Visible-Light-Driven Hydrogen Peroxide Production from Water and Dioxygen by Perylenetetracarboxylic Diimides Modified Titanium-Based Metal-Organic Frameworks
Visible-Light-Driven Hydrogen Peroxide Production from Water and Dioxygen by Perylenetetracarboxylic Diimides Modified Titanium-Based Metal-Organic Frameworks
复制标题
可见光驱动苝四甲二酰亚胺改性钛基金属有机骨架从水和分子氧生产过氧化氢
DOI：
10.1039/d1ta08036a
复制
发表时间：
2021
影响因子：
11.9
通讯作者：
and H. Yamashita
中科院分区：
文献类型：
--
作者：
X. Chen;Y. Kondo;S. Li;Y. Kuwahara;K. Mori;D. Zhang;C. Louis;and H. Yamashita
金属有机骨架（mof）是光催化水（H2O）和双氧（O2）制备过氧化氢（H2O2）的重要材料。然而，由于MOF基质中光生电荷的快速重组，利用MOF从H2O和O2中生成H2O2仍然具有挑战性。本文通过在钛基MOF （MIL-125-NH2）上修饰有机半导体苝四羧酸二亚胺（PDI），构建异质结结构，形成MIL-125-PDI，促进PDI与MOF之间光生电荷的分离。光/电化学表征证实了所构建的异质结构确实促进了光生电荷的分离和转移。结果表明，在可见光（λ > 420 nm）照射下，MIL-125-PDI的H2O2产率为4800 μM g−1 h−1，是原始MIL-125-NH2的4.3倍。此外，MIL-125-PDI比MIL-125-NH2表现出更好的耐久性。捕获实验和活性物质生成H2O2的电子自旋共振（ESR）光谱结果表明，MIL-125-PDI中出现了一个新的一步双电子还原H2O2过程，而MIL-125-NH2中观察到的原过程为两步单电子还原过程。本研究将mof作为光催化剂的主要活性成分，开辟了mof在光催化中的新应用，为设计基于mof的清洁液体燃料人工光合作用光催化剂提供了有效的策略。
Metal–organic frameworks (MOFs) are promising materials for photocatalytic hydrogen peroxide (H2O2) production from water (H2O) and dioxygen (O2). However, H2O2 production from H2O and O2 using MOFs has remained challenging due to the fast recombination of photogenerated charges in the MOF matrix. Herein, a heterojunction structure was constructed by modification of an organic semiconductor, perylenetetracarboxylic diimide (PDI), upon a titanium-based MOF (MIL-125-NH2), forming MIL-125-PDI to promote the separation of photogenerated charges between PDI and MOFs. Photo/electrochemical characterizations confirmed that the constructed heterostructure indeed promoted the separation and transfer of photogenerated charges. As a result, the as-formed MIL-125-PDI displayed a H2O2 production rate of 4800 μM g−1 h−1, which was 4.3 times that of the pristine MIL-125-NH2 under visible-light irradiation (λ > 420 nm). Furthermore, MIL-125-PDI exhibited a better durability compared with MIL-125-NH2 with noble-metal Pt nanoparticles as co-catalysts. The results of trapping experiments and electron spin resonance (ESR) spectra of active species for H2O2 production indicated that a new one-step two-electron process of O2 reduction to H2O2 occurred in MIL-125-PDI, while the original one observed in MIL-125-NH2 was a two-step one-electron process. This work used MOFs as the main active component in photocatalysts, which opens up the new application of MOFs in photocatalysis and provides an effective strategy to design MOF-based photocatalysts for artificial photosynthesis of clean liquid fuels.