非共价改性纳米颗粒稳定Pickering乳液的制备及可逆调控

doi:10.11949/0438-1157.20191061

摘要/Abstract

摘要：

用具有氧化还原活性分子乙酰基二茂铁吖嗪(Fc⁺A)对磁性纳米颗粒Fe₃O₄@SiO₂进行非共价疏水改性，将改性颗粒作为乳化剂制备Pickering乳液。通过TEM、SEM、FTIR、XRD、接触角测量、光学显微镜等对纳米颗粒及Pickering乳液的结构、形貌和性能进行表征。结果表明：制备的核壳结构纳米颗粒粒径为150 nm左右，分散均匀；Fc⁺A成功修饰到纳米颗粒表面，且随Fc⁺A浓度的增加，改性颗粒的接触角明显增大；Fc⁺A浓度为12.5 mmol/L，乳化剂浓度为0.3%(质量)，油水比为4∶6，搅拌速率为10000 r/min，得到的Pickering乳液具有良好的稳定性。而且，所得乳液具双重响应性，通过氧化还原和磁场可实现对乳液稳定性的可逆调控。

关键词: Pickering乳液, 非共价, 稳定性, 氧化还原, 磁场

Abstract:

Non-covalent hydrophobic modification of magnetic nanoparticles Fe₃O₄@SiO₂ with a redox-active molecule acetylferrocene azine (Fc⁺A), and the modified particles were used as emulsifiers to prepare Pickering emulsions. The modified particles were used as emulsifiers to prepare Pickering emulsion. The structure and properties of nanoparticles and Pickering emulsion were characterized by TEM, SEM, FTIR, XRD, contact angle measurement and optical microscopy. The experimental results showed that the mono-dispersed nanoparticles with particle size 150 nm were synthesized and Fc⁺A was successfully introduced onto the surface of nanoparticles. With the increase of Fc⁺A concentration, the contact angel of nanoparticles increased. The Pickering emulsion obtained could be stabilized when the concentration of Fc⁺A was 12.5 mmol/L, the emulsifier concentration was 0.3%(mass), oil-water ratio was 4∶6 and rotation speed was 10000 r/min. Finally, the stability of emulsion was reversibly regulated by redox and magnetic field.

Key words: Pickering emulsion, non-covalent, stability, redox, magnetic field

中图分类号:

TB 34

罗东琴, 孙宁, 李秋红, 隋鹏亮, 姜秋艳, 隋晓飞, 李爱香. 非共价改性纳米颗粒稳定Pickering乳液的制备及可逆调控[J]. 化工学报, 2020, 71(4): 1859-1870.

Dongqin LUO, Ning SUN, Qiuhong LI, Pengliang SUI, Qiuyan JIANG, Xiaofei SUI, Aixiang LI. Preparation and modulation of Pickering emulsion stabilized by non-covalent hydrophobic modified nanoparticles[J]. CIESC Journal, 2020, 71(4): 1859-1870.

图/表 12

图1 FcA的1H NMR谱图

Fig.1 1H NMR spectrum of FcA in DMSO[D6]

图2 Fe3O4及Fe3O4@SiO2的XRD谱图

Fig.2 XRD patterns of Fe3O4 and Fe3O4@SiO2 nanoparticles

图3 Fe3O4@SiO2纳米颗粒的透射电镜图

Fig.3 TEM images of Fe3O4@SiO2 nanoparticles

图4 Fe3O4@SiO2和Fc+A修饰的Fe3O4@SiO2纳米颗粒扫描电镜及EDS元素分布图

Fig.4 SEM images of Fe3O4@SiO2, Fc+A-modified Fe3O4@SiO2, and EDS element distribution of C, N, O, Si and Fe for Fc+A-modified nanoparticles

图5 纳米颗粒的红外光谱图

Fig.5 FTIR spectra of nanoparticles

图6 不同浓度Fc+A改性Fe3O4@SiO2颗粒的接触角示意图

Fig.6 Contact angle images of nanoparticles with different Fc+A concentration

图7 不同Fc+A浓度改性纳米颗粒稳定的Pickering乳液的显微、宏观图片及粒径分布

Fig.7 Optical micrographic images, visual appearance and droplets size distribution of emulsions stabilized by modified-Fe3O4@SiO2 nanoparticles with different Fc+A concentration

图8 不同乳化剂浓度的Pickering乳液的显微、宏观照片与粒径分布

Fig.8 Optical micrographic images, visual appearance and droplets size distribution of emulsions at different mass fractions of emulsifier

图9 不同油水比的Pickering乳液的显微、宏观照片及粒径分布

Fig.9 Optical micrographic images, visual appearance and droplets size distribution of emulsions at different oil-water ratio

图10 不同搅拌速度的Pickering乳液的显微照片和粒径分布

Fig.10 Optical micrographic images and droplets size distribution of emulsions at different rotation speed

图11 FcA的荧光光谱、Pickering乳液的氧化还原和磁场调控

Fig.11 Fluorescence sprctra of FcA, redox and magnetic field responses of Pickering emulsions and corresponding optical micrographic images

图12 Fc+A修饰Fe3O4@SiO2纳米颗粒的结构及磁场和氧化还原激励响应Pickering乳液的调控示意图

Fig.12 Structural description for redox conversion of FcA and Fc+A-modified Fe3O4@SiO2 particles (top) and strategy for emulsification and demulsification of Pickering emulsions triggered by redox (bottom)

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