Electrophoretic and potentiometric signatures of multistage CaCO3 nucleation

JOURNAL OF COLLOID AND INTERFACE SCIENCE

卷:544

Article

Prus, Marzena¹  Szymanek, Karolina²  Mills, Jennifer³  Lammers, Laura Nielsen³  Piasecki, Wojciech²  Kedra-Krolik, Karolina¹  Zarzycki, Piotr^1,4 

[1] Polish Acad Sci, Inst Phys Chem, Warsaw, Poland

[2] Jozef Pilsudski Univ Phys Educ, Dept Chem & Biochem, Warsaw, Poland

[3] Univ Calif Berkeley, Dept Environm Sci Policy & Management, Berkeley, CA 94720 USA

[4] Lawrence Berkeley Natl Lab, Energy Geosci Div, 1 Cyclotron Rd, Berkeley, CA USA

关键词: Calcium carbonate;    Amorphous calcium carbonate;    Vaterite;    Calcite;    Multistage nucleation pathway;    zeta-potential;    Electrical double layer;    Carbonate speciation;   

DOI  :  10.1016/j.jcis.2019.03.002

来源: Elsevier

【 摘 要 】

Hypothesis: Calcium carbonate nucleation is often a complex and multistep process that is difficult to follow in situ. The time-resolved electrochemical and electrophoretic methods can provide a new insight into the nucleation pathway. Experiments: Here, we used a combination of speciation calculations with time-resolved electrophoretic and potentiometric methods to monitor calcium carbonate precipitation from a slightly supersaturated solution. Findings: After an initial mixing period of three minutes in which metastable CaCO3 phases may have nucleated and subsequently dissolved due to locally-high supersaturations, bulk solution pH and Ca2+ concentrations stabilize before decreasing in tandem with the precipitation of a CaCO3 phase. After an hour, the precipitate is dominated by calcite that grows at the expense of dissolving vaterite. The time-dependent electrokinetic potential shows analogous signatures of multistage nucleation process: initial rapid changes in zeta-potential are followed by much slower equilibration starting about one hour after reagents are mixed. The changes in zeta-potential, solution pH, saturation indexes, and particle morphology are consistent with vaterite to calcite transformation via dissolution of the former and recrystallization of the latter. These findings highlight the potential use of zeta-potential measurements for monitoring polymorphic transformations of carbonate phases in-situ. (C) 2019 Elsevier Inc. All rights reserved.

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