Crumpling of graphene oxide through evaporative confinement in nanodroplets produced by electrohydrodynamic aerosolization

Abstract

Restacking of graphene oxide (GO) nanosheets results in loss of surface area and creates limitations in its widespread use for applications. Previously, two-dimensional (2D) GO sheets have been crumpled into 3D structures to prevent restacking using different techniques. However, synthesis of nanometer size crumpled graphene particles and their direct deposition onto a substrate have not been demonstrated under room temperature condition so far. In this work, the evaporative crumpling of GO sheets into very small size (<100 nm) crumpled structures using an electrohydrodynamic atomization technique is described. Systematic study of the effect of different electrohydrodynamic atomization parameters, such as (1) substrate-to-needle distance, (2) GO concentration in the precursor solution, and (3) flow rate (droplet size) on the GO crumpling, is explored. Crumpled GO (CGO) particles are characterized online using a scanning mobility particle sizer (SMPS) and off-line using electron microscopy. The relation between the confinement force and the factors affecting the crumpled structure is established. Furthermore, to expand the application horizons of the structure, crumpled GO–TiO2 nanocomposites are synthesized. The method described here allows a simple and controlled production of graphene-based particles/composites with direct deposition onto any kind of substrate for a variety of applications.

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References

  1. Balankin AS, Silva IC, Martinez OA, Huerta OS (2007) Scaling properties of randomly folded plastic sheets. Phys Rev E 75:051117

    Article  Google Scholar 

  2. Basak S, Chen D-R, Biswas P (2007) Electrospray of ionic precursor solutions to synthesize iron oxide nanoparticles: modified scaling law. Chem Eng Sci 62:1263–1268

    Article  Google Scholar 

  3. Becton M, Zhang L, Wang X (2015) On the crumpling of polycrystalline graphene by molecular dynamics simulation. Phys Chem Chem Phys 17:6297–6304

    Article  Google Scholar 

  4. Chae SY, Park MK, Lee SK, Kim TY, Kim SK, Lee WI (2003) Preparation of size-controlled TiO2 nanoparticles and derivation of optically transparent photocatalytic films. Chem Mater 15:3326–3331

    Article  Google Scholar 

  5. Chen D-R, Pui DY (1997) Experimental investigation of scaling laws for electrospraying: dielectric constant effect. Aerosol Sci Technol 27:367–380

    Article  Google Scholar 

  6. Chen D, Feng H, Li J (2012a) Graphene oxide: preparation, functionalization, and electrochemical applications. Chem Rev 112:6027–6053

    Article  Google Scholar 

  7. Chen Y et al (2012b) Aerosol synthesis of cargo-filled graphene nanosacks. Nano Lett 12:1996–2002

    Article  Google Scholar 

  8. Compton OC, Nguyen ST (2010) Graphene oxide, highly reduced graphene oxide, and graphene: versatile building blocks for carbon-based materials. Small 6:711–723

    Article  Google Scholar 

  9. Cranford SW, Buehler MJ (2011) Packing efficiency and accessible surface area of crumpled graphene. Phys Rev B 84:205451

    Article  Google Scholar 

  10. De La Mora JF, Loscertales IG (1994) The current emitted by highly conducting Taylor cones. J Fluid Mech 260:155–184

    Article  Google Scholar 

  11. Deng W, Klemic JF, Li X, Reed MA, Gomez A (2006) Increase of electrospray throughput using multiplexed microfabricated sources for the scalable generation of monodisperse droplets. J Aerosol Sci 37:696–714

    Article  Google Scholar 

  12. Dreyer DR, Park S, Bielawski CW, Ruoff RS (2010) The chemistry of graphene oxide. Chem Soc Rev 39:228–240

    Article  Google Scholar 

  13. Guo F, Creighton M, Chen Y, Hurt R, Külaots I (2014) Porous structures in stacked, crumpled and pillared graphene-based 3D materials. Carbon 66:476–484

    Article  Google Scholar 

  14. He Y, Zhang N, Gong Q, Qiu H, Wang W, Liu Y, Gao J (2012) Alginate/graphene oxide fibers with enhanced mechanical strength prepared by wet spinning. Carbohydr Polym 88:1100–1108

    Article  Google Scholar 

  15. Hinds WC (1982) Aerosol technology: properties, behavior, and measurement of airborne particles. John Wiley & Sons, New York

  16. Huang Y, Liang J, Chen Y (2012) An overview of the applications of graphene-based materials in supercapacitors. Small 8:1805–1834

    Article  Google Scholar 

  17. Hummers WS Jr, Offeman RE (1958) Preparation of graphitic oxide. J Am Chem Soc 80:1339–1339

    Article  Google Scholar 

  18. Jaworek A (2007) Electrospray droplet sources for thin film deposition. J Mater Sci 42:266–297

    Article  Google Scholar 

  19. Jiang Y, Wang W-N, Biswas P, Fortner JD (2014) Facile aerosol synthesis and characterization of ternary crumpled graphene–TiO2–magnetite nanocomposites for advanced water treatment. ACS Appl Mater Interfaces 6:11766–11774

    Article  Google Scholar 

  20. Jiang Y et al (2015) Engineered crumpled graphene oxide nanocomposite membrane assemblies for advanced water treatment processes. Environmental Science & Technology 49:6846–6854

    Article  Google Scholar 

  21. Kavadiya S, Chadha TS, Liu H, Shah VB, Blankenship RE, Biswas P (2016) Directed assembly of the thylakoid membrane on nanostructured TiO2 for a photo-electrochemical cell. Nanoscale 8:1868–1872

    Article  Google Scholar 

  22. Krpoun R, Shea H (2009) Integrated out-of-plane nanoelectrospray thruster arrays for spacecraft propulsion. J Micromech Microeng 19:045019

    Article  Google Scholar 

  23. Li W, Zhang Y, Xu Z, Yang A, Meng Q, Zhang G (2014) Self-assembled graphene oxide microcapsules with adjustable permeability and yolk–shell superstructures derived from atomized droplets. Chem Commun 50:15867–15869

    Article  Google Scholar 

  24. Loh KP, Bao Q, Eda G, Chhowalla M (2010) Graphene oxide as a chemically tunable platform for optical applications. Nat Chem 2:1015–1024

    Article  Google Scholar 

  25. Luo J et al (2011) Compression and aggregation-resistant particles of crumpled soft sheets. ACS Nano 5:8943–8949

    Article  Google Scholar 

  26. Ma X, Zachariah MR, Zangmeister CD (2011) Crumpled nanopaper from graphene oxide. Nano Lett 12:486–489

    Article  Google Scholar 

  27. Mao P, Wang H-T, Yang P, Wang D (2011) Multinozzle emitter arrays for nanoelectrospray mass spectrometry. Anal Chem 83:6082–6089

    Article  Google Scholar 

  28. Mao S, Wen Z, Kim H, Lu G, Hurley P, Chen J (2012) A general approach to one-pot fabrication of crumpled graphene-based nanohybrids for energy applications. ACS Nano 6:7505–7513

    Article  Google Scholar 

  29. Mei Q, Jiang C, Guan G, Zhang K, Liu B, Liu R, Zhang Z (2012) Fluorescent graphene oxide logic gates for discrimination of iron (3+) and iron (2+) in living cells by imaging. Chem Commun 48:7468–7470

    Article  Google Scholar 

  30. Mkhoyan KA et al (2009) Atomic and electronic structure of graphene-oxide. Nano Lett 9:1058–1063

    Article  Google Scholar 

  31. Olvera-Trejo D, Velásquez-García L (2016) Additively manufactured MEMS multiplexed coaxial electrospray sources for high-throughput, uniform generation of core–shell microparticles. Lab Chip 16:4121–4132

    Article  Google Scholar 

  32. Paredes J, Villar-Rodil S, Martinez-Alonso A, Tascon J (2008) Graphene oxide dispersions in organic solvents. Langmuir 24:10560–10564

    Article  Google Scholar 

  33. Park S-H et al (2015) Spray-assisted deep-frying process for the in situ spherical assembly of graphene for energy-storage devices. Chem Mater 27:457–465

    Article  Google Scholar 

  34. Parviz D, Metzler SD, Das S, Irin F, Green MJ (2015) Tailored crumpling and unfolding of spray-dried pristine graphene and graphene oxide sheets. Small 11(22):2661–2668

  35. Qiu H, Bechtold T, Le L, Lee WY (2015) Evaporative assembly of graphene oxide for electric double-layer capacitor electrode application. Powder Technol 270:192–196

    Article  Google Scholar 

  36. Shah VB, Biswas P (2014) Aerosolized droplet mediated self-assembly of photosynthetic pigment analogues and deposition onto substrates. ACS Nano 8:1429–1438

    Article  Google Scholar 

  37. Shah VB, Henson WR, Chadha TS, Lakin G, Liu H, Blankenship RE, Biswas P (2015) Linker-free deposition and adhesion of photosystem I onto nanostructured TiO2 for biohybrid photoelectrochemical cells. Langmuir 31:1675–1682

    Article  Google Scholar 

  38. Shah VB, Orf GS, Reisch S, Harrington LB, Prado M, Blankenship RE, Biswas P (2012) Characterization and deposition of various light-harvesting antenna complexes by electrospray atomization. Anal Bioanal Chem 404:2329–2338

    Article  Google Scholar 

  39. Shao Y, Wang J, Engelhard M, Wang C, Lin Y (2010) Facile and controllable electrochemical reduction of graphene oxide and its applications. J Mater Chem 20:743–748

    Article  Google Scholar 

  40. Song Y, Qu K, Zhao C, Ren J, Qu X (2010) Graphene oxide: intrinsic peroxidase catalytic activity and its application to glucose detection. Adv Mater 22:2206–2210

    Article  Google Scholar 

  41. Stankovich S et al (2006) Graphene-based composite materials. Nature 442:282–286

    Article  Google Scholar 

  42. Taflin DC, Ward TL, Davis EJ (1989) Electrified droplet fission and the Rayleigh limit. Langmuir 5:376–384

    Article  Google Scholar 

  43. Tang H, Yang C, Lin Z, Yang Q, Kang F, Wong CP (2015) Electrospray-deposition of graphene electrodes: a simple technique to build high-performance supercapacitors. Nanoscale 7:9133–9139

    Article  Google Scholar 

  44. Taylor AP, Velásquez-García LF (2015) Electrospray-printed nanostructured graphene oxide gas sensors. Nanotechnology 26:505301

    Article  Google Scholar 

  45. Taylor G (1964) Disintegration of water drops in an electric field. In: Proceedings of the Royal Society of London A: Mathematical, Physical and Engineering Sciences. The Royal Society, pp 383–397

  46. Thomas AV, Andow BC, Suresh S, Eksik O, Yin J, Dyson AH, Koratkar N (2015) Controlled crumpling of graphene oxide films for tunable optical transmittance. Adv Mater 3256–3265. doi:10.1002/adma.201405821

  47. Tian Y, Wu G, Tian X, Tao X, Chen W (2013) Novel erythrocyte-like graphene microspheres with high quality and mass production capability via electrospray assisted self-assembly. Sci Rep 3:3327. doi:10.1038/srep03327

  48. Velásquez-García LF (2015) SLA 3-D printed arrays of miniaturized, internally fed, polymer electrospray emitters. J Microelectromech Syst 24:2117–2127

    Article  Google Scholar 

  49. Velásquez-García LF, Akinwande AI, Martinez-Sanchez M (2006) A planar array of micro-fabricated electrospray emitters for thruster applications. J Microelectromech Syst 15:1272–1280

    Article  Google Scholar 

  50. Wang W-N, Jiang Y, Biswas P (2012) Evaporation-induced crumpling of graphene oxide nanosheets in aerosolized droplets: confinement force relationship. The Journal of Physical Chemistry Letters 3:3228–3233

    Article  Google Scholar 

  51. Wang W-N, Jiang Y, Fortner JD, Biswas P (2014) Nanostructured graphene-titanium dioxide composites synthesized by a single-step aerosol process for photoreduction of carbon dioxide. Environ Eng Sci 31:428–434

    Article  Google Scholar 

  52. Wang Y, Li Z, Wang J, Li J, Lin Y (2011) Graphene and graphene oxide: biofunctionalization and applications in biotechnology. Trends Biotechnol 29:205–212

    Article  Google Scholar 

  53. Wu Z-S, Zhou G, Yin L-C, Ren W, Li F, Cheng H-M (2012) Graphene/metal oxide composite electrode materials for energy storage. Nano Energy 1:107–131

    Article  Google Scholar 

  54. Xiang C et al (2013) Large flake graphene oxide fibers with unconventional 100% knot efficiency and highly aligned small flake graphene oxide fibers. Adv Mater 25:4592–4597

    Article  Google Scholar 

  55. Xiao L, Damien J, Luo J, Jang HD, Huang J, He Z (2012) Crumpled graphene particles for microbial fuel cell electrodes. J Power Sources 208:187–192

    Article  Google Scholar 

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Acknowledgement

This research is based upon work supported by the Solar Energy Research Institute for India and the USA (SERIIUS) funded jointly by the US Department of Energy subcontract DE AC36-08G028308 (Office of Science, Office of Basic Energy Sciences, and Energy Efficiency and Renewable Energy, Solar Energy Technology Program, with support from the Office of International Affairs) and the Government of India subcontract IUSSTF/JCERDC-SERIIUS/2012 dated 22 Nov. 2012. Electron microscopy work was performed at the Nano Research Facility (NRF), Department of Energy, Environmental, and Chemical Engineering at Washington University in St. Louis.

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Correspondence to Pratim Biswas.

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Kavadiya, S., Raliya, R., Schrock, M. et al. Crumpling of graphene oxide through evaporative confinement in nanodroplets produced by electrohydrodynamic aerosolization. J Nanopart Res 19, 43 (2017). https://doi.org/10.1007/s11051-017-3738-5

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Keywords

  • Crumpling
  • Crumpling force
  • Crumpled graphene oxide
  • Electrospray
  • Graphene oxide
  • Synthesis