Reactivity of Monolayer Protected Silver Clusters Towards Excess Ligand: A Calorimetric Study

Handle URI:
http://hdl.handle.net/10754/626133
Title:
Reactivity of Monolayer Protected Silver Clusters Towards Excess Ligand: A Calorimetric Study
Authors:
Baksi, Ananya; Bootharaju, Megalamane Siddaramappa ( 0000-0002-8276-6987 ) ; Chhotaray, Pratap K.; Chakraborty, Papri; Mondal, Biswajit; Bhat, Shridevi; Gardas, Ramesh L.; Pradeep, Thalappil
Abstract:
Reactivity of monolayer protected atomically precise clusters of noble metals is of significant research interest. Till date very few experimental data are available on the reaction thermodynamics of such clusters. Here we report a calorimetric study of the reaction of glutathione (GSH) protected silver clusters in presence of excess ligand, GSH using isothermal titration calorimetry (ITC). We have studied Ag11(SG)7 and Ag32(SG)19 clusters and compared their reactivity with GSH protected silver nanoparticles (AgNPs) and silver ions. Clusters show intermediate reactivity towards excess ligand com-pared to nanoparticles and silver ions. Several control experiments were performed to understand the degradation mech-anism of these silver clusters and nanoparticles. Effect of dissolved oxygen in the degradation process was studied in de-tail and found that it did not have a significant role, although alternate pathways of degradation with the involvement of oxygen cannot be ruled out. Direct confirmation of the fact that functionalized metal clusters fall in-between NPs and atomic systems in their stability is obtained experimentally for the first time. Several other thermophysical parameters of these clusters were also determined including, density, speed of sound, isentropic compressibility and coefficient of thermal expansion.
KAUST Department:
KAUST Catalysis Center (KCC); Physical Sciences and Engineering (PSE) Division
Citation:
Baksi A, Bootharaju MS, Chhotaray PK, Chakraborty P, Mondal B, et al. (2017) Reactivity of Monolayer Protected Silver Clusters Towards Excess Ligand: A Calorimetric Study. The Journal of Physical Chemistry C. Available: http://dx.doi.org/10.1021/acs.jpcc.7b07557.
Publisher:
American Chemical Society (ACS)
Journal:
The Journal of Physical Chemistry C
Issue Date:
31-Oct-2017
DOI:
10.1021/acs.jpcc.7b07557
Type:
Article
ISSN:
1932-7447; 1932-7455
Sponsors:
A.B. and T.P. thank the Department of Science and Technology, Government of India for continuous support our of research program on nanomaterials. A.B. thanks Indian Institute of Technology Madras for fellowship.
Additional Links:
http://pubs.acs.org/doi/abs/10.1021/acs.jpcc.7b07557
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; KAUST Catalysis Center (KCC)

Full metadata record

DC FieldValue Language
dc.contributor.authorBaksi, Ananyaen
dc.contributor.authorBootharaju, Megalamane Siddaramappaen
dc.contributor.authorChhotaray, Pratap K.en
dc.contributor.authorChakraborty, Paprien
dc.contributor.authorMondal, Biswajiten
dc.contributor.authorBhat, Shridevien
dc.contributor.authorGardas, Ramesh L.en
dc.contributor.authorPradeep, Thalappilen
dc.date.accessioned2017-11-09T06:33:07Z-
dc.date.available2017-11-09T06:33:07Z-
dc.date.issued2017-10-31en
dc.identifier.citationBaksi A, Bootharaju MS, Chhotaray PK, Chakraborty P, Mondal B, et al. (2017) Reactivity of Monolayer Protected Silver Clusters Towards Excess Ligand: A Calorimetric Study. The Journal of Physical Chemistry C. Available: http://dx.doi.org/10.1021/acs.jpcc.7b07557.en
dc.identifier.issn1932-7447en
dc.identifier.issn1932-7455en
dc.identifier.doi10.1021/acs.jpcc.7b07557en
dc.identifier.urihttp://hdl.handle.net/10754/626133-
dc.description.abstractReactivity of monolayer protected atomically precise clusters of noble metals is of significant research interest. Till date very few experimental data are available on the reaction thermodynamics of such clusters. Here we report a calorimetric study of the reaction of glutathione (GSH) protected silver clusters in presence of excess ligand, GSH using isothermal titration calorimetry (ITC). We have studied Ag11(SG)7 and Ag32(SG)19 clusters and compared their reactivity with GSH protected silver nanoparticles (AgNPs) and silver ions. Clusters show intermediate reactivity towards excess ligand com-pared to nanoparticles and silver ions. Several control experiments were performed to understand the degradation mech-anism of these silver clusters and nanoparticles. Effect of dissolved oxygen in the degradation process was studied in de-tail and found that it did not have a significant role, although alternate pathways of degradation with the involvement of oxygen cannot be ruled out. Direct confirmation of the fact that functionalized metal clusters fall in-between NPs and atomic systems in their stability is obtained experimentally for the first time. Several other thermophysical parameters of these clusters were also determined including, density, speed of sound, isentropic compressibility and coefficient of thermal expansion.en
dc.description.sponsorshipA.B. and T.P. thank the Department of Science and Technology, Government of India for continuous support our of research program on nanomaterials. A.B. thanks Indian Institute of Technology Madras for fellowship.en
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/abs/10.1021/acs.jpcc.7b07557en
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in The Journal of Physical Chemistry C, 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.jpcc.7b07557.en
dc.titleReactivity of Monolayer Protected Silver Clusters Towards Excess Ligand: A Calorimetric Studyen
dc.typeArticleen
dc.contributor.departmentKAUST Catalysis Center (KCC)en
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalThe Journal of Physical Chemistry Cen
dc.eprint.versionPost-printen
dc.contributor.institutionKarlsruhe Institute of Technology, Germany.en
dc.contributor.institutionDST Unit of Nanoscience and Thematic Unit of Excellence, Department of Chemistry, Indian Institute of Technology Madras, Chennai – 600036, India.en
dc.contributor.institutionDepartment of Chemistry, The University of Alabama, Tuscaloosa, AL 35487, USA.en
dc.contributor.institutionDepartment of Chemistry, Institute of Technology Madras, Chennai – 600036, India.en
kaust.authorBootharaju, Megalamane Siddaramappaen
All Items in KAUST are protected by copyright, with all rights reserved, unless otherwise indicated.