Encapsulation of Single Iron Sites in a Metal-Porphyrin Framework for High-Performance Photocatalytic CO2 Reduction
Encapsulation of Single Iron Sites in a Metal-Porphyrin Framework for High-Performance Photocatalytic CO2 Reduction
复制标题
将单个铁位点封装在金属卟啉框架中用于高性能光催化二氧化碳还原
DOI：
10.1021/acs.inorgchem.0c00407
复制
发表时间：
2020
影响因子：
4.6
通讯作者：
Lu Tong-Bu
中科院分区：
文献类型：
--
作者：
Wang Sha-Sha;Huang Hai-Hua;Liu Meng;Yao Shuang;Guo Song;Wang Jia-Wei;Zhang Zhi-Ming;Lu Tong-Bu
利用地球上丰富的光催化剂高效还原CO2是一个非常有吸引力但对化学家来说非常具有挑战性的过程。本文中，我们合成了铟卟啉骨架In（H2 TCPP）（1-n）[Fe（TCPP）（H2O）]（1-n）[DEA]（1-n），（In-FenTCPP-MOF; H2 TCPP =四（4-苯甲酸）卟啉; DEA =二乙胺），具有卟啉环支撑的单中心铁用于高性能可见光驱动的CO2到CO的转化。3469 μmol g-1的高CO产率1可以通过24 h的光催化反应实现，具有高CO选择性（约. 99.5%）。该活性远高于其钴类似物或不含Fe的铟基金属有机框架（MOF）。系统的实验和理论研究表明，MOF基质中卟啉负载的铁中心是有效的活性中心，可以从光激发的MOF中接受电子，从而介导CO2的还原。
Efficient CO2reduction with earth-abundant photocatalysts is a highly attractive but very challenging process for chemists. Herein, we synthesized an indium–porphyrin framework, In(H2TCPP)(1-n)[Fe(TCPP)(H2O)](1-n)[DEA](1-n)(In–FenTCPP-MOF; H2TCPP = tetrakis(4-benzoic acid)porphyrine; DEA = diethylamine), with a porphyrin ring supporting the single-site iron for the high-performance visible-light-driven conversion of CO2to CO. A high CO yield of 3469 μmol g–1can be achieved by a 24 h photocatalytic reaction with a high CO selectivity (ca. 99.5%). This activity was much higher than that of its cobalt analogues or the Fe-free indium-based metal–organic framework (MOF). Systematic experimental and theoretical studies indicate that the porphyrin-supported iron centers in the MOF matrix serve as efficient active sites, which can accept electrons from the photoexcited MOFs in order to mediate CO2reduction.