Acta Phys. -Chim. Sin. ›› 2011, Vol. 27 ›› Issue (03): 513-519.doi: 10.3866/PKU.WHXB20110304

• Invited Aticle • Previous Articles     Next Articles

Doping 25-Atom and 38-Atom Gold Nanoclusters with Palladium

QIAN Huifeng1, BARRY Ellen2, ZHU Yan1, JIN Rongchao1   

  1. 1. Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, USA;
    2. Department of Chemistry, University of Pittsburgh, Pittsburgh, Pennsylvania 15260, USA
  • Received:2010-11-04 Revised:2011-01-10 Published:2011-03-03
  • Contact: JIN Rongchao E-mail:rongchao@andrew.cmu.edu
  • Supported by:

    The project was supported by Carnegie Mellon University (CMU), the Air Force Office of Scientific Research (AFOSR) and the National Institute for ccupational Safety and Health (NIOSH), USA. BARRY Ellen was supported by the National Science Foundation-Research Experiences for Undergraduates, USA (NSF grant DMR #1005076).

Abstract:

In this work, we describe two synthetic procedures for preparing palladium doped 25-atom nanoclusters (referred to as Pd1Au24(SR)18, where ―SR represents thiolate, R=C2H4Ph). Pure Pd1Au24(SC2H4Ph)18 nanoclusters are isolated by solvent extraction and size exclusion chromatography. Mass spectrometry and optical spectroscopy analyses demonstrate that the Pd1Au24(SC2H4Ph)18 nanocluster adopts the same core-shell structure as that of the homogold Au25(SC2H4Ph)18 nanocluster, that is, a Pd- or Au-centered icosahedron surrounded by six Au2(SR)3 “staple”-like motifs. Similar doping behavior has also been observed in 38-atom M38(SR)24 (M: metal) nanoclusters, indicating the unique behavior of Pd dopant being preferentially located in the icosahedral center. The catalytic activity of Pd1Au24(SC2H4Ph)18 has also been evaluated for the selective hydrogenation of α,β-unsaturated ketone (e.g., benzalacetone) to α,β- unsaturated alcohol, and a 42% conversion of benzalacetone is attained.

Key words: Gold, Nanocluster, Doping, Palladium