Unveiling the High-Temperature oxidation mechanism of TiCl4 via deep potential molecular dynamics toward TiO2 synthesis.
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| Title: | Unveiling the High-Temperature oxidation mechanism of TiCl4 via deep potential molecular dynamics toward TiO2 synthesis. |
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| Authors: | Li, Dongqin1,2 (AUTHOR), Li, Linfei1 (AUTHOR), Lu, Ping2 (AUTHOR), Zhou, Jie1 (AUTHOR), Chen, Yunmin3 (AUTHOR), Sheng, Zhuo1,2 (AUTHOR), Li, Liang4 (AUTHOR), Chen, Xiumin1,5 (AUTHOR) chenxiumin9@outlook.com, Liu, Dachun1,5 (AUTHOR) lcd_2002@sina.com |
| Source: | Chemical Engineering Science. Mar2026, Vol. 323, pN.PAG-N.PAG. 1p. |
| Subjects: | Titanium dioxide, Oxidation, Titanium tetrachloride, Steric hindrance, Molecular dynamics, Polymer aggregates, Chemical kinetics, Electronic materials |
| Abstract: | [Display omitted] • Reveals high-temperature mechanism of TiCl 4 oxidation via FPMD/DPMD. • Uncovers electronic and steric drivers for Ti-O bond formation and Ti-Cl cleavage. • Synergy of complexation and radical pathways directs polynuclear aggregate growth. • Provides mechanistic foundation for future rational design of TiO 2 synthesis processes. Titanium dioxide (TiO 2) exhibits significant potential in various applications, including coatings, photocatalysis, and energy storage. However, the high-temperature oxidation mechanism of its common precursor (TiCl 4), remains poorly understood, impeding the rational design of synthesis processes for tailored material properties. To address this core challenge in chemical engineering science, we elucidate the atomic-scale details of this pivotal reaction by integrating first-principles molecular dynamics (FPMD) and deep potential molecular dynamics (DPMD) simulations. The research findings clarified the following: (1) The reaction is initiated by a synergistic electronic effect, where a significant positive charge on the Ti atom and a narrowed HOMO-LUMO gap facilitate nucleophilic attack and electron transfer from O 2. (2) The reaction kinetics are influenced by steric hindrance, which drives an asynchronous synergy whereby nascent Ti-O bond formation promotes and accelerates Ti-Cl bond dissociation. (3) Polynuclear aggregate growth proceeds via two synergistic pathways: The "collision-complexation" mechanism involving direct interaction between molecular O 2 and TiCl 4 , and the "free-radical reaction" mechanism, characterized by reactive oxygen radicals (O∙) rapidly reacting with TiCl 4. The agreement between FPMD and DPMD simulations validates the DPMD as a powerful tool for extending the accessible scales of ab initio-accurate modeling. This work provides a fundamental mechanistic understanding of a critical industrial process, offering foundational insights for its future optimization and scale-up, which lies at the heart of reaction engineering and process design. [ABSTRACT FROM AUTHOR] |
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| Database: | Engineering Source |
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