Distinct metal-exchange pathways of doped Ag25 nanoclusters

Handle URI:
http://hdl.handle.net/10754/622389
Title:
Distinct metal-exchange pathways of doped Ag25 nanoclusters
Authors:
Bootharaju, Megalamane Siddaramappa ( 0000-0002-8276-6987 ) ; Sinatra, Lutfan ( 0000-0001-7034-7745 ) ; Bakr, Osman M. ( 0000-0002-3428-1002 )
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 noncentral 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.
KAUST Department:
Physical Sciences and Engineering (PSE) Division; Solar and Photovoltaic Engineering Research Center (SPERC)
Citation:
Bootharaju MS, Sinatra L, Bakr OM (2016) Distinct metal-exchange pathways of doped Ag25 nanoclusters. Nanoscale 8: 17333–17339. Available: http://dx.doi.org/10.1039/c6nr06353e.
Publisher:
Royal Society of Chemistry (RSC)
Journal:
Nanoscale
Issue Date:
9-Sep-2016
DOI:
10.1039/c6nr06353e
Type:
Article
ISSN:
2040-3364; 2040-3372
Sponsors:
Financial support for the work presented here was provided by KAUST.
Additional Links:
http://pubs.rsc.org/en/Content/ArticleLanding/2016/NR/C6NR06353E
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Solar and Photovoltaic Engineering Research Center (SPERC)

Full metadata record

DC FieldValue Language
dc.contributor.authorBootharaju, Megalamane Siddaramappaen
dc.contributor.authorSinatra, Lutfanen
dc.contributor.authorBakr, Osman M.en
dc.date.accessioned2017-01-02T09:28:28Z-
dc.date.available2017-01-02T09:28:28Z-
dc.date.issued2016-09-09en
dc.identifier.citationBootharaju MS, Sinatra L, Bakr OM (2016) Distinct metal-exchange pathways of doped Ag25 nanoclusters. Nanoscale 8: 17333–17339. Available: http://dx.doi.org/10.1039/c6nr06353e.en
dc.identifier.issn2040-3364en
dc.identifier.issn2040-3372en
dc.identifier.doi10.1039/c6nr06353een
dc.identifier.urihttp://hdl.handle.net/10754/622389-
dc.description.abstractAtomically 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 noncentral 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.en
dc.description.sponsorshipFinancial support for the work presented here was provided by KAUST.en
dc.publisherRoyal Society of Chemistry (RSC)en
dc.relation.urlhttp://pubs.rsc.org/en/Content/ArticleLanding/2016/NR/C6NR06353Een
dc.titleDistinct metal-exchange pathways of doped Ag25 nanoclustersen
dc.typeArticleen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentSolar and Photovoltaic Engineering Research Center (SPERC)en
dc.identifier.journalNanoscaleen
kaust.authorBootharaju, Megalamane Siddaramappaen
kaust.authorSinatra, Lutfanen
kaust.authorBakr, Osman M.en
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