1. Crystallization via Oriented Attachment of Nanoclusters with Short-Range Order in Solution
- Author
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Paul H. H. Bomans, Yifei Xu, Nico A. J. M. Sommerdijk, Heiner Friedrich, Hao Su, Materials and Interface Chemistry, Institute for Complex Molecular Systems, Physical Chemistry, ICMS Core, EAISI, and EIRES
- Subjects
Aqueous solution ,Materials science ,02 engineering and technology ,010402 general chemistry ,021001 nanoscience & nanotechnology ,01 natural sciences ,0104 chemical sciences ,Surfaces, Coatings and Films ,Electronic, Optical and Magnetic Materials ,Nanoclusters ,law.invention ,All institutes and research themes of the Radboud University Medical Center ,General Energy ,Chemical engineering ,law ,Short range order ,Physical and Theoretical Chemistry ,Crystallization ,0210 nano-technology ,Nanomedicine Radboud Institute for Molecular Life Sciences [Radboudumc 19] - Abstract
Many mineral crystallization processes in aqueous solutions involve formation of nanoclusters with short-range order. Their transformation into crystalline products is not well understood. Here we investigate the formation of long-range crystalline order within networks of cobalt-based nanoclusters. High-resolution cryogenic transmission electron microscopy (cryoTEM) together with NMR and FTIR spectroscopies shows the formation of ∼0.8 nm sized (Co)(NH3)5CO3 complexes at the initial stage. By ligand exchange, those complexes become bridged by CO32-/OH- ligands and form ∼2 nm sized clusters, which subsequently aggregate into sheetlike networks due to the structural heterogeneity of the clusters. By further ligand change and adjustment in cluster orientations, long-range order is established, which leads to the nucleation of ammonium cobalt kambaldaite nanocrystals. Our observations demonstrate that nanoclusters with short-range order can form crystals via an oriented-attachment pathway, which provides new insights into multistep crystallization processes.
- Published
- 2021