A scalable synthesis of highly stable and water dispersible Ag 44(SR)30 nanoclusters

Handle URI:
http://hdl.handle.net/10754/562519
Title:
A scalable synthesis of highly stable and water dispersible Ag 44(SR)30 nanoclusters
Authors:
AbdulHalim, Lina G. ( 0000-0003-0818-234X ) ; Ashraf, Sumaira; Katsiev, Khabiboulakh; Kirmani, Ahmad R. ( 0000-0002-8351-3762 ) ; Kothalawala, Nuwan; Anjum, Dalaver H.; Abbas, Sikandar Zameer; Amassian, Aram ( 0000-0002-5734-1194 ) ; Stellacci, Francesco; Dass, Amala; Hussain, Irshad; Bakr, Osman M. ( 0000-0002-3428-1002 )
Abstract:
We report the synthesis of atomically monodisperse thiol-protected silver nanoclusters [Ag44(SR)30] m, (SR = 5-mercapto-2-nitrobenzoic acid) in which the product nanocluster is highly stable in contrast to previous preparation methods. The method is one-pot, scalable, and produces nanoclusters that are stable in aqueous solution for at least 9 months at room temperature under ambient conditions, with very little degradation to their unique UV-Vis optical absorption spectrum. The composition, size, and monodispersity were determined by electrospray ionization mass spectrometry and analytical ultracentrifugation. The produced nanoclusters are likely to be in a superatom charge-state of m = 4-, due to the fact that their optical absorption spectrum shares most of the unique features of the intense and broadly absorbing nanoparticles identified as [Ag44(SR) 30]4- by Harkness et al. (Nanoscale, 2012, 4, 4269). A protocol to transfer the nanoclusters to organic solvents is also described. Using the disperse nanoclusters in organic media, we fabricated solid-state films of [Ag44(SR)30]m that retained all the distinct features of the optical absorption spectrum of the nanoclusters in solution. The films were studied by X-ray diffraction and photoelectron spectroscopy in order to investigate their crystallinity, atomic composition and valence band structure. The stability, scalability, and the film fabrication method demonstrated in this work pave the way towards the crystallization of [Ag44(SR)30]m and its full structural determination by single crystal X-ray diffraction. Moreover, due to their unique and attractive optical properties with multiple optical transitions, we anticipate these clusters to find practical applications in light-harvesting, such as photovoltaics and photocatalysis, which have been hindered so far by the instability of previous generations of the cluster. © 2013 The Royal Society of Chemistry.
KAUST Department:
Physical Sciences and Engineering (PSE) Division; Solar and Photovoltaic Engineering Research Center (SPERC); Materials Science and Engineering Program; Advanced Nanofabrication, Imaging and Characterization Core Lab; Core Labs; Organic Electronics and Photovoltaics Group; Functional Nanomaterials Lab (FuNL)
Publisher:
Royal Society of Chemistry
Journal:
Journal of Materials Chemistry A
Issue Date:
2013
DOI:
10.1039/c3ta11785e
Type:
Article
ISSN:
20507488
Appears in Collections:
Articles; Advanced Nanofabrication, Imaging and Characterization Core Lab; Physical Sciences and Engineering (PSE) Division; Materials Science and Engineering Program; Solar and Photovoltaic Engineering Research Center (SPERC)

Full metadata record

DC FieldValue Language
dc.contributor.authorAbdulHalim, Lina G.en
dc.contributor.authorAshraf, Sumairaen
dc.contributor.authorKatsiev, Khabiboulakhen
dc.contributor.authorKirmani, Ahmad R.en
dc.contributor.authorKothalawala, Nuwanen
dc.contributor.authorAnjum, Dalaver H.en
dc.contributor.authorAbbas, Sikandar Zameeren
dc.contributor.authorAmassian, Aramen
dc.contributor.authorStellacci, Francescoen
dc.contributor.authorDass, Amalaen
dc.contributor.authorHussain, Irshaden
dc.contributor.authorBakr, Osman M.en
dc.date.accessioned2015-08-03T10:41:08Zen
dc.date.available2015-08-03T10:41:08Zen
dc.date.issued2013en
dc.identifier.issn20507488en
dc.identifier.doi10.1039/c3ta11785een
dc.identifier.urihttp://hdl.handle.net/10754/562519en
dc.description.abstractWe report the synthesis of atomically monodisperse thiol-protected silver nanoclusters [Ag44(SR)30] m, (SR = 5-mercapto-2-nitrobenzoic acid) in which the product nanocluster is highly stable in contrast to previous preparation methods. The method is one-pot, scalable, and produces nanoclusters that are stable in aqueous solution for at least 9 months at room temperature under ambient conditions, with very little degradation to their unique UV-Vis optical absorption spectrum. The composition, size, and monodispersity were determined by electrospray ionization mass spectrometry and analytical ultracentrifugation. The produced nanoclusters are likely to be in a superatom charge-state of m = 4-, due to the fact that their optical absorption spectrum shares most of the unique features of the intense and broadly absorbing nanoparticles identified as [Ag44(SR) 30]4- by Harkness et al. (Nanoscale, 2012, 4, 4269). A protocol to transfer the nanoclusters to organic solvents is also described. Using the disperse nanoclusters in organic media, we fabricated solid-state films of [Ag44(SR)30]m that retained all the distinct features of the optical absorption spectrum of the nanoclusters in solution. The films were studied by X-ray diffraction and photoelectron spectroscopy in order to investigate their crystallinity, atomic composition and valence band structure. The stability, scalability, and the film fabrication method demonstrated in this work pave the way towards the crystallization of [Ag44(SR)30]m and its full structural determination by single crystal X-ray diffraction. Moreover, due to their unique and attractive optical properties with multiple optical transitions, we anticipate these clusters to find practical applications in light-harvesting, such as photovoltaics and photocatalysis, which have been hindered so far by the instability of previous generations of the cluster. © 2013 The Royal Society of Chemistry.en
dc.publisherRoyal Society of Chemistryen
dc.titleA scalable synthesis of highly stable and water dispersible Ag 44(SR)30 nanoclustersen
dc.typeArticleen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentSolar and Photovoltaic Engineering Research Center (SPERC)en
dc.contributor.departmentMaterials Science and Engineering Programen
dc.contributor.departmentAdvanced Nanofabrication, Imaging and Characterization Core Laben
dc.contributor.departmentCore Labsen
dc.contributor.departmentOrganic Electronics and Photovoltaics Groupen
dc.contributor.departmentFunctional Nanomaterials Lab (FuNL)en
dc.identifier.journalJournal of Materials Chemistry Aen
dc.contributor.institutionDepartment of Metallurgy and Materials Engineering, Pakistan Institute of Engineering and Applied Sciences (PIEAS), Nilore Islamabad, Pakistanen
dc.contributor.institutionDepartment of Chemistry and Biochemistry, University of Mississippi, University MS 38677, United Statesen
dc.contributor.institutionDepartment of Chemistry, SBA School of Science and Engineering (SSE), Lahore University of Management Sciences (LUMS), DHA, Lahore Cantt-54792, Pakistanen
dc.contributor.institutionInstitute of Materials, Ecole Polytechnique Fédérale de Lausanne, Switzerlanden
kaust.authorKatsiev, Khabiboulakhen
kaust.authorAnjum, Dalaver H.en
kaust.authorAmassian, Aramen
kaust.authorBakr, Osman M.en
kaust.authorAbdulHalim, Lina G.en
kaust.authorKirmani, Ahmad R.en
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