Morphogenesis of magnetite mesocrystals: interplay between nanoparticle morphology and solvation shell

DOI: 10.1021/acs.chemmater.1c01941

Authors: Julian Schlotheuber Né Brunner (Universität Konstanz) , Britta Maier (Universität Konstanz) , Sabrina L. J. Thoma (University of Bayreuth; RWTH Aachen University) , Felizitas Kirner (Universität Konstanz) , Igor A. Baburin (TU Dresden) , Dmitry Lapkin (Deutsches Elektronen-Synchrotron DESY) , Rose Rosenberg (Universität Konstanz) , Sebastian Sturm (Leibniz Institute for Solid State and Materials Research (IFW)) , Dameli Assalauova (Deutsches Elektronen-Synchrotron DESY) , Jerome Carnis (Deutsches Elektronen-Synchrotron DESY) , Young Yong Kim (Deutsches Elektronen-Synchrotron DESY) , Zhe Ren (Deutsches Elektronen-Synchrotron DESY) , Fabian Westermeier (Deutsches Elektronen-Synchrotron DESY) , Sebastian Theiss (Universität Konstanz; Leibniz-University Hannover) , Horst Borrmann (Max-Planck-Institute for Chemical Physics of Solids) , Sebastian Polarz (Universität Konstanz; Leibniz-University Hannover) , Alexander Eychmüller (TU Dresden) , Axel Lubk (Leibniz Institute for Solid State and Materials Research (IFW)) , Ivan A. Vartanyants (Deutsches Elektronen-Synchrotron DESY; Nuclear University MEPhI (Moscow Engineering Physics Institute)) , Helmut Cölfen (Universität Konstanz) , Mirijam Zobel (University of Bayreuth; RWTH Aachen University) , Elena V. Sturm (Universität Konstanz)
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Chemistry Of Materials , VOL 161

State: Published (Approved)
Published: November 2021
Diamond Proposal Number(s): 17345

Abstract: Nanoparticle assemblies with long-range packing order and preferred crystallographic orientation of building blocks, i.e., mesocrystals, are of high interest not only because of their unique physical properties but also due to their complex structure and morphogenesis. In this study, faceted mesocrystals have been assembled from the dispersion of truncated cubic-shaped iron oxide nanoparticles stabilized by oleic acid (OA) molecules using the nonsolvent “gas phase diffusion technique” into an organic solvent. The effects of synthesis conditions as well as of the nanoparticle size and shape on the structure and morphogenesis of mesocrystals were examined. The interactions of OA-capped iron oxide nanoparticles with solvent molecules were probed by analytical ultracentrifugation and double difference pair distribution function analysis. It was shown that the structure of the organic shell significantly depends on the nature and polarity of solvent molecules. For the nonpolar solvents, the interaction of the aliphatic chains of OA molecules with the solvent molecules is favorable and the chains extend into the solvent. The solvation shell around the nanoparticles is more extended in nonpolar and more compact in polar solvents. There is a clear trend for more spherical particles to be assembled into the fcc superlattice, whereas less truncated cubes form rhombohedral and tetragonal structures. The observed changes in packing symmetry are reminiscent of structural polymorphism known for “classical” (atomic and molecular) crystals.

Journal Keywords: Crystals; Nanoparticles; Colloids; Solvents; Nanocrystals

Subject Areas: Chemistry, Materials


Instruments: I15-1-X-ray Pair Distribution Function (XPDF)

Other Facilities: ID15-ERH at ESRF; P10 at PETRA III

Added On: 29/11/2021 08:39

Discipline Tags:

Chemistry Materials Science Nanoscience/Nanotechnology

Technical Tags:

Scattering Pair Distribution Function (PDF)