Catalysts based on combinations between copper and cerium oxides are analyzed with respect to their catalytic properties for preferential oxidation of CO in a H2-rich stream (CO-PROX) by means of DRIFTS, XANES, and Raman under Operando conditions. The results allow analyzing entities/species responsible for the CO and H2 oxidation reactions taking place during the CO-PROX process. While CO oxidation takes place at copper oxide support interfacial sites and its activity correlates with the degree of reduction achieved on the dispersed copper oxide particles, H2 oxidation apparently proceeds when a massive copper oxide reduction occurs. This opens the possibility to modulate the catalytic behavior of these types of catalysts by acting, respectively, on the interfacial redox properties and on the dispersed copper oxide redox properties.

Understanding and improving the behaviour of supported precious-metal catalysts for a vast array of environmentally and economically important processes is a central area of research in catalysis. The removal of toxic gases such as CO and NO, without forming others (such as N(2)O), is particularly important. By combining energy-dispersive extended X-ray absorption fine-structure spectroscopy with a vibrational spectroscopy (infrared) and mass spectrometry, at high time resolution, in a single in situ experiment, we dynamically observe and quantify CO-, and subsequent NO-, induced size and shape changes of Pd nanoparticles during CO/NO cycling. In doing so we demonstrate a novel, non-oxidative redispersion (for example, an increase in metal surface area) mechanism, and suggest a model to bridge the structural and reactive functions of supported Pd catalysts.

No abstract

N-containing TiO(2)-based nanostructured materials (average particle size approximately 10 nm) with an anatase-type structure were investigated using oxygen (O) K-edge and titanium (Ti) K- and L-edge X-ray absorption near-edge spectroscopy (XANES). The Ti K pre-edge features indicate that samples predominantly contain ([6])Ti with some ([5])Ti, and there is no evidence for ([4])Ti. We observed that those samples with a larger fraction of Ti in a fivefold coordination, that is, with a significant number of oxygen vacancies, also present a modified Ti environment at the medium-range scale. The presence of these defects drastically modifies the electronic structure of the conduction band, as evidenced by the O K XANES spectra, but does not result in the presence of reduced Ti(3+) states. We discuss the influence of N-doping on titania nanoparticles and their structure, electronics and photocatalytic activity.

Four metakaolins were prepared by calcination of a natural Spanish kaolin (Navalacruz deposit, Zamora province) at 600, 700, 800, and 900 °C. These four metakaolins, more reactive than the parent kaolin, were submitted to acid and alkaline activations. Acid activation was carried out with 6 M HCl at room temperature and at 90 °C under reflux conditions, with times of treatment of 6 and 24 h. Treatment at room temperature did not produce any alteration in the structure or in the properties of the metakaolins. Treatment under reflux conditions for 6 h led to the removal of most of the octahedral Al 3+ cations, and the formation of an amorphous silica phase, with surface area up to 219 m 2 /g, because of a high development of both the internal and the external surface of the solids. Acid treatment under stronger conditions (reflux, 24 h) also removed the octahedral cations, but provoked an amorphization of the silica obtained (S ≈ 23 m 2 /g). The metakaolin prepared by calcination at 900 °C showed a lower reactivity than those synthesized at the other temperatures considered. The alkaline treatments were carried out with 1 M and 5 M KOH solutions, the treatments with the concentrated solution, both at room temperature and, especially, under reflux, led to the dissolution of the metakaolins and to the formation of well-crystallized K-F zeolite. The solids obtained by acid treatments are promising as adsorbents and catalyst supports, while treatment in alkaline conditions may be a good method for preparing K-F zeolite.

No abstract

Nanoparticulated TiO2 materials with anatase structure were synthesized by using a microemulsion method. Three different syntheses with varying surfactant-to-water molar ratio (ω) were used to obtain amorphous solid precipitates at room temperature. The structural characteristics of these solid precursors were studied by using X-ray absorption structure (X-ray absorption near-edge structure and extended X-ray absorption fine structure) and Raman spectroscopies, which showed that all lack 3D (tridimensional) order but contain a different degree of 2D-confined connectivity. While heating such solid precursors under dry air, marked differences appeared in the phase behavior; the onset temperature for anatase crystallization increases ca. 150 °C while the ω parameter decreases and only one of the samples shows the anatase-to-rutile transformation below 900 °C. In all cases, the crystallization of the anatase structure does not follow a traditional nucleation and growth mechanism and its analysis using the Avrami formalism gives conclusive evidence of a surface nucleation-dominated process. This appears as a distinctive feature of anatase-TiO2 nanomaterials, far from the corresponding behavior of microsized or bulk materials. After nucleation, the grain growth of anatase nanoparticles was found to follow the kinetic equation D 2 − D 0 2 = k 0 exp(−E a/RT), where the activation energy is a function of several structural properties of the solid materials mainly related to the hydration characteristics of the surface layer. A combined in situ X-ray diffraction/Raman/infrared study aimed to unveil the physical basis of the phase behavior and to interpret key variables allowing control of the crystallization mechanism and morphological properties, particularly primary particle size, in the nanometer regime.

This review analyzes the preparation and characterization of metal organic frameworks (MOFs) and their application as photocatalysts for water purification. The study begins by highlighting the problem of water scarcity and the different solutions for purification, including photocatalysis with semiconductors, such as MOFs. It also describes the different methodologies that can be used for the synthesis of MOFs, paying attention to the purification and activation steps. The characterization of MOFs and the different approaches that can be followed to learn the photocatalytic processes are also detailed. Finally, the work reviews literature focused on the degradation of contaminants from water using MOF-based photocatalysts under light irradiation.