Photoreduction of Carbondioxide on Surface Functionalized Nanoporous Catalysts

Nanoporous photocatalysts have been designed to exhibit unique photocatalytic activities through framework substitution of titanium species or surface immobilization of rhenium complex onto mesoporous silica. This article summarizes recent work on the synthesis, characterization and photocatalytic activities of the designed porous photocatalysts performed by the present authors. Various spectroscopic investigations revealed that the photo-excited states of these catalysts play a vital role in the photocatalytic reactions and their photocatalytic reactivities are strongly dependent on structures of active sites, which are confined and immobilized in the restricted framework structure of the mesoporous silica. Highly dispersed titanium oxide species incorporated in the framework of mesoporous silica exhibited high and unique photocatalytic reactivity for the reduction of CO₂ with H₂O to produce CH₄ and CH₃OH under UV irradiation, its reactivity being much higher than bulk TiO₂. The cationic rhenium(I) complex was encapsulated into a mesoporous AlMCM-41 material by ion-exchange method, yielding a visible light photocatalyst to be active for photocatalytic reduction of CO₂.     

Selective separation of water from water–ethanol solution through quarternized poly(4-vinylpyridine-co-acrylonitrile) membranes by pervaporation technique

Polymer membranes having cationic charge site, poly(1-alkyl-4-vinylpyridinium iodide-co-acrylonitrile) (alkyl: methyl, butyl, or octyl) were prepared in terms of coulombic interaction for separation of water–ethanol mixtures. The incorporation of cationic charge site into the membrane led to improve not only separation factors (selectivity toward water) but also flux number in the separation of aqueous ethanol solution by pervaporation technique. Target values, which were requested to have from the viewpoint of industrial utilization for separation of aqueous ethanol solution were attained as follows: separation factor toward water over 50 and flux value over 500 g m^?2 h^?1, through poly(1-methyl-4-vinylpyridinium iodide-co-acrylonitrile) (membrane 3 ) (quarternized fraction of pyridinium moiety, 89.5%; mol fraction of pyridinium moiety, 0.034) and poly(1-butyl-4-vinylpyridinium iodide-co-acrylonitrile) (membrane 5 ) (quarternized fraction, 100%; mol fraction of pyridinium moiety, 0.038). It was found that the introduction of cationic charge site into the membrane was one of feasible methods to obtain suitable membranes for water permselective membranes in the separation of water–ethanol mixtures.     

Photocatalytic Decomposition of Formic Acid Under Visible Light Irradiation Over V-ion-implanted TiO2 Thin Film Photocatalysts Prepared on Quartz Substrate by Ionized Cluster Beam (ICB) Deposition Method

Unique visible-light-responsive TiO₂ photocatalysts (λ>450 nm) were successfully developed by implantation of V ions into the TiO₂ thin films prepared on a quartz substrate by an ionized cluster beam (ICB) deposition method. After V ions implantation into TiO₂ thin film, the photocatalytic activity of the thin films for the decomposition of formic acid into CO₂ and H₂O was found to proceed efficiently under visible light irradiation longer than 450 nm. The TiO₂ thin film photocatalysts were characterized by XRD, UV-vis, XPS, FE-SEM and AFM.     

Preparation of ion exchange membranes by preirradiation induced grafting of styrene/divinylbenzene into crosslinked PTFE films and successive sulfonation

Ion exchange membranes (IEMs) were prepared by preirradiation induced grafting of styrene with or without divinylbenzene (DVB) into crosslinked polytetrafluoroethylene (RX‐PTFE) films and successively sulfonated by chlorosulfonic acid. The effects of the DVB concentration and solvent on the kinetic of the graft polymerization were studied. The ion exchange capacity (IEC) values of the prepared membranes ranging from 1.5 to 2.8 mequiv/g were obtained. The degree of swelling increased with the increase in the degree of grafting, while higher crosslinking density of both the RX‐PTFE matrices and the grafts suppressed the degree of swelling. The chemical stabilities of the IEMs were tested by recording the weight of the membranes being soaked in hot H₂O₂ solutions. The weight‐time curves of the prepared membranes showed one‐step quick decrease due to the decomposition of the poly(styrene‐sulfonic acid) (PSSA) grafts. Higher crosslinking density in both the RX‐PTFE matrices and the grafts improved the chemical stability of the IEMs. The ionic conductivity of the IEMs increases with the increase in the IEC values. The IEMs with IEC values higher than 2.2 mequiv/g hold the higher ionic conductivity than that of Nafion® 112 membrane. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3587–3599, 2006     

Effect of ultrasound on micromixing

It is well known that the apparent reaction rate constant is increased by exposing the reactor to ultrasound. The authors reveal in this paper that another effect of ultrasound, that is, the decrease of the segregation of points in the sense of Danckwerts, also appears and that this effect is probably due to some hammering action caused by the collapse of cavities. The saponification of ethyl acetate in a continuous stirred tank reactor is chosen for the experimental work.     

Oxidative dehydrogenation of methanol over a ruthenium-containing polyoxomolybdate supported on metal oxides chemically modified with silane coupling agent

A salt of ruthenium-containing polyoxomolybdate anion ([Ru₂Mo₁₄O₅₀]¹⁰⁻ or [Ru₂Mo₁₄O₅₂]¹⁴⁻; Ru₂Mo₁₄) was synthesized by mixing ruthenium chloride and sodium molybdate in a buffer solution (acetic acid–ammonium acetate) at pH 5. The polyanion, Ru₂Mo₁₄, was loaded on a silica carrier chemically modified with a silane coupling agent having a 1,2-diaminoethyl group (DAPS–SiO₂). X-ray diffraction, FT-IR and surface area measurements revealed that Ru₂Mo₁₄ was highly dispersed on DAPS–SiO₂ up to 20 wt.% loading. The highly dispersed Ru₂Mo₁₄ exhibited a high level of activity for oxidative dehydrogenation of methanol to formaldehyde with a high selectivity, whereas combustion of methanol occurred on the bulky salt of Ru₂Mo₁₄ and ruthenium catalyst supported on a SiO₂ carrier.     

Pervaporation of methanol/methyl tert‐butyl ether mixtures through agarose/hydroxyethylcellulose blended membranes

In this study, we investigated methanol (MeOH)/methyl tert‐butyl ether (MTBE) separation with hydroxyethylcellulose (HEC)/agarose blended membranes by applying a pervaporation technique. The membranes permeated MeOH in preference to MTBE from MeOH/MTBE mixtures. From pervaporation and sorption data, the permselectivity of HEC/agarose blended membrane was dominantly due to solubility selectivity. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3408–3411, 2002     

Photocatalytic decomposition of NO on titanium oxide thin film photocatalysts prepared by an ionized cluster beam technique

Transparent TiO₂ thin film photocatalysts were prepared on transparent porous Vycor glass (PVG) by an ionized cluster beam (ICB) method. The UV‐VIS absorption spectra of these films show specific interference fringes, indicating that uniform and transparent TiO₂ thin films are formed. The results of XRD measurements indicate that these TiO₂ thin films consist of both anatase and rutile structures. UV light (λ > 270 nm) irradiation of these TiO₂ thin films in the presence of NO led to the photocatalytic decomposition of NO into N₂, O₂ and N₂O. The reactivity of these TiO₂ thin films for the photocatalytic decomposition of NO is strongly dependent on the film thickness, i.e., the thinner the TiO₂ thin films, the higher the reactivity. This revised version was published online in July 2006 with corrections to the Cover Date.     

Photoluminescence properties of La2O3 methane coupling catalysts

La₂O₃ catalysts prepared at 923 K (La₂O₃-LT) and 1073 K (La₂O₃-HT) exhibit different photoluminescence properties due to notably different concentrations of ions in position of low coordination at the surface or coordinatively unsaturated surface sites (cus). The catalyst which exhibits the higher yields of photoluminescence due to the higher concentration of cus corresponds to the one which gives the higher C₂₊ selectivity in the oxidative methane coupling reaction. On leave of absence from Laboratoire de Réactivité de Surface, Université Pierre et Marie Curie, URA 1106-CNRS, 75252 Paris Cedex, France.     

Synthesis of Pd Nanoparticles in La-doped Mesoporous Titania with Polycrystalline Framework

A simple synthetic method to prepare highly dispersed Pd nanoparticles in La-doped mesoporous titania with polycrystalline framework by coassembly and photoreduction is reported. The mesoporous materials were characterized by thermogravimetric (TGA)/differential scanning calorimetric (DSC), low angle and wide angle X-ray diffraction (XRD), transmission electron microscope (TEM), high-resolution transmission electron microscopy (HRTEM) and N₂ adsorption–desorption. The photocatalytic activities of the prepared mesoporous materials were evaluated by the photodegradation of methyl orange.