Crystallization Pathway of Monohydrocalcite via Amorphous Calcium Carbonate Regulated by Magnesium Ion

doi:10.15541/jim20240075

Abstract

Abstract:

Amorphous calcium carbonate (ACC) plays a crucial role in biomineralization which crystallization process has attracted significant attention. Magnesium ions (Mg²⁺) can effectively regulate the crystallization of ACC, but the mechanism by which it controls the transformation of ACC into monohydrocalcite (MHC, CaCO₃·H₂O) is not well understood. In this study, Mg²⁺ was used as an additive, and the transformation process from ACC to MHC was investigated in situ using an automatic potentiometric titration system. It was found that Mg²⁺ can enhance the stability of ACC and inhibit the formation of calcite and vaterite. During the transformation of ACC to MHC, partial dissolution firstly occurred, and the molar ratio of Mg/Ca in the solution increased with the consumption of Ca²⁺. Mg²⁺further adsorbed onto the surface of ACC particles, inhibiting surface dissolution of ACC and promoting internal dissolution of ACC, resulting in the formation of hollow structures rich in Mg²⁺ and smaller-sized nanoparticles. Subsequently, MHC crystallized and grew through particle aggregation. These results elucidate the mechanism by which Mg²⁺ regulates the transformation of ACC into MHC through a non-classical crystallization pathway, enhancing an understanding of the biomineralization mechanism from ACC precursor.

Key words: biomineralization, amorphous calcium carbonate, magnesium ion, monohydrocalcite, crystal growth

CLC Number:

TB321

CAI Hao, WANG Qihang, ZOU Zhaoyong. Crystallization Pathway of Monohydrocalcite via Amorphous Calcium Carbonate Regulated by Magnesium Ion[J]. Journal of Inorganic Materials, 2024, 39(11): 1275-1282.

Figures/Tables 6

Fig. 1 (a-c) XRD patterns and (d-f) FT-IR spectra of crystallized products prepared at different carbonate concentrations of (a, d) 10, (b, e) 20, (c, f) 40 mmol/L and different ratios of Mg/(Mg+Ca) Colorful figures are available on website

Fig. 2 SEM images of crystallized products at carbonate concentration of 10 mmol/L and different ratios of Mg/(Mg+Ca) (a, b) 0.5; (c, d) 0.6; (e, f) 0.7; (g, h) 0.8

Fig. 3 In-situ monitoring of solution changes during crystallization of Mg-ACC and structural characterization of products at different time points (a) Ca2+ activity; (b) pH evolution; (c) XRD patterns and (d) FT-IR spectra of the crystallized products at different crystallization stages. Concentration of carbonate: 10 mmol/L; Mg/(Mg+Ca) ratio: 0.6

Fig. 4 SEM images of the products at different stages during ACC crystallization (a) 180 s; (b) 3000 s; (c, d) 4800 s; (e, f) 6900 s. Concentration of carbonate: 10 mmol/L; Mg/(Mg+Ca) ratio: 0.6

Fig. 5 TEM images of the products at different stages during ACC crystallization (a) 180 s; (b) 3000 s; (c, d) 4800 s; (e, f) 6900 s. Concentration of carbonate: 10 mmol/L; Mg/(Mg+Ca) ratio: 0.6

Fig. 6 Mg/Ca molar ratios of the products and solutions at different stages during ACC crystallization (a-c) HAADF images and their corresponding EDS mappings of products during crystallization for |(a) 180, (b) 4800 and (c) 6900 s; (d) Mg/Ca molar ratio in solution after different crystallization time. Concentration of carbonate: 10 mmol/L; Mg/(Mg+Ca) ratio: 0.6

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