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.
Original language | English |
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Pages (from-to) | 1143-1149 |
Number of pages | 7 |
Journal | Journal of Physical Chemistry C |
Volume | 125 |
Issue number | 1 |
DOIs | |
Publication status | Published - 4 Jan 2021 |
Funding
The authors gratefully acknowledge Shell Global Solutions and The Netherlands Association of Scientific Research (NWO) for funding through the CHIPP program. The research of Y.X. was supported by a Leverhulme research project grant (RPG-2017-178). The authors would like to thank Prof. Joseph Patterson (University of California, Irvine) for helpful discussions on the GOx cryoTEM experiments.
Funders | Funder number |
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European Union's Horizon 2020 - Research and Innovation Framework Programme | 885795 |
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Center for Multiscale Electron Microscopy (CMEM)
Friedrich, H. (Manager), Bransen, M. (Education/research officer), Schmit, P. (Education/research officer), Schreur - Piet, I. (Other) & Spoelstra, A. (Education/research officer)
Physical ChemistryFacility/equipment: Research lab