Abstract Two-dimensional (2D) nitrogenated holey carbon materials are promising non-precious photocatalysts for clean energy production. However, their efficiency is limited by the fast electron-hole recombination and lack of active sites. To overcome these drawbacks, here for the first time, we show that loading subnanometer p-block metal oxide clusters on 2D porous carbon-based semiconductors can trigger peculiar synergistic effect and offer an effective route for manipulating the photocatalytic behavior at atomic precision. As a prototype system, g-C3N4 monolayer decorated by MgO tubular clusters for overall water splitting is explored by time-dependent ab initio nonadiabatic molecular dynamic simulations. Such novel (MgO)n/g-C3N4 heterostructures possess excellent stability in aqueous solution, high activity for water splitting, and superior photocarrier transport properties. The basic rules for optimally steering the relaxation pathway and lifetime of excited carriers and creating bifunctional reaction centers by controlling the concentration and size of oxide clusters are thoroughly unveiled. Our work provides a new strategy to modify 2D porous carbon materials for practical solar energy conversion and shines light on utilizing subnanometer p-block oxide clusters with earth-abundant and low-cost elements for precisely dictating the performance of hybrid photocatalysts.

中文翻译：

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亚纳米氧化物簇装饰的 g-C3N4 上的可见光整体水分解

摘要 二维（2D）氮化多孔碳材料是用于清洁能源生产的有前途的非贵重光催化剂。然而，它们的效率受到快速电子-空穴复合和缺乏活性位点的限制。为了克服这些缺点，我们首次表明在二维多孔碳基半导体上加载亚纳米 p 块金属氧化物簇可以触发特殊的协同效应，并为以原子精度操纵光催化行为提供有效途径。作为原型系统，由 MgO 管状簇装饰的 g-C3N4 单层用于整体水分解，通过时间相关的 ab initio 非绝热分子动力学模拟进行了探索。这种新型 (MgO)n/g-C3N4 异质结构在水溶液中具有优异的稳定性、高的水分解活性、和优越的光载流子传输特性。彻底揭示了通过控制氧化物簇的浓度和大小来优化控制激发载流子的弛豫路径和寿命以及创建双功能反应中心的基本规则。我们的工作提供了一种新的策略来修改二维多孔碳材料以用于实际的太阳能转换，并为利用具有地球丰富且低成本元素的亚纳米 p 块氧化物簇精确控制混合光催化剂的性能提供了新的思路。