Abstract The surface morphology of the materials is known to have significant influence on the overall photocatalytic performance. Therefore, identifying the corresponding electronic structures associated with the surface redox centers is essential for the rational design of Ag2O-based photocatalysts. In this study, comprehensive and systematic theoretical calculations revealed the connection between electronic structure and morphology responsible for the photo-induced mechanism. First-principles calculations showed that the activity of Ag+ cations on the exposed surfaces is dependent of their local coordination and electronic configuration. Electrons were found to migrate to the energetically favorable (1 1 1) surface, while holes are concentrated in the more unstable (1 0 0) and (1 1 0) surfaces. The complete set of available morphologies was obtained, enabling us to rationalize the photocatalytic activity in terms of composition, geometry, and electronic structure of the exposed surfaces. Moreover, the localization and characterization of excited electronic states of both bulk material and exposed surfaces allow us to discuss the fundamental reactions involved in the photocatalytic mechanism underlying the morphological evolution and would promote significantly the development and application of singlet-triplet mechanism. The detailed insights provided by our work could benefit the design and preparation of new efficient photocatalysts based on Ag2O.

中文翻译：

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连接 Ag2O 的表面结构、形貌和光催化活性：深入统一的理论研究

摘要 已知材料的表面形貌对整体光催化性能有显着影响。因此，识别与表面氧化还原中心相关的相应电子结构对于合理设计基于 Ag2O 的光催化剂至关重要。在这项研究中，全面和系统的理论计​​算揭示了电子结构与负责光致机制的形态之间的联系。第一性原理计算表明，Ag+ 阳离子在暴露表面的活性取决于它们的局部配位和电子配置。发现电子迁移到能量有利的 (1 1 1) 表面，而空穴集中在更不稳定的 (1 0 0) 和 (1 1 0) 表面。获得了完整的可用形态，使我们能够在暴露表面的组成、几何形状和电子结构方面合理化光催化活性。此外，大块材料和暴露表面的激发电子态的定位和表征使我们能够讨论形态演化背后的光催化机制中涉及的基本反应，并将显着促进单线态-三线态机制的发展和应用。我们的工作提供的详细见解有助于设计和制备基于 Ag2O 的新型高效光催化剂。大块材料和暴露表面的激发电子态的定位和表征使我们能够讨论涉及形态演变的光催化机制的基本反应，并将显着促进单线态-三线态机制的发展和应用。我们的工作提供的详细见解有助于设计和制备基于 Ag2O 的新型高效光催化剂。大块材料和暴露表面的激发电子态的定位和表征使我们能够讨论涉及形态演变的光催化机制的基本反应，并将显着促进单线态-三线态机制的发展和应用。我们的工作提供的详细见解有助于设计和制备基于 Ag2O 的新型高效光催化剂。