Correlation between the surface electronic structure and CO-oxidation activity of Pt alloys

Literature Information

Publication Date 2014-09-17
DOI 10.1039/C4CP03406F
Impact Factor 3.676
Authors

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


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Abstract

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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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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