Abstract
Conjugated microporous polymers (CMPs) have conjugated skeleton and permanent porosity, and exhibit huge potential in developing novel functional materials for resolving the challenging energy and environment issues. Metal-containing CMPs often exhibited unique properties. In the present manuscript, ferrocene-based conjugated microporous polymers (FcCMPs) were designed and synthesized with 1,1′-dibromoferrocene and 5,10,15,20-Tetrakis(4- bromophenyl) porphyrin (FcCMP-1) or Tetra (p-bromophenyl) methane (FcCMP-2) as building units via Yamamoto coupling. FcCMPs were amorphous, and exhibited excellent thermal and physicochemical stability. The BET surface area of FcCMP-1 and FcCMP-2 was 638 m2/g and 422 m2/g, respectively. In comparison with FcCMP-2, FcCMP-1 displayed better gas storage capacity due to higher porosity. FcCMPs were also used as an adsorbent for removal of methyl violet from aqueous solution, and exhibited excellent adsorption properties due to the interaction between electron-rich conjugated structure of the polymers and methyl violet with cationic groups. Moreover, FcCMPs could be extracted and regenerated by an eluent and then re-used for high efficient removal of methyl violet.
Highlights
Conjugated microporous polymers (CMPs) are a kind of amorphous polymers with a three-dimensional network structure, which possess π-conjugated skeletons and permanent nanopores.The unique structure are unavailable in other porous polymers, which are usually not π-conjugated.CMPs have the characteristics of high specific surface area, light-weight, and attracted much attention in the past decade for great potential application in gas uptake [1,2], gas separations [3,4], and gas storage [5,6] as well as in photoredox catalysts [7,8,9]
The peaks from 66.2 to 69.5 ppm proved the existence of ferrocene units in ferrocene-based conjugated microporous polymers (FcCMPs), which was in agreement with the results of Okada et al
[23] The signal at 120.5 ppm could be assigned to the quaternary carbon of the benzene ring, which was linked to ferrocene units in the signal in FcCMP-2 moved to 125.2 ppm due to different chemical environments
Summary
Conjugated microporous polymers (CMPs) are a kind of amorphous polymers with a three-dimensional network structure, which possess π-conjugated skeletons and permanent nanopores. Polycyclic aromatics, styryl derivatives to heterocyclic compounds can be employed as the building units, and active groups include bromine, iodine, boric acid, cyano, amino, aldehyde, and acetylene et al a variety of building units and extensiveness of active groups dramatically improved the design flexibility of CMPs skeleton and pore structure This fact makes CMPs one of the most important platforms for developing novel organic porous polymers. Ferrocene and its derivatives are a kind of special organometallic compounds, and often used for designing polymers with special properties With these in mind, ion-containing CMPs were designed and prepared by Yamamoto coupling of 1,1’-dibromoferrocene and 5,10,15,20-Tetrakis(4-bromophenyl)porphyrin or Tetra(p-bromophenyl)methane. The gas storage capacity and removal efficiency of dye from aqueous solution of ion-containing CMPs were investigated
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