Jump to main content
Jump to site search
Access to RSC content Close the message box

Continue to access RSC content when you are not at your institution. Follow our step-by-step guide.


Issue 39, 2016
Previous Article Next Article

Distinct metal-exchange pathways of doped Ag25 nanoclusters

Author affiliations

Abstract

Atomically precise metal nanoclusters (NCs) containing more than one type of metal atom (i.e., doped or alloyed), due to synergistic effects, open new avenues for engineering the catalytic and optical properties of NCs in a manner that homometal NCs cannot. Unfortunately, it is still a major challenge to controllably introduce multimetallic dopants in NCs, understanding the dopants’ positions, mechanism, and synergistic effects. To overcome these challenges, we designed a metal-exchange approach involving NCs as molecular templates and metal ions as the source of the incoming dopant. In particular, two structurally similar monodoped silver-rich NCs, [MAg24(SR)18]2− (M = Pd/Pt and SR: thiolate), were synthesized as templates to study their mechanistic transformation in response to the introduction of gold atoms. The controllable incorporation of Au atoms into the MAg24 framework facilitated the elucidation of distinct doping pathways through high-resolution mass spectrometry, optical spectroscopy and elemental analysis. Interestingly, gold replaced the central Pd atom of [PdAg24(SR)18]2− clusters to produce predominantly bimetallic [AuAg24(SR)18] clusters along with a minor product of an [Au2Ag23(SR)18] cluster. In contrast, the central Pt atom remained intact in [PtAg24(SR)18]2− clusters, and gold replaced the non-central Ag atoms to form trimetallic [AuxPtAg24−x(SR)18]2− NCs, where x = 1–2, with a portion of the starting [PtAg24(SR)18]2− NCs remaining. This study reveals some of the unusual metal-exchange pathways of doped NCs and the important role played by the initial metal dopant in directing the position of a second dopant in the final product.

Graphical abstract: Distinct metal-exchange pathways of doped Ag25 nanoclusters

Back to tab navigation

Supplementary files

Article information


Submitted
10 Aug 2016
Accepted
06 Sep 2016
First published
09 Sep 2016

Nanoscale, 2016,8, 17333-17339
Article type
Paper

Distinct metal-exchange pathways of doped Ag25 nanoclusters

M. S. Bootharaju, L. Sinatra and O. M. Bakr, Nanoscale, 2016, 8, 17333
DOI: 10.1039/C6NR06353E

Social activity

Search articles by author

Spotlight

Advertisements