Monoplatinum doping of gold nanoclusters and catalytic application

Huifeng Qian; De-en Jiang; Gao Li; Chakicherla Gayathri; Anindita Das; Roberto R Gil; Rongchao Jin

doi:10.1021/ja307657a

Monoplatinum doping of gold nanoclusters and catalytic application

J Am Chem Soc. 2012 Oct 3;134(39):16159-62. doi: 10.1021/ja307657a. Epub 2012 Sep 19.

Authors

Huifeng Qian¹, De-en Jiang, Gao Li, Chakicherla Gayathri, Anindita Das, Roberto R Gil, Rongchao Jin

Affiliation

¹ Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, USA.

PMID: 22992034
DOI: 10.1021/ja307657a

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).