Photo-generated dinuclear {Eu(II)}2 active sites for selective CO2 reduction in a photosensitizing metal-organic framework

• Published in: Nature communications Vol. 9; no. 1; pp. 1 - 9
• Main Authors: Yan, Zhi-Hao, Du, Ming-Hao, Liu, Junxue, Jin, Shengye, Wang, Cheng, Zhuang, Gui-Lin, Kong, Xiang-Jian, Long, La-Sheng, Zheng, Lan-Sun
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 22.08.2018; Nature Publishing Group; Nature Portfolio
• Subjects: 140/146; 140/58; 639/301/299/890; 639/4077/909/4101/4050; 639/638/298/921; 639/638/439/890; Carbon dioxide; Catalysis; Catalysts; Chemical energy; Clusters; Electron transfer; Electrons; Energy conversion; Energy conversion efficiency; Humanities and Social Sciences; Metal-organic frameworks; multidisciplinary; Nodes; Organic chemistry; Photocatalysis; Photosensitization; Reduction; Reduction (metal working); Science; Science (multidisciplinary); Separation processes; Solar energy
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/s41467-018-05659-7

Photocatalytic reduction of CO 2 is a promising approach to achieve solar-to-chemical energy conversion. However, traditional catalysts usually suffer from low efficiency, poor stability, and selectivity. Here we demonstrate that a large porous and stable metal-organic framework featuring dinuclear Eu(III) 2 clusters as connecting nodes and Ru(phen) 3 -derived ligands as linkers is constructed to catalyze visible-light-driven CO 2 reduction. Photo-excitation of the metalloligands initiates electron injection into the nodes to generate dinuclear {Eu(II)} 2 active sites, which can selectively reduce CO 2 to formate in a two-electron process with a remarkable rate of 321.9 μmol h −1  mmol MOF −1 . The electron transfer from Ru metalloligands to Eu(III) 2 catalytic centers are studied via transient absorption and theoretical calculations, shedding light on the photocatalytic mechanism. This work highlights opportunities in photo-generation of highly active lanthanide clusters stabilized in MOFs, which not only enables efficient photocatalysis but also facilitates mechanistic investigation of photo-driven charge separation processes. Solar-to-chemical CO 2 reduction provides a means to use light’s energy for CO 2 removal and upgrading to useful products, although this photochemical conversion is challenging. Here, authors construct a Europium-containing metal-organic framework that selectively converts CO 2 to formate with light.