂ and Al(NO₃)₃ to a citrate, malate, or tartrate solution at a constant pH of 10.5. These Mg–Al LDHs were found to take up Cu²⁺ and Cd²⁺ rapidly from an aqueous solution at a constant pH of 5.0. This capacity was mainly attributable to the formation of the citrate–metal, malate–metal, and tartrate–metal complexes in the interlayers of the Mg–Al LDHs. The uptake of Cu²⁺ increased in the order malate·Mg–Al LDH < tartrate·Mg–Al LDH < citrate·Mg–Al LDH. The uptake of Cd²⁺ increased in the order malate·Mg–Al LDH < tartrate·Mg–Al LDH = citrate·Mg–Al LDH. These differences in Cu²⁺ and Cd²⁺ uptake were attributable to differences in the stabilities of the citrate–metal, malate–metal, and tartrate–metal complexes. These results indicate that citrate³⁻, malate²⁻, and tartrate²⁻ were adequately active as chelating agents in the interlayers of Mg–Al LDHs.     

Hydrogen production by methanol steam reforming carried out in membrane reactor on Cu/Zn/Mg-based catalyst

The methanol steam reforming (MSR) reaction was studied by using both a dense Pd-Ag membrane reactor (MR) and a fixed bed reactor (FBR). Both the FBR and the MR were packed with a new catalyst based on CuOAl₂O₃ZnOMgO, having an upper temperature limit of around 350 °C. A constant sweep gas flow rate in counter-current mode was used in MR and the experiments were carried out by varying the water/methanol feed molar ratio in the range 3/1–9/1 and the reaction temperature in the range 250–300 °C. The catalyst shows high activity and selectivity towards the CO₂ and the H₂ formation in the temperature range investigated. Under the same operative conditions, the MR shows higher conversions than FBR and, in particular, at 300 °C and H₂O/CH₃OH molar ratio higher than 5/1 the MR shows complete methanol conversion.     

An efficient electron transfer at the Fe/iron oxide interface for the photoassisted degradation of pollutants with H2O2

Fe-200 was synthesized through the calcination of iron powder at 200 °C for 30 min in air. On the basis of characterization by X-ray diffraction and X-ray photoelectron spectroscopy, Fe-200 had a core–shell structure, in which the surface layer was mainly composed of Fe₂O₃ with some FeOOH and FeO, and the core retained metallic iron. The kinetics and mechanism of the interfacial electron transfer on Fe-200 were investigated in detail for the photoassisted degradation of organic pollutants with H₂O₂. Under deoxygenated conditions in the dark, the generation of hydroxyl radicals in aqueous Fe-200 dispersion verified that galvanic cells existed at the interface of Fe⁰/iron oxide, indicating the electron transfer from Fe⁰ to Fe³⁺. Furthermore, the effects of hydrogen peroxide and different organic pollutants on the interfacial electron transfer were examined by the change rate of the Fe³⁺ concentration in the solution. The results indicated that hydrogen peroxide provided a driving force in the electron transfer from Fe²⁺ to Fe³⁺, while the degradation of organic pollutants increased the electron transfer at the interface of Fe⁰/iron oxide due to their reaction with OH.     

Enhanced activity of iron oxide dispersed on bentonite for the catalytic degradation of organic dye under visible light

Natural clay-supported iron oxide was prepared by deposition method, and dried at 120 °C. It was found that under visible light in the presence of H₂O₂, this catalyst was highly active for degradation of cationic (malachite and fuchsin basic) and anionic dyes (orange II and X3B) in water at pH 6.5, as compared with bare iron oxide or the clay-supported iron oxide sintered at 350 °C. The excellent performance of the catalyst is correlated with its high sorption capacity toward both types of dyes, thus resulting in enhanced dye degradation via a photosensitization pathway. The catalyst was characterized by XRD, nitrogen adsorption, infrared, and UV–visible spectroscopy.     

Preparation of cobalt ferrite from the thermolysis of cobalt tris(malonato)ferrate(III)trihydrate precursor

Thermal decomposition of cobalt tris(malonato)ferrate(III)trihydrate precursor, Co₃[Fe(CH₂C₂O₄)₃]·3H₂O has been investigated from ambient temperature to 600 °C in static air atmosphere using various physico-chemical techniques, i.e. TG–DTG–DSC, XRD, Mössbauer and IR spectroscopic techniques. The precursor undergoes dehydration and decomposition simultaneously to yield cobalt malonate and iron(II) malonate intermediates at 205 °C. At higher temperature (325 °C) these intermediate species undergo exothermic decomposition to yield CoO and α-Fe₂O₃, respectively. Finally cobalt ferrite, CoFe₂O₄, has been obtained as a result of solid–solid reaction between Fe₂O₃ and CoO at a temperature (380 °C) much lower than that of ceramic method. SEM analysis of the final thermolysis product reveals the formation of monodisperse cobalt ferrite nano-particles with an average particle size of 45 nm. Magnetic studies show that these particles have a saturation magnetization of 3095 G and Curie temperature of 504 °C. Lower magnitude of these parameters as compared to the bulk values is attributed to the smaller particle size.     

Activation of the hydrolytic polymerization of ε-caprolactam by ester functions: Straightforward route to aliphatic polyesteramides

The hydrolytic polymerization of ε-caprolactam (CLa) was carried out in bulk (in absence of solvent) at 250 °C in the presence of carboxylic esters and aqueous H₃PO₂. It turned out that by conducting the ring opening polymerization (ROP) of CLa in the presence of PEO–C(O)–O–C₅H₁₁, a selected model ester (PEO = poly(ethylene oxide)), a remarkable activating effect of the ester function on the hydrolytic polymerization of the lactam was observed yielding PEO–b–PCLa diblock copolymers. The comparison of the CLa monomer conversions obtained with or without the model ester activated by H₃PO₂, as determined by ¹H NMR spectroscopy, has enabled to propose a multi-step mechanism in which three major reactions occurred: (i) ester and lactam hydrolysis, (ii) aminolysis of the carboxylic ester by the resulting primary amine of the hydrolyzed/opened lactam ring and (iii) condensation reactions between carboxylic acids and both amine/hydroxyl functions. The overall result of this multi-step mechanism can be assimilated as an “insertion” of the opened lactam into the ester function. By conducting the hydrolytic polymerization of CLa in the presence of an aliphatic polyester chain, such as poly(ε-caprolactone) (PCLo), polyesteramides were recovered with high yields and random distributions of the CLa and CLo repetitive units as determined by ¹³C NMR.     

One-step synthesis of fine SrTiO3 particles using SrSO4 ore under alkaline hydrothermal conditions

The employment of mineral SrSO₄ crystals and powders for preparing SrTiO₃ compound was investigated, with coexistence of Ti(OH)₄·4.5H₂O gel under hydrothermal conditions, at various temperatures (150–250 °C) for different reaction intervals (0.08–96 h) in KOH solutions with different concentrations. The complete dissolution of the SrSO₄ crystal occurred at 250 °C for 96 h in a 5 M KOH solution, resulting in the synthesis of SrTiO₃ particles with two different shapes (peanut-like and cubic). In contrast, very fine SrTiO₃ pseudospherical particles were crystallized when SrSO₄ powders were employed as precursor. Variations on the SrTiO₃ particle shape and size were found to be caused by the differences in the dissolution rate of the SrSO₄ phase in the alkaline KOH solution. The crystallization of SrTiO₃ particles was achieved by a bulk dissolution–precipitation mechanism of the raw precursors, and this mechanism was further accelerated by increasing the reaction temperature and concentration of the alkaline media. Kinetic data depicted that the activation energy required for the formation of SrTiO₃ powders from the complete consumption of a SrSO₄ single crystal plate under hydrothermal conditions, is 27.9 kJ mol⁻¹. In contrast, when SrSO₄ powders were employed (28–38 μm), the formation of SrTiO₃ powder proceeded very fast even for a short reaction interval of 3 h at 250 °C in a 5 M KOH solution.     

Alkaline earth metal-based catalyst and process for selective hydrocarbon conversion to acetylene and carbon monoxide

A multi-step process that employs a Ni-modified mixed alkaline earth metal oxides (AEMO) has been developed for the selective conversion of hydrocarbons to C₂H₂ and CO. The initial process step is the catalytic decomposition of a gaseous hydrocarbon mixture at an elevated temperature (ca. 800 °C) over Ni/AEMO, generating H₂, trace CO, carbon (C), and trace alkaline earth metal carbide (MC₂). The Ni/AEMO/C/MC₂ material is then heated to consume the remaining carbon, generate more MC₂, and evolve CO. Then, Ni/AEMO/MC₂ is cooled and reacted with excess H₂O at a low temperature (20 < T (°C) < 80) to selectively generate C₂H₂ and Ni/AEM(OH)₂·zH₂O. In the final process step, Ni/AEM(OH)₂·zH₂O is decomposed to yield H₂O and Ni/AEMO, which is recycled within the process. The most advanced Ni/AEMO materials developed thus far exhibit intrinsic production capacities exceeding 2000 μmoles of C₂H₂ per gram of Ni/AEMO per process cycle.     

A {Cu6}-containing inorganic-metal-organic sandwich-type tungstoantimonite and its 3D supramolecular framework

A hexagonal {Cu₆} cluster-containing tungstoantimonite, [Cu(enMe)₂(H₂O)]₂{Cu(enMe)₂[Cu(enMe)]₃[Cu(H₂O)]₃(SbW₉O₃₃)₂}·5H₂O (1, enMe = 1,2-diaminopropane) has been successfully synthesized under hydrothermal conditions. The {Cu₆} cluster in 1 is stabilized by both the inorganic O-donor ligand {B-α-SbW₉O₃₃}⁹⁻ and the organic N-donor ligand enMe, leading to a hybrid inorganic-metal-organic sandwich-type polyoxometalate. The sandwich-type polyoxoanions are further connected into a 3D supramolecular framework via hydrogen bonding interactions between 1,2-enMe molecules and the sandwich-type polyoxoanions. The magnetic study indicates that intramolecular ferromagnetic Cu–Cu interactions exist in the hexanuclear metal-cluster.     

Selective oxidation of ethane: Developing an orthorhombic phase in Mo–V–X (X = Nb, Sb, Te) mixed oxides

Mo–V–X (X = Nb, Sb and/or Te) mixed oxides have been prepared by hydrothermal synthesis and heat-treated in N₂ at 450 °C or 600 °C for 2 h. The calcination temperature and the presence or absence of Nb determines the nature of crystalline phases in the catalyst. Nb-containing catalysts heat-treated at 450 °C are mostly amorphous solids, while Nb-free catalysts heat-treated at 450 °C and samples treated at 600 °C clearly contain crystalline phases. TPR-H₂ experiments show higher H₂-consumption on catalysts with amorphous phases. Catalytic results in the oxidative dehydrogenation of ethane indicate that the selective production of the olefin is strongly related to the development of the orthorhombic Te₂M₂₀O₅₇ or (SbO)₂M₂₀O₅₆ (M = Mo, V, Nb) phase (the so-called M1 phase), which is mainly formed at 600 °C. This active and selective crystalline phase is characterized to show moderate reducibility and active centers enough for the selective oxidative activation of ethane with the minimum quantity possible of active centers for ethylene activation. In this sense, the best yield to ethylene has been achieved on a Mo–V–Te–Nb mixed oxide.