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Journal of Materials Science

, Volume 55, Issue 5, pp 1946–1958 | Cite as

Modified reduced graphene oxide as stabilizer for Pickering w/o emulsions

  • Xue MiEmail author
  • Xingrui Wang
  • Chunjuan Gao
  • Weijun Su
  • Yuying Zhang
  • Xiaoyue Tan
  • Jianping Gao
  • Yu LiuEmail author
Chemical routes to materials
  • 102 Downloads

Abstract

Polystyrene with π-conjugated end groups (BPS) synthesized by reversible addition–fragmentation transfer polymerization was used to modify the surface of reduced graphene oxide (rGO) sheets through ππ stacking (BPS–rGO) in order to increase their hydrophobicity and dispersibility. The modification of rGO makes it possible for BPS–rGO to stabilize Pickering w/o (water-in-oil) emulsions of small droplets, in which toluene is taken as the continuous phase and distilled water as the dispersed phase. The effects of the BPS–rGO concentration and the water/oil ratio on the Pickering emulsions were investigated. The results indicate that increasing hydrophobicity of BPS–rGO was favorable to forming stable w/o emulsions and the emulsion stability was increased with the increase in the BPS–rGO concentration or with the decrease in water/oil ratio. Using BPS–rGO to stabilize Pickering w/o emulsions is an effective and versatile approach to fabricate active materials that can be employed as catalysts for chemical reactions.

Notes

Acknowledgements

This work was supported by the National Natural Science Foundation of China (81502297, 51573126, 81402407, 81871487, 31971388), Natural Science Foundation of Shanxi Province (2013021011-5) and Tianjin Research Program of Application Foundation and Advanced Technology (15JCQNJC14600, 16JCYBJC26300).

Supplementary material

10853_2019_4066_MOESM1_ESM.doc (3.2 mb)
Supplementary material 1 (DOC 3268 kb)

References

  1. 1.
    Soldano C, Mahmood A, Dujardin E (2010) Production, properties and potential of graphene. Carbon 48(8):2127–2150Google Scholar
  2. 2.
    Pei SF, Cheng HM (2012) The reduction of graphene oxide. Carbon 50(9):3210–3228Google Scholar
  3. 3.
    Suk JW, Piner RD, An J, Ruoff RS (2010) Mechanical properties of monolayer graphene oxide. ACS Nano 4(11):6557–6564Google Scholar
  4. 4.
    Guo YQ, Sun XY, Liu Y, Wang W, Qiu HX, Gao JP (2012) One pot preparation of reduced graphene oxide (RGO) or Au (Ag) nanoparticle-RGO hybrids using chitosan as a reducing and stabilizing agent and their use in methanol electrooxidation. Carbon 50(7):2513–2523Google Scholar
  5. 5.
    Berry V (2013) Impermeability of graphene and its applications. Carbon 62:1–10Google Scholar
  6. 6.
    Park SJ, Ruoff RS (2009) Chemical methods for the production of graphenes. Nat Nanotechnol 4(4):217–224Google Scholar
  7. 7.
    Segal M (2009) Selling graphene by the ton. Nat Nanotechnol 4(10):612–614Google Scholar
  8. 8.
    He YQ, Wang XR, Wu D, Gong QJ, Qiu HX, Liu Y, Wu T, Ma JK (2013) Biodegradable amylose films reinforced by graphene oxide and polyvinyl alcohol. Mater Chem Phys 142(1):1–11Google Scholar
  9. 9.
    Saleh M, Chandra V, Kemp KC, Kim KS (2013) Synthesis of N-doped microporous carbon via chemical activation of polyindole-modified graphene oxide sheets for selective carbon dioxide adsorption. Nanotechnology 24(25):255702Google Scholar
  10. 10.
    Mi X, Huang GB, Xie WS, Wang W, Liu Y, Gao JP (2012) Preparation of graphene oxide aerogel and its adsorption for Cu2+ ions. Carbon 50(13):4856–4864Google Scholar
  11. 11.
    Zhao JL, Tang ZH, Qiu YS, Gao XL, Wan J, Bi WR, Shen SL, Yang JH (2019) Porous crumpled graphene with improved specific surface area based on hydrophilic pre-reduction and its adsorption performance. J Mater Sci 54(11):8108–8120.  https://doi.org/10.1007/s10853-018-03288-5 CrossRefGoogle Scholar
  12. 12.
    Liu Y, Ma JK, Wu T, Wang XR, Huang GB, Liu Y, Qiu HX, Li Y, Wang W, Gao JP (2013) Cost-effective reduced graphene oxide-coated polyurethane sponge as a highly efficient and reusable oil-absorbent. ACS Appl Mater Interfaces 5(20):10018–10026Google Scholar
  13. 13.
    Tan R, Li CY, Luo JP, Kong Y, Zheng WG, Yin DH (2013) An effective heterogeneous l-proline catalyst for the direct asymmetric aldol reaction using graphene oxide as support. J Catal 298:138–147Google Scholar
  14. 14.
    Mayavan S, Jang HS, Lee MJ, Choi SH, Choi SM (2013) Enhancing the catalytic activity of Pt nanoparticles using poly sodium styrene sulfonate stabilized graphene supports for methanol oxidation. J Mater Chem A 1(10):3489–3494Google Scholar
  15. 15.
    Pour SR, Abdolmaleki A, Dinari M (2018) Immobilization of new macrocyclic Schiff base copper complex on graphene oxide nanosheets and its catalytic activity for olefins epoxidation. J Mater Sci 54(4):2885–2896.  https://doi.org/10.1007/s10853-018-3035-4 CrossRefGoogle Scholar
  16. 16.
    Grad O, Mihet M, Dan M, Blanita G, Radu T, Berghian-Grosan C, Lazar MD (2019) Au/reduced graphene oxide composites: eco-friendly preparation method and catalytic applications for formic acid dehydrogenation. J Mater Sci 54(9):6991–7004.  https://doi.org/10.1007/s10853-019-03394-y CrossRefGoogle Scholar
  17. 17.
    Kim J, Cote LJ, Kim F, Yuan W, Shull KR, Huang J (2010) Graphene oxide sheets at interfaces. J Am Chem Soc 132(23):8180–8186Google Scholar
  18. 18.
    He YQ, Wu F, Sun XY, Li RQ, Guo YQ, Li CB, Zhang L, Xing FB, Wang W, Gao JP (2013) Factors that affect pickering emulsions stabilized by graphene oxide. ACS Appl Mater Interfaces 5(11):4843–4855Google Scholar
  19. 19.
    Kaganyuk M, Mohraz A (2019) Role of particles in the rheology of solid-stabilized high internal phase emulsions. J Colloid Interface Sci 540:197–206Google Scholar
  20. 20.
    Thickett SC, Zetterlund PB (2015) Graphene oxide (GO) nanosheets as oil-in-water emulsion stabilizers: influence of oil phase polarity. J Colloid Interface Sci 442:67–74Google Scholar
  21. 21.
    Teo GH, Ng YH, Zetterlund PB, Thickett SC (2015) Factors influencing the preparation of hollow polymer–graphene oxide microcapsules via Pickering miniemulsion polymerization. Polymer 63:1–9Google Scholar
  22. 22.
    Man SHC, Ly D, Whittaker MR, Thickett SC, Zetterlund PB (2014) Nano-sized graphene oxide as sole surfactant in miniemulsion polymerization for nanocomposite synthesis: effect of pH and ionic strength. Polymer 55:3490–3497Google Scholar
  23. 23.
    Edgehouse K, Escamilla M, Wang L, Dent R, Pachuta K, Kendall L, Wei P, Sehirlioglu A, Pentzer E (2019) Stabilization of oil-in-water emulsions with graphene oxide and cobalt oxide nanosheets and preparation of armored polymer particles. J Colloid Interface Sci 541:269–278Google Scholar
  24. 24.
    Fang M, Wang KQ, Lu HB, Yang YL, Nutt S (2010) Single-layer graphene nanosheets with controlled grafting of polymer chains. J Mater Chem 20(10):1982–1992Google Scholar
  25. 25.
    Liu JQ, Yang WR, Tao L, Li D, Boyer C, Davis TP (2010) Thermosensitive graphene nanocomposites formed using pyrene-terminal polymers made by RAFT polymerization. J Polym Sci Part A Polym Chem 48(2):425–433Google Scholar
  26. 26.
    Villar-Rodil S, Paredes JI, Martínez-Alonso A, Tascón JMD (2009) Preparation of graphene dispersions and graphene–polymer composites in organic media. J Mater Chem 19(22):3591–3593Google Scholar
  27. 27.
    Zhang B, Chen Y, Zhuang XD, Liu G, Yu B, Kan ET, Zhu JH, Li Y (2010) Poly (N-vinylcarbazole) chemically modified graphene oxide. J Polym Sci Part A Polym Chem 48(12):2642–2649Google Scholar
  28. 28.
    Liu Z, Robinson JT, Sun XM, Dai HJ (2008) PEGylated nanographene oxide for delivery of water-insoluble cancer drugs. J Am Chem Soc 130(33):10876–10877Google Scholar
  29. 29.
    Xu YF, Liu ZB, Zhang XL, Wang Y, Tian JG, Huang Y, Ma YF, Zhang XY, Chen Y (2009) A graphene hybrid material covalently functionalized with porphyrin: synthesis and optical limiting property. Adv Mater 21(12):1275–1279Google Scholar
  30. 30.
    Chiefari J, Chong YK, Ercole F, Krstina J, Jeffery J, Le TPT, Mayadunne RTA, Meijs GF, Moad CL, Rizzardo E, Thang SH (1998) Living free-radical polymerization by reversible addition–fragmentation chain transfer: the RAFT process. Macromolecules 31(16):5559–5562Google Scholar
  31. 31.
    Matyjaszewski K, Coca S, Gaynor SG, Wei ML, Woodworth BE (1997) Zerovalent metals in controlled/“living” radical polymerization. Macromolecules 30(23):7348–7350Google Scholar
  32. 32.
    Lai JT, Filla D, Shea R (2002) Functional polymers from novel carboxyl-terminated trithiocarbonates as highly efficient RAFT agents. Macromolecules 35(18):6754–6756Google Scholar
  33. 33.
    Pickering SU (1907) Cxcvi.—emulsions. J Chem Soc Trans 91:2001–2021Google Scholar
  34. 34.
    Ma C, Bi X, Ngai T, Zhang G (2013) Polyurethane-based nanoparticles as stabilizers for oil-in-water or water-in-oil Pickering emulsions. J Mater Chem A 1(17):5353–5360Google Scholar
  35. 35.
    Wang LY, Gao JP, An ZL, Zhao XX, Yao HD, Zhang M, Tian Q, Zhai XG, Liu Y (2019) Polymer microsphere for water-soluble drug delivery via carbon dot-stabilizing W/O emulsion. J Mater Sci 54(6):5175–5260.  https://doi.org/10.1007/s10853-018-03197-7 CrossRefGoogle Scholar
  36. 36.
    Bon SA, Colver PJ (2007) Pickering miniemulsion polymerization using laponite clay as a stabilizer. Langmuir 23(16):8316–8322Google Scholar
  37. 37.
    Aveyard R, Binks BP, Clint JH (2003) Emulsions stabilised solely by colloidal particles. Adv Colloid Interface Sci 100:503–546Google Scholar
  38. 38.
    Zhang XF, Shao ZQ, Zhou Y, Wei J, He WD, Wang S, Dai XF, Ren JY (2019) Redispersibility of cellulose nanoparticles modified by phenyltrimethoxysilane and its application in stabilizing Pickering emulsions. J Mater Sci 54(17):11713–11725.  https://doi.org/10.1007/s10853-019-03691-6 CrossRefGoogle Scholar
  39. 39.
    Briggs TR (1921) Emulsions with finely divided solids. Ind Eng Chem 13(11):1008–1010Google Scholar
  40. 40.
    Binks BP, Lumsdon SO (2000) Influence of particle wettability on the type and stability of surfactant-free emulsions. Langmuir 16(23):8622–8631Google Scholar
  41. 41.
    Leal-Calderon F, Schmitt V (2008) Solid-stabilized emulsions. Curr Opin Colloid Interface Sci 13(4):217–227Google Scholar
  42. 42.
    Schrade A, Landfester K, Ziene U (2013) Pickering-type stabilized nanoparticles by heterophase polymerization. Chem Soc Rev 42(16):6823–6839Google Scholar
  43. 43.
    Zheng Z, Zheng XH, Wang HT, Du QG (2013) Macroporous graphene oxide–polymer composite prepared through Pickering high internal phase emulsions. ACS Appl Mater Interfaces 5(16):7974–7982Google Scholar
  44. 44.
    Zhang TT, Huang WB, Zhang N, Huang T, Yang JH (2017) Grafting of polystyrene onto reduced graphene oxide by emulsion polymerization for dielectric polymer composites: high dielectric constant and low dielectric loss tuned by varied grafting amount of polystyrene. Eur Polym J 94:196–207Google Scholar
  45. 45.
    Kim SD, Zhang WL, Choi HJ (2014) Pickering emulsion-fabricated polystyrene–graphene oxide microspheres and their electrorheology. J Mater Chem C 2(36):7541–7546Google Scholar
  46. 46.
    Dao TD, Erdenedelger G, Jeong HM (2014) Water-dispersible graphene designed as a Pickering stabilizer for the suspension polymerization of poly (methyl methacrylate)/graphene core–shell microsphere exhibiting ultra-low percolation threshold of electrical conductivity. Polymer 55(18):4709–4719Google Scholar
  47. 47.
    Lin KA, Yang HT, Petit C, Lee W (2015) Magnetically controllable Pickering emulsion prepared by a reduced graphene oxide–iron oxide composite. J Colloid Interface Sci 438:296–305Google Scholar
  48. 48.
    Zhou D, Zhu XL, Zhu J, Hu LH, Cheng ZP (2007) Influence of the chemical structure of dithiocarbamates with different R groups on the reversible addition-fragmentation chain transfer polymerization. J Appl Polym Sci 103(2):982–988Google Scholar
  49. 49.
    Becerril HA, Mao J, Liu ZF, Stoltenberg RM, Bao ZN, Chen YS (2008) Evaluation of solution-processed reduced graphene oxide films as transparent conductors. ACS Nano 2(3):463–470Google Scholar
  50. 50.
    Hirata M, Gotou T, Horiuchi S, Fujiwara M, Ohba M (2004) Thin-film particles of graphite oxide 1: high-yield synthesis and flexibility of the particles. Carbon 42(14):2929–2937Google Scholar
  51. 51.
    Chakravarty A, Bhowmik K, Mukherjee A, De G (2015) Cu2O nanoparticles anchored on amine-functionalized graphite nanosheet: a potential reusable catalyst. Langmuir 31(18):5210–5219Google Scholar
  52. 52.
    Deshmukh SP, Dhokale RK, Yadav HM, Achary SN, Delekar SD (2013) Titania-supported silver nanoparticles: an efficient and reusable catalyst for reduction of 4-nitrophenol. Appl Surf Sci 273:676–683Google Scholar
  53. 53.
    Chen J, Cheng G, Li Z, Miao F, Cui X, Zheng W (2013) Ultrafine Au nanodots on graphene oxide for catalytic reduction of 4-nitrophenol. Nano 8(03):1350034Google Scholar
  54. 54.
    Wu XQ, Wu XW, Huang Q, Shen JS, Zhang HW (2015) In situ synthesized gold nanoparticles in hydrogels for catalytic reduction of nitroaromatic compounds. Appl Surf Sci 331:210–218Google Scholar
  55. 55.
    Nasrollahzadeh M, Maham M, Sajadi SM (2015) Green synthesis of CuO nanoparticles by aqueous extract of Gundelia tournefortii and evaluation of their catalytic activity for the synthesis of N-monosubstituted ureas and reduction of 4-nitrophenol. J Colloid Interface Sci 455:245–253Google Scholar
  56. 56.
    Xu SL, Li HB, Wang L, Yue QL, Li R, Xue QW, Zhang YF, Liu JF (2015) Synthesis of carbon-encapsulated Cu–Ag dimetallic nanoparticles and their recyclable superior catalytic activity towards 4-nitrophenol reduction. Eur J Inorg Chem 28:4731–4736Google Scholar
  57. 57.
    Nasrollahzadeh M, Sajadi SM, Rostami-Vartooni A, Bagherzadeh M (2015) Green synthesis of Pd/CuO nanoparticles by Theobroma cacao L. seeds extract and their catalytic performance for the reduction of 4-nitrophenol and phosphine-free Heck coupling reaction under aerobic conditions. J Colloid Interface Sci 448:106–113Google Scholar
  58. 58.
    Deka P, Deka RC, Bharali P (2014) In situ generated copper nanoparticle catalyzed reduction of 4-nitrophenol. New J Chem 38(4):1789–1793Google Scholar
  59. 59.
    Seven F, Sahiner N (2014) Superporous P (2-hydroxyethyl methacrylate) cryogel-M (M: Co, Ni, Cu) composites as highly effective catalysts in H2 generation from hydrolysis of NaBH4 and NH3BH3. Int J Hydrog Energy 39(28):15455–15463Google Scholar
  60. 60.
    Chou CC, Hsieh CH, Chen BH (2015) Hydrogen generation from catalytic hydrolysis of sodium borohydride using bimetallic Ni–Co nanoparticles on reduced graphene oxide as catalysts. Energy 90:1973–1982Google Scholar
  61. 61.
    Xiang CL, Jiang DD, She Z, Zou YJ, Chu HL, Qiu SJ, Zhang HZ, Xu F, Tang CY (2015) Hydrogen generation by hydrolysis of alkaline sodium borohydride using a cobalt–zinc–boron/graphene nanocomposite treated with sodium hydroxide. Int J Hydrog Energy 40(11):4111–4118Google Scholar
  62. 62.
    Dai HB, Liang Y, Wang P, Yao XD, Rufford T, Lu M, Cheng HM (2008) High-performance cobalt–tungsten–boron catalyst supported on Ni foam for hydrogen generation from alkaline sodium borohydride solution. Int J Hydrog Energy 3(16):4405–4412Google Scholar

Copyright information

© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.School of Medicine, State Key Laboratory of Medicinal Chemical BiologyNankai UniversityTianjinPeople’s Republic of China
  2. 2.School of ScienceTianjin UniversityTianjinPeople’s Republic of China
  3. 3.Institude of Tianjin Seawater Desalination and Multipurpose UtilizationState Oceanic AdministrationTianjinPeople’s Republic of China
  4. 4.Key Laboratory of Sichuan Province for Metal Fuel CellDe YangPeople’s Republic of China

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