In Situ TEM Reveals Direct One-Step Reduction of van der Waals Crystal MoO<sub>3</sub> to Mo

Molybdenum oxides (MOs) exhibit rich polymorphism and tunable properties, yet their phase transformation pathways are poorly understood. Here, we employ in situ environmental transmission electron microscopy (TEM) to reveal a direct reduction of MoO<sub>3</sub> to metallic Mo, bypassing...

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Main Author: Wei Tu (486234) (author)
Other Authors: Fan Zhang (46132) (author), Xiankun Song (22184251) (author), Lu Jin (448623) (author), An Bai (7489721) (author), Zhen Zeng (238754) (author), Tianding Xu (9956216) (author), Xianhu Sun (11487274) (author), Yao Yang (543059) (author), Jianyu Huang (2138149) (author)
Published: 2025
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Summary:Molybdenum oxides (MOs) exhibit rich polymorphism and tunable properties, yet their phase transformation pathways are poorly understood. Here, we employ in situ environmental transmission electron microscopy (TEM) to reveal a direct reduction of MoO<sub>3</sub> to metallic Mo, bypassing known intermediate phases such as MoO<sub>2</sub> and Mo<sub>4</sub>O<sub>11</sub>. Surface nucleation begins at approximately 800 °C and is completed at 900 °C. Molecular dynamics (MD) and density functional theory (DFT) calculations attribute this unexpected transformation to the van der Waals (vdW) layered structure of MoO<sub>3</sub>, which lowers both the oxygen binding energy and the Gibbs free energy (ΔG) for oxygen desorption under high-vacuum and high-temperature conditions. Preferential oxygen removal from the weakly bonded vdW layers facilitates a rapid reduction to the metallic phase. These findings uncover a nonclassical reduction mechanism and provide a pathway for the rational design of MOs with controllable phases and properties.