Correlation between the surface electronic structure and CO-oxidation activity of Pt alloys
文献情報
Hideki Yoshikawa, Ya Xu, Gubbala V. Ramesh, Toyokazu Tanabe, Rajesh Kodiyath, Shigenori Ueda, Nobuaki Sekido, Yoko Yamabe-Mitarai, Masahiko Shimoda, Takahisa Ohno, Futoshi Matsumoto, Takayuki Komatsu
The surface electronic structure and CO-oxidation activity of Pt and Pt alloys, Pt3T (T = Ti, Hf, Ta, Pt), were investigated. At temperatures below 538 K, the CO-oxidation activities of Pt and Pt3T increased in the order Pt < Pt3Ti < Pt3hHf < Pt3Ta. The center-of-gravity of the Pt d-band (the d-band center) of Pt and Pt3T was theoretically calculated to follow the trend Pt3Ti < Pt3Ta < Pt3Hf < Pt. The CO-oxidation activity showed a volcano-type dependence on the d-band center, where Pt3Ta exhibited a maximum in activity. Theoretical calculations demonstrated that the adsorption energy of CO on the catalyst surface monotonically decreases with the lowering of the d-band center because of diminished hybridization of the surface d-band and the lowest-unoccupied molecular orbital (LUMO) of CO. The observed volcano-type correlation between the d-band center and the CO oxidation activity is rationalized in terms of the CO adsorption energy, which counterbalances the surface coverage by CO and the rate of CO oxidation.
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