Abstract
Calcium carbonate (CaCO3), the most abundant biogenic mineral on earth, plays a crucial role in various fields such as hydrosphere, biosphere, and climate regulation. Of the four polymorphs, calcite, aragonite, vaterite, and amorphous CaCO3, vaterite is the most enigmatic one due to an ongoing debate regarding its structure that has persisted for nearly a century. In this work, based on systematic transmission electron microscopy characterizations, crystallographic analysis and machine learning aided molecular dynamics simulations with ab initio accuracy, we reveal that vaterite can be regarded as a polytypic structure. The basic phase has a monoclinic lattice possessing pseudohexagonal symmetry. Direct imaging and atomic-scale simulations provide evidence that a single grain of vaterite can contain three orientation variants. Additionally, we find that vaterite undergoes a second-order phase transition with a critical point of ~190 K. These atomic scale insights provide a comprehensive understanding of the structure of vaterite and offer advanced perspectives on the biomineralization process of calcium carbonate.
| Original language | English (US) |
|---|---|
| Article number | 7858 |
| Journal | Nature communications |
| Volume | 14 |
| Issue number | 1 |
| DOIs | |
| State | Published - Dec 2023 |
Funding
X.S. acknowledges the National Natural Science Foundation of China (No. 51901065), the Nature Science Foundation of Hebei Province (No. E2020201023), and the Advanced Talents Incubation Program of Hebei University (No. 521000981164) for financial support. H.N. was supported by the National Science Fund for Excellent Young Scientist Fund Program (Overseas) of China, the National Natural Science Foundation of China (No.92370118), the Science and Technology Activities fund for Overseas Researchers of Shaanxi Province, and the Research Fund of the State Key Laboratory of Solidification Proceeding (NPU) of China (No. 2020-QZ-03). This work made use of the EPIC facility of Northwestern University’s NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-2025633), the International Institute for Nanotechnology (IIN), and Northwestern’s MRSEC program (NSF DMR-2308691). This work also made use of the Integrated Molecular Structure Education and Research Center (IMSERC) at Northwestern University, which has received support from the State of Illinois, Northwestern University, ShyNE Resource (NSF ECCS-2025633), NSFCHE-1048773, and the IIN. The authors are grateful to Prof. Qingling Feng at Tsinghua University for kindly providing the bulk pearl samples and Dr. Chi Zhang in Ocean University of China for many helpful discussions on vaterite structures. X.S. acknowledges the National Natural Science Foundation of China (No. 51901065), the Nature Science Foundation of Hebei Province (No. E2020201023), and the Advanced Talents Incubation Program of Hebei University (No. 521000981164) for financial support. H.N. was supported by the National Science Fund for Excellent Young Scientist Fund Program (Overseas) of China, the National Natural Science Foundation of China (No.92370118), the Science and Technology Activities fund for Overseas Researchers of Shaanxi Province, and the Research Fund of the State Key Laboratory of Solidification Proceeding (NPU) of China (No. 2020-QZ-03). This work made use of the EPIC facility of Northwestern University’s NUANCE Center, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-2025633), the International Institute for Nanotechnology (IIN), and Northwestern’s MRSEC program (NSF DMR-2308691). This work also made use of the Integrated Molecular Structure Education and Research Center (IMSERC) at Northwestern University, which has received support from the State of Illinois, Northwestern University, ShyNE Resource (NSF ECCS-2025633), NSFCHE-1048773, and the IIN. The authors are grateful to Prof. Qingling Feng at Tsinghua University for kindly providing the bulk pearl samples and Dr. Chi Zhang in Ocean University of China for many helpful discussions on vaterite structures.
ASJC Scopus subject areas
- General Chemistry
- General Biochemistry, Genetics and Molecular Biology
- General Physics and Astronomy