Pd-supported catalysts: evolution of support porous texture along Pd deposition and alkali-metal doping.
Adsorption of N2 at 77 K and scanning electron microscopy have been used to measure the changes in the support morphology, at nano- and microscale level, along the processes involved in the preparation of a supported Pd catalyst: Pd deposition, doping, and thermal treatments. Among the investigated supports, viz., activated carbons, gamma-Al2O3, SiO2, and SiO2-Al2O3 (SA), the SA one was found particularly sensitive to these processes, as a result of its high plasticity and reactivity. Involved processes can be summarized as follows: (i) During the Pd deposition, the support itself is partially dissolved and removed as a result of both the basicity of the precipitating agent and the final washing. (ii) When the undoped sample is thermally treated up to 823 K, only modest phenomena are observed. (iii) Upon doping with potassium carbonate, the support dissolution continues, and the greater the carbonate concentration, the greater the dissolution extent. In this case the dissolved material is not removed, but reprecipitates (partially outside the pores), during the subsequent drying at 393 K. (iv) When doped samples are thermally treated, the reaction between carbonate and support causes the mobilization of the support itself, with sintering phenomena that can reach the total collapse of the porous structure. The starting temperature of the pore collapse decreases with increasing potassium carbonate concentration. The modification of the support influences, directly or indirectly, the surface properties and the availability of Pd particles that can be doped or even covered by materials from support and made more or less accessible or even inaccessible by pore narrowing, widening, or blocking.
Chimet S.p.A-Catalyst Division, Via di Pescaiola 74, I-52041 Viciomaggio, Arezzo, Italy. riccardo.pellegrini@chimet.com
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Pellegrini
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Leofanti
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Agostini
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Groppo
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Rivallan
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Lamberti