Cu2Se and Cu Nanocrystals as Local Sources of Copper in Thermally Activated In Situ Cation Exchange

Handle URI:
http://hdl.handle.net/10754/595373
Title:
Cu2Se and Cu Nanocrystals as Local Sources of Copper in Thermally Activated In Situ Cation Exchange
Authors:
Casu, Alberto; Genovese, Alessandro; Manna, Liberato; Longo, Paolo; Buha, Joka; Botton, Gianluigi A.; Lazar, Sorin; Kahaly, M. Upadhyay; Schwingenschlögl, Udo ( 0000-0003-4179-7231 ) ; Prato, Mirko; Li, Hongbo; Ghosh, Sandeep; Palazon, Francisco; De Donato, Francesco; Lentijo Mozo, Sergio; Zuddas, Efisio; Falqui, Andrea ( 0000-0002-1476-7742 )
Abstract:
Among the different synthesis approaches to colloidal nanocrystals a recently developed toolkit is represented by cation exchange reactions, where the use of template nanocrystals gives access to materials that would be hardly attainable via direct synthesis. Besides, post-synthetic treatments, such as thermally activated solid state reactions, represent a further flourishing route to promote finely controlled cation exchange. Here, we report that, upon in situ heating in a transmission electron microscope, Cu2Se nanocrystals deposited on an amorphous solid substrate undergo partial loss of Cu atoms, which are then engaged in local cation exchange reactions with Cu “acceptors” phases represented by rod- and wire- shaped CdSe nanocrystals. This thermal treatment slowly transforms the initial CdSe nanocrystals into Cu2-xSe nanocrystals, through the complete sublimation of Cd and the partial sublimation of Se atoms. Both Cu “donor” and “acceptor” particles were not always in direct contact with each other, hence the gradual transfer of Cu species from Cu2Se or metallic Cu to CdSe nanocrystals was mediated by the substrate and depended on the distance between the donor and acceptor nanostructures. Differently from what happens in the comparably faster cation exchange reactions performed in liquid solution, this study shows that slow cation exchange reactions can be performed at the solid state, and helps to shed light on the intermediate steps involved in such reactions.
KAUST Department:
NABLA Lab; Biological and Environmental Sciences and Engineering (BESE) Division; Physical Sciences and Engineering (PSE) Division
Citation:
Cu2Se and Cu Nanocrystals as Local Sources of Copper in Thermally Activated In Situ Cation Exchange 2016 ACS Nano
Publisher:
American Chemical Society (ACS)
Journal:
ACS Nano
Issue Date:
27-Jan-2016
DOI:
10.1021/acsnano.5b07219
Type:
Article
ISSN:
1936-0851; 1936-086X
Additional Links:
http://pubs.acs.org/doi/abs/10.1021/acsnano.5b07219
Appears in Collections:
Articles; Physical Sciences and Engineering (PSE) Division; Biological and Environmental Sciences and Engineering (BESE) Division

Full metadata record

DC FieldValue Language
dc.contributor.authorCasu, Albertoen
dc.contributor.authorGenovese, Alessandroen
dc.contributor.authorManna, Liberatoen
dc.contributor.authorLongo, Paoloen
dc.contributor.authorBuha, Jokaen
dc.contributor.authorBotton, Gianluigi A.en
dc.contributor.authorLazar, Sorinen
dc.contributor.authorKahaly, M. Upadhyayen
dc.contributor.authorSchwingenschlögl, Udoen
dc.contributor.authorPrato, Mirkoen
dc.contributor.authorLi, Hongboen
dc.contributor.authorGhosh, Sandeepen
dc.contributor.authorPalazon, Franciscoen
dc.contributor.authorDe Donato, Francescoen
dc.contributor.authorLentijo Mozo, Sergioen
dc.contributor.authorZuddas, Efisioen
dc.contributor.authorFalqui, Andreaen
dc.date.accessioned2016-02-01T13:50:10Zen
dc.date.available2016-02-01T13:50:10Zen
dc.date.issued2016-01-27en
dc.identifier.citationCu2Se and Cu Nanocrystals as Local Sources of Copper in Thermally Activated In Situ Cation Exchange 2016 ACS Nanoen
dc.identifier.issn1936-0851en
dc.identifier.issn1936-086Xen
dc.identifier.doi10.1021/acsnano.5b07219en
dc.identifier.urihttp://hdl.handle.net/10754/595373en
dc.description.abstractAmong the different synthesis approaches to colloidal nanocrystals a recently developed toolkit is represented by cation exchange reactions, where the use of template nanocrystals gives access to materials that would be hardly attainable via direct synthesis. Besides, post-synthetic treatments, such as thermally activated solid state reactions, represent a further flourishing route to promote finely controlled cation exchange. Here, we report that, upon in situ heating in a transmission electron microscope, Cu2Se nanocrystals deposited on an amorphous solid substrate undergo partial loss of Cu atoms, which are then engaged in local cation exchange reactions with Cu “acceptors” phases represented by rod- and wire- shaped CdSe nanocrystals. This thermal treatment slowly transforms the initial CdSe nanocrystals into Cu2-xSe nanocrystals, through the complete sublimation of Cd and the partial sublimation of Se atoms. Both Cu “donor” and “acceptor” particles were not always in direct contact with each other, hence the gradual transfer of Cu species from Cu2Se or metallic Cu to CdSe nanocrystals was mediated by the substrate and depended on the distance between the donor and acceptor nanostructures. Differently from what happens in the comparably faster cation exchange reactions performed in liquid solution, this study shows that slow cation exchange reactions can be performed at the solid state, and helps to shed light on the intermediate steps involved in such reactions.en
dc.language.isoenen
dc.publisherAmerican Chemical Society (ACS)en
dc.relation.urlhttp://pubs.acs.org/doi/abs/10.1021/acsnano.5b07219en
dc.rightsThis document is the Accepted Manuscript version of a Published Work that appeared in final form in ACS Nano, 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/acsnano.5b07219.en
dc.titleCu2Se and Cu Nanocrystals as Local Sources of Copper in Thermally Activated In Situ Cation Exchangeen
dc.typeArticleen
dc.contributor.departmentNABLA Laben
dc.contributor.departmentBiological and Environmental Sciences and Engineering (BESE) Divisionen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.identifier.journalACS Nanoen
dc.eprint.versionPost-printen
dc.contributor.institutionDepartment of Nanochemistry, Istituto Italiano di Tecnologia, Via Morego 30, 16163 Genova, Italyen
dc.contributor.institutionGatan, Inc., 5794 W Las Positas BLVD, Pleasanton, California, United Statesen
dc.contributor.institutionDepartment of Materials Science and Engineering, Mc Master University, Hamilton, Ontario, Canadaen
dc.contributor.institutionFEI Electron Optics, Achtseweg Noord 5, Eindhoven, 5600 KA, Netherlandsen
dc.contributor.institutionChemistry Division, Los Alamos National Laboratory, New Mexico, United Statesen
dc.contributor.affiliationKing Abdullah University of Science and Technology (KAUST)en
kaust.authorCasu, Albertoen
kaust.authorGenovese, Alessandroen
kaust.authorKahaly, M. Upadhyayen
kaust.authorSchwingenschlögl, Udoen
kaust.authorLentijo Mozo, Sergioen
kaust.authorZuddas, Efisioen
kaust.authorFalqui, Andreaen
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