Surface science studies of strong metal-oxide interactions on model catalysts

The strong metal support interaction (SMSI) was first described in 1978 by Tauster [1-4]. The effect was observed as a severely negative effect on CO and H2 uptake on the catalyst after high temperature calcination under reducing conditions (heating above ~ 700 K) [1,2]. It also had a negative effect on the reaction rate for reactions, such as alkane hydrogenolysis [5,6]. It appeared that the effect occurred for catalysts comprised of reducible supports which were treated at elevated temperature in reducing conditions [2-4]. A classic support which has manifested this behaviour in many studies is TiO2. Over the years following the first discovery of SMSI it has been recognised that the effect is not always negative – for instance for the CO-H2 reaction for which it appears to have a positive effect [5,6]. Further it was noted that hydrogen reduction was not necessary to observe the effect of CO adsorption suppression, it also occurs by vacuum treatment [7], though it should be noted that vacuum treatment at elevated temperature is, in effect, a reducing environment.

Predicting the orientation of lipid cubic phase films

Lipid cubic phase films are of increasingly widespread importance, both in the analysis of the cubic phases themselves by techniques including microscopy and X-ray scattering, and in their applications, especially as electrode coatings for electrochemical sensors and for templates for the electrodeposition of nanostructured metal. In this work we demonstrate that the crystallographic orientation adopted by these films is governed by minimization of interfacial energy. This is shown by the agreement between experimental data obtained using grazing-incidence small-angle X-ray scattering (GI-SAXS), and the predicted lowest energy orientation determined using a theoretical approach we have recently developed. GI-SAXS data show a high degree of orientation for films of both the double diamond phase and the gyroid phase, with the [111] and [110] directions respectively perpendicular to the planar substrate. In each case, this matches the lowest energy facet calculated for that particular phase.

Catalyst

A water gas shift catalyst comprising metal particles and a metal oxide material is disclosed. The metal particles comprise at least one precious metal and the metal oxide material comprises at least one reducible metal oxide. Substantially all of the metal particles are encapsulated by the metal oxide material such that the catalyst has substantially no activity for methanation. The loading of the metal particles is between 0.5-25wt% based on the weight of the metal oxide material. A process for preparing the catalyst is also disclosed.

Aligned platinum nanowire networks from surface-oriented lipid cubic phase templates

Mesoporous metal structures featuring a bicontinuous cubic morphology have a wide range of potential applications and novel opto-electronic properties, often orientation-dependent. We describe the production of nanostructured metal films 1–2 microns thick featuring 3D-periodic ‘single diamond’ morphology that show high out-of-plane alignment, with the (111) plane oriented parallel to the substrate. These are produced by electrodeposition of platinum through a lipid cubic phase (QII) template. Further investigation into the mechanism for the orientation revealed the surprising result that the QII template, which is tens of microns thick, is polydomain with no overall orientation. When thicker platinum films are grown, they also show increased orientational disorder. These results suggest that polydomain QII samples display a region of uniaxial orientation at the lipid/substrate interface up to approximately 2.8 ± 0.3 μm away from the solid surface. Our approach gives previously unavailable information on the arrangement of cubic phases at solid interfaces, which is important for many applications of QII phases. Most significantly, we have produced a previously unreported class of oriented nanomaterial, with potential applications including metamaterials and lithographic masks.

Non-stoichiometric oxide and metal interfaces and reactions

We have employed a combination of experimental surface science techniques and density functional calculations to study the reduction of TiO2(110) surfaces through the doping with submonolayer transition metals. We concentrate on the role of Ti adatoms in self doping of rutile and contrast the behaviour to that of Cr. DFT+U calculations enable identification of probable adsorption structures and their spectroscopic characteristics. Adsorption of both metals leads to a broken symmetry and an asymmetric charge transfer localised around the defect site of a mixed localised/delocalised character. Charge transfer creates defect states with Ti 3d character in the band gap at similar to 1-eV binding energy. Cr adsorption, however, leads to a very large shift in the valence-band edge to higher binding energy and the creation of Cr 3d states at 2.8-eV binding energy. Low-temperature oxidation lifts the Ti-derived band-gap states and modifies the intensity of the Cr features, indicative of a change of oxidation state from Cr3+ to Cr4+. Higher temperature processing leads to a loss of Cr from the surface region, indicative of its substitution into the bulk.

Metalloporphyrin anion sensors: the effect of the metal centre on the anion binding properties of amide-functionalised and tetraphenyl metalloporphyrins

This article describes the synthesis and anion binding properties of a series of ‘picket fence’ metalloporphyrin complexes, within which the metal centre is systematically varied. The porphyrin structure contains four amide bonds and is the same for each metal. The anion binding properties of these receptors are further contrasted with those of their tetraphenylporphyrin congeners to elucidate both the effect of the metal centre and the influence of the amide groups on the anion recognition process. Anion binding was demonstrated using UV/visible and 1H NMR spectroscopies, electrochemistry and luminescence. The metal centre was found to be highly influential in the strength and selectivity of binding; for example, the cadmium and mercury complexes exhibited far greater affinities for anions than the zinc complexes in competitive solvents such as DMSO. The amide functionalities were found to enhance the anion binding process.

Use of HNO3 as the source of NO to prepare a nitric oxide complex of ruthenium

Reaction of cis-Ru(bisox)(2)Cl-2, where bisox is 4,4,4',4'-tetramethyl-2,2'-bisoxazoline, with HNO3 in 1 : 4 molar proportion in boiling water under N-2 atmosphere and subsequent addition of an excess of NaClO4 center dot H2O yields [Ru(bisox)(HL)(NO)](ClO4)(NO3) (1). HL is a hydrolysed form of bisox where one of the oxazoline rings opens up. X-Ray crystallography shows that 1 contains an octahedral RuN5O core. HL binds the metal through an imino N, an amide N and an alcoholic O atom. Reaction of cis-Ru(bisox)(2)Cl-2 with an excess of NaNO2 in water gives cis-Ru(bisox)(2)(NO2)(2) (2). On acidification by HClO4 in methanol, 2 is smoothly converted to cis-[Ru(bisox)(2)(NO2)(NO)](ClO4)(2) (3) due to equilibrium (1).

Exploring the applications of a pulsating jet hydrodynamic modulated voltammetric (HMV) system - electrochemistry of nanostructured Pt electrodes and trace analysis

The electrochemistry of nanostructured electrodes is investigated using hydrodynamic modulated voltammetry (HMV). Here a liquid crystal templating process is used to produce a platinum modified electrode with a relatively high surface area (Roughness factor, Rf = 42.4). The electroreduction of molecular oxygen at a nanostructured platinum surface is used to demonstrate the ability of HMV to discriminate between Faradaic and non-Faradaic electrode reactions. The HMV approach shows that the reduction of molecular oxygen shows considerable hysteresis correlating with the formation and stripping of oxide species at the platinum surface. Without the HMV analysis it is difficult to discern the same detail under the conditions employed. In addition the detection limit of the apparatus is explored and shown, under ideal conditions, to be of the order of 45 nmol dm(-3) employing [Fe(CN)(6)](4-) as a test species. (C) 2009 Elsevier B.V. All rights reserved.

Layer-by-layer deposition of praseodymium oxide on tin-doped indium oxide (ITO) surface

Praseodymium oxide as a thin film of controllable layer is known to display many unique physiochemical properties, which can be useful to ceramic, semiconductive and sensor industries. Here in this short paper, we describe a new chemical method of depositing praseodymium oxide on tin-doped indium oxide (ITO) surface using a layer-by-layer approach. The process is carried out by dipping the ITO in solutions of adsorbable polycationic chitosan and alkaline praseodymium hydroxide Pr(OH)(3) alternatively in order to build up the well-defined multi-layers. XRD suggests that the predominant form of the oxide is Pr6O11, obtained after heat treatment of the deposited ITO in static air at 500 degrees C. Microscopic studies including AFM, TEM and SEM indicate that the deposited oxide particles are uniform in size and shape (cylindrical), mesoporous and the thickness of the film can be controlled. AC impedance measurements of the deposited materials also reveal that the oxide layers display a high electrical conductivity hence suitable for sensor uses. (c) 2006 Elsevier B.V. All rights reserved.

Engineering Pt in ceria for a maximum metal-support interaction in catalysis

Conventional supported metal catalysts are metal nanoparticles deposited on high surface area oxide supports with a poorly defined metal−support interface. Typically, the traditionally prepared Pt/ceria catalyzes both methanation (H2/CO to CH4) and water−gas shift (CO/H2O to CO2/H2) reactions. By using simple nanochemistry techniques, we show for the first time that Pt or PtAu metal can be created inside each CeO2 particle with tailored dimensions. The encapsulated metal is shown to interact with the thin CeO2 overlayer in each single particle in an optimum geometry to create a unique interface, giving high activity and excellent selectivity for the water−gas shift reaction, but is totally inert for methanation. Thus, this work clearly demonstrates the significance of nanoengineering of a single catalyst particle by a bottom-up construction approach in modern catalyst design which could enable exploitation of catalyst site differentiation, leading to new catalytic properties.

Aerogel-coated metal nanoparticle colloids as novel entities for the synthesis of defined supported metal catalysts

Nanometer metal particles of tailored size (3-5 nm) and composition prepared via inverse microemulsion were encapsulated by ultrathin coatings (<2.5 nm) of inorganic porous aerogels covered with surface -OH groups. These composite materials formed metastable colloids in solvent(s), and the organic surfactant molecules were subsequently removed without leading to aggregation (the ethanolic colloid solution was shown to be stable against flocculation for at least weeks). We demonstrate that the totally inorganic-based composite colloids, after the removal of surfactant, can be anchored to conventional solid supports (gamma-alumina, carbons) upon mixing. Application of a high temperature resulted in the formation of strong covalent linkages between the colloids and the support because of the condensation of surface groups at the interface. Detailed characterizations (X-ray diffraction (XRD), pore analysis, transmission electron microscopy (TEM), CO chemisorption) and catalytic testing (butane combustion) showed that there was no significant metal aggregation from the fine metal particles individually coated with porous aerogel oxide. Most of these metal sites on the coated nanoparticles with and without support are fully accessible by small molecules hence giving extremely active metal catalysts. Thus, the product and technology described may be suitable to synthesize these precursor entities of defined metal sizes (as inks) for wash coat/impregnation applications in catalysis. The advantages of developing inorganic nanocomposite chemical precursors are also discussed.