TY - JOUR
T1 - Interfacial properties of ZrO2 supported precious metal catalysts
T2 - A density functional study
AU - Jung, Changho
AU - Ishimoto, Ryota
AU - Tsuboi, Hideyuki
AU - Koyama, Michihisa
AU - Endou, Akira
AU - Kubo, Momoji
AU - Del Carpio, Carlos A.
AU - Miyamoto, Akira
PY - 2006/5/17
Y1 - 2006/5/17
N2 - In this study, we performed periodic DFT calculations to clarify the interfacial properties of zirconia-supported precious metal catalyst systems. Atomic precious metals (Pt, Pd and Rh) and four-metal-atom clusters (Pt4, Pd4 and Rh4) were deposited on the ZrO2(1 1 1) surface. The Pt and Rh show much stronger interaction with the ZrO2(1 1 1) surface than the Pd, indicating that the Pt-ZrO2 and Rh-ZrO2 interfaces are energetically more stable than the corresponding Pd-ZrO2 interface. The effect of support relaxation on the adsorption energies reveals that a larger support relaxation effect can be observed on the Pt-ZrO2 interface compared to the Pd-ZrO2 interface. The Pt adsorption was associated with the largest support rearrangement with strong Pt-Zr interaction. The precious metal atoms on the ZrO2(1 1 1) surface were positively charged. The electron transferred from the precious metal to the ZrO2(1 1 1) surface was localized on the Zr atom. Moreover, electron exchanges on the Pt-ZrO2 and Rh-ZrO2 interfaces were more significant than that on the Pd-ZrO2 interface. Additionally, the oxidization effects on the interaction between the precious metals and the ZrO2 support were also investigated. The oxidization weakened the metal-metal interaction of the M4 cluster, while the metal-ZrO2 interaction was increased by the oxidization.
AB - In this study, we performed periodic DFT calculations to clarify the interfacial properties of zirconia-supported precious metal catalyst systems. Atomic precious metals (Pt, Pd and Rh) and four-metal-atom clusters (Pt4, Pd4 and Rh4) were deposited on the ZrO2(1 1 1) surface. The Pt and Rh show much stronger interaction with the ZrO2(1 1 1) surface than the Pd, indicating that the Pt-ZrO2 and Rh-ZrO2 interfaces are energetically more stable than the corresponding Pd-ZrO2 interface. The effect of support relaxation on the adsorption energies reveals that a larger support relaxation effect can be observed on the Pt-ZrO2 interface compared to the Pd-ZrO2 interface. The Pt adsorption was associated with the largest support rearrangement with strong Pt-Zr interaction. The precious metal atoms on the ZrO2(1 1 1) surface were positively charged. The electron transferred from the precious metal to the ZrO2(1 1 1) surface was localized on the Zr atom. Moreover, electron exchanges on the Pt-ZrO2 and Rh-ZrO2 interfaces were more significant than that on the Pd-ZrO2 interface. Additionally, the oxidization effects on the interaction between the precious metals and the ZrO2 support were also investigated. The oxidization weakened the metal-metal interaction of the M4 cluster, while the metal-ZrO2 interaction was increased by the oxidization.
KW - Automotive catalyst
KW - Density functional theory
KW - Precious metal
KW - ZrO
UR - http://www.scopus.com/inward/record.url?scp=33646123994&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=33646123994&partnerID=8YFLogxK
U2 - 10.1016/j.apcata.2006.02.050
DO - 10.1016/j.apcata.2006.02.050
M3 - Article
AN - SCOPUS:33646123994
SN - 0926-860X
VL - 305
SP - 102
EP - 109
JO - Applied Catalysis A: General
JF - Applied Catalysis A: General
IS - 1
ER -