Reversible Size Control of Silver Nanoclusters via Ligand-exchange

Handle URI:
http://hdl.handle.net/10754/555643
Title:
Reversible Size Control of Silver Nanoclusters via Ligand-exchange
Authors:
Bootharaju, Megalamane Siddaramappa ( 0000-0002-8276-6987 ) ; Burlakov, Victor M.; Besong, Tabot M.D. ( 0000-0002-3572-1428 ) ; Joshi, Chakra Prasad; AbdulHalim, L; Black, David; Whetten, Robert; Goriely, Alain; Bakr, Osman M. ( 0000-0002-3428-1002 )
Abstract:
The properties of atomically monodisperse noble metal nanoclusters (NCs) are intricately intertwined with their precise molecular formula. The vast majority of size-specific NC syntheses start from the reduction of the metal salt and thiol ligand mixture. Only in gold was it recently shown that ligand-exchange could induce the growth of NCs from one atomically precise species to another; a process of yet unknown reversibility. Here, we present a process for the ligand-exchange-induced growth of atomically precise silver NCs, in a biphasic liquid-liquid system, which is particularly of interest because of its complete reversibility and ability to occur at room temperature. We explore this phenomenon in-depth using Ag35(SG)18 [SG= glutathionate] and Ag44(4-FTP)30 [4-FTP= 4-fluorothiophenol] as model systems. We show that the ligand-exchange conversion of Ag35(SG)18 into Ag44(4-FTP)30 is rapid (< 5 min) and direct, while the reverse process proceeds slowly through intermediate cluster sizes. We adapt a recently developed theory of reverse Ostwald ripening to model the NCs’ interconvertibility. The model’s predictions are in good agreement with the experimental observations, and they highlight the importance of small changes in the ligand-metal binding energy in determining the final equilibrium NC size. Based on the insight provided by this model, we demonstrated experimentally that by varying the choice of ligands, ligand-exchange can be used to obtain different sized NCs. The findings in this work establish ligand-exchange as a versatile tool for tuning cluster sizes.
KAUST Department:
Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC); KAUST Solar Center (KSC); Materials Science and Engineering Program
Citation:
Reversible Size Control of Silver Nanoclusters via Ligand-exchange 2015:150521100629001 Chemistry of Materials
Publisher:
American Chemical Society (ACS)
Journal:
Chemistry of Materials
Issue Date:
21-May-2015
DOI:
10.1021/acs.chemmater.5b00650
Type:
Article
ISSN:
0897-4756; 1520-5002
Additional Links:
http://pubs.acs.org/doi/abs/10.1021/acs.chemmater.5b00650
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Physical Sciences and Engineering (PSE) Division; Materials Science and Engineering Program; KAUST Catalysis Center (KCC); KAUST Solar Center (KSC); KAUST Solar Center (KSC)

Full metadata record

DC FieldValue Language
dc.contributor.authorBootharaju, Megalamane Siddaramappaen
dc.contributor.authorBurlakov, Victor M.en
dc.contributor.authorBesong, Tabot M.D.en
dc.contributor.authorJoshi, Chakra Prasaden
dc.contributor.authorAbdulHalim, Len
dc.contributor.authorBlack, Daviden
dc.contributor.authorWhetten, Roberten
dc.contributor.authorGoriely, Alainen
dc.contributor.authorBakr, Osman M.en
dc.date.accessioned2015-05-25T08:12:06Zen
dc.date.available2015-05-25T08:12:06Zen
dc.date.issued2015-05-21en
dc.identifier.citationReversible Size Control of Silver Nanoclusters via Ligand-exchange 2015:150521100629001 Chemistry of Materialsen
dc.identifier.issn0897-4756en
dc.identifier.issn1520-5002en
dc.identifier.doi10.1021/acs.chemmater.5b00650en
dc.identifier.urihttp://hdl.handle.net/10754/555643en
dc.description.abstractThe properties of atomically monodisperse noble metal nanoclusters (NCs) are intricately intertwined with their precise molecular formula. The vast majority of size-specific NC syntheses start from the reduction of the metal salt and thiol ligand mixture. Only in gold was it recently shown that ligand-exchange could induce the growth of NCs from one atomically precise species to another; a process of yet unknown reversibility. Here, we present a process for the ligand-exchange-induced growth of atomically precise silver NCs, in a biphasic liquid-liquid system, which is particularly of interest because of its complete reversibility and ability to occur at room temperature. We explore this phenomenon in-depth using Ag35(SG)18 [SG= glutathionate] and Ag44(4-FTP)30 [4-FTP= 4-fluorothiophenol] as model systems. We show that the ligand-exchange conversion of Ag35(SG)18 into Ag44(4-FTP)30 is rapid (< 5 min) and direct, while the reverse process proceeds slowly through intermediate cluster sizes. We adapt a recently developed theory of reverse Ostwald ripening to model the NCs’ interconvertibility. The model’s predictions are in good agreement with the experimental observations, and they highlight the importance of small changes in the ligand-metal binding energy in determining the final equilibrium NC size. Based on the insight provided by this model, we demonstrated experimentally that by varying the choice of ligands, ligand-exchange can be used to obtain different sized NCs. The findings in this work establish ligand-exchange as a versatile tool for tuning cluster sizes.en
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/abs/10.1021/acs.chemmater.5b00650en
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in Chemistry of Materials, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/acs.chemmater.5b00650.en
dc.titleReversible Size Control of Silver Nanoclusters via Ligand-exchangeen
dc.typeArticleen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentKAUST Solar Center (KSC)en
dc.contributor.departmentMaterials Science and Engineering Programen
dc.identifier.journalChemistry of Materialsen
dc.eprint.versionPost-printen
dc.contributor.institutionMathematical Institute, University of Oxford, Woodstock Road, Oxford, OX2 6GG, UKen
dc.contributor.institutionDepartment of Physics and Astronomy, The University of Texas at San Antonio, One UTSA Circle, San Antonio, Texas 78249, United Statesen
kaust.authorBakr, Osman M.en
kaust.authorBootharaju, Megalamane Siddaramappaen
kaust.authorBesong, Tabot M.D.en
kaust.authorJoshi, Chakra Prasaden
kaust.authorAbdulHalim, Lina G.en
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