abstract
A simple one-pot approach based on the "benzyl alcohol route" is introduced for the fabrication of highly ordered supercrystals composed of highly uniform 3-4 nm zirconia and rare-earth stabilized zirconia nanoparticles. The as-fabricated supercrystals reach sizes larger than 10 mu m and present well-defined 3D morphologies such as flower-like, rhombic dodecahedron, and bipyramids. This system is unique In that the supercrystals are formed in one-step directly in the reaction medium where the nanoparticles are synthesized. The uniformity in nanocrystal shape and size is attributed to the in situ formation of benzoate species that directs the nanoparticle growth and assembly. The low colloidal stabilization of the benzoate-capped nanoparticles in benzyl alcohol promotes the formation of supercrystals in solution by pi-pi interaction between the in situ formed benzoate ligands attached to neighboring particles. By varying the reaction temperature and the nature of the doping the way the nanobulding blocks assemble in the supercrystals could be controlled. Standard FCC superlattice packings were found together with more unusual ones with P6/mmm and R (3) over barm symmetries.
keywords
ZIRCONIA NANOCRYSTALS; LAMELLAR NANOHYBRIDS; SCALE SYNTHESIS; NANOSTRUCTURES; DNA; ORGANIZATION
subject category
Chemistry; Science & Technology - Other Topics; Materials Science
authors
Pucci, A; Willinger, MG; Liu, F; Zeng, XB; Rebuttini, V; Clavel, G; Bai, X; Ungar, G; Pinna, N
our authors
Nicola Pinna
Researcher
Xue Bai
Post-doc FellowshipGroups
Projects
Structural and chemical characterization at the nanometer scale (PTDC/CTM/100468/2008)
RMNE-UA-National Network of Electron Microscopy (REDE/1509/RME/2005 )
acknowledgements
This work was partially supported by the WCU (World Class University) program through the National Research Foundation (NRF) of Korea funded by the Ministry of Education, Science and Technology (R31-10013), by FCT projects PTDC/CTM/100468/2008, REDE/1509/RME/2005, SFRH/BPD/71671/2010, SFRH/BD/68810/2010, and SFRH/BD/45177/2008, and by the EU FP7 project NANOGOLD (No. 228455). We are grateful to O. Bikondoa, D. Mannix, S. Brown and P. Thompson at BM28 (XMaS) beamline, ESRF, and to J. Hiller and N. Terrill at 122 at Diamond for help with the SAXD experiments, and to A.J.S. Fernandes from the Physics Department of the University of Aveiro for Raman spectroscopy. Prof. Edson Roberto Leite from Federal University of Sao Carlos is warmly acknowledged for a discussion at the MRS fall meeting 2011 on the zirconium oxide synthesis following the