Li Xiaojiang, Zhu Peiyao, Lv Xin, Yan Guijiang, Lu Hongsheng
College of Chemistry and Chemical Engineering, Southwest Petroleum University, Chengdu 610500, P. R. China.
State Key Laboratory of Natural Gas Hydrates, Beijing 100028, P. R. China.
Langmuir. 2020 Dec 1;36(47):14288-14295. doi: 10.1021/acs.langmuir.0c02505. Epub 2020 Nov 17.
In this work, a novel Pickering emulsion is stabilized by silica nanoparticles functioned with a redox and pH-responsive surfactant FA-DMDA-Ox that is prepared simply by direct neutralization of ferrocenecarboxylic acid (FA) and ,-dimethyldodecylamine (DMDA) and exhibits redox and doubly pH-switchable behavior. Here, the Pickering emulsion can be stabilized easily by combining hydrophilic silica nanoparticles with less than 0.1 wt % FA-DMDA-Ox. After adding NaSO and HO alternately, the demulsification and emulsification of this Pickering emulsion are controlled reversibly. Moreover, the emulsion is switched "off" upon the addition of HCl and switched "on" upon the addition of NaOH and is also switched off upon the addition of NaOH and switched on upon the addition of HCl, which demonstrate the doubly pH-switchable behavior. Based on the analysis of ζ-potential, contact angle, and adsorbed amount of silica nanoparticles, the pH and redox-switchable mechanism of the Pickering emulsion are analyzed. Here, the redox-switchable behavior is induced by the reversible adsorption and desorption of FA-DMDA-Ox on the surface of silica nanoparticles. The pH-switchable behavior is driven by the controllable dispersion systems of silica nanoparticles and FA-DMDA-Ox because of the doubly pH switchability of FA-DMDA-Ox. More importantly, upon adding fresh oil after removing the original oil, the Pickering emulsion is recycled three times. Hence, the multiswitchable Pickering emulsion can be expected to be treated as a multifunctional material in practical applications, such as oil or wax removal in the petroleum industry.
在本工作中,一种新型的皮克林乳液由二氧化硅纳米颗粒稳定,该二氧化硅纳米颗粒与一种氧化还原和pH响应型表面活性剂FA-DMDA-Ox协同作用,FA-DMDA-Ox通过二茂铁羧酸(FA)与N,N-二甲基十二烷基胺(DMDA)直接中和简单制备而成,具有氧化还原和双重pH可切换行为。在此,通过将亲水性二氧化硅纳米颗粒与含量低于0.1 wt%的FA-DMDA-Ox相结合,可轻松稳定皮克林乳液。交替加入NaSO和HO后,该皮克林乳液的破乳和乳化过程可被可逆控制。此外,加入HCl时乳液“关闭”,加入NaOH时乳液“开启”,加入NaOH时乳液也会“关闭”,加入HCl时乳液又会“开启”,这证明了其双重pH可切换行为。基于对二氧化硅纳米颗粒的ζ电位、接触角和吸附量的分析,对皮克林乳液的pH和氧化还原可切换机制进行了分析。在此,氧化还原可切换行为是由FA-DMDA-Ox在二氧化硅纳米颗粒表面的可逆吸附和解吸诱导的。由于FA-DMDA-Ox的双重pH可切换性,pH可切换行为由二氧化硅纳米颗粒和FA-DMDA-Ox的可控分散体系驱动。更重要的是,去除原始油后加入新鲜油,皮克林乳液可循环使用三次。因此,这种多可切换皮克林乳液有望在实际应用中被视为多功能材料,如石油工业中的除油或除蜡。