Fabrication of electron-acceptor staggered AB Covalent triazine-based frameworks for enhanced visible-light-driven H2 evolution.
Fabrication of electron-acceptor staggered AB Covalent triazine-based frameworks for enhanced visible-light-driven H2 evolution.
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DOI：
10.1016/j.jcis.2021.10.100
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发表时间：
2021-10
影响因子：
9.9
通讯作者：
Yinyin Li;Rui Zhang;Cuiyan Li;Hui Li;Q. Fang;T. Xie
中科院分区：
文献类型：
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作者：
Yinyin Li;Rui Zhang;Cuiyan Li;Hui Li;Q. Fang;T. Xie
共价三嗪基骨架材料是一种很有前途的光催化分解水的有机材料。然而，所有的CTFs仅以AA堆积模型的形式参与水分解。通过调节反应温度，得到了两种不同堆积模式（重叠AA，交错AB）的CTF-1异构体。有趣的是，实验和理论计算表明，结晶AB堆叠CTF-1首次具有比AA堆叠CTF-1（70 µmol h−1g − 1）高得多的光化学析氢活性（362 μmol g−1h − 1）。其优异的光化学性能可归因于其独特的结构特征，允许更多的具有更高吸电子性能的N原子参与水还原反应。值得注意的是，作为PEC水还原的阴极材料，AB堆叠CTF-1还表现出在0 V vs. RHE下高达77 µA cm− 2的优异饱和光电流密度，这上级优于AA堆叠CTF-1（47 µA cm−2）。此外，还研究了CTF-1的堆积模型与光催化放氢的相关性。本研究为设计最佳光催化剂和拓展CTF基材料的新应用铺平了道路。
Covalent triazine-based frameworks (CTFs) have been emerged as a promising organic material for photocatalytic water splitting. However, all of the CTFs only are in the form of AA stacking model to participate in water splitting. Herein, two CTF-1 isomers with different stacking models (eclipsed AA, staggered AB) were obtained by modulating the reaction temperature. Interestingly, experimental and theoretical calculations showed that the crystalline AB stacking CTF-1 possessed a much higher activity for photochemical hydrogen evolution (362 μmol g−1h−1) than AA stacking CTF-1 (70 µmol h−1g−1) for the first time. The outstanding photochemical performance could be attributed to its distinct structural feature that allows more N atoms with higher electron-withdrawing property to be involved in the water reduction reaction. Notably, as a cathode material for PEC water reduction, AB stacking CTF-1 also demonstrated an excellent saturated photocurrent density up to 77 µA cm−2at 0 V vs. RHE, which was superior to the AA stacking CTF-1 (47 µA cm−2). Furthermore, the correlation between stacking models and photocatalytic H2evolution of CTF-1 were investigated. This study thus paves the path for designing optimal photocatalyst and extending the novel applications of CTF-based materials.