Metal-support interactions titania supported metals

S. H. Overbury, L. Ortiz-Soto, H. G. Zhu, B. Lee, M. D. Amiridis, and S. Dai, Comparison of Au catalysts supported on mesoporous titania and silica Investigation of Au particle size effects and metal-support interactions, Catal. Lett. 95(3-4), 99-106 (2004). 

The focus of these studies has been on identifying mild activation conditions to prevent nanoparticle agglomeration. Infrared spectroscopy indicated that titania plays an active role in dendrimer adsorption and decomposition in contrast, adsorption of DENs on silica is dominated by metal-support interactions. Relatively mild (150° C) activation conditions were identified and optimized for Pt and Au catalysts. Comparable conditions yield clean nanoparticles that are active CO oxidation catalysts. Supported Pt catalysts are also active in toluene hydrogenation test reactions. 

Salama, T. M., Hattori,H., Kita,H., Ebitani, K., and Tanaka, T., X-ray adsorption spectroscopic and electron paramagnetic resonance studies on the strong metal-support interaction of platinum supported on titania dispersed on silica, J. Chem. Soc. Faraday Trans. 89(12), 2067 (1993). 

In the Au/Al203/NiAl(100) system, hemispherical particles occur even at low coverage,7 unlike the situation with titania size distribution was narrow, and particles were stable to 600 K, implying low mobility of adsorbed atoms. Paradoxically, on alumina large particles migrate and coalesce faster than small ones, presumably because the metal-support interaction is weaker but with Au/FeO the diffusivity of atoms is higher due to a lower concentration of surface defects. 

Metal-support interactions have been recently reviewed by Bond (93), who drew special attention to catalysts that gave evidence for strong metal-support interactions (SMSI). This condition was first observed in 1978 by Tauster et al. (94) for Pt on titania catalysts. The catalysts seemed to lose their capacity for H2 and CO chemisorption but nevertheless retained and enhanced their activity for only two types of reaction methanation and Fischer-Tropsch synthesis. Since then a considerable number of papers devoted to SMSI studies have been published all over the world. 

Burch and Flambard (113) have recently studied the H2 chemisorption capacities and CO/H2 activities of Ni on titania catalysts. They attributed the enhancement of the catalytic activities for the CO/H2 reaction (after activation in H2 at 450°C) to an interfacial metal-support interaction (IFMSI). This interaction is between large particles of Ni and reduced titanium ions the Ti3+ is promoted by hydrogen spillover from Ni to the support, as pictured in Fig. 8. The IFMSI state differs from the SMSI state since hydrogen still chemisorbs in a normal way however, if the activation temperature is raised to 650°C, both the CO/H2 activity and the hydrogen chemisorption are suppressed. They define this condition as a total SMSI state. Between the temperature limits, they assumed a progressive transition from IFMSI to SMSI. Such an intermediate continuous sequence had been... 

When considering metal-support interaction effects, the whole set of Electron Microscopy data presented in the previous section point out some important differences between the behaviour of noble metal catalysts supported on ceria and that of titania-supported catalysts. Much higher reduction temperatures are required in the case of ceria-type supports to observe nanostructural features similar to those described for the so called SMS I efTect. 

To summarise the results concerning the study of reversibility of metal-support interaction states, we could first state that the classic reoxidation treatment at 773 K does not allow the recovery of the NM/Ce02 catalysts from the decorated or alloyed states. The noble metal/ceria phase separation may only be achieved upon reoxidation at temperatures well above 773 K. This observation represents an additional major difference between titania and ceria supported noble metal catalysts. Moreover, the likely regeneration of NM/CcOi catalysts reduced at 773 K by reoxidation at 773 K would actually prove, in good agreement with earlier HREM studies on the reduced catalysts (117,194), that the observed deactivation effects are not due to decoration or alloying phenomena, rather consisting of purely electronic effects (105). 

Santos J, Phillips J, Dumesic J (1983) Metal support interactions between iron and titania for catalysts prepared by thermal-decomposition of iron pentacarbonyl and by impregnation. J Catal 84 147... 

Beard BC, Ross PN (1986) Pt-Ti alloy formation from high-temperature reduction of a titania-impregnated Pt catalyst - implications for strong metal support interaction. J Phys Chem 90 6811... 

Titania-supported Metals. - After reduction at 473 K, platinum-group metals supported on Ti02 chemisorbed both hydrogen and carbon monoxide in quantities indicative of moderate-to-high dispersion, but following reduction at 773 K chemisorption was drastically lowered e.g., H/Mt <0.01 for Pt, Ir, and Rh, 0.05-0.06 for Pd and Ru, and 0.11 for Os). Agglomeration, encapsulation, and impurities were eliminated as possible causes and a strong metal-support interaction (SMSI) was proposed. Titania is not unique in its SMSI properties and 11 oxides used to support iridium were classified as follows ... 

We have presented evidence that the strong metal-support interactions observed with titania and niobia are due to an oxide layer over the metal catalyst. This layer interacts chemically with the metal, as evidenced by the fact that the titania layers on Pt, Rh, and Pd do have slightly different properties. The fact that the methanation rates for a titania-covered and a niobia-covered Pt foil are identical indicates that the reason for enhanced methanation activity on the oxide-covered surface is likely due to geometric and not electronic cons id er at ions. 

A number of investigations have indicated that so-called "strong metal-support interactions (SMSI)" are caused by the migration of partially reduced oxide species onto the surface of titania supported metal particles (1 8). While this is an attractive theory in that it can account for the observed modifications in chemical properties of the metal particles, there is no agreed mechanism by which the postulated transport processes occur. 

Recently titania appeared as a non-conventional support for noble metal catalysts, since it was found to induce perturbations in their H2 or CO adsorption capacities as well as in their catalytic activities, This phenomenon, discovered by the EXXON group, was denoted "Strong Metal-Support Interactions" (SMSI effect) (1) and later extended to other reducible oxide supports (2). Two symposia were devoted to SMSI, one in Lyon-Ecully (1982) (3) and the present one in Miami (1985) (4) and presently, two main explanations are generally proposed to account for SMSI (i) either the occurence of an electronic effect (2,5-13) or (ii) the migration of suboxide species on the metal particles (14-20). The second hypothesis was essentially illustrated on model catalysts with spectroscopic techniques.lt can be noted that both possibilities do not necessarily exclude each other and can be considered simultaneously (21). 

More recent work has concentrated on the study of model systems in which the characteristic metal-support interaction effects were reproduced by depositing controlled amounts of titania species on metal surfaces (116-124). To ascertain the chemisorption and catalytic consequences of the TiOx overlayer, the evaporation has usually been carried out under 10-7-10-6 torr of oxygen. In this section we analyze the more relevant metaI/Ti02 and TiOx/metal model studies and their impact on our understanding of the metal-support interactions taking place on real supported catalysts. 

Before proceeding to consider kinetic equations and implied reaction mechanisms, we may note some other pertinent features of these reactions. (A) Benzene hydrogenation was subject to the influence of the Strong Metal-Support Interaction (Section 3.35) when titania and vanadium sesquioxide were used as supports for rhodium, platinum and iridium - even Pt/Si02 and Ni/Si02 when heated... 

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