Density functional study on the activation of methane over Pd2, PdO, and Pd2O clusters

✍ Scribed by Ewa Broclawik; Ryo Yamauchi; Akira Endou; Momoji Kubo; Akira Miyamoto

• Publisher: John Wiley and Sons
• Year: 1997
• Tongue: English
• Weight: 250 KB
• Volume: 61
• Category: Article
• ISSN: 0020-7608
• DOI: 10.1002/(sici)1097-461x(1997)61:4<673::aid-qua9>3.0.co;2-t

✦ Synopsis

Simple functional models for elementary steps in the total oxidation of methane over supported palladium catalysts were investigated using density functional theory. Three simple cluster models were proposed, namely, the palladium dimer and PdO diatomic and linear Pd O, to probe the mechanism of the methane activation on metallic and 2 oxidized palladium phases, respectively. The strongest adsorption was found on Pd , 2 where also the CᎏH bond became easily activated; however, no stable product of the C ᎏH bond scission was indicated. Similar hydrogen activation took place on Pd O and, in 2 addition, adsorbed methyl and OH species formed the most stable system after crossing a moderate energy barrier. The same product was previously found stable also in the case of PdO dimer but the activation barrier was high. On the Pd O cluster, the process 2 of energy barrier crossing was accomplished in two steps: easy formation of a free hydrogen moiety and actual oxidation, which made the overall process less demanding energetically.