Microdynamic changes of moisture-induced crystallization of amorphous calcium carbonate revealed via in situ FTIR spectroscopy

Literature Information

Publication Date 2019-09-06
DOI 10.1039/C9CP04440J
Impact Factor 3.676
Authors

Meng Cheng, Shengtong Sun, Peiyi Wu


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Abstract

Amorphous calcium carbonate (ACC) is the most important intermediate phase in the nucleation/crystallization process of CaCO3, and thus the proper interpretation of how ACC transforms into final crystals at the molecular level is crucial to understand various biomineralization phenomena. Herein, we successfully monitored the moisture-induced crystallization process of ACC via in situ FTIR spectroscopy, which is very sensitive to the specific changes of the different vibrational modes of carbonates and water molecules. In combination with the tools of perturbation correlation moving window and two-dimensional correlation spectroscopy, it is found that the driving force of ACC crystallization is the fracture of hydrogen bonds formed by H2O⋯CO32−. The bending vibrations of carbonate are more sensitive to moisture permeation than the stretching modes, and the whole crystallization process can be divided into three sequential stages, i.e., the hydrated ACC first loses its structural water and converts to the dehydrated ACC, which then gradually transforms into vaterite, followed by the final growth of vaterite crystals. Anhydrous ACC microdomains are found to be already existing in the as-prepared ACCs.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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