Controlled synthesis of palladium icosahedra nanocrystals by reducing H2PdCl4 with tetraethylene glycol

The controlled synthesis of Pd icosahedra in tetraethylene glycol with H₂PdCl₄ as a precursor and polyvinylpyrrolidone (PVP) as a stabilizer was demonstrated. Tetraethylene glycol served as both solvent and reducing agent, and uniform Pd icosahedra with a mean size of 45 ± 5 nm were successfully synthesized with a high yield of over 90% in oil-bath at 160 °C for 2.5 h. A certain affinity for the metal particles, a higher viscosity and a milder reducing power of tetraethylene glycol would be responsible for the formation of uniform and stable Pd icosahedra with a high yield. The optimum KOH/Pd(II) ratio, PVP/Pd(II) ratio, temperature, and heating time for the reaction system was 1.4/1, 1/1, 160 °C, and 2.5 h, respectively.     

Synthesis of silica–silver wires by a sol–gel technique

SiO₂–Ag wires were synthesized by a sol–gel technique. A two step approach was followed, focusing mainly on the effect of acid concentration on the first stage and processing temperature on the second. This acid-catalyzed reaction on the first stage yielded SiO₂–AgCl wires with diameters as low as 800 nm average, and lengths ranging up to 100 μm, as determined by LV-SEM and TEM. A thermal treatment at different temperatures on the second step, under H₂ atmosphere, yields silica–silver unidirectional structures. The chemical composition of these structures was determined by EDS, indicating the presence of Si, O and Ag. The transformation of the wires as a function of temperature under reducing atmosphere was followed by electron microscopy analysis. At 400 °C and above the silica starts to cover the reduced silver while maintaining the unidirectional conformation, suggesting a tendency to form silver wires covered by a silica layer.     

Oxygen production at low temperature using dense perovskite hollow fiber membranes

A dense perovskite hollow fiber made of BaCo_xFe_yZr_zO_3−δ (BCFZ) was evaluated for the oxygen separation at low temperatures (400–500 °C). An oxygen permeation flux of 0.45 ml/min cm² was obtained at 500 °C, which is the first oxygen permeation data reported at such low temperature so far. A degradation of the oxygen permeation at 500 °C was observed, but the oxygen fluxes through the hollow fiber membrane can be regenerated by thermal treatment at 925 °C for 1 h in air. Energy-dispersive X-ray spectroscopy (EDXS) shows that a strong element segregation occurs in the membrane during operation at low temperature.     

Hydrogenation of arenes, alkenes and alkynes catalyzed by a sol–gel entrapped mixture of [Rh(cod)Cl]2 and Na[HRu3(CO)11]

A sol–gel entrapped 1:3 mixture of [Rh(cod)Cl]₂ and Na[HRu₃(CO)₁₁] catalyzes the hydrogenation of various unsaturated substrates by two distinguishable mechanisms. Under 13.8 bar H₂ and 20 °C methylated arenes react rapidly to give cycloalkane derivatives. XRD and TEM studies showed that under these conditions the hydrogenation proceeds without the generation of free metal particles. The hydrogenation of non-methylated arenes, as well as that of alkenes and alkynes, require a temperature of 80–120 °C at which the entrapped complexes form metallic nano-particles of 3–5 nm. Chloroarenes are also hydrodechlorinated at 120 °C, but require a hydrogen pressure of ≥25 bar. At both temperature ranges the catalysts are reusable at least four times. The high efficiency of the hydrogenation process at 20 °C is rationalized by a synergistic effect between the two different metal atoms of the combined catalyst. This may be related to a remote control model through a hydrogen spillover mechanism.     

TGA–FTIR study of a lead zirconate titanate gel made from a triol-based sol–gel system

A Pb(Zr,Ti)O₃ precursor gel made from a sol prepared using 1,1,1,-tris(hydroxymethyl)ethane, lead acetate and zirconium and titanium propoxides, stabilised with acetylacetone, was analysed using TGA–FTIR analysis. Decomposition under nitrogen (N₂) gave rise to evolved gas absorbance peaks at 215 °C, 279 °C, 300 °C and 386 °C, but organic vapours continued to be evolved, along with CO₂ and CO until 950 °C. The final TGA step in N₂ is thought to relate to decomposition of an intermediate carbonate phase and the final elimination of residues of triol or acetylacetonate species which form part of the polymeric gel structure. By contrast, heating in air promoted oxidative pyrolysis of the final organic groups at ≤450 °C. In air, an intermediate carbonate phase was decomposed by heating at 550 °C, allowing Pb(Zr,Ti)O₃ to be produced some 400 °C below the equivalent N₂ decomposition temperature.     

Three steps in the anode reaction of the polymer electrolyte membrane fuel cell. Effect of CO

We studied the influence of CO poisoning of the anode in the polymer electrolyte membrane fuel cell (PEMFC) using electrochemical impedance spectroscopy (EIS). The anode impedance was found by first feeding neat hydrogen gas and next hydrogen with CO into one of the electrodes, keeping neat hydrogen gas on the other electrode as a reference. The electrodes were E-TEK Elat gas-diffusion electrodes with 0.5 mg Pt/cm², and the membrane was Nafion^® 117. The CO concentration was 103 ppm, and the total pressures were 1, 2.5 and 4 bar. Operating temperatures were kept constant, 30.0 °C or 50.0 ± 0.1 °C. Bias voltages of 0 and 0.05 V were used. Three steps were revealed in the reaction mechanism, the slow adsorption/diffusion step, the charge transfer step and the proton hydration step, confirming earlier results. Carbon monoxide affects the charge transfer step by blocking active sites and by affecting the surface polarisation. We further conclude that CO adsorbs to the porous carbon matrix, and reduces significantly the rate of surface diffusion of hydrogen to the surface.     

Effect of organic and inorganic compounds on dissolution kinetics of chalcopyrite in hydrogen peroxide– Hydrochloric acid system

The addition of 2-Propanol as an organic substance and NaCl as an inorganic compound in hydrochloric acid with hydrogen peroxide as a strong leaching agent of chalcopyrite was investigated. The effects of the leaching parameters on copper extraction, such as stirring speed, H₂O₂ concentration, temperature, HCl concentration and solid/liquid ratio were studied. The maximum final copper extraction of 54.55% was obtained with 600 rpm stirring speed, 1.5 M H₂O₂, 0.5 M HCl, 600 rpm, 50 °C, 240 min of the reaction and particle size of ?106 +75 µm. Further experiments were performed when the solid-to-liquid ratio (S/L), stirring speed, temperature, HCl, H₂O₂ and leaching time were kept constant to examine the influence of NaCl and 2-Propanol concentrations in the range of 0–0.5 M and 0–3 M, respectively. The results showed that the copper extraction was increased up to 58.11% with addition of NaCl. While copper extraction yield reached 94.25% in case of addition of 2-propanol with the optimum parameters(0.5 M HCl,50 °C, 1.5 M H₂O₂, 600 rpm, particle size ?106 +75 μm, solid liquid ratio 2g/L, 3 M 2-propanol). The chalcopyrite leaching in hydrogen peroxide– hydrochloric acid system was found to be described by the interface transfer and diffusion across the product layer with activation energy of 77.14 kJ/mol. Addition of 2-propanol suggested that the reaction was under product layer diffusion control and decreased the activation energy of chalcopyrite leaching to 67.98 kJ/mol.     

The oxidative stream reforming of methane to syngas in a thin tubular mixed-conducting membrane reactor

The oxidative stream reforming of methane (OSRM) to syngas, involving coupling of exothermic partial oxidation of methane (POM) and endothermic steam reforming of methane (SRM) processes, was studied in a thin tubular Al₂O₃-doped SrCo_0.8Fe_0.2O_3−δ membrane reactor packed with a Ni/γ-Al₂O₃ catalyst. The influences of the temperature and feed concentration on the membrane reaction performances were investigated in detail. The methane and steam conversions increased with increasing the temperature and high conversions were obtained in 850–900 °C. Different from the POM reaction, in the OSRM reaction the temperature and H₂O/CH₄ profoundly influenced the CO selectivity, H₂/CO and heat of the reaction. The CO selectivity increased with increasing the temperature or decreasing the H₂O/CH₄ ratio in the feed owing to the water gas shift reaction (H₂O + CO → CO₂ + H₂). And the H₂ selectivity based on methane conversion was always 100% because the net steam conversion was greater than zero. The H₂/CO in product could be tuned from 1.9 to 2.8 by adjusting the reaction temperature or H₂O/CH₄. Depending on the temperature or H₂O/CH₄, furthermore, the OSRM process could be performed auto-thermally with idealized reaction condition.     

Système ternaire : H2O–Fe(NO3)3–Co(NO3)2 isotherme : 30 °C

Ternary system: H₂O–Fe(NO₃)₃–Co(NO₃)₂ isotherm: 30 °C. The H₂O–Co(NO₃)₂ binary system has been investigated in the –28 to 50 °C temperature range. The solid–liquid equilibria of the ternary system H₂O–Fe(NO₃)₃–Co(NO₃)₂ were studied by using a synthetic method based on conductivity measurements. One isotherm is established at 30 °C, and the stable solid phases that appear are iron nitrate nonahydrate: Fe(NO₃)₃·9 H₂O, iron nitrate hexahydrate: Fe(NO₃)₃·6 H₂O, cobalt nitrate hexahydrate: Co(NO₃)₂·6 H₂O, and cobalt nitrate trihydrate: Co(NO₃)₂·3 H₂O. To cite this article: B. El Goundali et M. Kaddami, C. R. Chimie 9 (2006).     

Hydrothermal synthesis of precursors of neodymium oxide nanoparticles

The nanometric precursors of neodymium oxide of various morphologies were prepared via a hydrothermal reaction route. The precursors and their thermal evolution to neodymium oxide phase were characterised by means of X-ray diffraction (XRD), transmission electron microscopy (TEM, HRTEM), thermal analysis (TG, DTA, EGA-MS), FTIR and atomic force microscopy (AFM). It was found that the reaction conditions (temperature, pressure) played a key role for the product formation of desired morphology and structure. At mild conditions (140 °C) precursor with unusual fibrous morphology and Nd(OH)_2.45(Ac)_0.550.45H₂O stoichiometry was obtained. Upon heating this phase transformed, via intermediate cubic oxide, into trigonal Nd₂O₃ at 800 °C. Nd(OH)₃ hydroxide obtained at severe conditions (180 °C) transformed upon heating into cubic Nd₂O₃ phase at about 500 °C and this phase was stabilised even at 800 °C. The fibrous precursors appeared to be a convenient material for preparation of homogeneous thin coatings on planar substrates is shown.     

The kinetics and mechanism of polymer-based NHC-Pd-pyridine catalyzed heterogeneous Suzuki reaction in aqueous media

One of the most important challenges of the Suzuki reaction is a green synthesis of reaction products. In terms of economy and ecology, the Suzuki reaction details must be characterized for the industrial-scale Suzuki reaction processes. In this paper, for the first time, a kinetic and mechanistic study on the Suzuki reaction catalyzed with hydrogel-supported PEPPSI (pyridine-enhanced precatalyst preparation stabilization (and) initiation) type NHC-Pd-pyridine composite has been investigated. To determine the rate-limiting step, the effects of reactants and experimental conditions on the heterogeneous Suzuki reaction have been experimentally defined. The experimental results demonstrated that it is possible to reach 100% yield under the optimum reaction conditions, which were found as 75 × 10⁻³ mol/L of phenylboronic acid (FBA), 50 × 10⁻³ mol/L of bromoacetophenone (Brac), 125 × 10⁻³ mol/L of K₂CO₃, 1 g/L of catalyst, 80°C of reaction temperature, 400 rpm of mixing rate, and 3 h of reaction time. The transmetalation step in the cycle was defined as the rate-limiting step. On the basis of kinetic results, a mathematical reaction rate expression was presented assuming the steady-state approach to steps of the catalytic cycle. The activation energy (E_a) of the reaction was estimated to be 34.88 kJ/mol.     

Efficient hydrogen peroxide generation from organic matter in a bioelectrochemical system

Hydrogen peroxide (H₂O₂) is an important industrial chemical, but its current production methods are highly energy-intensive. This study presents a novel process for the production of H₂O₂ based on the bioelectrochemical oxidation of wastewater organics at an anode coupled to the cathodic reduction of oxygen to H₂O₂. At an applied voltage of 0.5 V, this system was capable of producing 1.9 ± 0.2 kg H₂O₂/m³/day from acetate at an overall efficiency of 83.1 ± 4.8%. As most of the required energy was derived from the acetate, the system had a low energy requirement of 0.93 kWh/kg H₂O₂.     

Preparation and characterization of calcium hydroxyapatite and balloon-like calcium phosphate particles from forced hydrolysis of Ca(OH)2–triphosphate solution

Calcium phosphate particles were prepared by aging a solution of dissolved Ca(OH)₂ and sodium triphosphate (sodium tripolyphosphate, Natpp: Na₅P₃O₁₀) at 100–150 °C for 18 h in a Teflon-lined screw-capped Pyrex test tube. Large spherical and/or small aggregated spherical particles were precipitated with an extremely fast rate of reaction under 100 °C. The large spherical particles were amorphous and the small aggregated ones were α-CaNa₂P₂O₇^.4H₂O. The former amorphous ones crystallized to β-Ca₂P₂O₇ after being calcined above 600 °C. Calcium hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂, Hap), with rod-like and ellipsoidal or spherical aggregated shapes, was successfully produced using polyphosphates as a source of orthophosphate ions. Time resolved TEM measurement revealed that the crystallization of Hap particles takes place on the surface of tiny amorphous particles precipitated before aging. The tiny particles played the role of nuclei for Hap crystallization. The aging temperature drastically varied the particle shape under conditions for producing uniform amorphous spherical particles; solid spherical particles were produced with an aging temperature of up to 120 °C, whilst transparent balloon-like hollow spheres were precipitated at 125 °C. Finally, fully transparent balloon-like hollow spheres were produced with mere trace amounts of small rod-like particles after aging the solution above 127 °C. The time resolved TEM observation and ICP-AES measurements revealed that the balloon-like hollow spheres were produced by dissolving the interior of solid spherical particles after reinforcing their shell by the adsorption of unhydrolyzed tpp and/or pyrophosphate (pp) ions, which are the hydrolysis product of tpp. The balloon-like hollow spheres of calcium phosphate may have the potential use as drug delivery vehicles and have biocompatibility advantages.     

Theoretical Thermodynamic Efficiency Limit of Isothermal Solar Fuel Generation from H2O/CO2 Splitting in Membrane Reactors

Solar fuel generation from thermochemical H₂O or CO₂ splitting is a promising and attractive approach for harvesting fuel without CO₂ emissions. Yet, low conversion and high reaction temperature restrict its application. One method of increasing conversion at a lower temperature is to implement oxygen permeable membranes (OPM) into a membrane reactor configuration. This allows for the selective separation of generated oxygen and causes a forward shift in the equilibrium of H₂O or CO₂ splitting reactions. In this research, solar-driven fuel production via H₂O or CO₂ splitting with an OPM reactor is modeled in isothermal operation, with an emphasis on the calculation of the theoretical thermodynamic efficiency of the system. In addition to the energy required for the high temperature of the reaction, the energy required for maintaining low oxygen permeate pressure for oxygen removal has a large influence on the overall thermodynamic efficiency. The theoretical first-law thermodynamic efficiency is calculated using separation exergy, an electrochemical O₂ pump, and a vacuum pump, which shows a maximum efficiency of 63.8%, 61.7%, and 8.00% for H₂O splitting, respectively, and 63.6%, 61.5%, and 16.7% for CO₂ splitting, respectively, in a temperature range of 800 °C to 2000 °C. The theoretical second-law thermodynamic efficiency is 55.7% and 65.7% for both H₂O splitting and CO₂ splitting at 2000 °C. An efficient O₂ separation method is extremely crucial to achieve high thermodynamic efficiency, especially in the separation efficiency range of 0–20% and in relatively low reaction temperatures. This research is also applicable in other isothermal H₂O or CO₂ splitting systems (e.g., chemical cycling) due to similar thermodynamics.     

Phosphate desorption kinetics from goethite as induced by arsenate

The kinetics of the arsenate-induced desorption of phosphate from goethite has been studied with a batch reactor system and ATR-FTIR spectroscopy. The effects of arsenate concentration, adsorbed phosphate, pH and temperature between 10 and 45 °C were investigated. Arsenate is able to promote phosphate desorption because both oxoanions compete for the same surface sites of goethite. The desorption occurs in two steps: a fast step that takes place in less than 5 min and a slow step that lasts several hours. In the slow step, arsenate ions exchange adsorbed phosphate ions in a 1:1 stoichiometry. The reaction is first order with respect to arsenate concentration and is independent of adsorbed phosphate under the experimental conditions of this work. The rate law is then r = k_r[As], where r is the desorption rate, k_r is the rate constant and [As] is the arsenate concentration in solution. The values of k_r at pH 7 are 1.87 × 10⁻⁵ L m⁻² min⁻¹ at 25 °C and 7.95 × 10⁻⁵ L m⁻² min⁻¹ at 45 °C. The apparent activation energy of the desorption process is 51 kJ mol⁻¹. Data suggest that the rate-controlling process is intraparticle diffusion of As species, probably As diffusion in pores. ATR-FTIR spectroscopy suggests that adsorbed phosphate species at pH 7 are mainly bidentate inner-sphere surface complexes. The identity of these complexes does not change during desorption, and there is no evidence for the formation of intermediate species during the reaction.     

Nano-sized lithium manganese oxide dispersed on carbon nanotubes for energy storage applications

Nano-sized lithium manganese oxide (LMO) dispersed on carbon nanotubes (CNT) has been synthesized successfully via a microwave-assisted hydrothermal reaction at 200 °C for 30 min using MnO₂-coated CNT and an aqueous LiOH solution. The initial specific capacity is 99.4 mAh/g at a 1.6 C-rate, and is maintained at 99.1 mAh/g even at a 16 C-rate. The initial specific capacity is also maintained up to the 50th cycle to give 97% capacity retention. The LMO/CNT nanocomposite shows excellent power performance and good structural reversibility as an electrode material in energy storage systems, such as lithium-ion batteries and electrochemical capacitors. This synthetic strategy opens a new avenue for the effective and facile synthesis of lithium transition metal oxide/CNT nanocomposite.     

Isomer-specific product detection of CN radical reactions with ethene and propene by tunable VUV photoionization mass spectrometry

Product detection studies of CN reactions with ethene and propene are conducted at room temperature (4 Torr, 533.3 Pa) using multiplexed time-resolved mass spectrometry with tunable synchrotron photoionization. Photoionization efficiency curves, i.e., the ion signal as a function of photon energy, are used to determine the products and distinguish isomers. Both reactions proceed predominantly via CN addition to the π orbital of the olefin. For CN + ethene, cyanoethene (C₂H₃CN) is detected as the sole product in agreement with recent studies on this reaction. Multiple products are identified for the CN + propene reaction with 75(±15)% of the detected products in the form of cyanoethene from a CH₃ elimination channel and 25(±15)% forming different isomers of C₄H₅N via H elimination. The C₄H₅N comprises 57(±15)% 1-cyanopropene, 43(±15)% 2-cyanopropene and <15% 3-cyanopropene. No evidence of direct H abstraction or indirect HCN formation is detected for either reaction. The results have relevance to the molecular weight growth chemistry on Saturn's largest moon Titan, where the formation of small unsaturated nitriles are proposed to be key steps in the early chemical stages of haze formation.     

Cobalt–silicon mixed oxide nanocomposites by modified sol–gel method

Cobalt–silicon mixed oxide materials (Co/Si=0.111, 0.250 and 0.428) were synthesised starting from Co(NO₃)₂·6H₂O and Si(OC₂H₅)₄ using a modified sol–gel method. Structural, textural and surface chemical properties were investigated by thermogravimetric/differential thermal analyses (TG/DTA), XRD, UV–vis, FT-IR spectroscopy and N₂ adsorption at −196 °C. The nature of cobalt species and their interactions with the siloxane matrix were strongly depending on both the cobalt loading and the heat treatment. All dried gels were amorphous and contained Co²⁺ ions forming both tetrahedral and octahedral complexes with the siloxane matrix. After treatment at 400 °C, the sample with lowest Co content appeared amorphous and contained only Co²⁺ tetrahedral complexes, while at higher cobalt loading Co₃O₄ was present as the only crystalline phase, besides Co²⁺ ions strongly interacting with siloxane matrix. At 850 °C, in all samples crystalline Co₂SiO₄ was formed and was the only crystallising phase for the nanocomposite with the lowest cobalt content. All materials retained high surface areas also after treatments at 600 °C and exhibited surface Lewis acidity, due to cationic sites. The presence of cobalt affected the textural properties of the siloxane matrix decreasing microporosity and increasing mesoporosity.     

Polymerization of aniline in the interlayer space of molybdenum trioxide and its electrochemical properties

Molybdenum trioxide/polyaniline (MoO₃/PANI) composite was prepared first by ion-exchange reaction between aniline (ANI) and dodecylamine (DDA) which was intercalated precursor, and then was formed under the polymerization of ANI within the interlayer space of MoO₃ at 120 °C for 3 d in air. According to powder X-ray diffraction, scanning electron microscopy, thermogravimetric analysis, infrared spectroscopy and electrochemical testing, MoO₃/PANI composite has layered structure, and its interlayer spacing is 1.127 nm. Moreover, it has high thermal stability with the compound and completes its weight loss at 751.9 °C. Electrochemical investigation shows that MoO₃ is the major active substance in the MoO₃/PANI electrode, and MoO₃/PANI electrode demonstrates better conductivity and electrochemical activity than pure MoO₃ electrode, attributed to the promotion of Li⁺ and/or electron transport. In addition, the alternating current impedance proves that if the resistance of MoO₃/PANI electrode reduces apparently, the electrochemical activity will increase correspondingly, the same as the relationship between the ohmic resistance and the electrical conductivity.     

Synthesis, crystal structures, phase transition characterization and thermal decomposition of a new dabcodiium hexaaquairon(II) bis(sulfate): (C6H14N2)[Fe(H2O)6](SO4)2

The crystal structures of 1,4-diazabicyclo[2.2.2]octane (dabco)-templated iron sulfate, (C₆H₁₄N₂)[Fe(H₂O)₆](SO₄)₂, were determined at room temperature and at −173 °C from single-crystal X-ray diffraction. At 20 °C, it crystallises in the monoclinic symmetry, centrosymmetric space group P2₁/n, Z=2, a=7.964(5), b=9.100(5), c=12.065(5) Å, β=95.426(5)° and V=870.5(8) ų. The structure consists of [Fe(H₂O)₆]²⁺ and disordered (C₆H₁₄N₂)²⁺ cations and (SO₄)²⁻ anions connected together by an extensive three-dimensional H-bond network. The title compound undergoes a reversible phase transition of the first-order at −2.3 °C, characterized by DSC, dielectric measurement and optical observations, that suggests a relaxor–ferroelectric behavior. Below the transition temperature, the compound crystallizes in the monoclinic system, non-centrosymmetric space group Cc, with eight times the volume of the ambient phase: a=15.883(3), b=36.409(7), c=13.747(3) Å, β=120.2304(8)°, Z=16 and V=6868.7(2) ų. The organic moiety is then fully ordered within a supramolecular structure. Thermodiffractometry and thermogravimetric analyses indicate that its decomposition proceeds through three stages giving rise to the iron oxide.