Synthesis and characterization of polypyrrole@copper pyromellitic and CO2 adsorption ability of separated polypyrrole
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摘要: 聚吡咯的合成方法不同，得到的聚吡咯的分子结构和性能都会有明显的差异。因此，以金属有机框架材料均苯三酸铜(Cu-BTC)为主体材料，采用碘氧化法在其三维孔道内实现了吡咯(Py)的自由基氧化聚合，得到了聚吡咯PPy@Cu-BTC复合材料。采用粉末XRD、SEM、FTIR、TG及N2吸脱附等方法对Cu-BTC、Py@Cu-BTC、PPy@Cu-BTC进行表征，证明孔内聚合的成功进行。Cu-BTC在聚合过程中保持了结构的稳定，其形貌也未发生改变。所制备的PPy@Cu-BTC复合材料基于主客体之间的电荷转移和π-π键的相互作用，其电导率为10−4 S/cm，相对于块体PPy及Cu-BTC模板至少提高四个数量级，是一种半导体材料。N2吸脱附表明，除去模板后分离得到的PPy具有多孔性，对CO2有着较好地吸收能力，其最大吸收值约为16 cm3/g，相对于块状聚吡咯，其吸收能力翻了一倍。Abstract: The molecular structure and performance of polypyrrole is very different due to the difference of its synthesis methods. Utilizing a metal-organic framework (MOF) named copper pyromellitic (Cu-BTC) with three-dimensipnal (3D) mesoporous channels as the host material, the radical polymerization of pyrrole (Py) was conducted in the pores by iodine oxidation method to obtain the composite material polypyrrole@Cu-BTC (PPy@Cu-BTC). XRD, SEM, FTIR, TG and N2 adsorption-desorption isotherm were used to characterize the prepared Cu-BTC, Py@Cu-BTC and PPy@Cu-BTC, showing the successful synthesis of polymerization in the pores. During the polymerization, the structure and morphology of Cu-BTC keep stable. Based on the charge transfer of host-guest complexation and π-π interaction, the PPy@Cu-BTC composite is a semiconductor material and has a conductivity of 10−4 S/cm which is at least four orders of magnitude higher than the conductivity of the template Cu-BTC and the as-prepared solid polypyrrole. N2 adsorption measurement indicated that the as-synthesized PPy separated from PPy@Cu-BTC composite is porous, which has excellent absorption ability of CO2 with a maximum absorption value of 16 cm3/g and twice as much as the absorption ability of the as-synthesized solid PPy.
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图 1 均苯三酸铜(Cu-BTC)的三维孔道结构及尺寸
Figure 1. 3D internconnected channel structure and pore size of copper pyromellitic (Cu-BTC)
图 3 活化后Cu-BTC (a)、吡咯(Py)@Cu-BTC (b)、聚吡咯(PPy)@Cu-BTC (c)和分离模板后得到的PPy (d) 的SEM图像
Figure 3. SEM images of actived Cu-BTC (a), pyrrole (Py)@Cu-BTC (b), polypyrrole (PPy)@Cu-BTC (c) and the isolated PPy from PPy@Cu-BTC (d)
图 4 Cu-BTC、Py@Cu-BTC、PPy@Cu-BTC和分离得到的PPy的XRD图谱
Figure 4. XRD patterns of actived Cu-BTC, Py@Cu-BTC, PPy@Cu-BTC and isolated PPy from PPy@Cu-BTC
图 5 Cu-BTC、Py@Cu-BTC、PPy@Cu-BTC和分离得到的PPy的FTIR图谱
Figure 5. FTIR spectra of actived Cu-BTC, Py@Cu-BTC, PPy@Cu-BTC and isolated PPy from PPy@Cu-BTC
图 6 Cu-BTC和PPy@Cu-BTC复合材料在77 K下的N2吸附-脱附曲线
Figure 6. N2 sorption isotherms of actived Cu-BTC and PPy@Cu-BTC composites at 77 K
STP—Standard temperature and pressure
图 8 Py@Cu-BTC和 PPy@Cu-BTC复合材料的热失重曲线
Figure 8. TGA curves of Py@Cu-BTC and PPy@Cu-BTC composites
图 9 Cu-BTC和PPy@Cu-BTC复合材料的电流-电压(I-V)关系
Figure 9. Current-voltage (I-V) plots of Cu-BTC and PPy@Cu-BTC composites
图 10 块状聚吡咯和PPy@Cu-BTC复合材料的I-V 关系
Figure 10. I-V plots of bulk PPy and PPy@Cu-BTC composites
图 11 块状聚吡咯及分离得到的PPy在77 K下的N2吸附曲线曲线
Figure 11. N2 sorption isotherms at 77 K of bulk PPy and the isolated PPy from PPy@Cu-BTC composite
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