Supramolecular metal-organic frameworks that display high homogeneous and heterogeneous photocatalytic activity for H2 production

• Published in: Nature communications Vol. 7; no. 1; p. 11580
• Main Authors: Tian, Jia, Xu, Zi-Yue, Zhang, Dan-Wei, Wang, Hui, Xie, Song-Hai, Xu, Da-Wen, Ren, Yuan-Hang, Wang, Hao, Liu, Yi, Li, Zhan-Ting
• Format: Journal Article
• Language: English
• Published: London Nature Publishing Group UK 10-05-2016; Nature Publishing Group; Nature Portfolio
• Subjects: 639/301/299/921; 639/638/263/406/77/890; Humanities and Social Sciences; INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; MATERIALS SCIENCE; metal-organic frameworks; multidisciplinary; Photocatalysis; Porous materials; Science; Science (multidisciplinary)
• ISSN: 2041-1723; 2041-1723
• DOI: 10.1038/ncomms11580

Self-assembly has a unique presence when it comes to creating complicated, ordered supramolecular architectures from simple components under mild conditions. Here, we describe a self-assembly strategy for the generation of the first homogeneous supramolecular metal-organic framework (SMOF-1) in water at room temperature from a hexaarmed [Ru(bpy)
3
]
2+
-based precursor and cucurbit[8]uril (CB[8]). The solution-phase periodicity of this cubic transition metal-cored supramolecular organic framework (MSOF) is confirmed by small-angle X-ray scattering and diffraction experiments, which, as supported by TEM imaging, is commensurate with the periodicity in the solid state. We further demonstrate that SMOF-1 adsorbs anionic Wells−Dawson-type polyoxometalates (WD-POMs) in a one-cage-one-guest manner to give WD-POM@SMOF-1 hybrid assemblies. Upon visible-light (500 nm) irradiation, such hybrids enable fast multi-electron injection from photosensitive [Ru(bpy)
3
]
2+
units to redox-active WD-POM units, leading to efficient hydrogen production in aqueous media and in organic media. The demonstrated strategy opens the door for the development of new classes of liquid-phase and solid-phase ordered porous materials.
Self-assembly is robust in creating advanced, homogeneous architectures under mild conditions. Here, the authors describe the generation of the first 3D metal-cored supramolecular organic framework using this strategy and illustrate its capacity in catalysing visible light-induced H
2
production.