Synthesis, characterization and electric conductivity of novel poly (divinyldioxythiophene@indium p-phthalic semi-conductor composites
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摘要: 由于单体间易发生交联反应而使聚乙烯基二氧噻吩(PEDOT)导电性能下降和造成后续成型加工的困难，因而寻找合适的聚合方法制备PEDOT显得尤为重要。以金属有机框架材料(MOFs)为反应模板，在对苯二甲酸铟配位聚合物(In-BDC)的一维孔道内实现了3, 4-二乙烯基二氧噻吩(EDOT)的自由基氧化聚合，得到了PEDOT@ In-BDC复合材料。采用XRD、SEM、FTIR、TG及N2吸脱附等方法对所制备的PEDOT@In-BDC复合材料进行了表征分析。结果表明，EDOT氧化聚合反应的单体转化率为91%；在整个EDOT单体的聚合过程中，In-BDC的框架结构保持稳定，其比表面积(BET)为45 m2/g；将EDOT单体引入In-BDC模板孔道内发生聚合反应得到的PEDOT@In-BDC复合材料可以提高金属有机框架材料In-BDC的热稳定性。电流-电压(I-V)线性扫描分析结果显示，PEDOT@In-BDC复合材料是基于PEDOT而具有导电性的一类新型半导体材料，其电导率为2.7×10−5 S/m；与功能性多孔材料In-BDC模板 (10−12 S/cm) 相比，PEDOT@In-BDC复合材料的电导率至少提高6个数量级。Abstract: Owing to the incidental crosslinking reaction of monomer, the as-prepared poly(divinyldioxythiophene (PEDOT) always has poor electric conductivity and difficult subsequent processing. Thus, it is very important to develop appropriate polymerization method to synthesis PEDOT. Poly(divinyldioxythiophene has been synthesized via free radical oxidation polymerization in the one-dimensional channel of indium p-phthalic coordination polymer (In-BDC) metal organic framework material (MOF) as a reactive template to form PEDOT@In-BDC composite. The PEDOT@In-BDC composites were characterized by XRD, SEM, FTIR, TG and N2-sorption isotherm analysis. The results show that the monomer conversion of divinyldioxythiophene (EDOT) is higher than 91%. During the polymerization reaction, the framework of In-BDC template keeps constant. The specific surface area (BET) value of PEDOT@In-BDC composite is 45 m2/g. Compared with In-BDC template, PEDOT@In-BDC composites obtained by free radical oxidation polymerization of monomer divinyldioxythiophene in MOF are more stable. The result of current-voltage (I-V) linear scan test indicates that the PEDOT@In-BDC composite is novel semiconductor material and conductive based on PEDOT. The conductivity of PEDOT@In-BDC composite reaches 2.7×10−5 S/m. Compared with the functional porous material In-BDC (10−12 S/cm) , the PEDOT@In-BDC composite has higher electric conductivity and is at least six orders higher than that of In-BDC template.
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图 1 孔径分别为1.7 nm(P1) 和0.6 nm(P2)的对苯二甲酸铟配位聚合物(In-BDC)的孔道结构
Figure 1. Channel structure of the indium p-phthalic coordination polymer (In-BDC) with the porediameters of 1.7 nm (P1) and 0.6 nm (P2)
图 3 活化后In-BDC (a)、3, 4-乙烯基二氧噻吩(EDOT)@In-BDC (b) 和聚乙烯基二氧噻吩(PEDOT)@In-BDC复合材料 (c) 的SEM图像
Figure 3. SEM images of actived In-BDC (a), divinyldioxythiophene (EDOT)@Cu-BTC (b) and poly(divinyldioxythiophene (PEDOT)@In-BDC composites (c)
图 4 In-BDC、EDOT@In-BDC和PEDOT@In-BDC复合材料的XRD图谱
Figure 4. XRD patterns of In-BDC, EDOT@In-BDC and PEDOT@In-BDC composites
图 5 In-BDC、EDOT@In-BDC和PEDOT@In-BDC复合材料的FTIR图谱
Figure 5. FTIR spectra of In-BDC, EDOT@In-BDC and PEDOT@In-BDC composites
图 6 EDOT@In-BDC 和PEDOT@In-BDC复合材料的TGA曲线
Figure 6. TGA curves of EDOT@In-BDC and PEDOT@In-BDC composites
图 7 PEDOT@In-BDC复合材料制备过程的结构演变
Figure 7. Structural change of PEDOT@In-BDC composites during its preparation
图 8 In-BDC和PEDOT@In-BDC复合材料在77 K下的N2吸附图
Figure 8. N2 adsorption isotherms of actived In-BDC and PEDOT@In-BDC composites at 77 K
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