Although understanding and controlling CaCO₃ nucleation is crucial for both biological and artificial mineralization, there are some fundamental issues, including the impact of surface free energy on CaCO₃ 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 CaCO₃ nucleation are poorly understood. Here, we investigate how halogen chemistry surfaces control CaCO₃ nucleation through constructing halogen (F₃, Cl, Br, I)-terminated self-assembled monolayers as model surfaces and measuring the nucleation kinetic/thermodynamic parameters of CaCO₃ on them for the first time. The results demonstrate that the abilities of halogen chemistry surfaces to promote CaCO₃ nucleation are determined by either thermodynamic or kinetic control, depending on the supersaturation range. Under thermodynamic control, the CaCO₃ nucleation efficiency on various halogen chemistry surfaces decreases in the order of F₃, 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 CaCO₃ nucleation and their surface free energies, and provides a simple strategy for controlling CaCO₃ nucleation.

尽管理解和控制CaCO _{3成核对于生物和人工矿化都至关重要，但仍存在一些基本问题，包括表面自由能对CaCO 3}成核的影响仍不清楚。此外，作为自然界中丰富的元素，卤素可以结合到有机基体中并参与成核过程。然而，它们对CaCO ₃成核的具体影响却知之甚少。在这里，我们通过构建卤素（F ₃，Cl，Br，I）封端的自组装单分子层作为模型表面并测量CaCO 3 的成核动力学/热力学参数，研究卤素化学表面如何控制CaCO _3成核。第一次接触他们。结果表明，卤素化学表面促进CaCO ₃成核的能力由热力学或动力学控制决定，具体取决于过饱和范围。在热力学控制下，各种卤素化学表面上的CaCO ₃成核效率按F ₃、Cl、Br和I的顺序降低，这与表面自由能的增加顺序一致。我们的工作为材料控制CaCO ₃成核的能力与其表面自由能之间的相关性提供了新的线索，并提供了控制CaCO ₃成核的简单策略。