Chen Rong, Zhuang Gui-Lin, Wang Zhi-Ye, Gao Yi-Jing, Li Zhe, Wang Cheng, Zhou Yang, Du Ming-Hao, Zeng Suyuan, Long La-Sheng, Kong Xiang-Jian, Zheng Lan-Sun
Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory of Physical Chemistry of Solid Surface and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310032, China.
Natl Sci Rev. 2020 Sep 14;8(9):nwaa234. doi: 10.1093/nsr/nwaa234. eCollection 2021 Sep.
Photosynthesis in nature uses the MnCaO cluster as the oxygen-evolving center to catalyze the water oxidation efficiently in photosystem II. Herein, we demonstrate bio-inspired heterometallic LnCo (Ln = Nd, Eu and Ce) clusters, which can be viewed as synthetic analogs of the CaMnO cluster. Anchoring LnCo on phosphorus-doped graphitic carbon nitrides (PCN) shows efficient overall water splitting without any sacrificial reagents. The NdCo/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 LnCo 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.
自然界中的光合作用利用锰钙氧簇作为析氧中心，在光系统II中高效催化水氧化。在此，我们展示了受生物启发的异金属镧钴（Ln = 钕、铕和铈）簇，其可被视为钙锰氧簇的合成类似物。将镧钴锚定在磷掺杂的石墨相氮化碳（PCN）上可实现高效的全水分解，且无需任何牺牲试剂。NdCo/PCN-c光催化剂表现出优异的水分解活性，在350 nm处的量子效率为2.0%。超快瞬态吸收光谱表明，光激发的电子和空穴分别转移到PCN和镧钴中以进行析氢和析氧反应。密度泛函理论（DFT）计算表明，镧系元素上的水协同活化以及过渡金属上的氧 - 氧键形成有助于水氧化。这项工作不仅制备了受生物启发的析氧中心的合成模型，还提供了一种实现光驱动全水分解的有效策略。
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