A new model describing the metal-support interaction in noble metal catalysts

被引:201
作者
Mojet, BL
Miller, JT
Ramaker, DE
Koningsberger, DC
机构
[1] Univ Utrecht, Debye Inst, Dept Inorgan Chem & Catalysis, NL-3508 TB Utrecht, Netherlands
[2] Amoco Res Ctr, Naperville, IL 60563 USA
[3] George Washington Univ, Dept Chem, Washington, DC 20052 USA
关键词
noble metal catalysts; metal-support interaction; neopentane hydrogenolysis; FTIR; XPS; XANES; shape resonance; AXAFS; new model;
D O I
10.1006/jcat.1999.2568
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The catalytic activity and spectroscopic properties of supported noble metal catalysts are strongly influenced by the acidity/ alkalinity of the support but are relatively independent of the metal (Pd or Pt) or the type of support (zeolite LTL or SiO2), As the alkalinity of the support increases, the TOF of the metal particles for neopentane hydrogenolysis decreases. At the same time, there is a decrease in the XPS binding energy and a shift from linear to bridge bonded CO in the IR spectra. Analysis of the shape resonance in XANES spectra indicates that in the presence of chemisorbed hydrogen the difference in energy between the Pt-II antibonding orbital and the Fermi level decreases as the alkalinity of the support increases, Based on the results from the IR, XPS, and shape resonance data a new model is proposed in which the interaction between the metal and support leads to a shift in the energy of the metal valence orbitals, The EXAFS structural analysis indicates that the small metal particles are in contact only with the oxide ions of the support. Finally, a new spectroscopic characterisation, Atomic XAFS, is presented which provides new insights into the origin of the electronic changes in the metal. As the alkalinity of the support increases, there is decrease in the metal ionisation potential. The primary interaction is a Coulomb attraction between metal particle and support oxygen ions, which affects the metal interatomic potential. This model for the metal-support interaction explicitly excludes the need for electron transfer, and it can account for all observed changes in the catalytic, electronic, and structural properties of the supported metal particles induced by support acidity ranging from acidic to neutral to alkaline, (C) 1999 Academic Press.
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页码:373 / 386
页数:14
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