Coordination-Supported Imidazolate Networks: Water- and Heat-Stable Mesoporous Polymers for Catalysis

5 years ago

Coordination-Supported Imidazolate Networks: Water- and Heat-Stable Mesoporous Polymers for Catalysis

Caili Huang, Matthew F. Chisholm, Shize Yang, Sheng Dai, Pengfei Zhang, Xueguang Jiang

The poor water stability of most porous coordination polymers (PCPs) or metal-organic frameworks (MOFs) is widely recognized as a barrier hampering their practical applications. Here, a facile and scalable route to prepare metal-containing polymers with a good stability in boiling water (100 °C, 24 h) and air (up to 390 °C) is presented. The bifunctional 1-vinylimidazole (VIm) with a coordinating site and a polymerizable organic group is introduced as the building block. This core strategy includes the synthesis of a rigid monomer with four VIm branches through a coordination process at room temperature, followed by a radical polymerization. We refer to this material as coordination-supported imidazolate networks (CINs). Interestingly, CINs are composed of rich mesopores from 2–15 nm, as characterized by low-energy (60 kV) STEM-HAADF images. In particular, the stable CINs illustrate a high turnover frequency (TOF) of 779 h−1 in the catalytic oxidation of phenol with H2O as the green solvent. Omni-stable polymers: Stable metal-containing polymers are designed from versatile 1-vinyl-imidazole (VIm) with both coordinating sites and reactive organic groups. The synthetic strategy includes the coordination between VIm and metal ions (Zn2+, Co2+, Ni2+), followed by a radical polymerization. This concept enables porous metal-based polymers with exceptional stability in water (100 °C, 24 h) and air (up to 390 °C).

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/chem.201702430