Details
| Translated title of the contribution | Ausgeprägte Nahordnung in kleinen amorphen Calciumcarbonat-Clustern (<2 nm) |
|---|---|
| Original language | English |
| Pages (from-to) | 12206-12209 |
| Number of pages | 4 |
| Journal | Angewandte Chemie-International Edition |
| Volume | 55 |
| Issue number | 40 |
| Early online date | 9 Sept 2016 |
| Publication status | Published - 19 Sept 2016 |
| Externally published | Yes |
Abstract
Amorphous intermediate phases are vital precursors in the crystallization of many biogenic minerals. While inherent short-range orders have been found in amorphous calcium carbonates (ACCs) relating to different crystalline forms, it has never been clarified experimentally whether such orders already exist in very small clusters less than 2 nm in size. Here, we studied the stability and structure of 10,12-pentacosadiynoic acid (PCDA) protected ACC clusters with a core size of ca. 1.4 nm consisting of only seven CaCO 3units. Ligand concentration and structure are shown to be key factors in stabilizing the ACC clusters. More importantly, even in such small CaCO 3entities, a proto-calcite short-range order can be identified but with a relatively high degree of disorder that arises from the very small size of the CaCO 3core. Our findings support the notion of a structural link between prenucleation clusters, amorphous intermediates, and final crystalline polymorphs, which appears central to the understanding of polymorph selection.
Keywords
- amorphous materials, calcium carbonate clusters, carboxylate ligands, EXAFS, short-range order
ASJC Scopus subject areas
- Chemistry(all)
- General Chemistry
- Chemical Engineering(all)
- Catalysis
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In: Angewandte Chemie-International Edition, Vol. 55, No. 40, 19.09.2016, p. 12206-12209.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Distinct Short-Range Order Is Inherent to Small Amorphous Calcium Carbonate Clusters (< 2 nm)
AU - Sun, Shengtong
AU - Chevrier, Daniel M.
AU - Zhang, Peng
AU - Gebauer, Denis
AU - Coelfen, Helmut
N1 - Publisher Copyright: © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2016/9/19
Y1 - 2016/9/19
N2 - Amorphous intermediate phases are vital precursors in the crystallization of many biogenic minerals. While inherent short-range orders have been found in amorphous calcium carbonates (ACCs) relating to different crystalline forms, it has never been clarified experimentally whether such orders already exist in very small clusters less than 2 nm in size. Here, we studied the stability and structure of 10,12-pentacosadiynoic acid (PCDA) protected ACC clusters with a core size of ca. 1.4 nm consisting of only seven CaCO 3units. Ligand concentration and structure are shown to be key factors in stabilizing the ACC clusters. More importantly, even in such small CaCO 3entities, a proto-calcite short-range order can be identified but with a relatively high degree of disorder that arises from the very small size of the CaCO 3core. Our findings support the notion of a structural link between prenucleation clusters, amorphous intermediates, and final crystalline polymorphs, which appears central to the understanding of polymorph selection.
AB - Amorphous intermediate phases are vital precursors in the crystallization of many biogenic minerals. While inherent short-range orders have been found in amorphous calcium carbonates (ACCs) relating to different crystalline forms, it has never been clarified experimentally whether such orders already exist in very small clusters less than 2 nm in size. Here, we studied the stability and structure of 10,12-pentacosadiynoic acid (PCDA) protected ACC clusters with a core size of ca. 1.4 nm consisting of only seven CaCO 3units. Ligand concentration and structure are shown to be key factors in stabilizing the ACC clusters. More importantly, even in such small CaCO 3entities, a proto-calcite short-range order can be identified but with a relatively high degree of disorder that arises from the very small size of the CaCO 3core. Our findings support the notion of a structural link between prenucleation clusters, amorphous intermediates, and final crystalline polymorphs, which appears central to the understanding of polymorph selection.
KW - amorphous materials
KW - calcium carbonate clusters
KW - carboxylate ligands
KW - EXAFS
KW - short-range order
UR - http://www.scopus.com/inward/record.url?scp=84990226567&partnerID=8YFLogxK
U2 - 10.1002/ange.201604179
DO - 10.1002/ange.201604179
M3 - Article
VL - 55
SP - 12206
EP - 12209
JO - Angewandte Chemie-International Edition
JF - Angewandte Chemie-International Edition
SN - 1521-3757
IS - 40
ER -