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Post-modification engineering of cerium metal-organic frameworks for efficient visible light-driven water oxidation

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Abstract

Metal-organic frameworks (MOFs) are highly desirable for promising photocatalytic water splitting, but their practical application is greatly limited due to their unstable chemical properties and insufficient visible light response as well as low charge-carries utilization, especially in photocatalytic O2 production. Herein, we present a post-modification engineering to modulate cerium metal-organic frameworks (Ce-MOFs) for realizing efficient photocatalytic water oxidation to liberate O2 by visible light. The one-step partial oxidation strategy is adopted to modify pristine Ce-MOFs, yielding the new Ce-MOFs (MV-Ce-MOFs) with mixed valence of Ce3+/Ce4+. Creating the Ce nodes of a mixed valence state can effectively extend the optical absorption to the visible region, expose more catalytically active sites and inhibit the recombination of photoinduced charges. Consequently, the MV-Ce-MOFs exhibit high activity for photocatalytic O2 evolution under visible light, manifesting an impressive 1.6% apparent quantum efficiency (AQY) under monochromatic irradiation of 405 nm. The regulation engineering of MOF metal node valence heralds a new paradigm for designing MOF-based photocatalysts.

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摘要

金属有机框架（MOFs）是一种非常理想的光催化水分解材料，但由于其化学性质不稳定、可见光响应不足以及较低的载流子利用率，限制了它的实际应用，尤其是在光催化O2的生成中。在此，我们提出了一种后改性工程来调控铈金属有机框架（Ce-MOFs），使其在可见光下实现光催化水氧化产生 O2。通过一步部分氧化策略改性原始的Ce-MOFs，从而得到具有Ce3+/Ce4+混合价态的新型Ce-MOFs (MV-Ce-MOFs)。金属节点混合价态的构建有效地拓展了其光吸收范围，暴露更多的催化活性位点，并有效地抑制了光生载流子的复合。因此，在可见光照射下，MV-Ce-MOFs展现出较高的光催化析氧活性，在405 nm的单色照射下表现出可观的表观量子效率（AQY）1.6%。MOF金属结点价态的调控工程为MOF基光催化剂的设计提供了新的思路。

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Acknowledgements

This work was financially supported by the Natural Science Foundation of Fujian Province (No. 2022J05269), the Research Project of Ningde Normal University (No. 2020Y016), the Education & Research Project for Young and Middle-aged Teachers of Fujian (No. JAT200698), the National Natural Science Foundation of China (No. 22302154 and 22372085).

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Authors and Affiliations

  1. Fujian Provincial Key Laboratory of Featured Biochemical and Chemical Materials, Fujian Province University Key Laboratory of Green Energy and Environment Catalysis, Ningde Normal University, Ningde, 352100, China

    Lin-Zhu Zhang, Lu Chen, Gui-Yang Yan & Ruo-Wen Liang

  2. School of Chemical Engineering and Technology, **’an Jiaotong University, **’an, 710049, China

    Hong-Hui Ou

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  1. Lin-Zhu Zhang
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  2. Lu Chen
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Zhang, LZ., Chen, L., Yan, GY. et al. Post-modification engineering of cerium metal-organic frameworks for efficient visible light-driven water oxidation. Rare Met. (2024). https://doi.org/10.1007/s12598-024-02844-0

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