Rodolfo Zanella

Photocatalytic hydrogen production by water/methanol decomposition using Au/TiO2 prepared by deposition–precipitation with urea

Gold nanoparticles deposited on TiO2 Degussa P25, prepared by deposition-precipitation with urea, were studied in the photocatalytic hydrogen production. The effect of parameters such as mass of catalyst, gold loading, thermal treatment, and atmosphere of treatment was evaluated and optimized. The presence of metallic gold on the titania surface showed to have contributed to the high improvement in the activity of bare TiO2 for hydrogen generation under UV light (λ=254 nm) using a lamp of low energy (2W) consumption. The optimal gold loading for the photocatalysts was 0.5 wt.%, the mass of catalyst in the reactor was 0.5 g/L in a water/methanol 1:1 vol. solution, and the thermal treatment that produced the most active gold nanoparticles was found at 300°C. The photocatalysts thermally treated under hydrogen at 300°C produced 1492 μmol g(-1)h(-1) of hydrogen; the same catalyst activated in air produced 1866 μmo lg(-1)h(-1) of hydrogen.

Photocatalytic degradation of trimethoprim by metallic nanoparticles supported on TiO2-P25

The effect of Au, Ag, Cu and Ni nanoparticles deposited on TiO2-P25 was studied on the photodegradation of trimethoprim, a commonly used antibiotic. The synthesized materials were characterized by ICP, EDS, XRD, BET, UV-vis, TEM and TPR. The metal loading was 0.5 wt.% and the average particle size was about 2 nm in all the studied samples. The deposition of metallic particles on TiO2-P25 produces an enhancement of the activity of the bare semiconductor; when the degradation of trimethoprim was carried out by pure TiO2-P25, the mineralization reached only 50% of the organic matter, while by using metallic nanoparticles deposited on TiO2-P25, the mineralization of organic matter increased up to 80% for the same reaction conditions and reaction time. The evaluation of the photocatalytic activity was made for solutions containing trimethoprim in concentrations of 40 ppm under UV light irradiation using a lamp with primary emission at 254 nm and 2.2 mW/cm(2). It is shown that the ability of the photocatalyst to mineralize trimethoprim depends on the electron affinity and the electronegativity of the deposited metal.

Photoconversion of 4-nitrophenol in the presence of hydrazine with AgNPs-TiO2 nanoparticles prepared by the sol-gel method.

The photocatalytic properties of functionalized TiO2 with silver nanoparticles (AgNPs) for the conversion of 4-nitrophenol to 4-aminophenol in the presence of hydrazine were investigated. The TiO2 semiconductor synthesized by the sol-gel method was functionalized with AgNPs at different loadings, and their structural and optical properties were characterized by several techniques. The functionalized TiO2 with 1.5wt% AgNPs presented the highest photocatalytic activity for the conversion of 4-nitrophenol with appropriate hydrazine concentrations (0.5M). The photoefficiency enhancement under UV light irradiation was attributed to the electron transfer from the TiO2 semiconductor surface to the adsorbed acceptor reactant (4-nitrophenol) through the deposited AgNPs.

Highly Stable Bimetallic AuIr/TiO2 Catalyst: Physical Origins of the Intrinsic High Stability against Sintering

It has been a long-lived research topic in the field of heterogeneous catalysts to find a way of stabilizing supported gold catalyst against sintering. Herein, we report highly stable AuIr bimetallic nanoparticles on TiO2 synthesized by sequential deposition-precipitation. To reveal the physical origin of the high stability of AuIr/TiO2, we used aberration-corrected scanning transmission electron microscopy (STEM), STEM-tomography, and density functional theory (DFT) calculations. Three-dimensional structures of AuIr/TiO2 obtained by STEM-tomography indicate that AuIr nanoparticles on TiO2 have intrinsically lower free energy and less driving force for sintering than Au nanoparticles. DFT calculations on segregation behavior of AuIr slabs on TiO2 showed that the presence of Ir near the TiO2 surface increases the adhesion energy of the bimetallic slabs to the TiO2 and the attractive interactions between Ir and TiO2 lead to higher stability of AuIr nanoparticles as compared to Au nanoparticles.

Gold nanoparticles supported on TiO2–Ni as catalysts for hydrogen purification via water–gas shift reaction

Gold nanoparticles deposited on TiO2–Ni prepared by sol–gel process catalyses the CO oxidation to hydrogen purification. Gold-catalysts were characterized by UV-Vis and Raman spectroscopies, X-ray diffraction, H2-TPR, N2 physisorption, HRTEM and STEM-HAADF microscopies. These catalysts were applied in the water–gas shift reaction at temperatures from 30 to 300 °C and this reaction was studied by DRIFTS to understand the catalytic surface phenomena. The best CO conversion was showed by doped Au/TiO2–Ni(1) with regard to Au/TiO2 sol–gel and Au/TiO2–P25 catalysts. DRIFTS confirm the strong and favorable effect of doping nickel ions into the reducible TiO2 framework. Nickel contents from 1 to 10% enhance the WGS reaction in contrast to the undoped catalyst. Ni-doped TiO2 support was practically inert for WGS reaction. These gold catalysts present significant activity in the water–gas shift reaction that allows purification of hydrogen from industrial sources at low-temperature.

Characterization of NaTaO3 synthesized by ultrasonic method

NaTaO(3) perovskite-like materials were synthesized using sodium acetate and tantalum ethoxide as precursors in an ultrasonic bath at room temperature. The pristine sample was thermally treated at 600 °C and characterized using XRD, N(2) physisorption, DRS, SEM and TEM techniques. The structural characterization by X-ray powder diffraction revealed that the crystallization of the NaTaO(3) phase prepared at 600 °C showed agglomerates sizes in the micrometric scale, as confirmed by scanning electron microscopy (SEM). On the other hand, well-defined NaTaO(3) particles in the nanometric scale were determined using TEM. It was found that, for the treated sample, the band gap and BET area was 3.8 eV and 9.5m(2) g(-1), respectively. The annealed perovskite, deposited onto ITO glass, presented an important variation in the open circuit potential transient during UV light irradiation in neutral solution, compared with its counterpart prepared by solid-state method. These intrinsic properties, given by the preparation route, might be appropriate for increase its photocatalytic activity.

Identification of Subnanometric Ag Species, Their Interaction with Supports and Role in Catalytic CO Oxidation

The nature and size of the real active species of nanoparticulated metal supported catalysts is still an unresolved question. The technique of choice to measure particle sizes at the nanoscale, HRTEM, has a practical limit of 1 nm. This work is aimed to identify the catalytic role of subnanometer species and methods to detect and characterize them. In this frame, we investigated the sensitivity to redox pretreatments of Ag/Fe/TiO2, Ag/Mg/TiO2 and Ag/Ce/TiO2 catalysts in CO oxidation. The joint application of HRTEM, SR-XRD, DRS, XPS, EXAFS and XANES methods indicated that most of the silver in all samples is in the form of Ag species with size <1 nm. The differences in catalytic properties and sensitivity to pretreatments, observed for the studied Ag catalysts, could not be explained taking into account only the Ag particles whose size distribution is measured by HRTEM, but may be explained by the presence of the subnanometer Ag species, undetectable by HRTEM, and their interaction with supports. This result highlights their role as active species and the need to take them into account to understand integrally the catalysis by supported nanometals.

Gold Particle Size Determination on Au/TiO2-CeO2 Catalysts by Means of Carbon Monoxide, Hydrogen Chemisorption and Transmission Electron Microscopy

Au/TiO2 and Au/TiO2-CeO2 catalysts were prepared by the sol-gel method and carbon monoxide, hydrogen chemisorption and TEM spectroscopy have been exploited to determine the size of gold particles. The gold nanoparticles (8.1 to 2.1 nm) were deposited by using the deposition-precipitation method. The XRD characterization shows the presence of anatase as the TiO2 crystalline phase; while by XPS spectroscopy, the presence of Au°, Au2O3, Ce3+ and Ce4+ species co-existing in the Au/TiO2-CeO2 catalysts is shown. The characterizations by TPD-CO as well as by TPD-H2 (temperature programmed desorption) showed that on catalysts containing cerium, the gold particle size can be determined with great accuracy by using these chemisorption methods. The gold particle size calculated from either the CO or H2 thermodesorption values is in good agreement with that obtained by High Resolution Transmission Electron Microscopy (HRTEM) and Scanning Transmission Electron Microscopy (STEM) analyses. It was proposed that the TPD-CO and/or TPD-H2 techniques could be helpful for the characterization of the gold particles by TEM; especially when the high contrast in the pictures of the supports containing CeO2 prevents the particle size from being determined.

Gold catalysts on ceria doped with MeOx (Me = Fe, Mn, Co and Sn) for complete benzene oxidation: effect of composition and structure of the mixed supports

Gold catalysts supported on ceria doped with different metal oxides (Fe, Mn, Co and Sn) were synthesized using two techniques: CP and mechanochemical activation. The catalytic activity in complete benzene oxidation (CBO) was studied. The samples were characterized by means of XRD and high resolution transmission electron microscopy, and non-significant differences in the average size and the distribution of gold particles were observed. This means that the main reason for the different catalytic behavior in CBO has to be searched in the composition and structure of the supports. In spite of the higher hydrogen consumption (e.g., higher oxygen mobility) estimated by means of TPR, the gold catalysts on ceria doped with transition metal oxides generally are less active than gold/ceria catalyst. This observation could be explained taking into consideration that the key factor for the high oxidation activity is not the oxygen supplying but the activation of the very stable benzene molecule. The higher catalytic activity in comparison with that of the gold/ceria catalyst was observed only using a mixed ceria–CoOx support mechanochemically prepared. Very high and stable catalytic activity in CBO was obtained over this sample.

Low temperature total oxidation of toluene by bimetallic Au–Ir catalysts

Bimetallic gold–iridium catalysts present a synergetic activity effect on the total oxidation of volatile organic compounds (e.g. toluene) with respect to their monometallic counterparts, leading to catalytic activity at lower temperatures. The enhancement of activity is facilitated by the intimate contact of the iridium and gold species, which modifies the electronic environment of the active sites, assisting in the oxygen activation at lower temperatures. In addition, the bimetallic system shows a considerably stronger metal–support interaction capable of diminishing the detrimental loss of activity associated with metal sintering at high reaction temperatures, in contrast to the monometallic cases whose activities are greatly lost. This paper contributes to the understanding of the key factors behind high activity and good stability of catalysts to achieve the low temperature activity of VOC compounds in air pollution remediation applications.