Iron-Catalyzed Chlorination of Titanium Oxides in Molten Salts: A Deep Neural Network-Based Mechanistic Study

Molten salt chlorination is a key industrial route for producing titanium tetrachloride (TiCl4), yet the atomistic catalytic role of iron (Fe) in the carbothermic chlorination of titanium oxides remains unclear. Here, the chlorination behavior of the NaCl–C–Cl2–FeTiO3 system was investigated by combining thermodynamic calculations with Ab Initio Molecular Dynamics (AIMD) and Deep Potential Molecular Dynamics (DPMD) simulations. AIMD results show that carbon adjacent to Fe exhibits enhanced reactivity, and that Fe-C synergistic electron transfer promotes both titanium oxide reduction and subsequent titanium chlorination. DPMD results further reveal that Fe not only accelerates these transformations, but also improves interfacial contact among carbon, titanium oxides, and molten salt, thereby enhancing mass transfer and shortening the formation time of TiCl4. Temperature-dependent analysis indicates that Fe-C and C-O coordination numbers remain high near 1073 K, where TiCl4 formation is efficient and relatively stable. Although increasing temperature can further enhance diffusion, its effect on reaction acceleration is limited, while excessively high temperatures weaken Fe-C interactions and reduce catalytic efficiency. These findings clarify the catalytic mechanism of Fe in molten salt chlorination at the atomic scale and provide theoretical support for process optimization.