Eloy del Río

Single-Step Process To Prepare CeO2 Nanotubes with Improved Catalytic Activity

CeO(2) nanotubes have been grown electrochemically using a porous alumina membrane as a template. The resulting material has been characterized by means of scanning electron microscopy (SEM), X-ray energy dispersive spectroscopy, high-angle annular dark-field scanning transmission electron microscopy tomography, high-resolution electron microscopy (HREM), and electron energy loss spectroscopy. According to SEM, the outer diameter of the nanotubes corresponds to the pore size (200 nm) of the alumina membrane, and their length ranges between 30 and 40 microm. HREM images have revealed that the width of the nanotube walls is about 6 nm. The catalytic activity of these novel materials for the CO oxidation reaction is compared to that of a polycrystalline powder CeO(2) sample prepared by a conventional route. The activity of the CeO(2) nanotubes is shown to be in the order of 400 times higher per gram of oxide at 200 degrees C (77.2 x 10(-2) cm(3) CO(2) (STP)/(gxs) for the nanotube-shaped CeO(2) and 0.16 x 10(-2) cm(3) CO(2) (STP)/(gxs) for the powder CeO(2)).

Fully Reversible Metal Deactivation Effects in Gold/Ceria–Zirconia Catalysts: Role of the Redox State of the Support

Gold nanoparticles supported on reducible oxides are highly interesting catalytic materials. In particular, they are known to exhibit exceptional activity for CO oxidation, lowtemperature water–gas shift (LT-WGS), and selective oxidation of CO in the presence of a large excess of hydrogen (PROX). 20–24] Despite the extraordinary research effort devoted to these catalysts, there are still some key questions about the nanostructural constitution and chemical properties of the gold sites involved in the above reactions that require further clarification. The relationship between the redox state of the support and the chemical properties of gold nanoparticles is one of these major open questions. 5] Its understanding, however, is critically important to fully interpret catalysis by Au/reducible oxide systems, particularly in the case of processes like LTWGS, 19] PROX, and hydrogenation reactions, which typically occur under net reducing conditions. To gain further information on this issue, we investigated CO adsorption on an Au/Ce0.62Zr0.38O2 (Au/CZ) sample subjected to different redox pretreatments. In our experimental approach, FTIR spectroscopic and volumetric adsorption techniques were combined with studies on ultimate oxygen storage capacity (OSC), metal dispersion, as determined by high-resolution TEM (HRTEM) and high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM), and X-ray photoelectron spectroscopy (XPS). By this approach, the influence of the redox state of the support on the CO adsorption capability of Au nanoparticles could be established on a quantitative basis. In contrast with earlier proposals suggesting that gold catalysts do not exhibit a strong metal/support interaction (SMSI) effect, the results presented and discussed herein indicate that the behavior of our Au/CZ shows close resemblances with those of a number of noble metal/reducible oxide systems which are acknowledged to show this effect. Our experimental approach also allowed us to show that the absorption coefficient of the n[CO(Au)] band depends on the redox state of the support. The implications of this finding for the use of integrated absorption data as a quantitative tool for characterizing the changes of CO adsorption capability occurring in gold nanoparticles supported on reducible oxides is discussed. Figure 1 shows the n(CO) FTIR spectra recorded on the same sample disk successively submitted to a) oxidizing treatment at 523 K (Au/CZ-O523); b) pretreatment (a) followed by reduction at 473 K (Au/CZ-O523-R473); and

Bridging the Gap between CO Adsorption Studies on Gold Model Surfaces and Supported Nanoparticles

An in-depth understanding of CO adsorption on highly dispersed gold nanoparticles (AuNPs) is critically important to fully interpret the catalytic behavior of supported gold systems in processes such as CO oxidation, PROX (selective oxidation of CO in presence of a large excess of H2), [5–7] or LT-WGS (low-temperature water gas-shift) reactions. Despite its relevance, the quantitative data and fundamental information presently available on the CO–Au interaction mainly comes from studies carried out on model single-crystal and thin-film surfaces under experimental conditions far from those at which catalytic assays on supported gold systems are typically run. Probably because of the very weak and singular nature of the CO–Au interaction, which on the basis of both theoretical and experimental studies is generally acknowledged to take place on low-coordination surface sites, and the additional contribution of the support, a few studies have been carried out that were aimed at estimating the amount of CO adsorbed at low temperature on powdered or model supported AuNPs. To our knowledge, however, none of these have arrived at a detailed quantitative description of this process under conditions close to those occurring in real catalytic reactions. To bridge this gap, we have developed an approach in which AuNP size distributions, as determined from HAADFSTEM (high-angle annular dark-field scanning transmission electron microscopy) and quantitative CO adsorption data, as determined from volumetric adsorption at 308 K, under CO partial pressures ranging from 6.65 10 Pa to 3.99 10 Pa, are jointly analyzed with the help of a nanostructural model for the gold particles. This model could be deduced from the analysis of images recorded in a parallel HRTEM (highresolution transmission electron microscopy) study. As discussed herein, this approach gives a substantial experimental support to the extension to supported gold catalysts of the chemical principles governing the CO adsorption on model surfaces. We investigated two catalyst samples, 2.5 wt% Au/ Ce0.62Zr0.38O2 (Au/CZ) and 1.5 wt% Au/Ce0.50Tb0.12Zr0.38O2 x (Au/CTZ), which have significantly different gold particle size distributions. Two consecutive CO volumetric adsorption isotherms were recorded on the gold catalysts and the corresponding supports. Prior to running the second isotherms, samples were evacuated (residual pressure Pres< 1.33 10 4 Pa) for 30 min at 308 K. By processing the volumetric data in a similar way to earlier studies (for details, see the Supporting Information), the amounts of CO adsorbed on the AuNPs, on the surface cations of the supports (weak adsorption), and on the surface anions of the supports, which mainly consist of strongly chemisorbed carbonate species, could be determined from the difference of the two isotherms. The amount of CO adsorbed on the AuNPs at PCO= 1.33 10 4 Pa (100 Torr) was used as a measurement of the saturation coverage. The corresponding data are reported in Table 1 and the Supporting Information, Figure S1. Gold particle size distributions were determined for each of the investigated catalysts from the analysis of series of experimental ultra-high-resolution HAADF-STEM images (Supporting Information, Figure S2). In accordance with the physical principles lying behind the mechanism of image formation, this technique is particularly suitable for obtaining reliable metal particle size distributions in oxide-supported metal catalysts. Moreover, as recently shown, this technique can be fruitfully applied to a very fine characterization of AuNPs dispersed on mixed oxides of heavy elements, as is the case of those investigated herein. (Size distributions for Au/CZ and Au/CTZ catalysts are shown in the Supporting Information, Figure S2). [*] M. L pez-Haro, Dr. J. J. Delgado, J. M. Cies, E. del Rio, S. Bernal, Dr. M. A. Cauqui, Dr. S. Trasobares, Dr. J. A. P rez-Omil, Dr. J. J. Calvino Departamento de Ciencia de los Materiales e Ingenier a Metalfflrgica y Qu mica Inorg nica Facultad de Ciencias, Universidad de C diz Campus Rio San Pedro, 11510-Puerto Real, C diz (Spain) Fax: (+34)956-016-288 E-mail: jose.calvino@uca.es

Strain Field in Ultrasmall Gold Nanoparticles Supported on Cerium-Based Mixed Oxides. Key Influence of the Support Redox State

Using a method that combines experimental and simulated Aberration-Corrected High Resolution Electron Microscopy images with digital image processing and structure modeling, strain distribution maps within gold nanoparticles relevant to real powder type catalysts, i.e., smaller than 3 nm, and supported on a ceria-based mixed oxide have been determined. The influence of the reduction state of the support and particle size has been examined. In this respect, it has been proven that reduction even at low temperatures induces a much larger compressive strain on the first {111} planes at the interface. This increase in compression fully explains, in accordance with previous DFT calculations, the loss of CO adsorption capacity of the interface area previously reported for Au supported on ceria-based oxides.