The Role of the Ferroelectric Polarization in the Enhancement of the Photocatalytic Response of Copper-Doped Graphene Oxide-TiO2 Nanotubes through the Addition of Strontium.

To evaluate the potential role of in situ formed Sr-Ti-O species as a ferroelectric component able to enhance the photocatalytic properties of an adjacent TiO2 semiconductor, Cu-doped/graphene oxide (GO)/TiO2 nanotubes (TiNTs) composites (with 0.5 wt % Cu and 1.0 wt % GO) have been synthesized while progressive amounts of strontium (up to 1.0 wt %) were incorporated at the surface of the composite through incipient wetness impregnation followed by post-thermal treatment at 400 °C. The different resulting photocatalytic systems were then first deeply characterized by means of N2 adsorption-desorption measurements, X-ray diffraction (XRD), UV-vis diffuse reflectance (UV-vis DR), Raman and photoluminescence (PL) spectroscopies, and scanning electron microscopy (SEM) (with energy-dispersive X-ray (EDX) spectroscopy and Z-mapping). In a second step, optimization of the kinetic response of the Sr-containing composites was performed for the formic acid photodegradation under UV irradiation. The Sr-containing Cu/GO/TiNT composites were then fully characterized by electrochemical impedance spectroscopy (EIS) for their dielectric properties showing clearly the implication of polarization induced by the Sr addition onto the stabilization of photogenerated charges. Finally, a perfect correlation between the photocatalytic kinetic evaluation and dielectric properties undoubtedly emphasizes the role of ferroelectric polarization as a very valuable approach to enhance the photocatalytic properties in an adjacent semiconductor.

Understanding and controlling the structure and segregation behaviour of AuRh nanocatalysts.

Heterogeneous catalysis, which is widely used in the chemical industry, makes a great use of supported late-transition-metal nanoparticles, and bimetallic catalysts often show superior catalytic performances as compared to their single metal counterparts. In order to optimize catalyst efficiency and discover new active combinations, an atomic-level understanding and control of the catalyst structure is desirable. In this work, the structure of catalytically active AuRh bimetallic nanoparticles prepared by colloidal methods and immobilized on rutile titania nanorods was investigated using aberration-corrected scanning transmission electron microscopy. Depending on the applied post-treatment, different types of segregation behaviours were evidenced, ranging from Rh core - Au shell to Janus via Rh ball - Au cup configuration. The stability of these structures was predicted by performing density-functional-theory calculations on unsupported and titania-supported Au-Rh clusters; it can be rationalized from the lower surface and cohesion energies of Au with respect to Rh, and the preferential binding of Rh with the titania support. The bulk-immiscible AuRh/TiO2 system can serve as a model to understand similar supported nanoalloy systems and their synergistic behaviour in catalysis.

Au-Rh and Au-Pd nanocatalysts supported on rutile titania nanorods: structure and chemical stability.

Au, Rh, Pd, Au-Rh and Au-Pd nanoparticles (NPs) were synthesized by colloidal chemical reduction and immobilized on hydrothermally-prepared rutile titania nanorods. The catalysts were characterized by aberration-corrected TEM/STEM, XPS, and FTIR, and were evaluated in the hydrogenation of tetralin in the presence of H2S. Oxidizing and reducing thermal treatments were employed to remove the polyvinyl alcohol (PVA) surfactant. Reduction in H2 at 350 °C was found efficient for removing the PVA while preserving the size (ca. 3 nm), shape and bimetallic nature of the NPs. While Au-Pd NPs are alloyed at the atomic scale, Au-Rh NPs contain randomly distributed single-phase domains. Calcination-reduction of Au-Rh NPs mostly leads to separated Au and Rh NPs, while pre-reduction generates a well-defined segregated structure with Rh located at the interface between Au and TiO2 and possibly present around the NPs as a thin overlayer. Both the titania support and gold increase the resistance of Rh and Pd to oxidation. Furthermore, although detrimental to tetralin hydrogenation initial activity, gold stabilizes the NPs against surface sulfidation in the presence of 50 ppm H2S, leading to increased catalytic performances of the Au-Rh and Au-Pd systems as compared to their Rh and Pd counterparts.

In-situ HRTEM study of the reactive carbide phase of Co/MoS2 catalyst.

Hydrotreatment catalytic operations are commonly performed industrially by layered molybdenum sulfide promoted by cobalt or nickel in order to remove heteroelements (S, N, O) from fossil fuels and biofuels. Indeed, these heteroelements are responsible of the emission of pollutants when these fuels are used in vehicles. In this respect, previous studies made by our research group have shown that the active phase under steady state conditions is partially carbided while strong bending effects of MoS2 slabs were also observed. However, up to now, the morphology of the resulting Co/MoSxCy carbided catalyst has not been fully characterized. In the present study, for the first time, a chemical reaction between the carbon content of a TEM Cu/C grid and a freshly sulfide Co/MoS2 catalyst was in situ observed at 300 °C and 450 °C by HRTEM experimental techniques at ~10 nm of resolution. Results indicate that bending of MoS2 layers occurred due to carbon addition on MoS2 edge sites, as observed in stabilized catalysts after HDS reaction. Using a silicon grid, only cracks of MoS2 slabs were observed without bending effect confirming the role of structural-carbon in this change of morphology.

One-pot deposition of palladium on hybrid TiO2 nanoparticles and catalytic applications in hydrogenation.

One-pot deposition of Pd onto TiO(2) has been achieved through directly contacting palladium(II) salt with nanosized functionalized TiO(2) support initially obtained by sol-gel process using titanium isopropoxide and citric acid. Citrate groups act as functional moieties able to directly reduce the Pd salt avoiding any further reducing treatment. Various palladium salts (Na(2)PdCl(4) and Pd(NH(3))(4)Cl(2)·H(2)O) and titanium to citrate (Ti/CA) ratios (20, 50, and 100) were used in order to study the effect of the nature of the precursor and of the citrate content on the final Pd particle size and catalytic properties of the as-obtained Pd/TiO(2) systems. Characterization was performed using N(2) adsorption-desorption isotherms, ICP-AES, FTIR, XRD, XPS, and TEM. The as-obtained hybrid Pd/TiO(2) catalysts were tested in the selective hydrogenation (HYD) of an α,ß-unsaturated aldehyde, i.e. cinnamaldehyde. Citrate-free Pd/TiO(2)-based catalysts present lower selectivity into saturated alcohol. However, citrate-functionalized Pd/TiO(2) catalyst seems to control the selectivity, the particle size and dispersion of Pd NPs leading to high intrinsic activity.

In situ XRD, XAS, and magnetic susceptibility study of the reduction of ammonium nickel phosphate NiNH4PO4 x H2O into nickel phosphide.

The reduction of the ammonium nickel phosphate NiNH(4)PO(4) x H(2)O precursor into nickel phosphide (Ni(2)P), a highly active phase in hydrotreating catalysis, was studied using a combination of magnetic susceptibility and in situ X-ray diffraction and X-ray absorption spectroscopy (XAS) techniques. The transformation of NiNH(4)PO(4) x H(2)O into Ni(2)P could be divided into three distinguishable zones: (1) from room temperature to 250 degrees C, the NiNH(4)PO(4) x H(2)O structure was essentially retained; (2) from 300 to 500 degrees C, only an amorphous phase was observed; (3) above 500 degrees C, a crystallization process occurred with the formation of Ni(2)P. An in situ XAS study and magnetic susceptibility measurements clearly revealed for the first time that the amorphous region corresponds to the nickel pyrophosphate phase alpha-Ni(2)P(2)O(7). The phosphate reduction into phosphide did not start before 550 degrees C and led to the selective formation of Ni(2)P at 650 degrees C.

Study of Pd(II) adsorption over titanate nanotubes of different diameters.

Hydrogenotitanates (HNTs) nanotubes with different diameters were prepared by hydrothermal treatment of TiO(2) (P25) followed by washing with HCl aqueous solution. The prepared samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, thermal analysis and N(2) adsorption/desorption. In order to determine the palladium uptake ability of different HNT samples, the interaction between HNTs and Pd(II) was subsequently studied in aqueous solution at pH 9 (NH(+)(4)/NH(3) buffer). Transmission electron microscopy showed that the diameter of the nanotubes depends on the preparation conditions. Chemical analysis of residual sodium and thermal studies showed that the chemical formula of the two prepared HNT was H(x)Na(2-x)Ti(2)O(5)H(2)O with x=1.61 or 1.65. The HNTs are mesoporous materials with a multi-walled nanotubular structure and high specific surface area. In order to determine the capacity of palladium retention of different HNTs samples, the interaction between HNTs and Pd(II) was subsequently studied in aqueous solution at pH 9 (NH(+)(4)/NH(3) buffer). The adsorption kinetics of Pd(II) on the HNTs was very fast. The isotherms of Pd(II) on the HNTs showed that the adsorption occurred (1) initially through cationic exchange and (2) when the concentration of Pd(II) is high by precipitation of different Pd salts. The adsorption capacity of Pd(II) is strongly altered by the morphology of the HNTs samples.

Tuning the shape of nanoparticles to control their catalytic properties: selective hydrogenation of 1,3-butadiene on Pd/Al2O3.

Shape-controlled Pd nanoparticles supported on powder alumina are more efficient for selective butadiene hydrogenation to butene when they exhibit high fractions of (111) facets.

Synchrotron and simulations techniques applied to problems in materials science: catalysts and Azul Maya pigments.

Development of synchrotron techniques for the determination of the structure of disordered, amorphous and surface materials has exploded over the past 20 years owing to the increasing availability of high-flux synchrotron radiation and the continuing development of increasingly powerful synchrotron techniques. These techniques are available to materials scientists who are not necessarily synchrotron scientists through interaction with effective user communities that exist at synchrotrons such as the Stanford Synchrotron Radiation Laboratory. In this article the application of multiple synchrotron characterization techniques to two classes of materials defined as 'surface compounds' is reviewed. One class of surface compounds are materials like MoS(2-x)C(x) that are widely used petroleum catalysts, used to improve the environmental properties of transportation fuels. These compounds may be viewed as 'sulfide-supported carbides' in their catalytically active states. The second class of 'surface compounds' are the 'Maya blue' pigments that are based on technology created by the ancient Maya. These compounds are organic/inorganic 'surface complexes' consisting of the dye indigo and palygorskite, common clay. The identification of both surface compounds relies on the application of synchrotron techniques as described here.