Synthesis of Cu3N and Cu3N-Cu2O multicomponent mesocrystals: non-classical crystallization and nanoscale Kirkendall effect
File(s)
Author(s)
Primc, Darinka
Indrizzi, Luca
Tervoort, Elena
Xie, Fang
Niederberger, Markus
Type
Journal Article
Abstract
Mesocrystals are superstructures of crystallographically aligned nanoparticles and are a rapidly emerging class of crystalline materials displaying sophisticated morphologies and properties, beyond those originating from size and shape of nanoparticles alone. This study reports the first synthesis of Cu3N mesocrystals employing structure-directing agents with a subtle tuning of the reaction parameters. Detailed structural characterizations carried out with a combination of transmission electron microscopy techniques (HRTEM, HAADF-STEM-EXDS) reveal that Cu3N mesocrystals form by non-classical crystallization, and variations in their sizes and morphologies are traced back to distinct attachment scenarios of corresponding mesocrystal subunits. In the presence of oleylamine, the mesocrystal subunits in the early reaction stages prealign in a crystallographic fashion and afterwards grow into the final mesocrystals, while in the presence of hexadecylamine the subunits come into contact through misaligned attachment, and subsequently, to some degree, realign in crystallographic register. Upon prolonged heating both types of mesocrystals undergo chemical conversion processes resulting in structural and morphological changes. A two-step mechanism of chemical conversion is proposed, involving Cu3N decomposition and anion exchange driven by the nanoscale Kirkendall effect, resulting first in multicomponent/heterostructured Cu3N–Cu2O mesocrystals, which subsequently convert into Cu2O nanocages. It is anticipated that combining nanostructured Cu3N and Cu2O in a mesocrystalline and hollow morphology will provide a platform to expand their application potential.
Date Issued
2021-10-08
Date Acceptance
2021-10-08
Citation
Nanoscale, 2021, 13 (41), pp.17521-17529
ISSN
2040-3364
Publisher
Royal Society of Chemistry
Start Page
17521
End Page
17529
Journal / Book Title
Nanoscale
Volume
13
Issue
41
Copyright Statement
© The Royal Society of Chemistry 2021
Identifier
http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000707425600001&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=1ba7043ffcc86c417c072aa74d649202
Subjects
Science & Technology
Physical Sciences
Technology
Chemistry, Multidisciplinary
Nanoscience & Nanotechnology
Materials Science, Multidisciplinary
Physics, Applied
Chemistry
Science & Technology - Other Topics
Materials Science
Physics
COPPER NITRIDE NANOCUBES
OPTICAL-PROPERTIES
NANOPARTICLES
SEMICONDUCTORS
FILMS
TIME
Publication Status
Published
Date Publish Online
2021-10-08