Loading, surface oxide-support interaction effect

Following deposition of an active metal upon a ceria surface, it is possible to study chemisorption on a surface that models many of the important aspects expected for actual ceria supported catalysts. Surface techniques offer the possibility to identify where the adsorbates are located and to identify intermediates that are formed in their interaction. By comparison of ceria surfaces, with and without metal, the synergisms between metal and support can be deduced. By controlled metal deposition, it is possible to study the effects of loading and particle size. By selected preparation of the ceria substrate it is possible to vary factors which may affect the interaction between the metal particle and the ceria, sueh as structure, defeet concentration or oxidation state of the ceria. The goal of chemisorption studies, summarized below, is to relate all these factors to the interaction of the model catalyst with particular adsorbates. 

Irrespective of the nature of the reaction intermediate, enolic type (11) or surface carbide (12), the dechne of the turnover number for the zeolites with higher Si/Al ratio can be explained as follows. For platinum (13) and palladium (14,15) loaded zeolites, support effects are known to exist. The higher the acidity (and the oxidizing power) of the zeolite, the higher will be the electron-deficient character of the supported metal. It also is well established now (16) that the average acidity of hydrogen zeohtes increases with the Si/Al ratio. This explains why the electron deficient character of ruthenium should increase with the Si/Al ratio of the zeolite, and a stronger interaction with adsorbed CO should be expected. Vannice (19,20) reported that the N value for CH4 formation decreases when the heat of adsorption for CO increases. All this explains why the tmnover number of the methanation reaction over ruthenium decreases when the Si/Al ratio of the zeolite support increases. 

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