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Postsynthetic ionization of an imidazole-containing metal-organic framework for the cycloaddition of carbon dioxide and epoxides.

ABSTRACT: A bifunctional imidazolium functionalized zirconium metal-organic framework (Zr-MOF), (I^-)Meim-UiO-66 (2), was successfully prepared from the imidazole-containing Zr-MOF Im-UiO-66 (1) by a post-synthetic modification (PSM) method. It was found that the crystal size and pore features of the imidazole-containing 1 could be tuned at the nanoscale. The bifunctional MOF 2, containing Brønsted acid sites and iodide ions, was shown to be an efficient and recyclable heterogeneous catalyst for the cycloaddition of carbon dioxide (CO₂) with epoxides, without the use of any co-catalyst, at ambient pressure. The solvent-free synthesis of the cyclic carbonate from CO₂ and an epoxide was monitored by in situ Fourier transform infrared spectroscopy (FT-IR) and an acid/base synergistic catalysis mechanism was proposed. We hope that our strategy provides an effective approach for the introduction of functional N-heterocyclic groups into MOFs for potential applications.

SUBMITTER: Liang J

PROVIDER: S-EPMC5359889 | biostudies-literature | 2017 Feb

REPOSITORIES: biostudies-literature

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Postsynthetic ionization of an imidazole-containing metal-organic framework for the cycloaddition of carbon dioxide and epoxides.

Liang Jun J Chen Rui-Ping RP Wang Xiu-Yun XY Liu Tao-Tao TT Wang Xu-Sheng XS Huang Yuan-Biao YB Cao Rong R

Chemical science 20161102 2

A bifunctional imidazolium functionalized zirconium metal-organic framework (Zr-MOF), (I-)Meim-UiO-66 (2), was successfully prepared from the imidazole-containing Zr-MOF Im-UiO-66 (1) by a post-synthetic modification (PSM) method. It was found that the crystal size and pore features of the imidazole-containing 1 could be tuned at the nanoscale. The bifunctional MOF 2, containing Brønsted acid sites and iodide ions, was shown to be an efficient and recyclabl ...[more]

PMID: 28451286

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Project description:The fixation of carbon dioxide with epoxides is one of the most attractive methods for the green utilisation of this greenhouse gas and leads to many valuable chemicals. This process is characterised by 100% atom efficiency; however, an efficient catalyst is required to achieve satisfactory yields. Metal-organic frameworks (MOFs) are recognised as being extremely promising for this purpose. Nevertheless, many of the proposed catalysts are based on ions of rare elements or elements not entirely safe for the environment; this is notable with commercially unavailable ligands. In an effort to develop novel catalysts for CO2 fixation on an industrial scale, we propose novel MOFs, which consist of aluminium ions coordinated with commercially available 1,4-naphthalene dicarboxylic acid (Al@NDC) and their nanocomposites with gold nanoparticles entrapped inside their structure (AlAu@NDC). Due to the application of 4-amino triazole and 5-amino tetrazole as crystallization mediators, the morphology of the synthesised materials can be modified. The introduction of gold nanoparticles (AuNPs) into the structure of the synthesised Al-based MOFs causes the change in morphology from nano cuboids to nanoflakes, simultaneously decreasing their porosity. However, the homogeneity of the nanostructures in the system is preserved. All synthesised MOF materials are highly crystalline, and the simulation of PXRD patterns suggests the same tetragonal crystallographic system for all fabricated nanomaterials. The fabricated materials are proven to be highly efficient catalysts for carbon dioxide cycloaddition with a series of model epoxides: epichlorohydrin; glycidol; styrene oxide; and propylene oxide. Applying the synthesised catalysts enables the reactions to be performed under mild conditions (90 °C; 1 MPa CO2) within a short time and with high conversion and yield (90% conversion of glycidol towards glycerol carbonate with 89% product yield within 2 h). The developed nanocatalysts can be easily separated from the reaction mixture and reused several times (both conversion and yield do not change after five cycles). The excellent performance of the fabricated catalytic materials might be explained by their high microporosity (from 421 m2 g-1 to 735 m2 g-1); many catalytic centres in the structure exhibit Lewis acids' behaviour, increased capacity for CO2 adsorption, and high stability. The presence of AuNPs in the synthesised nanocatalysts (0.8% w/w) enables the reaction to be performed with a higher yield within a shorter time; this is especially important for less-active epoxides such as propylene oxide (two times higher yield was obtained using a nanocomposite, in comparison with Al-MOF without nanoparticles).

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Postsynthetic ionization of an imidazole-containing metal-organic framework for the cycloaddition of carbon dioxide and epoxides.

Publications

Postsynthetic ionization of an imidazole-containing metal-organic framework for the cycloaddition of carbon dioxide and epoxides.

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