聚吡咯/石墨烯奈米複合材料之製備與特性分析

林家毅

doi:10.6845/NCHU.2014.01331

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聚吡咯/石墨烯奈米複合材料之製備與特性分析

Preparation and Characterization of Polypyrrole / Graphene Nanocomposites

林家毅 , Masters　　Advisor：吳震裕　　

繁體中文 DOI： 10.6845/NCHU.2014.01331

聚吡咯；石墨烯； Polypyrrole ； Graphene

Abstract │ Reference (151) │ Times Cited (1) │ Altmetrics

Abstract 〈TOP〉

本研究題目是以石墨(Graphite)利用化學改質製備氧化石墨烯(GO)
，再將GO分散在二甲基甲醯胺(DMF)溶劑中進行還原(RGOD)將表面含氧官能基移除。利用摻雜劑在GO及RGOD表面聚合?咯，分析導
電性質、耐熱性與結構型態。 
    本實驗以原位聚合法製備聚?咯 (Polypyrrole, PPy)與石墨烯之複合材料，其中複材分為兩個系統。系統(I)為在水溶液中GO吸附摻雜劑利用過硫酸鉀 (Potassium persulfate, KPS)原位氧化聚合?咯，使用摻雜劑為十二烷基苯磺酸鈉 (Dodecylbenzenesulfonic acid sodium salt, DBSNa)或聚苯乙烯磺酸鈉 (Sodium polystyrene 4-sulfonate, PSS)，其中摻雜劑為DBSNa，pyrrole(Py)與GO重量比(g/g)分別為100/1其聚合時間有1小時(D/100P/GO-K-a-1h)、2小時(D/100P/GO-K-a-2h)、3小時(D/ 100P/GO-K-a-3h)和4小時(D/100P/GO-K-a-4h)及5/1 其聚合時間有1小時(D/5P/GO-K-a-1h)、2小時(D/5P/GO-K-a-2h)和3小時(D/5P/GO-K-a -3h)；摻雜劑為PSS，Py與GO重量比(g/g)分別為5/1其聚合時間有1小時(S/5P/GO-K-a-1h)、2小時(S/5P/GO-K-a-2h)和3小時(S/5P/GO-K-a -3h), 3/1其聚合時間有1小時(S/3P/GO-K-a-1h)、2小時(S/3P/GO-K-a-2h)和3小時(S/3P/GO-K-a-3h)及1/1其聚合時間有1小時(S/1P/GO-K-a-1h)
、2小時(S/1P/GO-K-a-2h)和3小時(S/1P/GO-K-a-3h);系統(II)為在DMF溶劑中RGOD吸附PSS摻雜劑利用氧化劑原位聚合五倍?咯，其中氧化劑為KPS，Py與KPS莫耳比(mol/mol)為1/0.58其聚合時間有1小時(S/5P /RGO-K-d-1h)、2小時(S/5P/RGO-K-d-2h)和3小時(S/5P/RGO-K-d -3h)；氧化劑為三氯化鐵 (Ferric Chloride, FeCl3)，Py與FeCl3莫耳比(mol/mol)分別為1/0.5其聚合時間有1小時(S/5P/RGO-0.5Fe-d-1h)、2小時(S/5P/ RGO-0.5Fe-d-2h)和3小時(S/5P/RGO-0.5Fe-d-3h), 1/0.75其聚合時間有1小時(S/5P/RGO-0.75Fe-d-1h)、2小時(S/5P/RGO-0.75Fe-d- 2h)和3小時(S/ 5P/RGO-0.75Fe-d-3h)及1/1其聚合時間有1小時(S/5P/ RGO-1Fe-d-1h)、2小時(S/5P/RGO-1Fe-d-2h)和3小時(S/5P/RGO-1Fe 
-d-3h)。
    由FTIR分析可發現，聚?咯/石墨烯之奈米複合材料在1545 cm-1發現C-N asymmetric  ring stretching vibration，在1457 cm-1發現C-C symmetric  ring stretching vibration，在1174 cm-1發現breathing vibration of pyrrole ring ，在1091 cm-1發現NH2+ in-plane deformation，1040 cm-1發現C-H及N-H in-plane deformation，在905 cm-1發現C-H out of plane deformation，表示PPy確實有在石墨烯表面聚合成功。由XRD分析得知，GO在2θ = 9.1°存在繞射峰其層間距為0.97nm，D/100P/GO-K-a-4h、D/5P/GO-K-a-3h、S/5P/GO-K-a-3h與S/3P/GO-K-a-3h複材在2θ = 1.5° ~10° 之間沒有繞射峰，其層間距皆大於5.88 nm為脫層的現象，S/1P/ GO-K-a-3h的樣品在2θ = 9.1°其層間距為0.97 nm。RGOD、S/5P/RGO -K-d-3h、S/5P/RGO-0.5Fe-d-3h、S/5P/RGO-0.75Fe-d-3h及S/5P/RGO -1Fe-d-3h複材，因還原後RGOD的排列被打亂，使得2θ = 9.1°繞射峰消失。在2θ = 20- 30°有較寬廣繞射峰為聚?咯無定型區。由熱重損失分析，在200 oC熱重損失可發現，GO為19.3 %，D/100P /GO-K-a-4h為5.5 %，D/5P/GO-K-a-3h為16.1 %，S/5P/GO-K-a-3h為15.9 %，S/3P/ GO-K-a-3h為17.4 %，S/1P /GO-K-a-3h為17.2 %，隨著聚?咯比例增加其熱穩定性相對提升。S/5P/RGO-K-d-3h為11.1 %，S/5P/RGO-0.5Fe -d-3h為15.8 %，S/5P/RGO-0.75Fe-d-3h為11.7 %，S/5P/RGO-1Fe-d-3h為11.8 %，熱穩定性皆高於S/5P/GO-K-a -3h複材。由接觸角分析，S/5P/GO-K-a-3h、S/3P/GO-K-a-3h及S/1P/GO-K-a-3h角度分別為75.9 °、61.3 °及51.8 °，隨著表面聚合越多PPy其接觸角越高越親油。由四點探針分析可知，GO製備之複材中D/100P/GO-K-a-4h與D/5P/GO-K-a-3h之導電度為5.74與15.62 S/cm，S/5P/GO-K-a-3h、S/3P/GO-K-a-3h及S/1P/GO-K-a-3h之導電度為27.02、11.39及10.37 S/cm，導電度最佳化為單體添加五倍而摻雜劑為PSS。RGOD製備之複材中測得導電度S/5P/RGO-K-d-3h為3.67×10-1 S/cm，S/5P/RGO-0.5 Fe-d-3h、S/5P/RGO -0.75Fe-d-3h及S/5P/RGO-1Fe-d-3h分別為20.83、12.05及3.07 S/cm，導電度最佳化為FeCl3氧化劑及單體與氧化劑莫耳比1/0.5 (mol/mol)。由SEM分析可發現，GO製備之複材其表面聚?咯型態為圓球狀顆粒，S/5P/GO-K-a-3h、S/3P/GO-K-a-3h及S/1P/GO-K -a-3h複材隨單體添加量減少，其表面型態由圓球狀顆粒轉變為不規則形狀。RGOD製備之複材中S/5P/RGO-0.5Fe-d-3h其表面聚?咯型態有部份為為纖維條柱狀
結構。

Parallel Abstract 〈TOP〉

The purpose of this research is the graphene oxide (GO) can be prepared from natural graphite by the modified Hummers method from natural expanded graphite. Dimethylformamide (DMF) solvent is considered a good candidate for th prevention of irreversible graphene sheet aggregation during the hydrazine reduction of GO. A facile approach was used to prepare the GO and RGOD supported polypyrrole (PPy) nanoparticles via the in situ chemical oxidative polymerization of pyrrole (Py) onto the surfaces of the GO and RGOD modified with dodecylbenzenessulfonic acid sodium salt (DBSNa) or sodium polystyrene 4-sulfonate (PSS) as a dopant for PPy. The electrical conductivity、thermal stability、structure characteristics and morphology are investigated in this 
research.
In this study, the preparation of composites through in situ polymerization technique employing Py monomer and graphene was done with two kinds of composites synthesized. For system (I), PPy/GO composites, were chemically synthesized in water solution by decorating PPy nanoparticles onto the surfaces of the GO via facile in situ oxidation polymerization of potassium persulfate (KPS) by using DBSNa and PSS as an anionic dopant. The composites were prepared by in situ polymerization involving Py and GO with the dopant, DBSNa. The weight feed ratio of Py to GO was 100/1 which polymerize for 1hour、2hour、3hour and 4hour. The weight feed ratio of Py to GO was 5/1 which polymerize for 1hour、2hour and 3hour. The weight feed ratio 100/1 and 5/1 resulting composites were designated as D/100P/GO-K-a-1h、D/100P/GO-K-a-2h、D/100P/GO-K-a -3h and D/100P/GO-K-a-4h and D/5P/GO-K-a-1h、D/5P/GO-K-a-2h and D/5P/GO-K-a-3h ; while the composites were prepared by in situ polymerization involving Py and GO with the dopant, PSS. The weight feed ratio of Py to GO was 5/1, 3/1, and 1/1. Each of them polymerize for 1hour、2hour and 3hour. The weight feed ratio 5/1, 3/1 and 1/1 resulting composites were designated as S/5P/GO-K-a-1h、S/5P/GO-K-a-2h and 
S/5P/GO-K-a-3h, S/3P/GO-K-a-1h、S/3P/GO-K-a-2h and S/3P/GO-K-a-3h, and S/1P/GO-K-a-1h、S/1P/GO-K-a-2h and S/1P/GO-K-a-3h. For system (II) is PPy/RGOD composites chemically synthesized in DMF solvent by decorating PPy nanoparticles onto its surfaces of the RGOD via the in situ oxidation polymerization of the oxidant by using PSS as an anionic dopant.The oxidant, such as KPS and ferric Chloride (FeCl3). The composites were prepared by in situ polymerization involving Py and RGOD with dopant of PSS and oxidant of KPS. The weight feed ratio of Py to RGOD was 5/1 and the molar feed ratio of Py to KPS was 1/0.58 which polymerize for 1hour、2hour and 3hour. The resulting composites were designated as S/5P/RGO-K-d-1h、S/5P/RGO-K-d-2h and S/5P/RGO -K-d-3h; while the composites were prepared by in situ polymerization involving Py and RGOD with the dopant, PSS, and the oxidant, FeCl3. The weight feed ratio of Py to RGOD was 5/1 and the molar feed ratio of Py to FeCl3 was varied as 1/0.5, 1/0.75, and 1/1. Each of them polymerize for 1hour、2hour and 3hour. The molar feed ratio of Py to FeCl3 was 1/0.5, 1/0.75, and 1/1 resulting composites were designate as S/5P/RGO-0.5Fe-d- 1h、S/5P/RGO-0.5Fe-d-2h and S/5P/RGO-0.5Fe-d-3h, S/5P/RGO-0.75Fe- d-1h、S/5P/RGO-0.75Fe-d-2h and S/5P/RGO-0.75Fe-d-3h, and S/5P/RGO 
-1Fe-d-1h、S/5P/RGO-1Fe-d-3h and S/5P/RGO-1Fe-d-3h.
As show in the FTIR spectra of PPy/graphene nanocomposites, all the results demonstrate almost at the same peak positions of the main IR bands which are associated with the structure of the PPy. The peaks at 1545 and 1457 cm-1, which could be attributed to C-N and C-C asymmetric and symmetric ring-stretching. The breathing vibration of pyrrole ring occur at 1174 cm-1, 1091 cm-1 for NH2+ in-plane deformation stretching vibration, 1040 cm-1 for C-H and N-H in-plane deformation stretching vibration, and 905 cm-1 for C-H out of plane deformation stretching vibration. According to XRD analysis, the diffraction peak of pure GO appears at 2θ = 9.1°. It corresponds to a d-spacing of 0.97 nm with the XRD pattern of D/100P/GO -K-a-4h, D/5P/GO-K-a-3h, S/5P/GO-K-a-3h, and S/3P/GO-K-a-3h that their characteristic diffraction peaks of GO vanished. Besides, there is no apparent diffraction peak at 2θ = 1.5 °~10°. For the S/1P/GO-K-a-3h composite, the peak at 2θ = 9.1°(d = 0.97 nm) had as significant decrease in peak intensity. After hydrazine reduction, the diffraction peak of RGOD became extremely broad and shifted to wider angles up to 23.6°, which is approximately the peak of Graphite. However, it is evidence from the XRD pattern of the S/5P/RGO-K-d-3h, S/5P/RGO-0.5Fe-d-3h, S/5P/RGO-0.75 Fe-d-3h and S/5P/RGO-1Fe-d-3h composites that the peak is at 9.1° and has been disappeared completely indicating the reduction of the GO to RG OD. Pure PPy displays a broad band at 2θ = 20 °~30°. Thermogravimetric analysis shows nearly a 19.3 % weight loss of GO has occurred at 200 oC. 
The enhancement of the thermal stability of the PPy/GO composites can be attributed to the increasing dopant which promoted its thermal stability of PPy. As compared of the PPy/GO composites, 5.5 %, 16.1 %, 15.9 %, 17.4 % , and 17.2 % weight losses have been observed for the D/10 0P/GO-K-a- 4h, D/5P/GO-K-a-3h, S/5P/GO-K-a-3h, S/3P/GO-K-a-3h, and S/1P/GO-K -a-3h composites respectively. On the other hand, the weight losses of PPy in the PPy/RGOD composites, 11.1 %, 15.8 %, 11.7 % and 11.8 % weight losses have been observed for the S/5P/RGO-K-d-3h, S/5P/ RGO-0.5Fe-d-3h, S/5P/RGO-0.75Fe-d-3h, S/5P/RGO-1Fe-d-3h composites as a comparison for the PPy/GO composites which justified the improved thermal stability upon the PPy/RGOD composites. Static water contact angle measurement show contact angles for Composites (I) by increasing with Py fraction with its angles are 75.9 °, 61.3 °and 51.8 °and the resulting composites were designated as S/5P/GO-K-a-3h, S/3P/GO-K -a-3h and S/1P/GO-K-a-3h. Through four point probe resistivity measurement, it shows the conductivity for Composites (I). For D/100P/G O-K-a-4h and D/5P/GO-K-a-3h, the conductivities are 5.74 and 15.62 S/cm. For S/5P/GO-K-a-3h, S/3P/GO-K-a-3h and S/1P/GO-K-a-3h, the conductivities are 27.02, 11.39 and 10.37 S/cm. The optimal conductivity as the 5-fold Py fraction is with the dopant PSS. The conductivity of the PPy/RGOD composites, 3.67×10-1, 20.83, 12.05 and 3.07 S/cm are observed by the S/5P/RGO-K-d-3h, S/5P/RGO-0.5Fe-d-3h, S/5P/RGO-0.7 5Fe-d-3h, and S/5P/RGO-1Fe-d-3h composites. The optimal conductivity as molar feed ratio of Py to FeCl3 was 1/0.5 with the oxidant as FeCl3. Through SEM analysis, it reveals that for system (I), the PPy/GO composites, that its PPy particles shaped irregularly sphere aggregated as decreasing with Py fraction and the amount. for system (II), the PPy/RGOD composite, S/5P/RGO-0.5Fe-d-3h, shows that PPy are uniformly wrapped 
on RGOD with fiber structure.

Reference ( 151 ) 〈TOP〉

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連結：
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連結：

Times Cited (1) 〈TOP〉

王明月(2016)。聚吡咯/蒙脫土奈米複合材料之製備與水分散性之研究。中興大學化學工程學系所學位論文。2016。1-161。

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