Distinct Short-Range Order Is Inherent to Small Amorphous Calcium Carbonate Clusters (<2 nm)

© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, WeinheimAmorphous 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 bee...

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Main Authors: Sun, S., Chevrier, D., Zhang, P., Gebauer, Denis, Cölfen, H.
Format: Journal Article
Published: Wiley-VCH Verlag 2016
Online Access:http://hdl.handle.net/20.500.11937/52935
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author Sun, S.
Chevrier, D.
Zhang, P.
Gebauer, Denis
Cölfen, H.
author_facet Sun, S.
Chevrier, D.
Zhang, P.
Gebauer, Denis
Cölfen, H.
author_sort Sun, S.
building Curtin Institutional Repository
collection Online Access
description © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, WeinheimAmorphous 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 CaCO3 units. Ligand concentration and structure are shown to be key factors in stabilizing the ACC clusters. More importantly, even in such small CaCO3 entities, 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 CaCO3 core. 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.
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spelling curtin-20.500.11937-529352018-03-29T09:09:13Z Distinct Short-Range Order Is Inherent to Small Amorphous Calcium Carbonate Clusters (<2 nm) Sun, S. Chevrier, D. Zhang, P. Gebauer, Denis Cölfen, H. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, WeinheimAmorphous 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 CaCO3 units. Ligand concentration and structure are shown to be key factors in stabilizing the ACC clusters. More importantly, even in such small CaCO3 entities, 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 CaCO3 core. 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. 2016 Journal Article http://hdl.handle.net/20.500.11937/52935 10.1002/anie.201604179 Wiley-VCH Verlag restricted
spellingShingle Sun, S.
Chevrier, D.
Zhang, P.
Gebauer, Denis
Cölfen, H.
Distinct Short-Range Order Is Inherent to Small Amorphous Calcium Carbonate Clusters (<2 nm)
title Distinct Short-Range Order Is Inherent to Small Amorphous Calcium Carbonate Clusters (<2 nm)
title_full Distinct Short-Range Order Is Inherent to Small Amorphous Calcium Carbonate Clusters (<2 nm)
title_fullStr Distinct Short-Range Order Is Inherent to Small Amorphous Calcium Carbonate Clusters (<2 nm)
title_full_unstemmed Distinct Short-Range Order Is Inherent to Small Amorphous Calcium Carbonate Clusters (<2 nm)
title_short Distinct Short-Range Order Is Inherent to Small Amorphous Calcium Carbonate Clusters (<2 nm)
title_sort distinct short-range order is inherent to small amorphous calcium carbonate clusters (<2 nm)
url http://hdl.handle.net/20.500.11937/52935