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Published on: July 9, 2015
Monoplatinum doping of gold nanoclusters and catalytic application
Huifeng Qian1, De-en Jiang, Gao Li
1Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, USA.
Abstract:
We report single-atom doping of gold nanoclusters (NCs), and its drastic effects on the optical, electronic, and catalytic properties, using the 25-atom system as a model. In our synthetic approach, a mixture of Pt(1)Au(24)(SC(2)H(4)Ph)(18) and Au(25)(SC(2)H(4)Ph)(18) was produced via a size-focusing process, and then Pt(1)Au(24)(SC(2)H(4)Ph)(18) NCs were obtained by selective decomposition of Au(25)(SC(2)H(4)Ph)(18) in the mixture with concentrated H(2)O(2) followed by purification via size-exclusion chromatography. Experimental and theoretical analyses confirmed that Pt(1)Au(24)(SC(2)H(4)Ph)(18) possesses a Pt-centered icosahedral core capped by six Au(2)(SC(2)H(4)Ph)(3) staples. The Pt(1)Au(24)(SC(2)H(4)Ph)(18) cluster exhibits greatly enhanced stability and catalytic activity relative to Au(25)(SC(2)H(4)Ph)(18) but a smaller energy gap (E(g) ≈ 0.8 eV vs 1.3 eV for the homogold cluster).
