Abstract

Photosynthesis in nature uses the Mn₄CaO₅ cluster as the oxygen-evolving center to catalyze the water oxidation efficiently in photosystem II. Herein, we demonstrate bio-inspired heterometallic LnCo₃ (Ln = Nd, Eu and Ce) clusters, which can be viewed as synthetic analogs of the CaMn₄O₅ cluster. Anchoring LnCo₃ on phosphorus-doped graphitic carbon nitrides (PCN) shows efficient overall water splitting without any sacrificial reagents. The NdCo₃/PCN-c photocatalyst exhibits excellent water splitting activity and a quantum efficiency of 2.0% at 350 nm. Ultrafast transient absorption spectroscopy revealed the transfer of a photoexcited electron and hole into the PCN and LnCo₃ for hydrogen and oxygen evolution reactions, respectively. A density functional theory (DFT) calculation showed the cooperative water activation on lanthanide and O−O bond formation on transition metal for water oxidation. This work not only prepares a synthetic model of a bio-inspired oxygen-evolving center but also provides an effective strategy to realize light-driven overall water splitting.

中文翻译：

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生物启发的镧系元素-过渡金属簇和P掺杂的氮化碳的集成用于高效的光催化整体水分解

摘要

自然界中的光合作用使用 Mn ₄ CaO ₅簇作为析氧中心来有效催化光系统 II 中的水氧化。在此，我们展示了受生物启发的异金属 LnCo ₃ (Ln = Nd、Eu 和 Ce) 簇，可以将其视为 CaMn ₄ O ₅簇的合成类似物。将 LnCo ₃锚定在掺磷石墨碳氮化物 (PCN) 上显示出高效的整体水分解，无需任何牺牲试剂。铷₃/PCN-c 光催化剂表现出优异的水分解活性和 350 nm 下 2.0% 的量子效率。超快瞬态吸收光谱揭示了光激发的电子和空穴分别转移到 PCN 和 LnCo _{3 中}进行析氢和析氧反应。密度泛函理论 (DFT) 计算表明，镧系元素上的协同水活化和过渡金属上的 O-O 键形成用于水氧化。这项工作不仅准备了仿生氧演化中心的合成模型，而且为实现光驱动的整体水分解提供了有效的策略。