A theoretical insight into the catalytic effect of a mixed-metal oxide at the nanometer level: The case of the highly active metal/CeOx/TiO2(110) catalysts

The structural and electronic properties of CeOx species supported on the rutile TiO2 110 surface have been examined by means of periodic density-functional calculations that use a generalized gradient approximation functional including a Hubbard-like type correction. Deposition of Ce atoms leads in a first step to Ce3+ ions bound to the surface through bridge and in-plane oxygen atoms, the released electrons occupying the Ti 3d empty orbitals. Further addition of Ce and molecular oxygen gives place to Ce2O3 dimers diagonally arranged on the surface, in agreement with the spots observed in the scanning tunnel microscope images. The formation process of CeOx nanoparticles NPs on the TiO2 surface is highly exothermic and our calculations show that the redox properties of the Ce III-Ce IV couple are significantly altered when it is supported on TiO2. In particular the reactivity against CO/O2 indicates that on the surface the presence of Ce III is favored over Ce IV species. Our results also indicate that the CeOx /TiO2 interface should be seen like a real mixed-metal oxide rather than a supported NP of ceria. Finally, in the context of the high catalytic activity of the M /CeOx /TiO2 M =Au,Cu,Pt systems in the water-gas shift reaction, we have examined the dissociation of water on the CeOx /TiO2 surface and estimated a barrier as small as 0.04 eV, i.e. 8 times smaller than that computed for a TiO2 oxygen vacancy. This result agrees with the experimental superior catalytic activity of the M /CeOx /TiO2 systems over M /TiO2.Gobierno de España. Ministerio Ciencia e Innovación (MICINN) MAT2005-01872 y CSD2008-0023Junta de Andalucía FQM-132Departamento de Energía de EE. UU. División de Subvención de Ciencias Químicas DE-AC02-98CH1088

Microstructural properties of non-supported microporous ceramic membrane top-layers obtained by the sol-gel process

Dried and calcined non-supported membrane top-layers of SiO2, SiO2/TiO2, SiO2/ZrO2 (10, 20 and 30 mol% TiO2 and ZrO2, respectively) and SiO2/Al2O3 (10 mol% AlO1.5) were prepared using acid catalyzed hydrolysis and condensation of alkoxides in ethanol. The microstructure was determined using nitrogen physisorption. The modified Horváth-Kawazoe model for nitrogen adsorption in cylindrical pores was used for pore size assessment. SiO2 non-supported membrane top layers were 100% microporous with an average porosity of 30¿37%, depending on drying conditions. The bimodal pore size distribution shows a maximum at an effective pore diameter of 0.5 nm, and a broader tail with a weaker maximum around 0.75 nm. Microporous non-supported binary systems can be prepared with porosities between 15 and 40%. The high reactivity of the Ti, Zr, Al-alkoxides requires carefully chosen conditions. Too much water results in dense materials. The pore size distributions (PSDs) of the binary systems resemble the PSDs for silica

Structural analysis and corrosion studies on an ISO 5832-9 biomedical alloy with TiO2 sol–gel layers

The aim of this study was to demonstrate the relationship between the structural and corrosion properties of an ISO 5832-9 biomedical alloy modified with titanium dioxide (TiO2) layers. These layers were obtained via the sol–gel method by acid-catalyzed hydrolysis of titanium isopropoxide in isopropanol solution. To obtain TiO2 layers with different structural properties, the coated samples were annealed at temperatures of 200, 300, 400, 450, 500, 600 and 800 C for 2 h. For all the prepared samples, accelerated corrosion measurements were performed in Tyrode’s physiological solution using electrochemical methods. The most important corrosion parameters were determined: corrosion potential, polarization resistance, corrosion rate, breakdown and repassivation potentials. Corrosion damage was analyzed using scanning electron microscopy. Structural analysis was carried out for selected TiO2 coatings annealed at 200, 400, 600 and 800 C. In addition, the morphology, chemical composition, crystallinity, thickness and density of the deposited TiO2 layers were determined using suitable electron and X-ray measurement methods. It was shown that the structure and character of interactions between substrate and deposited TiO2 layers depended on annealing temperature. All the obtained TiO2 coatings exhibit anticorrosion properties, but these properties are related to the crystalline structure and character of substrate–layer interaction. From the point of view of corrosion, the best TiO2 sol–gel coatings for stainless steel intended for biomedical applications seem to be those obtained at 400 C.This study was supported by Grant No. N N507 501339 of the National Science Centre. The authors wish to express their thanks to J. Borowski (MEDGAL, Poland) for the Rex 734 alloy

Synthesis, characterization and photocatalytic activity of TiO2 supported natural palygorskite microfibers

This study deals with the synthesis of TiO2 supported Moroccan palygorskite fibers and their use as photocatalyst for the removal of Orange G pollutant from wastewater. The TiO2-palygorskite nanocomposite synthesis was accomplished according to a colloidal route involving a cationic surfactant as template (hexadecyltrimethylammonium bromide) assuring hence organophilic environment for the formation of TiO2 nanoparticles. The clay minerals samples were characterized before and after functionalization with TiO2. Anatase crystallizes above ca. 450 °C and remarkably remains stable up to 900 °C. In contrast, pure TiO2 xerogel obtained from titanium tetraisopropoxide (TTIP) showed before calcination a nanocrystalline structure of anatase. By increasing the temperature, anatase readily transforms into rutile beyond 600 °C. The remarkable stability at high temperature of anatase particles immobilized onto palygorskite microfibers was due to the hindrance of particles growth by sintering. Homogeneous monodisperse distribution of anatase particles with an average size of 8 nm was found by TEM and XRD onto palygorskite fibers. This anatase particle size remains below the nucleus critical size (ca. 11 nm) required for anatase–rutile transition. The TiO2 supported palygorskite sample annealed in air at 600 °C for 1 h exhibits the highest photocatalytic activity towards the degradation of Orange G compared to nanocomposite samples prepared under different conditions as well as pure TiO2 powders obtained from the xerogel route or commercially available as Degussa P25

Atomic Layer Deposition-Based Synthesis of Photoactive TiO2 Nanoparticle Chains by Using Carbon Nanotubes as Sacrificial Templates

Highly ordered and self supported anatase TiO2 nanoparticle chains were fabricated by calcining conformally TiO2 coated multi-walled carbon nanotubes (MWCNTs). During annealing, the thin tubular TiO2 coating that was deposited onto the MWCNTs by atomic layer deposition (ALD) was transformed into chains of TiO2 nanoparticles (~12 nm diameter) with an ultrahigh surface area (137 cm2 per cm2 of substrate), while at the same time the carbon from the MWCNTs was removed. Photocatalytic tests on the degradation of acetaldehyde proved that these forests of TiO2 nanoparticle chains are highly photo active under UV light because of their well crystallized anatase phase

Novel visible light-driven photocatalyst of mesoporous tud-1 supported chromium oxide doped titania for phenol photodegradation

Novel visible light driven mesoporous photocatalysts of Technische Universiteit Delft-1 (TUD-1) supported 1 mol% Cr oxide doped TiO2 (Cr-TiO2) were synthesized. Low angle XRD and FTIR results confirmed the amorphous and mesoporous silicate framework of TUD-1 in the materials. The mesostructure was further confirmed via N2 adsorption-desorption analysis showing type IV isotherm with narrow average pore size distribution (2.5 nm) and high surface area (864 m2/g). TEM analysis results indicated the attainment of nanoparticles and the porous channels in the synthesized materials. An increase in band-gap energy was observed after loading of Cr-TiO2 into TUD-1. As compared to the unsupported Cr-doped TiO2, all the TUD-1 supported Cr-doped TiO2 photocatalysts showed higher photocatalytic activity for phenol degradation under visible light irradiation. Amongst, sample Cr oxide doped TiO2 supported on TUD-1 with molar ratio Si/Ti = 30 exhibited the highest photodegradation of phenol (82%). The phenol photodegradation followed the Langmuir adsorption isotherm with first order kinetics

Photochemical deposition of Platinum over MWNT: making catalysts for selective hydrogenation of cinnamaldehyde

In the present study, the photochemical deposition method was compared against the usual incipient wetness procedure in the preparation of supported Pt catalysts. Particular attention was given to parameters such as nature of the support (multiwalled carbon nanotubes, MWNT vs. titanium dioxide, TiO2) and reduction temperature. Supported 1% wt Pt catalysts treated in hydrogen at 773K showed improved activity and selectivity towards cinnamyl alcohol (50.8 and 57.4% were observed in MWNT and TiO2 - SMSI effect, respectively) when comparing to those untreated (45.8 and 28.9, MWNT and TiO2, respectively). The best catalytic performance was achieved by a 5% wt Pt supported in TiO2 catalyst treated in hydrogen at 773K. Selectivity to unsaturated alcohol as high as 63.2% at 80% conversion was observed

Synthesis and textural properties of unsupported and supported rutile (TiO2) membranes

Two approaches were postulated for improving the stability of porous texture of titania membranes: (1) retarding the phase transformation and grain growth; (2) avoiding the phase transformation. Based on the second approach, rutile membranes were made directly from a rutile sol, prepared by the precipitation of titania on SnO2 nuclei. The rutile membranes were stable up to 800 °C, with a porosity of ca. 40%, whereas normal titania membranes (starting with anatase) show very little porosity above 600 °C. Alumina substitution retards grain growth and pore growth at 850 °C for unsupported as well as supported membranes. \u

Synthesis of Au-Cu/SBA(Ti) catalysts for photocatalytic applications

In this work, it has been synthesized several Au and Au-Cu alloy photocatalysts supported on two different mesoporous supports: a non-commercial SBA-15 and a post-synthesis TiO2 modified SBA-15 (TiSBA-15), with which a high dispersion of TiO2 species have been achieved maintaining the SBA-15 structure. In addition, it has also been obtained highly dispersed Au nanoparticles confined in SBA-15 pore channels. The photocatalysts have been preliminary tested in the preferential CO oxidation in a H2-rich stream (CO-PROX) at room temperature and atmospheric pressure under simulated solar light irradiation. In spite of the very low gold and copper loading (1.5 wt% and 0.5wt% respectively), the catalysts resulted active and selective in the low temperature photo-CO-PROX.Universidad de Málaga. Campus de Excelencia Internacional Andalucía Tech