title: Monoplatinum doping of gold nanoclusters and catalytic application.
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).
authors.affiliation: Department of Chemistry, Carnegie Mellon University, Pittsburgh, Pennsylvania 15213, USA.
authors.forename: Huifeng
authors.initials: H
authors.lastname: Qian
authors.forename: De-en
authors.initials: DE
authors.lastname: Jiang
authors.forename: Gao
authors.initials: G
authors.lastname: Li
authors.forename: Chakicherla
authors.initials: C
authors.lastname: Gayathri
authors.forename: Anindita
authors.initials: A
authors.lastname: Das
authors.forename: Roberto R
authors.initials: RR
authors.lastname: Gil
authors.forename: Rongchao
authors.initials: R
authors.lastname: Jin