Zhao Xue, Xu Qiang, Han Jingwei, Zhang Wenwen, Rao Heng, Du Dong-Ying, She Ping, Qin Jun-Sheng
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, College of Chemistry and International Center of Future Science, Jilin University, Changchun 130012, P.R. China.
Department of Chemistry, Northeast Normal University, Changchun 130024, P. R. China.
ACS Appl Mater Interfaces. 2024 May 22;16(20):26272-26279. doi: 10.1021/acsami.4c04219. Epub 2024 May 10.
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.
基于卟啉的金属有机框架（MOF）是用于CO还原的多相光催化剂的理想平台。为了进一步探索光催化MOF体系，还需要考虑它们微调活性位点微环境的能力，这会影响其整体催化操作。在此，将一种离子液体（IL，此处为3-丁酸-1-甲基咪唑溴盐，BAMeImBr）以不同量锚定到铁卟啉Zr-MOF上，以获得IL@MOF-526（MOF-526 = ZrO(OH)(FeTCBPP)，FeTCBPP = 铁5,10,15,20-四[4-(4'-羧基苯基)苯基]卟啉， = 100、200和400）。设计IL@MOF-526系列以研究引入IL片段后微环境和电子结构修饰对CO光化学还原效率和选择性的影响。与母体MOF-526相比，IL@MOF-526系列在可见光下无任何光敏剂的情况下，CO的产量和选择性得到了极大提高。其中，IL200@MOF-526在72小时内的CO产率高达14.0 mmol g，CO选择性高达97%，优于未进行BAMeIm修饰的MOF-526和其他负载量的BAMeIm。此外，进行了密度泛函理论计算以研究CO还原的机理。
