Journal Home Online First Current Issue Archive For Authors Journal Information 中文版

Engineering >> 2022, Volume 12, Issue 5 doi: 10.1016/j.eng.2020.08.031

A CO2/N2-Responsive Pickering Emulsion Stabilized by Novel Switchable Surface-Active Alumina Nanoparticles

a State Key Laboratory of Chemical Engineering, Department of Chemical Engineering, Tsinghua University, Beijing 100084, China
b Department of Chemical and Materials Engineering, University of Alberta, Edmonton, AB T6G 1H9, Canada

Received: 2020-03-31 Revised: 2020-06-16 Accepted: 2021-08-05 Available online: 2022-04-09

Next Previous

Abstract

This article reports the development of a novel switchable Pickering emulsion with rapid CO2/N2 responsiveness, which is stabilized using alumina nanoparticles hydrophobized in situ with a trace amount of a switchable superamphiphile via electrostatic interactions. With the introduction of CO2 for 30 s, the Pickering emulsion can be spontaneously demulsified with complete phase separation; the emulsion can then be reconstructed in response to N2 purging for 10 min followed by homogenization. Moreover, the stable Pickering emulsion can be stored for more than 60 days at room temperature without any visible change. The CO2/N2-responsive behavior of the switchable Pickering emulsion is attributed to the reversible desorption/adsorption of the switchable surfactants on the surfaces of the alumina nanoparticles upon the alternative bubbling of CO2 or N2. Thanks to the simple fabrication of the surfactant and the hydrophobization of the alumina nanoparticles, this research has developed an extremely facile and cost-efficient method for preparing a rapidly CO2/N2-responsive switchable Pickering emulsion. The dosage of the switchable surfactants has been significantly reduced by nearly 1500 times (from 150 to 0.1 mmol∙L−1) as compared with the dosage used in previous studies. Moreover, the as-prepared CO2/N2-responsive switchable Pickering emulsion is environmentally friendly, mild, and nontoxic; thus, it holds great potential for practical applications with considerable economic and environmental benefits, such as oil transport, fossil fuel production, environmental gases detection, and the encapsulation and release of active ingredients.

SupplementaryMaterials

Figures

Fig. 1

Fig. 2

Fig. 3

Fig. 4

Fig. 5

Fig. 6

Fig. 7

References

[ 1 ] Martínez-Palou R, Reyes J, Cerón-Camacho R, Ramírez-de-Santiago M, Villanueva D, Vallejo AA, et al. Study of the formation and breaking of extraheavy-crude-oil-in-water emulsions—a proposed strategy for transporting extra heavy crude oils. Chem Eng Process 2015;98:112–22. link1

[ 2 ] Liang C, Harjani JR, Robert T, Rogel E, Kuehne D, Ovalles C, et al. Use of CO2- triggered switchable surfactants for the stabilization of oil-in-water emulsions. Energy Fuels 2012;26(1):488–94. link1

[ 3 ] Li Y, Zhu L, Grishkewich N, Tam KC, Yuan J, Mao Z, et al. CO2-responsive cellulose nanofibers aerogels for switchable oil–water separation. ACS Appl Mater Interfaces 2019;11(9):9367–73. link1

[ 4 ] Chu Z, Feng Y. pH-switchable wormlike micelles. Chem Commun 2010;46 (47):9028–30. link1

[ 5 ] Liu K, Jiang J, Cui Z, Binks BP. pH-responsive Pickering emulsions stabilized by silica nanoparticles in combination with a conventional zwitterionic surfactant. Langmuir 2017;33(9):2296–305. link1

[ 6 ] Yang H, Zhou T, Zhang W. A strategy for separating and recycling solid catalysts based on the pH-triggered Pickering-emulsion inversion. Angew Chem Int Ed Engl 2013;52(29):7455–9. link1

[ 7 ] Feng H, Verstappen NAL, Kuehne AJC, Sprakel J. Well-defined temperaturesensitive surfactants for controlled emulsion coalescence. Polym Chem 2013;4 (6):1842–7. link1

[ 8 ] Zhang W, Liu N, Zhang Q, Qu R, Liu Y, Li X, et al. Thermo-driven controllable emulsion separation by a polymer-decorated membrane with switchable wettability. Angew Chem Int Ed Engl 2018;57(20):5740–5. link1

[ 9 ] Liu Y, Jessop PG, Cunningham M, Eckert CA, Liotta CL. Switchable surfactants. Science 2006;313(5789):958–60. link1

[10] Jiang J, Ma Y, Cui Z, Binks BP. Pickering emulsions responsive to CO2/N2 and light dual stimuli at ambient temperature. Langmuir 2016;32(34):8668–75. link1

[11] Xu P, Wang Z, Xu Z, Hao J, Sun D. Highly effective emulsification/ demulsification with a CO2-switchable superamphiphile. J Colloid Interface Sci 2016;480:198–204. link1

[12] Chen X, Ma X, Yan C, Sun D, Yeung T, Xu Z. CO2-responsive O/W microemulsions prepared using a switchable superamphiphile assembled by electrostatic interactions. J Colloid Interface Sci 2019;534:595–604. link1

[13] Wang Z, Ren G, Yang J, Xu Z, Sun D. CO2-responsive aqueous foams stabilized by pseudogemini surfactants. J Colloid Interface Sci 2019;536:381–8. link1

[14] Khoukh S, Oda R, Labrot T, Perrin P, Tribet C. Light-responsive hydrophobic association of azobenzene-modified poly(acrylic acid) with neutral surfactants. Langmuir 2007;23(1):94–104. link1

[15] Takahashi Y, Fukuyasu K, Horiuchi T, Kondo Y, Stroeve P. Photoinduced demulsification of emulsions using a photoresponsive gemini surfactant. Langmuir 2014;30(1):41–7. link1

[16] Brown P, Bushmelev A, Butts CP, Cheng J, Eastoe J, Grillo I, et al. Magnetic control over liquid surface properties with responsive surfactants. Angew Chem Int Ed Engl 2012;51(10):2414–6. link1

[17] Yang H, Hou Q, Wang S, Guo D, Hu G, Xu Y, et al. Magnetic-responsive switchable emulsions based on Fe3O4@SiO2–NH2 nanoparticles. Chem Commun 2018;54(76):10679–82. link1

[18] Kong W, Guo S, Wu S, Liu X, Zhang Y. Redox-controllable interfacial properties of zwitterionic surfactant featuring selenium atoms. Langmuir 2016;32 (38):9846–53. link1

[19] Tsuchiya K, Orihara Y, Kondo Y, Yoshino N, Ohkubo T, Sakai H, et al. Control of viscoelasticity using redox reaction. J Am Chem Soc 2004;126(39):12282–3. link1

[20] Rahman MM, Chehimi MM, Fessi H, Elaissari A. Highly temperature responsive core–shell magnetic particles: synthesis, characterization and colloidal properties. J Colloid Interface Sci 2011;360(2):556–64. link1

[21] Tang J, Lee MFX, Zhang W, Zhao B, Berry RM, Tam KC. Dual responsive Pickering emulsion stabilized by poly[2-(dimethylamino)ethyl methacrylate] grafted cellulose nanocrystals. Biomacromolecules 2014;15(8):3052–60. link1

[22] Yi C, Liu N, Zheng J, Jiang J, Liu X. Dual-responsive poly(styrene-alt-maleic acid)-graft-poly(N-isopropyl acrylamide) micelles as switchable emulsifiers. J Colloid Interface Sci 2012;380(1):90–8. link1

[23] Fameau AL, Lam S, Velev OD. Multi-stimuli responsive foams combining particles and self-assembling fatty acids. Chem Sci 2013;4(10):3874–81. link1

[24] Jin Q, Liu G, Ji J. Micelles and reverse micelles with a photo and thermo doubleresponsive block copolymer. J Polym Sci A Polym Chem 2010;48(13):2855–61. link1

[25] Jiang J, Wang G, Ma Y, Cui Z, Binks BP. Smart worm-like micelles responsive to CO2/N2 and light dual stimuli. Soft Matter 2017;13(15):2727–32. link1

[26] Zhang Y, Guo S, Ren X, Liu X, Fang Y. CO2 and redox dual responsive Pickering emulsion. Langmuir 2017;33(45):12973–81. link1

[27] Jiang J, Zhu Y, Cui Z, Binks BP. Switchable Pickering emulsions stabilized by silica nanoparticles hydrophobized in situ with a switchable surfactant. Angew Chem Int Ed Engl 2013;52(47):12373–6. link1

[28] Aveyard R, Binks BP, Clint JH. Emulsions stabilised solely by colloidal particles. Adv Colloid Interface Sci 2003;100–102:503–46. link1

[29] Chen D, Amstad E, Zhao CX, Cai L, Fan J, Chen Q, et al. Biocompatible amphiphilic hydrogel–solid dimer particles as colloidal surfactants. ACS Nano 2017;11(12):11978–85. link1

[30] Zhang M, Wang W, Xie R, Ju X, Liu Z, Jiang L, et al. Controllable microfluidic strategies for fabricating microparticles using emulsions as templates. Particuology 2016;24:18–31. link1

[31] Duan G, Haase MF, Stebe KJ, Lee D. One-step generation of salt-responsive polyelectrolyte microcapsules via surfactant-organized nanoscale interfacial complexation in emulsions (SO NICE). Langmuir 2018;34(3):847–53. link1

[32] Liang C, Liu Q, Xu Z. Surfactant-free switchable emulsions using CO2- responsive particles. ACS Appl Mater Interfaces 2014;6(9):6898–904. link1

[33] Xu M, Jiang J, Pei X, Song B, Cui Z, Binks BP. Novel oil-in-water emulsions stabilised by ionic surfactant and similarly charged nanoparticles at very low concentrations. Angew Chem Int Ed Engl 2018;57(26):7738–42. link1

[34] Xu M, Zhang W, Pei X, Jiang J, Cui Z, Binks BP. CO2/N2 triggered switchable Pickering emulsions stabilized by alumina nanoparticles in combination with a conventional anionic surfactant. RSC Adv 2017;7(47):29742–51. link1

[35] Zhu Y, Jiang J, Liu K, Cui Z, Binks BP. Switchable Pickering emulsions stabilized by silica nanoparticles hydrophobized in situ with a conventional cationic surfactant. Langmuir 2015;31(11):3301–7. link1

[36] Ren G, Wang M, Wang L, Wang Z, Chen Q, Xu Z, et al. Dynamic covalent silica nanoparticles for pH-switchable Pickering emulsions. Langmuir 2018;34 (20):5798–806. link1

[37] Zhang Q, Bai RX, Guo T, Meng T. Switchable Pickering emulsions stabilized by awakened TiO2 nanoparticle emulsifiers using UV/dark actuation. ACS Appl Mater Interfaces 2015;7(33):18240–6. link1

[38] Sarker M, Tomczak N, Lim S. Protein nanocage as a pH-switchable Pickering emulsifier. ACS Appl Mater Interfaces 2017;9(12):11193–201. link1

[39] Pudney PDA, Mutch KJ, Zhu S. Characterising the phase behaviour of stearic acid and its triethanolamine soap and acid–soap by infrared spectroscopy. Phys Chem Chem Phys 2009;11(25):5010–8. link1

[40] Rosen MJ, Kunjappu JT. Surfactants and interfacial phenomena. 4th ed. Hoboken: John Wiley & Sons; 2012. link1

[41] Chen Q, Wang L, Ren G, Liu Q, Xu Z, Sun D. A fatty acid solvent of switchable miscibility. J Colloid Interface Sci 2017;504:645–51. link1

Related Research