Miguel López-Haro

Comparative Structural and Chemical Studies of Ferritin Cores with Gradual Removal of their Iron Contents

Transmission Electron Microscopy (TEM), X-ray Absorption Near Edge Spectroscopy (XANES), Electron Energy-Loss Spectroscopy (EELS), Small-Angle X-ray Scattering (SAXS), and SQUID magnetic studies were performed in a batch of horse spleen ferritins from which iron had been gradually removed, yielding samples containing 2200, 1200, 500, and 200 iron atoms. Taken together, findings obtained demonstrate that the ferritin iron core consists of a polyphasic structure (ferrihydrite, magnetite, hematite) and that the proportion of phases is modified by iron removal. Thus, the relative amount of magnetite in ferritin containing 2200 to 200 iron atoms rose steadily from approximately 20% to approximately 70% whereas the percentage of ferrihydrite fell from approximately 60% to approximately 20%. These results indicate a ferrihydrite-magnetite core-shell structure. It was also found that the magnetite in the ferritin iron core is not a source of free toxic ferrous iron, as previously believed. Therefore, the presence of magnetite in the ferritin cores of patients with Alzheimers disease is not a cause of their increased brain iron(II) concentration.

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)).

Three-dimensional analysis of Nafion layers in fuel cell electrodes

Proton exchange membrane fuel cell is one of the most promising zero-emission power sources for automotive or stationary applications. However, their cost and lifetime remain the two major key issues for a widespread commercialization. Consequently, much attention has been devoted to optimizing the membrane/electrode assembly that constitute the fuel cell core. The electrodes consist of carbon black supporting Pt nanoparticles and Nafion as the ionomer binder. Although the ionomer plays a crucial role as ionic conductor through the electrode, little is known about its distribution inside the electrode. Here we report the three-dimensional morphology of the Nafion thin layer surrounding the carbon particles, which is imaged using electron tomography. The analyses reveal that doubling the amount of Nafion in the electrode leads to a twofold increase in its degree of coverage of the carbon, while the thickness of the layer, around 7 nm, is unchanged.

3 D Characterization of Gold Nanoparticles Supported on Heavy Metal Oxide Catalysts by HAADF‐STEM Electron Tomography

Living on the edge: Three-dimensional reconstructions from electron tomography data recorded from Au/Ce(0.50)Tb(0.12)Zr(0.38)O(2-x) catalysts show that gold nanoparticles (see picture; yellow) are preferentially located on stepped facets and nanocrystal boundaries. An epitaxial relationship between the metal and support plays a key role in the structural stabilization of the gold nanoparticles.

Synthesis, Internal Structure, and Formation Mechanism of Monodisperse Tin Sulfide Nanoplatelets

Tin sulfide nanoparticles have a great potential for use in a broad range of applications related to solar energy conversion (photovoltaics, photocatalysis), electrochemical energy storage, and thermoelectrics. The development of chemical synthesis methods allowing for the precise control of size, shape, composition, and crystalline phase is essential. We present a novel approach giving access to monodisperse square SnS nanoplatelets, whose dimensions can be adjusted in the range of 4-15 nm (thickness) and 15-100 nm (edge length). Their growth occurs via controlled assembly of initially formed polyhedral seed nanoparticles, which themselves originate from an intermediate tetrachlorotin-oleate complex. The SnS nanoplatelets crystallize in the α-SnS orthorhombic herzenbergite structure (space group Pnma) with no evidence of secondary phases. Electron tomography, high angle annular dark field scanning transmission electron microscopy and electron diffraction combined with image simulations evidence the presence of ordered Sn vacancy rich (100) planes within the SnS nanoplatelets, in accordance with their slightly S-rich composition observed. When using elemental sulfur instead of thioacetamide as the sulfur source, the same reaction yields small (2-3 nm) spherical SnS2 nanoparticles, which crystallize in the berndtite 4H crystallographic phase (space group P3m1). They exhibit quantum confinement (E(g) = 2.8 eV vs 2.2 eV in the bulk) and room temperature photoluminescence. By means of electrochemical measurements we determined their electron affinity EA = -4.8 eV, indicating the possibility to use them as a substitute for CdS (EA = -4.6 eV) in the buffer layer of thin film solar cells.

Beyond conventional electrocatalysts: hollow nanoparticles for improved and sustainable oxygen reduction reaction activity

Long-term catalytic performance of electrode materials is a well-established research priority in electrochemical energy conversion and storage systems, such as proton-exchange membrane fuel cells. Despite extensive efforts in research and development, Pt-based nanoparticles remain the only – but an unstable – electrocatalyst able to accelerate efficiently the rate of the oxygen reduction reaction. This paper describes the synthesis and the atomic-scale characterization of hollow Pt-rich/C nanocrystallites, which achieve 4-fold and 5-fold enhancement in specific activity for the oxygen reduction reaction over standard solid Pt/C nanocrystallites of the same size in liquid electrolyte and during real proton-exchange membrane fuel cell (PEMFC) testing, respectively. More importantly, the hollow nanocrystallites can sustain this level of performance during accelerated stress tests, therefore opening new perspectives for the design of improved PEMFC cathode materials.

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

Chemical Imaging at Atomic Resolution as a Technique To Refine the Local Structure of Nanocrystals

The challenging problem of mapping the chemical composition of cation columns in individual nanocrystals at atomic resolution is addressed by using a method based on aberration-corrected electron microscopy, core-loss electron energyloss spectroscopy, and simulations. The potential of this novel approach to provide unique structural information, which is the key to rationalizing macroscopic behavior, is illustrated with the analysis of ceria–zirconia mixed oxides, which are nanomaterials with substantial technological impact. Metal nanoparticles supported on this family of oxides are currently materials of interest as catalysts in a variety of chemical transformations in the area of environmental protection, such as low-temperature water-gas shift, selective oxidation of CO in the presence of large amounts of hydrogen, or three-way catalysis. Strong variations in the chemistry of ceria–zirconia mixed oxide catalysts have been observed after they have undergone redox cycles involving reduction treatments at high temperatures ( 1173 K) then oxidation at mild temperatures ( 823 K). In particular their reducibility is significantly enhanced after such aging treatments. Scanning transmission electron microscopy (STEM) techniques have provided crucial information to account for these changes in the redox behavior. High-resolution electron microscopy (HREM) combined with high-angle annular dark-field (HAADF) imaging and tomography have revealed the occurrence of a disorder–order transformation in the cationic sublattice of these oxides, which tend to rearrange into a distribution characteristic of the so called pyrochlore phase. This phase is an archetype structure for A2B2O7 (A= + 3 cation, B=+ 4 cation) compounds and can be considered a fluorite superstructure. The structural transformation takes place during the reduction step of the cycle, in which the fully reduced mixed oxide with Ce/Zr molar ratio 1:1 adopts the Ce2Zr2O7 stoichiometry. Nevertheless, HAADF studies have clearly shown that, in the case of ceria–zirconia mixed oxides, this cation-ordered arrangement is preserved even after full reoxidation, that is, in the oxide with Ce2Zr2O8 stoichiometry, whenever the oxidation temperature does not exceed 823 K. Electron-microscopy studies have also revealed another remarkable feature of the ceria–zirconia aged oxides with the pyrochlore-type cation sublattice: the occurrence of compositional heterogeneities at the nanometer scale. Taking these observations into account and also considering that the disorder–order transition may not be completed in the time scale and under the temperature conditions used in the redox-cycling treatments, the important question arises whether these heterogeneities are in fact occurring on a finer scale, that is, at the atomic level. Such heterogeneities, compatible with the HREM and HAADF observations, will strongly influence the details of the counterpart oxygen sublattice and, consequently, the chemical and catalytic response of these oxides. To date, the atomic-column by atomic-column compositional analysis of the oxidized pyrochlore required to justify such a possibility has not been accomplished. Herein, using the capabilities of an aberration-corrected Nion UltraSTEM microscope (operated at 100 kV) we not only provide the first direct chemical evidence of the cationic order present in the Ce2Zr2O8 oxidized pyrochlore but we also show how atomicresolution electron energy-loss spectroscopy (EELS) mapping, based on core–shell ionization, can be combined with EELS image simulation to detect quite subtle local deviations in the cation sublattice from the completely ordered structure. This information provides a much more accurate structural description of the active catalyst nanocrystals, which must be considered to model both their oxygen-exchange capabilities and, eventually, their catalytic performance. [*] Dr. S. Trasobares, Dr. M. L pez-Haro, Dr. J. A. Perez-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)956-016286 E-mail: susana.trasobares@uca.es Homepage: http://www.uca.es/tem-uca

Imaging nanostructural modifications induced by electronic metal-support interaction effects at Au||cerium-based oxide nanointerfaces.

A variety of advanced (scanning) transmission electron microscopy experiments, carried out in aberration-corrected equipment, provide direct evidence about subtle structural changes taking place at nanometer-sized Au||ceria oxide interfaces, which agrees with the occurrence of charge transfer effects between the reduced support and supported gold nanoparticles suggested by macroscopic techniques. Tighter binding of the gold nanoparticles onto the ceria oxide support when this is reduced is revealed by the structural analysis. This structural modification is accompanied by parallel deactivation of the CO chemisorption capacity of the gold nanoparticles, which is interpreted in exact quantitative terms as due to deactivation of the gold atoms at the perimeter of the Au||cerium oxide interface.