Ionic Liquid Modified Fe-Porphyrinic Metal-Organic Frameworks as Efficient and Selective Photocatalysts for CO Reduction.

Porphyrin-based metal-organic frameworks (MOFs) are ideal platforms for heterogeneous photocatalysts toward CO reduction. To further explore photocatalytic MOF systems, it is also necessary to consider their ability to fine-tune the microenvironments of the active sites, which affects their overall catalytic operation. Herein, a kind of ionic liquid (IL, here is 3-butyric acid-1-methyl imidazolium bromide, BAMeImBr) was anchored to iron-porphyrinic Zr-MOFs with different amounts to obtain IL@MOF-526 (MOF-526 = ZrO(OH)(FeTCBPP), FeTCBPP = iron 5,10,15,20-tetra[4-(4'-carboxyphenyl)phenyl]-porphyrin, = 100, 200, and 400). IL@MOF-526 series was designed to investigate the effects of the microenvironmental and electronic structural modification on the efficiency and selectivity of the photochemical reduction of CO after introducing IL fragments. Compared to parent MOF-526, the production and selectivity of CO were greatly improved in the absence of any photosensitizer under visible light by the IL@MOF-526 series. Among them, the CO yield of IL200@MOF-526 was up to 14.0 mmol g within 72 h with a remarkable CO selectivity of 97%, which is superior to that of MOF-526 without BAMeIm modification and other amounts of BAMeIm loaded. Furthermore, density functional theory calculations were performed to study the mechanism of the CO reduction.