Controlling CaCO3 nucleation with halogen-terminated self-assembled monolayers

Although understanding and controlling CaCO 3 nucleation is crucial for both biological and artificial mineralization, there are some fundamental issues, including the impact of surface free energy on CaCO 3 nucleation remains unclear. Furthermore, as the abundant elements in nature, halogens can incorporate into organic matrices and participate in the nucleation process. However, their specific influences on CaCO 3 nucleation are poorly understood. Here, we investigate how halogen chemistry surfaces control CaCO 3 nucleation through constructing halogen (F 3 , Cl, Br, I)-terminated self-assembled monolayers as model surfaces and measuring the nucleation kinetic/thermodynamic parameters of CaCO 3 on them for the first time. The results demonstrate that the abilities of halogen chemistry surfaces to promote CaCO 3 nucleation are determined by either thermodynamic or kinetic control, depending on the supersaturation range. Under thermodynamic control, the CaCO 3 nucleation efficiency on various halogen chemistry surfaces decreases in the order of F 3 , Cl, Br and I, which is consistent with the increasing order of surface free energy. Our work sheds new lights on the correlation between materials’ abilities to control CaCO 3 nucleation and their surface free energies, and provides a simple strategy for controlling CaCO 3 nucleation.