Ferrocene-linked porous organic polymers for carbon dioxide and hydrogen sorption
Graphical abstract
Ferrocene-linked porous organic polymers derived from 1,1’-diethynylferrocene and tetrahedral silicon-centered monomers show high porosity and comparable carbondioxide and hydrogen capacities.
Introduction
In recent decades, intense efforts have been devoted to develop porous organic polymers (POPs) because of their extensively potential applications in the fields of gas storage, gas separation, heterogeneous catalysis, chemosensors, light harvesting and energy storage, etc [[1], [2], [3], [4], [5], [6]]. In particular, metal atoms containing POPs have attracted specific attention since the introduction of metal sites can endow resultant materials intriguing properties such as catalytic activity [[7], [8], [9], [10]] and enhanced gas adsorption performance [[11], [12], [13], [14]]. For example, Ru- or Ag- metalated mesoporous poly(triphenylphosphine) with azo functionality were discovered to be highly efficient catalysts for CO2 transformation [15]. Alkali-metal doped POPs (e.g., Li-PAF-1) could efficiently promote H2 and CO2 uptakes with improved isosteric heat of gas adsorption values [12]. To date, most of these materials were constructed by post metalation-treating with well-designed POPs containing coordinating atoms such as N, O, P or functional groups [[11], [12], [13], [14]]. However, this strategy commonly requires at least two steps to achieve the final objectives and the metal sites are prone to aggregate in the frameworks. In contrast, it is of high convenience by direct synthetic methodology based on predesigned monomers containing metal atoms through diversified organic reactions such as Sonogashira-Hagihara reaction, Yamamoto reaction, cyclotrimerization reaction, Schiff-base reaction, etc [1,2]. Moreover, this strategy endows the POP materials with a regular and homogenous dispersion of metal sites, permitting a strong interaction between the networks and guest gases [16].
Among various metal-containing monomers, ferrocene and their derivatives are a class of special organometallic compounds with high stability, unique rigid and double-deck sandwish-like structure and have been widely applied in the fields of electrocatalysis, magnetism, photonic crystal displays and ceramic precursors [[17], [18], [19], [20], [21], [22], [23], [24], [25], [26], [27], [28]]. The introduction of ferrocene units in the porous networks has an intriguing advantage, i.e., enhancing the gas sorption property due to the strong interaction between the metal sites and gas molecules [16,[29], [30], [31], [32], [33]]. For example, Fu et al. constructed ferrocene-functionalized microporous aromatic polymers (FMAPs) by cost-effective one-pot Friedel-Crafts reaction of ferrocene and s-triazine monomers; FMAP-1 has a moderate BET surface area of 875 m2 g−1 and good gas adsorption [16]. Liu et al. reported a ferrocene-based nanoporous polymer exhibiting moderate porosity with BET surface area of 752.4 m2 g−1 and total pore volume of 1.32 cm3 g−1 and excellent gas storage capacities by Schiff-base coupling reaction of 1,1′-ferrocene-dicaboxaldehyde and melamine [32]. However, the preparation and applications of ferrocene-containing POP materials are still rarely investigated and only few examples have been reported in recent years [16,[29], [30], [31], [32], [33]].
With this fact in mind, herein, we present two novel ferrocene-containing porous organic polymers (FPOPs) by using 1,1′-diethynylferrocene and tetrahedral silicon-centered compounds as monomers via classic Sonogashira-Hagihara coupling reactions (Scheme 1). The selection of tetrahedral silicon-centered monomers is inspired by their remarkable advantage, i.e., facile achievement of large specific surface area [34]. The resultant materials show high thermal stability and high porosity with BET surface area of up to ∼1000 m2 g−1. Moreover, the applications in CO2 and H2 sorption were also explored.
Section snippets
Materials
Unless otherwise stated, all chemicals were obtained from commercial suppliers and used without further purification. 1,1′-Diethynylferrocene, tri(4-bromophenyl)phenylsilane and tetrakis(4-bromophenyl)silane were synthesized according to previous reports [[35], [36], [37]]. N,N-Dimethylformamide (DMF) was dehydrated with CaH2 at 80 °C for 12 h, distilled under vacuum pressure and stored with 4 Å molecule sieves prior to use. Diisopropylamine (i-Pr2NH) was dried over CaH2 and used freshly.
Characterization
Synthesis and characterization
As shown in Scheme 1, two novel ferrocene-based porous organic polymers, FPOP-1 and FPOP-2, were synthesized through the palladium-catalyzed Sonogashira-Hagihara coupling reactions of 1,1′-diethynylferrocene with tetrahedral silanes containing tri- or tetrakis-bromophenyl groups in high yields. The reactions were performed using Pd(PPh3)/CuI as the catalyst, i-Pr2NH as the acid absorbent in DMF at 85 °C for 72 h. After the reaction, the crude products were filtrated, washed with several
Conclusion
In conclusion, we have synthesized two novel ferrocene-containing porous organic polymers (FPOPs) using 1,1′-diethynylferrocene and tetrahedral silicon-centered compounds containing tri- or tetrakis- 4-bromophenyl groups as monomers via Sonogashira-Hagihara coupling reactions. The resultant polymers show high thermal stability and high porosity with BET surface areas of up to 954 m2 g−1 and total pore volumes of up to 0.74 cm3 g−1. The porosity is higher than other ferrocene-containing porous
Acknowledgements
This work was financially supported by the National Natural Science Foundation of China (Grant 51373069) and the Natural Science Foundation of Shandong Province (Grant ZR2016EMM07).
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