Boosting Photocatalytic Hydrogen Peroxide Production from Oxygen and Water Using a Hafnium-Based Metal-Organic Framework with Missing-Linker Defects and Nickel Single Atoms
Boosting Photocatalytic Hydrogen Peroxide Production from Oxygen and Water Using a Hafnium-Based Metal-Organic Framework with Missing-Linker Defects and Nickel Single Atoms
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DOI：
10.1021/acscatal.2c04940
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发表时间：
2022-11-22
期刊：
影响因子：
12.9
通讯作者：
Yamashita, Hiromi
中科院分区：
文献类型：
--
作者：
Kondo, Yoshifumi;Honda, Kotaro;Yamashita, Hiromi
金属有机骨架（mof）是光催化过氧化氢（H2O2）的最有前途的候选材料之一。然而，MOF驱动的H2O2从O2和水生成仍然是一个挑战，因为MOF光催化剂需要在水反应体系中表现出高度的结构稳定性，同时抑制H2O2分解。在本研究中，我们证明了含有缺失连接缺陷和Ni单原子的hf基UiO-66-NH2在可见光（λ > 420 nm）照射下显著促进O2和水的光催化生成H2O2。而Ni单原子共催化剂则促进了光生电荷的分离和水的选择性双电子氧化生成H2O2。缺失连接子缺陷与Ni单原子的协同作用显著提高了光催化H2O2的生成，活性比原始Hf-UiO-66-NH2提高了6.3倍。该研究不仅为MOF光催化剂的缺陷工程提供了新的见解，而且为通过O2还原和水氧化实现高选择性H2O2生产提供了重要策略。
Metal-organic frameworks (MOFs) are one of the most promising candidates for photocatalytic hydrogen peroxide (H2O2) production from dioxygen (O2) and water. However, MOF-driven H2O2 production from O2 and water remains a challenge because MOF photocatalysts need to exhibit high structural stability in aqueous reaction systems while suppressing H2O2 decomposition. In the present study, we demonstrate that a Hf-based UiO-66-NH2 with missing-linker defects and Ni single atoms dramatically promotes the photocatalytic production of H2O2 from O2 and water under visible-light (lambda > 420 nm) irradiation. The acetate-capped missing-linker defects lead to suppression of the non radiative relaxation of organic linkers and to the prevention of H2O2 decomposition, whereas the Ni single-atom cocatalysts promote the separation of photogenerated charges and selective two-electron oxidation of water to generate H2O2. The synergetic effect of missing-linker defects and Ni single atoms dramatically improves photocatalytic H2O2 production, resulting in a 6.3-fold increase in activity compared with that of pristine Hf-UiO-66-NH2. This study provides not only new insights into defect engineering in MOF photocatalysts but also an important strategy for achieving highly selective H2O2 production via O2 reduction and water oxidation.