TY - JOUR
T1 - Crystallization via Oriented Attachment of Nanoclusters with Short-Range Order in Solution
AU - Su, Hao
AU - Bomans, Paul H.H.
AU - Friedrich, Heiner
AU - Xu, Yifei
AU - Sommerdijk, Nico
PY - 2021/1/4
Y1 - 2021/1/4
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=85099646177&partnerID=8YFLogxK
U2 - 10.1021/acs.jpcc.0c10323
DO - 10.1021/acs.jpcc.0c10323
M3 - Article
AN - SCOPUS:85099646177
VL - 125
SP - 1143
EP - 1149
JO - Journal of Physical Chemistry C
JF - Journal of Physical Chemistry C
SN - 1932-7455
IS - 1
ER -