High Photoreactivity on a Reconstructed Anatase TiO2(001) Surface Predicted by Ab Initio Nonadiabatic Molecular Dynamics.
High Photoreactivity on a Reconstructed Anatase TiO2(001) Surface Predicted by Ab Initio Nonadiabatic Molecular Dynamics.
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DOI：
10.1021/acs.jpclett.2c01417
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发表时间：
2022-06
期刊：
影响因子：
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通讯作者：
Y. Tu;Weibin Chu;Yongliang Shi;Wenguang Zhu;Qijing Zheng;Jin Zhao
中科院分区：
文献类型：
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作者：
Y. Tu;Weibin Chu;Yongliang Shi;Wenguang Zhu;Qijing Zheng;Jin Zhao
(4×1)重构的锐钛矿型二氧化钛(001)表面是一种高活性的催化表面。在这项工作中，我们用时间域从头算非绝热分子动力学，揭示了锐钛矿型(001)表面重构形成的脊状结构是空穴迁移和俘获的光反应中心。此外，低覆盖度的CH3OH吸附破坏了脊状结构，导致其高光反应性受到抑制。然而，当CH3OH覆盖度增加并形成分子间氢键(H键)时，脊状结构及其高的光反应性被恢复。此外，空穴捕获动力学与分子间氢键结构中的分子间质子转移有很强的相关性。我们的研究证明，锐钛矿型二氧化钛(001)-(4×1)是一个高度光反应的表面，其中脊部是空穴捕获的光反应中心，这与质子转移过程是一致的。
Anatase TiO2(001) surface with (4 × 1) reconstruction is proposed to be a highly active catalytic surface. In this work, using time-domain ab initio nonadiabatic molecular dynamics, we reveal that the ridge structure formed by anatase(001) surface reconstruction is the photoreactive site for hole migration and trapping. Moreover, the ridge structure is destroyed by low-coverage CH3OH adsorption, leading to the suppression of its high photoreactivity. However, when the CH3OH coverage is increased and intermolecular hydrogen bonds (H-bonds) form, the ridge structure and its high photoreactivity are restored. Furthermore, the hole trapping dynamics is strongly coherent with intermolecular proton transfer in structures with intermolecular H-bonds. Our study proves that anatase TiO2(001)-(4 × 1) is a highly photoreactive surface where the ridge is the photoreactive site for hole trapping, which is coherent with the proton transfer process.