Sulfate-Controlled Heterogeneous CaCO3 Nucleation and Its Non-linear Interfacial Energy Evolution

Zhu, Yaguang; Li, Qingyun; Kim, Doyoon; Min, Yujia; Lee, Byeongdu; Jun, Young-Shin

doi:10.1021/acs.est.1c02865

Title: Sulfate-Controlled Heterogeneous CaCO₃ Nucleation and Its Non-linear Interfacial Energy Evolution

Journal Article · 26 July 2021 · Environmental Science and Technology

DOI: https://doi.org/10.1021/acs.est.1c02865 · OSTI ID:1840567

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^[1]; Lee, Byeongdu ^[2];

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Washington Univ., St. Louis, MO (United States)
Argonne National Lab. (ANL), Argonne, IL (United States)

Unveiling the effects of an environmental abundant anion “sulfate” on the formation of calcium carbonate (CaCO₃) is essential to understand the formation mechanisms of biominerals like corals and brachiopod shells, as well as the scale formation in desalination systems. However, it was experimentally challenging to elucidate the sulfate–CaCO₃ interactions at the explicit first step of CaCO₃ formation: nucleation. In addition, there is limited quantitative information on the precise control of nucleation kinetics. Here, heterogeneous CaCO₃ nucleation is monitored in real time as a function of sulfate concentrations (0–10 mM Na₂SO₄) using synchrotron-based grazing incidence X-ray scattering techniques. The results showed that sulfate can be incorporated in the nuclei, resulting in a nearly 90% decrease in the CaCO₃ nucleation rate, causing a 120% increase in the CaCO₃ nucleus size, and inhibiting the vaterite-to-calcite phase transformation. Moreover, this work quantitatively relates sulfate concentrations to the effective interfacial energies of CaCO₃ and finds a non-linear trend, suggesting that CaCO₃ heterogeneous nucleation is more sensitive at a low sulfate concentration. This study can be readily extended to study other additives and obtain quantitative relationships between additive concentrations and CaCO₃ interfacial energies, a key step toward achieving natural and engineered controls on CaCO₃ nucleation.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Contributing Organization:: Energy Frontier Research Center

Grant/Contract Number:: AC02-05CH11231; AC02-06CH11357

OSTI ID:: 1840567

Journal Information:: Environmental Science and Technology, Journal Name: Environmental Science and Technology Journal Issue: 16 Vol. 55; ISSN 0013-936X

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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heterogeneous nucleation
interfacial energy
sulfate
vaterite

Title: Sulfate-Controlled Heterogeneous CaCO3 Nucleation and Its Non-linear Interfacial Energy Evolution

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Title: Sulfate-Controlled Heterogeneous CaCO₃ Nucleation and Its Non-linear Interfacial Energy Evolution