A PVA-assisted hydrothermal synthesis route was utilized to fabricate single-phase Bi25FeO40 crystallites.X-ray diffraction results indicated that sillenite Bi25FeO40 have been synthesized at the temperature of 200 ℃ using the KOH concentration of 7 M. Scanning electron microscopy showed the morphology of the as-prepared products were cubic shape with side length of 26μm. The band gap of Bi25FeO40 was determined to be 1.8 eV (688 nm) by using UV-vis diffuse reflectance spectroscopy. It was found that Bi25FeO40 exhibited a high photocatalytic activity for the degradation of methyl orange under UV-Vis irradiation, being a potential material for photocatalytic decomposition of organic contaminants.

In the preparation of zeolite nanocrystals from the hydrothermal reaction of clear solution, the zeolite products are typically collected by high speed centrifugation. For Beta zeolite, the crystalline yield is often low, thus a good fraction of silicates reminds in the supernatant. These XRD amorphous materials turn out to be uniform nanoparticles that, after calcination, showed similar micropore structure as that of the collected beta zeolite nanocrystals. TPD measurements of hexane isomers further indicated that both the crystalline and the amorphous products were more selective toward the smaller hexane molecule.

Ordered mesoporous silicas continue to find widespread use as supports for diverse applications such as catalysis, separations, and sensors. They provide a versatile platform for these studies because of their high surface area and the ability to control pore size, topology, and surface properties over wide ranges. Furthermore, there is a diverse array of synthetic methodologies for tailoring the pore surface with organic, organometallic, and inorganic functional groups. In this paper, we will discuss two examples of tailored mesoporous silicas and the resultant impact on chemical reactivity. First, we explore the impact of pore confinement on the thermochemical reactivity of phenethyl phenyl ether (PhCH2CH2OPh, PPE), which is a model of the dominant β-aryl ether linkage present in lignin derived from woody biomass. The influence of PPE surface immobilization, grafting density, silica pore diameter, and presence of a second surface-grafted inert “spacer” molecule on the product selectivity has been examined. We will show that the product selectivity can be substantially altered compared with the inherent gas-phase selectivity. Second, we have recently initiated an investigation of mesoporous silica supported, heterobimetallic oxide materials for photocatalytic conversion of carbon dioxide. Through surface organometallic chemistry, isolated M-O-M’ species can be generated on mesoporous silicas that, upon irradiation, form metal to metal charge transfer bands capable of converting CO2 into CO. Initial results from studies of Ti(IV)-O-Sn(II) on SBA-15 will be presented.

Experiments on the reactivity of CO for Au nanoclusters have shown a local maximum in the adsorption of the first molecule for Au18 and its cation, whereas O2 adsorption has been observed in Au18-1. In this work we present a theoretical analysis of the preferential sites for the adsorption of the CO and O2 molecules on neutral and single ionized Au18 clusters with C2v symmetry, which has been shown both theoretical and experimentally, to be the most stable isomer of the Au18 cluster. We report the results of the calculation for the binding energies of CO and O2 for non-equivalent sites and compare with the available experimental values. The oxidation mechanism is studied in first instance by the subsequent adsorption of the CO on the O2 molecule, which was previously adsorbed on the respective gold cluster. The study is based on a DFT-GGA calculation with the PW91 functional.

We have prepared a number of Pt-TM(transition metals) alloys with various TM elements and evaluated their catalytic abilities by means of hydrogenation of methyl acrylate. High catalytic activities are obtained when the crystalline structures are similar, i.e., fcc structure, indicating that the crystal structure of a catalyst plays an important role in hydrogenation of methyl acrylate. Furthermore, for a certain TM element, i.e., Mo, the catalytic activity is found to surpass that of Pt metal.

Heterogeneous catalysis is a field of major interest in the surface science and development of new supported model catalysts with a narrow size distribution. The possibility to create narrow size distributions is to use the faceted surface structures as self assembled templates on which metal nanoclusters can grow. In the present study, new aspects of adsorbate induced faceting and nanoscale phenomena on adsorbate-covered metallic surfaces are studied on atomically-rough morphologically unstable metallic fcc (Rh) and hcp (Re) surfaces. Formation of oxygen induced faceting of atomically-rough Rh (210) surface has been studied and characterized by means of LEED, STM and AES. The LEED studies confirm the formation of three sided faceted (nanoscale pyramidal structure) Rh(210) surface when the oxygen covered Rh surface annealed to temperature higher than 550K. The facet orientations of the nanopyramid are characterized as two {731} face and a reconstructed (110) face. The excess oxygen overlayer can be removed from pyramidal faceted Rh(210) surface via catalytic reaction at low temperature using CO oxidation or H2 reaction while preserving the pyramidal structure. The average size of the nanopyramids is observed to be dependent on annealing temperature and vary from 12nm to 21nm. The atomically resolved STM images confirm the LEED observations and also revealed that (110) face of nanopyramids exhibits various reconstructions (1×n, n = 2-4) depending on oxygen coverage. Further, oxygen induced nanoscale faceted Re (12-31) surface has been formed which consist of nano-trenches (two sided ridges) with facets in (11-21) and (01-10) direction. These two- sided faceted Re (12-31) surface is used as a template to grow gold nanostructures. Under controlled growth conditions, the gold induced nanostructures are formed on oxygen induced nano-trenched Re (12-31) surface. It is observed that gold grows in the form of islands on the faceted rhenium substrate i.e. at lower coverages (≥0.8ML), it forms 2D islands whereby for higher coverages 3D islands are formed on top of the nano-ridges. The surfaces morphology of the gold covered faceted Re surface changes drastically on annealing, for the temperature >870 K, gold atoms wet the rhenium template while annealing to higher temperature (˜970K) led to the development of a three sided nanopyramids. On further annealing to higher temperatures (>1100K) cause the complete destruction of the faceted structure. LEED and STM studies revealed that the gold induced three sided nanopyramids consists of two faces of original two sided ridges with (11-20), (01-10) orientation and an additional facet in (12-32) direction. The high resolution STM images revealed that the (12-32) facet of the nanopyramid is fully decorated with single atomic zigzag gold nanochain. These faceted surfaces can be potential template for heterogeneous catalysis and development of new supported model catalysts with a narrow size distribution.

Nanocomposite cermet materials comprised of NiO/YSZ (20-90 wt. %) co-promoted with SmPrCeZrO or LaPrMnCrO complex oxides and Pt, Pd or Ru were synthesized by Pechini method. These materials were characterized by BET, TEM with EDX, and CH4 TPR. The catalytic properties were studied for the steam reforming (SR) of CH4 at short contact times. Factors controlling performance of these composites in CH4 SR (Ni content, interaction between components in composites as dependent upon their chemical composition) were determined. Ru-promoted composite supported on Ni-Al foam demonstrated a high (up to 75%) methane conversion at 650° in the feed containing 20% CH4 and 40% H2O in Ar

Bimetallic nanoparticles of PtCu and PtNi supported on iron oxide particles were synthesized by a new method employing a 4.8-MeV electron beam as a trigger for reduction of their aqueous ions, and their CO oxidation catalysis was evaluated to find activities enhanced by the alloying. Sample materials of PtCu (PtNi) bimetallic grains supported on γ-Fe2O3 particles were synthesized by irradiating with the electron beam a glass vial containing precursors in an aqueous solution. The vial contains aqueous ions of platinum and copper (nickel) and γ-Fe2O3 particles of average size of 30 nm. The irradiation induces water radiolysis generating reducing species, such as hydrated electrons, and metallic nanograins are formed and stabilized on the support material. The irradiation was finished in several seconds without using any organic solvent and any surfactant. The average grain sizes observed with a TEM were around 3 nm in diameter. XRD patterns of PtCu samples exhibited the FCC structure with peak shifts obeying the Vegard’s law at low Cu concentrations. X-ray absorption spectra measured at edges of the constituent elements indicated that Pt is in the metallic state and coordinates certainly with Cu or Ni. Catalytic activity of CO oxidation of the material was evaluated by measuring residual CO contents in air in contact with the sample material by using a gas-chromatograph. The activities of the PtCu and PtNi samples were higher than that of monolithic Pt on γ-Fe2O3. The correlation between the atomic structure in these nanograins and their activities was investigated, which indicated that the random alloy enhances the activity. These bimetallic nanoparticles are expected as catalysts for preferential oxidation of CO in hydrogen gas fed to fuel cells.

It has been shown that Au and Ag nanoparticles present catalytic properties of pollutant gases, product of the hydrocarbons combustion processes, whose efficiency is strongly dependant on their size, morphology and supporting material. The activity of Ag subnanometric particles supported on alumina in the NOx reduction mechanism, for the reaction HC-SCR (Hydrocarbon Selective Catalytic Reaction) is a good example of these catalytic properties. It is also well established that both Au and Ag nanoparticles are oxygen poisoning resistant and that in certain reactions the bimetallic combination may be more efficient than their isolated parts. In this work we present a DFT calculation of the NOx (x =1, 2, 3) adsorption energies on the Au12Ag6 cluster surface. It is also discussed the possible synergetic effect of the different configurations, forming small Ag islands composed of one to five atoms, on the surface of the bimetallic cluster. The analysis was done using DFT in the ZORA approximation.

High-quality Pt-Cu nanocubes were prepared through simultaneous reduction of platinum (II) acetylacetonate and copper II) acetylacetonate in 1-octadecene by 1,2–tetradecanediol in the presence of tetraoctylammonium bromide, oleylamine, and 1-dodecanethiol. The growth process of Pt-Cu nanocubes was explored based on the observation of intermediates. The electrocatalytic behavior indicates that cubic Pt-Cu nanocrystals are more active than spherical Pt-Cu nanocrystals and Pt nanocrystals towards methanol oxidation reaction.

Silver nanoparticles having different size and plasmon resonances were synthesized through a single step aqueous based method. The current procedure was based on the reduction of silver ions by ascorbic acid in the presence of sodiumborohydride and trisodium citrate. Triangular colloidal nanoparticles having different plasmon resonances (and hence different size and colours) were synthesized by varying only the concentration of ascorbic acid. These nanoparticles were found to be stable without using any surfactants or polymers. This study revealed a strong correlation between particle growth and concentration of constituent chemicals. Crystallinity and phase purity of the silver samples were investigated through powder X-ray diffraction studies (XRD). Absorption spectra of various silver particles were recorded using UV/Vis/NIR spectrometer. Morphological analysis was performed using transmission electron microscopy (TEM) and average edge lengths of nanoparticles were also calculated.

The synthesis of ceria nanoparticles using an inverse microemulsion technique and precipitation method was investigated. Ceria nanoparticles were synthesized by adding diluted ammonia to a microemulsion consisting of n-heptane, Marlophen NP5 and cerium nitrate. The micelle and particle size were adjustable in the range of 5-12nm by varying the molar ratio of water to surfactant and analyzed by dynamic light scattering (DLS), small angle X-ray scattering (SAXS) and high-resolution transmission electron microscopy (HRTEM). After isolation through precipitation, the nanoparticles were subsequently treated at 100-600 °C. The catalytic activity of particles annealed at 400 and 600 °C were tested in soot combustion reactions and characterized by temperature-programmed oxidation (TPO) indicating a size-dependant activity. To prevent the nanoparticles from aggregation, the microemulsion technique was adopted to integrate the nanoparticles homogeneously into a mesoporous SiC matrix through the use of a preceramic polymer. The obtained composite material was also tested in soot combustion reactions.

Heterogeneous catalysts consisting of nanoparticles dispersed on an oxide support are a mainstay in industrial reactions, and are often made via thermal reduction of metal salts dispersed onto a pre-synthesized support. Herein we document a route towards the design of xerogel-supported nanoparticle catalysts by trapping compositionally-tuned polymer-stabilized nanoparticle precursors into sol-gel matrices. Such a route allows in principle for the tuning of the size, composition, architecture, and electronic properties of nanoparticle catalysts, which allows for the development of highly efficient and selective catalysts. As proof of concept we detail the synthesis of co-reduced PdAu nanoparticles in titania supports. The final materials are well-characterized by HRTEM and energy dispersive spectroscopy (EDS), which confirm the compositional uniformity of the nanoparticles. The importance of controlling calcination conditions in order to retain designed nanoparticle compositions is stressed; high temperature calcination conditions lead to a large degree of sintering and loss of compositional uniformity, while mild calcination temperatures can be used to retain nanoparticle compositions and sizes.