2D Covalent Organic Frameworks with an Incorporated Manganese Complex for Light Driven Carbon Dioxide Reduction
2D Covalent Organic Frameworks with an Incorporated Manganese Complex for Light Driven Carbon Dioxide Reduction
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具有掺入锰络合物的二维共价有机框架，用于光驱动二氧化碳还原
DOI：
10.1002/cptc.202100123
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发表时间：
2021
期刊：
影响因子：
3.7
通讯作者：
Huang, Jier
中科院分区：
文献类型：
--
作者：
Wang, Denan;Streater, Daniel;Peng, Yun;Huang, Jier
共价有机骨架材料（COFs）具有比表面积大、孔隙率可调、结构刚性好等特点，是一类新型的结晶多孔光催化材料。在这项工作中，我们报告了直接掺入锰CO2分子催化剂（MC）到COFs结果表明，Mn − TTA-COF的光催化活性较低，主要原因是Mn MC中的CO配体在光照下被消除，导致其催化反应持续时间较短。虽然这是进一步使用Mn-TTA-COF作为CO2还原催化剂的核心问题，但我们发现Mn MC的稳定性和效率在并入COF后相对于其均相形式大大增强，表明COF作为非均相平台并入MC并改善MC的催化性能的能力。此外，瞬态吸收光谱研究表明，Mn掺入的COF的分子内电荷转移寿命比母体COF中的长，这表明从母体COF到Mn部分可能发生电荷分离（CS）。这些结果共同表明，COF可能显示出作为创建具有内置光敏剂和MC的下一代光催化剂的平台的前景，这可以促进CS并提高所并入的MC的稳定性和效率。
Covalent organic frameworks (COFs) have emerged as a novel class of crystalline porous photocatalytic materials due to their unique properties such as large surface area, tunable porosity, and rigid structure. In this work, we report the direct incorporation of a manganese CO2molecular catalyst (MC) into COFs (Mn−TTA‐COF) and the evaluation of its capability as photocatalyst for visible light driven CO2reduction to form CO. We found that the photocatalytic activity of Mn−TTA‐COF is quite low, which mainly results from the elimination of the CO ligand in the Mn MC upon light illumination, rendering its short duration in the catalytic reaction. While this is a central concern for the further use Mn−TTA‐COF as a CO2reduction catalyst, we found that the stability and efficiency of Mn MC is largely enhanced after being incorporated into COFs with respect to its homogeneous version, suggesting the capability of COFs as heterogeneous platform to incorporate MC and improve the catalytic performance of MC. Moreover, transient absorption spectroscopic studies show that the intramolecular charge transfer lifetime of the Mn‐incorporated COF is longer than that in the parent COF, which suggests that charge separation (CS) may occur from the parent COF to the Mn moiety. These results together suggest that COFs may show promise as a platform for creating next‐generation photocatalysts with a built‐in photosensitizer and MC, which can facilitate CS and enhance the stability and efficiency of the incorporated MC.