不同分子結構表面活性劑對低氧化度氧化石墨插層機理的探索

胡陽; 解鑫; 孫春寶; 寇玨

doi:10.13374/j.issn2095-9389.2019.06.03.001

不同分子結構表面活性劑對低氧化度氧化石墨插層機理的探索

doi: 10.13374/j.issn2095-9389.2019.06.03.001

北京科技大學土木與資源工程學院，北京 100083

基金項目: 國家自然科學青年基金資助項目（51804021）

詳細信息

通訊作者:
E-mail：koujue@ustb.edu.cn

中圖分類號: TB32
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出版歷程
- 收稿日期: 2019-06-03
- 刊出日期: 2020-01-01

Study of the intercalation mechanisms of surfactants with different molecular structures on mildly oxidized graphite

School of Civil and Resources Engineering, University of Science and Technology Beijing, Beijing 100083, China

More Information

Corresponding author: E-mail：koujue@ustb.edu.cn

摘要

摘要: 以人造石墨為原料制備了低氧化程度的氧化石墨（MOG），并研究了具有不同極性基團和不同碳鏈長度的表面活性劑對氧化石墨的插層機理。通過X射線衍射（XRD）、紅外光譜（FT-IR）、X射線光電子能譜（XPS）、拉曼光譜（Raman）和Zeta電位儀對插層前后的氧化石墨進行表征，探討表面活性劑的分子結構對其插層能力的影響以及表面活性劑的插層機理。結果表明陽離子表面活性劑主要通過其極性端與氧化石墨的羧基、羥基之間的靜電吸引作用進入氧化石墨層間進行插層，其插層效果優于陰離子表面活性劑，更容易增大氧化石墨的層間距。陰離子表面活性劑則通過與氧化石墨之間形成氫鍵和疏水作用力來進行插層。研究表明：表面活性劑極性基團的分子大小越大，非極性端的碳鏈越長，其插層能力越強。上述研究成果有助于深入認識表面活性在氧化石墨層間的插層機理，同時也對氧化石墨插層改性材料的制備和應用具有重要的指導意義。
- 人造石墨 /
- 陰離子表面活性劑 /
- 陽離子表面活性劑 /
- 低氧化度氧化石墨 /
- 插層 /
- 層間距 /
- 疏水作用力
Abstract: As a star material, graphene has attracted much attention because of its excellent mechanical, optical, electrical, and thermal properties. The chemical conversion of graphene oxide is considered to be a promising approach to economically produce graphene in significant quantities, but the reduced graphene oxide prepared from this method suffers a lot of defects, such as vacancies and the presence of residual oxygen groups. In this case, graphite oxide with a low oxidation degree was used to prepare graphene to decrease the residual oxygen groups and vacancies caused by the removal of oxygen groups during reduction. However, this kind of mildly oxidized graphite (MOG) is hard to exfoliate to prepare graphene oxide; it is necessary to increase the basal spacing of MOG to facilitate the exfoliation. According to the literature, the intercalation of surfactants is usually used to enlarge the basal spacing of graphite and graphite oxide, but the intercalation mechanism of surfactants with different structures in MOG remains unknown. In this work, MOG was prepared from artificial graphite powder, and the intercalations of surfactants with different polar parts and carbon chain lengths on MOG were studied. The effect of surfactant molecular structures on their intercalation ability and the intercalation mechanism were studied through measurements with X-ray diffraction spectroscopy (XRD), Fourier-transform infrared spectroscopy (FT-IR), X-ray photoelectron spectroscopy (XPS), and Raman and Zeta potential measurements. The results show that the cationic surfactants intercalate MOG mainly through the attractive electrostatic interaction between them, and their intercalation capacity is better than that of anionic surfactants as they can enlarge the basal spacing of MOG more easily. The anionic surfactants intercalated MOG through the formation of hydrogen bonds and the hydrophobic intercalation force between them. It was found that the larger the polar part and the longer the carbon chain, the stronger the intercalation ability of surfactants. These research results may help to better understand the intercalation mechanism of the surface in MOG interlayers and guide the preparation and application of MOG intercalation-modified materials.
- artificial graphite /
- anionic surfactant /
- cationic surfactant /
- mildly oxidized graphite /
- intercalation /
- basal spacing /
- hydrophobic force

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圖 1 氧化石墨和石墨的X射線衍射譜圖

Figure 1. XRD patterns of graphite and MOG

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圖 2 不同pH下氧化石墨的Zeta電位圖

Figure 2. Zeta potential of MOG at different pH values

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圖 3 十二烷胺鹽酸鹽、十二烷基三甲基氯化銨、十二烷基二甲基芐基氯化銨和月桂酸鈉的分子結構式

Figure 3. Molecular formula of DDACl、DTAC、DDBAC, and SL

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圖 4 十二烷胺鹽酸鹽、十二烷基三甲基氯化銨、十二烷基二甲基芐基氯化銨和月桂酸鈉插層氧化石墨前后的X射線衍射譜圖

Figure 4. XRD patterns of MOG, MOG?DDACl, MOG?DTAC, MOG?DDBAC, and MOG?SL

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圖 5 乙酸鈉、月桂酸鈉和硬脂酸鈉的分子結構式

Figure 5. Molecular formula of SA, SL, and SS

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圖 6 乙酸鈉、月桂酸鈉和硬脂酸鈉插層氧化石墨前后的X射線衍射譜圖

Figure 6. XRD patterns of MOG, MOG?SA, MOG?SL, and MOG?SS

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圖 7 不同表面活性劑插層前后氧化石墨的Zeta電位

Figure 7. Zeta potential of MOG and MOG intercalated with different surfactants

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圖 8 十二烷胺鹽酸鹽和月桂酸鈉插層氧化石墨前后的紅外光譜譜圖

Figure 8. FTIR spectra of MOG、MOG?DDACl, and MOG?SL

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圖 9 C 1s的X射線光電子能譜譜圖。（a）氧化石墨；（b）氧化石墨?十二烷胺鹽酸鹽；（c）氧化石墨?月桂酸鈉

Figure 9. XPS spectra of C 1s: (a) MOG; (b) MOG?DDACl; (c) MOG?SL

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圖 10 十二烷胺鹽酸鹽和月桂酸鈉插層前后的氧化石墨的拉曼譜圖

Figure 10. Raman spectra of MOG, MOG?DDACl, and MOG?SL

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