Nonadiabatic Dynamics of Photocatalytic Water Splitting on A Polymeric Semiconductor.
Nonadiabatic Dynamics of Photocatalytic Water Splitting on A Polymeric Semiconductor.
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DOI：
10.1021/acs.nanolett.1c01187
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发表时间：
2021-07
期刊：
影响因子：
10.8
通讯作者：
Peiwei You;C. Lian;Daqiang Chen;Jiyu Xu;Cui Zhang;S. Meng;E. Wang
中科院分区：
文献类型：
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作者：
Peiwei You;C. Lian;Daqiang Chen;Jiyu Xu;Cui Zhang;S. Meng;E. Wang
为了阐明光驱动的光催化水分解的性质，一个聚合物催化剂-石墨氮化碳（g-C3 N4）-已被选为原型基板，用于研究原子的水吐在现实环境中的过程。我们的非绝热量子动力学模拟的基础上，实时含时密度泛函理论揭示明确的光生电荷载流子在g-C3 N4/水界面的传输通道，这表明了很强的相关性，以键的重新形成。提出了一个三步光反应机制，而空穴驱动的氢转移和界面水配置的关键作用被确定。紧接着光催化水裂解，证明了两个解离的氢原子彼此接近并形成H2气体分子的原子路径，而残留的OH自由基可以形成中间产物（例如，H2O2）。这些结果提供了关键的新见解的表征和进一步发展的高效水裂解光催化剂从动态的角度来看。
To elucidate the nature of light-driven photocatalytic water splitting, a polymeric semiconductor-graphitic carbon nitride (g-C3N4)-has been chosen as a prototype substrate for studying atomistic water spitting processes in realistic environments. Our nonadiabatic quantum dynamics simulations based on real-time time-dependent density functional theory reveal explicitly the transport channel of photogenerated charge carriers at the g-C3N4/water interface, which shows a strong correlation to bond re-forming. A three-step photoreaction mechanism is proposed, whereas the key roles of hole-driven hydrogen transfer and interfacial water configurations were identified. Immediately following photocatalytic water splitting, atomic pathways for the two dissociated hydrogen atoms approaching each other and forming the H2 gas molecule are demonstrated, while the remanent OH radicals may form intermediate products (e.g., H2O2). These results provide critical new insights for the characterization and further development of efficient water-splitting photocatalysts from a dynamic perspective.