Water Vapor Sorption on Mesoporous Gamma-Alumina Prepared by the Selective Leaching Method

Water vapor adsorption and desorption properties of mesoporous -alumina prepared by the selective leaching method were investigated. The -alumina was prepared by selective leaching of amorphous silica from calcined kaolinite and mesopores were formed in the inside of the pseudomorph particles of kaolinite. It showed a very narrow unimodal pore size distribution at a radius of 3 nm. The specific surface area and total pore volume measured at –196°C by the BET method using nitrogen gas as adsorbate were around 240 m² g^-1 and 0.7 ml g^-1, respectively. Water vapor sorption isotherm measured at 25°C showed a type IV isotherm and a type H1 hysteresis loop at high partial pressure (P/P₀ region. The steep increase of water adsorption by capillary condensation occurred from around P/P₀=0.8 whereas that of water desorption by evaporation occurred from around P/P₀=0.75. 0These observed P/P₀ values shown were in good agreement with those calculated from the Kelvin equation using the pore radius of 3 nm. The maximum adsorption capacity of water vapor was ca. 600 ml g^-1 at P/P₀ = 0.9 and was larger than that of the commercial -alumina. The statistical thickness of water adsorbed on the surface of the samples calculated from the water adsorption and nitrogen adsorption isotherms of this -alumina was apparently thinner than that of the commercial -alumina and this difference was attributed to the characteristic microtexture of this -alumina. The effects of K₂O and SiO₂ components for the water vapor sorption isotherms of the -alumina were also discussed.     

Ethylene carbonate-based organic electrolytes for electric double layer capacitors

A new electrolytic solution based on a mixed solvent of ethylene carbonate (EC) with sulfolane (SL) or -butyrolactone (-BL) has been examined as an electric double layer capacitor. Fundamental properties, such as electrolytic conductivity, viscosity, and thermal stability, were measured for solutions containing quaternary alkylammonium salts as the supporting electrolyte. Maximum conductivities were obtained for the solutions with mixed solvent of 20–40 mol % EC in the EC+-BL system: 1.2–1.3×10^–2S cm^–1 for EC+-BL dissolving 0.5 M Et₄ NBF₄ (Et=C₂H₅). The electrochemical and the thermal stabilities of the solution were dependent on the electrolytic salt as well as the solvent composition. A stable discharge capacitance and a high coulombic efficiency were obtained in a model capacitor using carbon fibre electrodes and the organic electrolyte of EC+-BL/Et₄NBF₄ (or EC+-BL/Et₄NPF₆).     

Uranyl ion adsorptivity of N-vinyl 2-pyrrolidone/acrylonitrile copolymeric hydrogels containing amidoxime groups

Summary N-vinyl 2-pyrrolidone (VP) / Acrylonitrile (AN) copolymeric hydrogels were synthesized by using γ-radiation and amidoximated for the purpose of uranyl ion adsorption. Optimum amidoximation time was determined by following the uranyl ion, UO₂ ²⁺, adsorption capacity. The adsorption of amidoximated copolymers was studied from different uranyl ion solutions (1000–1850 ppm). The results of all adsorption studies showed that the interaction between UO₂ ²⁺ and amidoxime groups comply with Langmuir type isotherm. The adsorption capacity was found as 0.54 g UO₂ ²⁺ /g dry amidoximated copolymeric hydrogels. From the stoichiometric calculations, it was found that the bonding between UO₂ ²⁺ and amidoxime groups is 1 to 4. Received: 7 September 1999/Revised version: 21 February 2000/Accepted: 18 March 2000     

Porous Properties of γ-Alumina/Potassium Aluminosilicate Gel Composites Prepared by Selective Leaching and Precipitation Method

Composites of mesoporous -alumina and potassium aluminosilicate (KAS) gel were prepared by selective leaching of calcined kaolinite using KOH solution followed by neutralization of the solution at pH 5.5 with nitric acid. The porous properties of the composites were characterized by N₂ gas adsorption and their microtextures were observed by electron microscope. The resultant composites have specific surface areas of about 290 m²/g, pore sizes of about 1.85 nm in radius and pore volumes of about 0.5 ml/g. The porous properties of the composites are compared with those of -alumina and KAS gel.     

Dynamic mechanical properties of crosslinked polyisoprene under deformation

Summary Molecular motions of elastomers under deformations were observed through dynamic mechanical measurements. Composite master curves of dynamic moduli E and E and loss tangent tan over a wide range of frequency and in a state of elongation were obtained by the time-temperature superposition procedure. It is found that both moduli increase with strain, . The slope of the dispersion curve of E become more gradual with the increase in , while that of E is almost unchanged. The increment of E is generally larger than that of E, which does not agree with the N. W. Tschoegl prediction, E ^* ()=f() E _o ^* (), where E ^* () and E _o ^* () are complex moduli at the strain of and O, respectively, and f() is the function of only . The difference in the strain dependence of E from E was found to correspond to the strain dependence of the equilibrium modulus.     

Thiophene adsorption studies on clean and hydrogen-preadsorbed MoS2(100) surface

It is known from temperature-programmed desorption studies that the binding energy of thiophene over Mo/-Al₂O₃ and Co-Mo/-Al₂O₃, hydrodesulfurization catalysts, is lower in the presence of hydrogen. The adsorption of thiophene on clean and hydrogen-adsorbed MoS₂ was modelled using extended Hückel tight binding band structure calculations. In the ¹ adsorption configuration the calculations show a lower binding energy for adsorption on the hydrogen-preadsorbed surface similar to that observed experimentally. The lowering is due to an increased occupancy of the Mo density of states in the presence of hydrogen.     

Functionalized nanostructured silica by tetradentate-amine chelating ligand as efficient heavy metals adsorbent : Applications to industrial effluent treatment

Organofunctionalized nanostructured silica SBA-15 with tri(2-aminoethyl)amine tetradentate-amine ligand was synthesized and applied as adsorbent for the removal of Cu²⁺, Pb²⁺, and Cd²⁺ from both synthetic wastewater and real paper mill and electroplating industrial effluents. The prepared materials were characterized by XRD, N₂ adsorption-desorption, TGA, and FT-IR analysis. The Tren-SBA-15 was found to be a fast adsorbent for heavy metal ions from single solution with affinity for Cu²⁺, Pb²⁺, than for Cd²⁺ due to the complicated impacts of metal ion electronegativity. The kinetic rate constant decreased with increasing metal ion concentration due to increasing of ion repulsion force. The equilibrium batch experimental data is well described by the Langmuir isotherm. The maximum adsorption capacity was 1.85 mmol g^?1 for Cu²⁺, 1.34 mmol g^?1 for Pb²⁺, and 1.08 mmol g^?1 for Cd²⁺ at the optimized adsorption conditions (pH=4, T=323 K, t=2 h, C₀=3 mmol L^?1, and adsorbent dose=1 g L^?1). All Gibbs energy was negative as expected for spontaneous interactions, and the positive entropic values from 103.7 to 138.7 J mol^?1 K^?1 also reinforced this favorable adsorption process in heterogeneous system. Experiment with real wastewaters showed that approximately a half fraction of the total amount of studied metal ions was removed within the first cycle of adsorption. Hence, desorption experiments were performed by 0.3M HCl eluent, and Tren-SBA-15 successfully reused for four adsorption/desorption cycles to complete removal of metal ions from real effluents. The regenerated Tren-SBA-15 displayed almost similar adsorption capacity of Cu²⁺, Pb²⁺, and Cd²⁺ even after four recycles. The results suggest that Tren-SBA-15 is a good candidate as an adsorbent in the removal of Cu²⁺, Pb²⁺, and Cd²⁺ from aqueous solutions.     

Preparation of Benzylamine by Highly Selective Reductive Amination of Benzaldehyde Over Ru on an Acidic Activated Carbon Support as the Catalyst

Platinum particles (<1.5 nm) have been shown to behave as bases in their interaction with -alumina. FTIR spectra of adsorbed pyridine probe molecules showed that the acid strength of the -alumina was decreased by the presence of (<1.5 nm) Pt particles. Ammonium chloride treatment converts the primary Pt clusters to H _x Pt _y Cl _z intermediates that de-anchor from the support. Consequently, agglomeration to 8 nm Pt particles was observed following treatment in hydrogen at a relatively mild temperature. For the treated catalyst the IR data of absorbed pyridine show a 3 cm^-1 increase relative to the original Pt/-Al₂O₃ catalyst, indicating a strengthening of the acidity. Changes in the Pt particle size were confirmed by FTIR spectroscopy of CO absorbed onto the Pt particles before and after treatment. Consecutive CO and pyridine probe adsorption demonstrated the electronic interplay between the Pt particles and the support. Pyridine adsorption onto the -alumina support of a Pt/Al₂O₃ catalyst pre-dosed with CO produces a nearly 40 cm^-1 lowering of the CO peak position, indicative of CO bond weakening. In the case of CO adsorbed onto a catalyst pre-dosed with pyridine, a shift in the pyridine IR spectrum was only observed from the original highly dispersed catalyst.     

Spectroscopic and thermal studies of poly[(N‐vinylimidazole)‐co‐(maleic acid)] hydrogel and its quaternized form

BACKGROUND: In this study, poly[(N‐vinylimidazole)‐co‐(maleic acid)] (poly(VIm/MA)) hydrogels were prepared by γ‐irradiation of ternary mixtures of N‐vinylimidazole–maleic acid–water using a ⁶⁰Co γ‐source. Spectroscopic and thermal analyses of these hydrogels as a function of protonation showed that the results are consistent with the existence of an H‐bridged complex when the imidazole rings are partially protonated. Finally, the efficiency and binding trends of Cu²⁺, Co²⁺, Cd²⁺ and Pb²⁺ ions with both protonated and unprotonated poly(VIm/MA) hydrogels were determined. RESULTS: Gelation of 90% was reached at around 180 kGy dose at the end of irradiation. The poly(VIm/MA) hydrogels synthesized were further protonated in HCl solutions with different concentrations. Hydrogels originally showed 450% volumetric swelling; this ratio reached 1900% after protonation at pH = 5.0. Fourier transform infrared spectral changes in the ⁺N? H stretching region (3200–3600 and 1173 cm^?1) and the ring mode deformation at 915 cm^?1 are consistent with the formation of an H‐bridged complex between the protonated and unprotonated imidazole rings upon partial protonation. Similar changes were obtained from NMR spectra of both the protonated and unprotonated forms of the hydrogels. CONCLUSION: Protonated and unprotonated hydrogels have been used in heavy metal ion adsorption studies for environmental purposes. Adsorption decreased with decreasing pH value due to the protonation of the VIm ring. The adsorption of Me²⁺ ions decreased in the order Cu²⁺ > Co²⁺ > Cd²⁺ > Pb²⁺, which is related to the complexation stability as well as the ionic radius of the metal ions. These results show that P(VIm/MA) hydrogels can be used efficiently to remove heavy metal ions from aqueous solutions. However, the protonated form is a bad choice for heavy metal ion adsorption due to electrostatic repulsion forces; it can nevertheless be assumed to be a good choice for anion adsorption from environmental waste water systems. Copyright © 2007 Society of Chemical Industry     

Highly active rare earth catalysts for the solution polymerization of ε-caprolactone

Summary By using -butyrolactone (-BL) as the reaction media, highly active catalysts--light rare earth chloride-epoxidy---BL-for the solution polymerization of -caprolactone, have been obtained for the first time. With these catalyst, PCL with molecular weight as his as 40x10⁴(Mv) can be prepared at 60°C for 1.5 hr. The amount of epoxide in catalyst solution, catalyst aging temperature and time affect the catalyst activity significantly. The mechanism study shows that in -BL, the weakening of Ln-Cl bonds by the donation of coordinated -BL with Ln³⁺ and the homogenous effect promote the reaction between light rare earth chloride and epoxide. The produced rare earth alkoxide initiates CL polymerization via a coordination-insertion mechanism with Acyl-oxygen bond cleavage.     

Molybdenum nitride for the direct decomposition of NO

The physico-chemical properties of passivated -Mo₂N have been investigated. The material showed high activities for NO direct decomposition: nearly 100% NO conversion and 95% N₂ selectivity were achieved at 450C. The amount of O₂ taken up by -Mo₂N increased with temperature rise and reached 3133.9 molg^–1 at 450C; we conclude that there formation of Mo₂O_xN_y occurred. This oxygen-saturated -Mo₂N material was catalytically active: NO conversion and N₂ selectivity were 89 and 92% at 450C. We found that by means of H₂ reduction at 450C, Mo₂O_xN_y could be reduced back to -Mo₂N and the oxidation/reduction cycle is repeatable; such a behaviour and the high oxygen capacity (3133.9 molg^–1) of -Mo₂N suggest that -Mo₂N is a promising catalytic material for automobile exhaust purification.     

Metal ion removal by dyed cellulosic materials

Further studies on adsorption of different metal ions by the four dyed and undyed cellulosic substrates namely cotton fibers, bleached bamboo pulp, jute fibers, and sawdust were carried out. Different metal ions adsorbed were Fe²⁺, Fe³⁺, Pb²⁺, and Hg²⁺. The equilibrium metal adsorption was studied by EDTA method. The control and dyed substrates adsorbed these metal ions to a significant extent, thus providing an effective and cheap method for adsorption of costly but polluting and toxic metals like Pb²⁺ and Hg²⁺. The adsorption levels varied up to 95% for various substrate–dye–metal ion combinations.     

Synergistic Catalysis of Carbon Dioxide Hydrogenation into Methanol by Yttria-Doped Ceria/γ-Alumina-Supported Copper Oxide Catalysts: Effect of Support and Dopant

Methanol synthesis from carbon dioxide hydrogenation was studied over ceria/-alumina- and yttria-doped ceria (YDC)/-alumina-supported copper oxide catalysts to seek insight into the catalysis at metal–support interfaces. It was found that, in comparison with Cu/-Al₂O₃, the Cu/CeO₂/-Al₂O₃ and Cu/YDC/-Al₂O₃ catalysts exhibited substantial enhancement in activity and selectivity toward methanol formation. The extent of enhancement was augmented by increased ceria loading on -alumina and with increased yttria doping into ceria. The enhancement is inferred to result from the synergistic effect between copper oxide and surface oxygen vacancies of ceria.     

The influence of an intermediate MoO3 layer on the solid state reaction of cobalt oxide withγ-Al2O3

In view of the importance for Co_xO_y,-MoO₃/-Al₂O₃ hydrodesulphurization (HDS) catalysts, the reactivity of cobalt oxide layers towards cobalt aluminate formation was investigated on both MoO₃-covered and bare -Al₂O₃ substrates. Co₃O₄/MoO₃/-Al₂O₃ and Co₃O₄/-Al₂O₃ systems were prepared by vapour-deposition of MoO₃ (12 × 10¹⁵ Mo atoms/cm²) and Co (400 × 10¹⁵ Co atoms/cm²) layers onto a -Al₂O₃ substrate, followed by oxidation of the Co layer to Co₃O₄. After annealing at 800°C for 40 h, the interfacial reaction to cobalt aluminate was assessed using Rutherford backscattering spectrometry. The presence of molybdenum oxide appeared to enhance cobalt aluminate formation. The Mo atoms, which spread out over the entire cobalt-containing layer, presumably caused a high defect density, which explains the observed higher reaction rate. The amount of MoO₃ was much too low to stabilize all cobalt atoms by cobalt molybdate formation.     

Corrosion inhibition of copper in near neutral aqueous solutions by gamma-pyrodiphenone

The inhibition effect of gamma-pyrodiphenone (PD) on copper corrosion in near neutral sulphate solutions was investigated. Weight loss and polarization measurements show a high inhibition efficiency (>96%) of PD on copper corrosion at extremely low concentrations. PD suppresses active copper dissolution and oxygen reduction. The potentiodynamic cathodic reduction measurements showed an inhibition of oxide formation and stabilization of the Cu2O oxide in the presence of PD. XPS measurements suggested that the high inhibition effect of PD on copper corrosion is due to the adsorption of PD molecules, as a first stage, and the formation of a film with a polymer-like structure by coordination of PD with Cu2O on prolonged exposure.     

Radiation Synthesis and Characterization Study of Imprinted Hydrogels for Metal Ion Adsorption

Nickel ions were imprinted in the prepared acrylamide/citric acid P(AAm/CA) hydrogels by using gamma rays. The conditions influencing the preparation of imprinted hydrogels are optimized. The porosity and the characterization of the prepared P(AAm), P(AAm/CA), P(AAm/CA)-M hydrogels was preformed using (TGA) and (SEM). The gel content increases by increasing the monomer concentration and the irradiation dose up to 25 kGy. The swelling (%), rate constant (k), equilibrium ratio (Seq), diffusion constant (n) and the swelling behavior in response to pH value was studied. The Ni²⁺ imprinted hydrogel can considerably enhance the adsorption capacity and selectivity of the metal ion from wastewater.     

Reduction of NO by H2 and CO on PdO-MoO3/γ-Al2O3 of low molybdena loading

The activity and selectivity in the catalytic reduction of NO by a mixture of CO and H₂ of three PdO-MoO₃/-Al₂O₃ catalysts are compared in the presence of varying amounts of oxygen at reaction temperatures from 100 to 550°C. The catalysts were prepared by different methods and contain about 2% Mo and 2% Pd. Results are compared with those for PdO/-Al₂O₃, PdO-MoO₃/-Al₂O₃ containing 2% Pd and 20% Mo, and a commercial Pt-Rh catalyst. The PdO-MoO₃/-Al₂O₃ catalysts are more active for the selective reduction of NO to N₂ and N₂O than PdO/-Al₂O₃ under slightly oxidizing conditions at temperatures from 300 to 550°C. At these reaction conditions, the fresh PdO-MoO₃/-Al₂O₃ catalysts are comparable with a commercial Pt-Rh catalyst. The improved activity of PdO-MoO₃/-Al₂O₃ relative to PdO/-Al₂O₃ is believed to be due to the interaction between Pd and Mo. The effect of O₂ on the activity and selectivity of these catalysts is different in the reduction of NO by H₂, by CO, and by a mixture of H₂ and CO. The results using the mixture of reductants cannot be inferred from the results with the single reductants.     

Surface interaction model ofγ-alumina-supported metal oxides

An incorporation model has been proposed and used to discuss the interaction between various metal oxides and -alumina. The dispersion capacities of various metal oxides are predicted and the surface hydroxyl group density on -alumina estimated, based on the assumption that the (110) plane is preferentially exposed on the surface of -alumina. These results are in good agreement with the available experimental data.     

Lithium cycling efficiency and conductivity for γ-lactone-based electrolytes

Lithium cycling efficiency on a lithium substrate as well as conductivity were examined for-lactonebased electrolytes incorporating LiClO₄ for use in nonaqueous lithium secondary batteries.-butyrolactone (BL),-valerolactone and-octanoiclactone were used. Conductivity increased with a decrease in viscosity for lactone. Lithium cycling efficiency tended to increase with a decrease in reactivity between lithium and lactone, which would be expected from the oxidation potential for lactone. In order to decrease viscosity, tetrahydrofuran (THF) was mixed with lactone. Conductivity for lactone/THF was higher than those for systems using either lactone or THF alone. For example, 1 M LiClO₄-BL/THF (mixing volume ratio =11) showed conductivity of 13.0 × 10^–3 S cm^–1, approximately 20% higher than that for BL. Lithium cycling efficiency for BL/THF, which exceeded 90%, was also higher than that for BL. Morphology of the deposited lithium in BL/THF was smoother than that in BL and similar to that in THF, as observed with a scanning electron microscope. The reason for the enhancement of the lithium cycling efficiency for BL/THF seems to be the adsorption of THF or THF-Li⁺ around the deposited Li, which has lower reactivity to Li and higher solvation power to Li⁺ than BL.     

Microcalorimetric studies of ammonia adsorption on γ-Al2O3, HNa-Y zeolite,and H-mordenite

The acidities of-Al₂O₃, HNa-Y zeolite, and H-mordenite have been examined by microcalorimetric measurements of ammonia adsorption at 423 K. The differential heat of adsorption on -Al₂O₃ decreases continuously with ammonia coverage from an initial value of 165 kJ/ mol at low coverages to a value of 70 kJ/mol at higher coverages. The differential heat of adsorption on HNa-Y zeolite shows similar behavior, with a plateau of nearly constant heat at 115 kJ/mol. H-mordenite exhibits a nearly constant heat of adsorption equal to 155 kJ/mol. The results from these microcalorimetric measurements are in agreement with thermogravimetric and temperature-programmed desorption results collected at higher temperatures. Adsorbed ammonia has sufficient mobility at 423 K to equilibrate with the catalyst surface on the time scale of microcalorimetric measurements, and these measurements provide an effective method for quantifying acid site distributions of solid-acid catalysts.