Switching Excited State Distribution of Metal-Organic Framework for Dramatically Boosting Photocatalysis
Switching Excited State Distribution of Metal-Organic Framework for Dramatically Boosting Photocatalysis
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DOI：
10.1002/anie.202206193
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发表时间：
2022-05-31
影响因子：
16.6
通讯作者：
Zhang, Zhi-Ming
中科院分区：
文献类型：
--
作者：
Guo, Song;Kong, Li-Hui;Zhang, Zhi-Ming
与电子/能量转移相关的光敏化代表了自然光合作用的核心科学。在此，我们提出了一种协议，通过将金属有机框架（MOF）的激发态分布从（MLCT）-M-3（金属到配体电荷转移）切换到（IL）-I-3（配体内），显着提高金属有机框架（MOF）的敏化能力。 (IL)-I-3 MOFs和Co/Cu催化剂的分级组织促进了电子转移，实现高效光催化H-2析出，产量达到26 844.6 mu mol g(-1)，并实现CO2光还原，在所有MOF光催化剂中，HCOOH产量达到创纪录的4807.6 mu mol g(-1)。系统研究表明，(IL)-I-3 MOF 中强可见光吸收、长寿命激发态和巧妙的多组分协同作用可以促进界面和框架内电子转移，从而促进光催化。这项工作开辟了一条通过在分子水平上设计敏化中心来促进太阳能转换的途径。
Photosensitization associated with electron/energy transfer represents the central science of natural photosynthesis. Herein, we proposed a protocol to dramatically improve the sensitizing ability of metal-organic frameworks (MOFs) by switching their excited state distribution from (MLCT)-M-3 (metal-to-ligand charge transfer) to (IL)-I-3 (intraligand). The hierarchical organization of (IL)-I-3 MOFs and Co/Cu catalysts facilitates electron transfer for efficient photocatalytic H-2 evolution with a yield of 26 844.6 mu mol g(-1) and CO2 photoreduction with a record HCOOH yield of 4807.6 mu mol g(-1) among all the MOF photocatalysts. Systematic investigations demonstrate that strong visible-light-absorption, long-lived excited state and ingenious multi-component synergy in the (IL)-I-3 MOFs can facilitate both interface and intra-framework electron transfer to boost photocatalysis. This work opens up an avenue to boost solar-energy conversion by engineering sensitizing centers at a molecular level.