TY - JOUR
T1 - Nuclear magnetic resonance study of Pt-Rh bimetallic clusters
AU - Wang, Zhiyne
AU - Ansermet, Jean Philippe
AU - Slichter, Charles P.
AU - Sinfelt, J. H.
PY - 1988/12/1
Y1 - 1988/12/1
N2 - The use of pulsed nuclear magnetic resonance to study supported Pt-Rh bimetallic clusters is described. Using energy-dispersive spectroscopy it has been shown that each individual cluster contains both Pt and Rh. For lower-dispersion samples (larger metal particles) the centre of the particles is pure Pt. For higher-dispersion samples (smaller metal particles) the Pt concentration in the surface layer of the clusters has been measured from observation of the dependence of the height of the Pt spin echo on the time, τ, between pulses of the echo sequence. For clusters on which 13CO has been adsorbed, the 13CO resonance frequency varies with the Pt-Rh ratio. 195Pt-13C spin-echo double resonance (SEDOR) has been employed to measure the fraction of Pt atoms in the surface layer of the cluster. By studying how the SEDOR signal depends on the frequency of the 13CO exciting pulse, it has been shown that the resonance frequency of 13CO is independent of whether the CO is bonded to Pt or Rh in a given sample. This result shows that the frequency shift of the 13CO is a non-local rather than a local phenomenon. The 13CO shift corresponds to that of pure Rh particles, even for surfaces which contain a substantial Pt content. The significance of this result is explained in terms of the mixing of the molecular and metallic wave-functions.
AB - The use of pulsed nuclear magnetic resonance to study supported Pt-Rh bimetallic clusters is described. Using energy-dispersive spectroscopy it has been shown that each individual cluster contains both Pt and Rh. For lower-dispersion samples (larger metal particles) the centre of the particles is pure Pt. For higher-dispersion samples (smaller metal particles) the Pt concentration in the surface layer of the clusters has been measured from observation of the dependence of the height of the Pt spin echo on the time, τ, between pulses of the echo sequence. For clusters on which 13CO has been adsorbed, the 13CO resonance frequency varies with the Pt-Rh ratio. 195Pt-13C spin-echo double resonance (SEDOR) has been employed to measure the fraction of Pt atoms in the surface layer of the cluster. By studying how the SEDOR signal depends on the frequency of the 13CO exciting pulse, it has been shown that the resonance frequency of 13CO is independent of whether the CO is bonded to Pt or Rh in a given sample. This result shows that the frequency shift of the 13CO is a non-local rather than a local phenomenon. The 13CO shift corresponds to that of pure Rh particles, even for surfaces which contain a substantial Pt content. The significance of this result is explained in terms of the mixing of the molecular and metallic wave-functions.
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U2 - 10.1039/F19888403785
DO - 10.1039/F19888403785
M3 - Article
AN - SCOPUS:0042416553
SN - 0300-9599
VL - 84
SP - 3785
EP - 3802
JO - Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases
JF - Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases
IS - 11
ER -