A Microkinetic Model of Calcite Step Growth
A Microkinetic Model of Calcite Step Growth
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DOI：
10.1002/anie.201604357
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发表时间：
2016-09-05
影响因子：
16.6
通讯作者：
Stipp, S. L. S.
中科院分区：
文献类型：
--
作者：
Andersson, M. P.;Dobberschutz, S.;Stipp, S. L. S.
尽管经过几十年的研究，基于离子附着和脱离速率的矿物生长模型未能预测超出狭窄范围的条件下的行为。在这里，我们提出了一个微观动力学模型，准确地再现方解石的生长在一个非常广泛的范围内公布的实验数据的溶液组成，饱和指数，pH值和杂质。我们表明，多核配合物在矿物生长中发挥核心作用，在高过饱和度和经典的络合模型是足以重现测量速率。脱水的附着物种，而不是矿物表面，是速率限制。密度泛函理论支持我们的结论。该模型提供了新的见解矿物生长的分子机制，控制生物矿化，矿物结垢和工业材料合成。
In spite of decades of research, mineral growth models based on ion attachment and detachment rates fail to predict behavior beyond a narrow range of conditions. Here we present a microkinetic model that accurately reproduces calcite growth over a very wide range of published experimental data for solution composition, saturation index, pH and impurities. We demonstrate that polynuclear complexes play a central role in mineral growth at high supersaturation and that a classical complexation model is sufficient to reproduce measured rates. Dehydration of the attaching species, not the mineral surface, is rate limiting. Density functional theory supports our conclusions. The model provides new insights into the molecular mechanisms of mineral growth that control biomineralization, mineral scaling and industrial material synthesis.