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Continuous synthesis of plate-like silica microparticles using microfluidics

Journal of Flow Chemistry volume 9, pages 161–174 (2019)Cite this article

Abstract

The synthesis of plate-like silica particles, which are of importance for a variety of applications, are mainly based on the widely adopted method of the sol-gel reaction of silicon alkoxides in traditional batch-wise instrumentation. In this study, continuous-flow synthesis of amorphous plate-like silica particles is reported through combining droplet-based microfluidics and the sol-gel reaction of tetraethyl orthosilicate. The reaction was conducted at the surface of oil droplets, comprising tetraethyl orthosilicate (TEOS), suspended in acidic (HCl) water, resulting in silica particles on the surface of the droplets, leaving the device with outlet flow. The synthesized particles had plate-like structure with thickness less than 1 μm and microscale in two other dimensions. The influences of experimental parameters (TEOS and HCl concentrations and the flow rate of aqueous phase) on the silica production rate were examined. With increase in the TEOS and HCl concentrations, the production rate increases monotonically. With increase in the flow rate of aqueous phase, the production rate increases up to a specific flow rate. Beyond the flow rate, the production rate decreases with increase in the flow rate. A phenomenological model is proposed to address the production rate using the droplet-based microfluidic system. In addition, response surface methodology (RSM) was used to statistically model and optimize the production rate. At optimum values for the experimental parameters, the experimentally measured production rate was considerably comparable to that predicted by RSM.

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References

  1. Xiong Y, Wiley BJ, Xia Y (2007) Nanocrystals with unconventional shapes—a class of promising catalysts. Angew Chem Int Ed 46:7157–7159

    Article  CAS  Google Scholar 

  2. Anker JN, Hall WP, Lyandres O, Shah NC, Zhao J, Van Duyne RP (2008) Biosensing with plasmonic nanosensors. Nat Mater 7:442–453

    Article  CAS  PubMed  Google Scholar 

  3. Linic S, Christopher P, Ingram DB (2011) Plasmonic-metal nanostructures for efficient conversion of solar to chemical energy. Nat Mater 10:911–921

    Article  CAS  PubMed  Google Scholar 

  4. Liong M, Lu J, Kovochich M, Xia T, Ruehm SG, Nel AE et al (2008) Multifunctional inorganic nanoparticles for imaging, targeting, and drug delivery. ACS Nano 2:889–896

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  5. Huang X, El-Sayed IH, Qian W, El-Sayed MA (2006) Cancer cell imaging and photothermal therapy in the near-infrared region by using gold nanorods. J Am Chem Soc 128:2115–2120

    Article  CAS  PubMed  Google Scholar 

  6. Lee K, Losego MD, Parsons GN (2014) High performance photocatalytic metal oxide synthetic bi-component nanosheets formed by atomic layer deposition. Materials Horizons 1:419–423

    Article  CAS  Google Scholar 

  7. Kumar DR, Kulkarni A, Prasad B (2014) Microfluidic platform for continuous flow synthesis of triangular gold nanoplates. Colloids Surf A Physicochem Eng Asp 443:149–155

    Article  CAS  Google Scholar 

  8. Liu P (2008) Preparation and characterization of conducting polyaniline/silica nanosheet composites. Curr Opinion Solid State Mater Sci 12:9–13

    Article  CAS  Google Scholar 

  9. Luo D, Wang F, Zhu J, Cao F, Liu Y, Li X et al (2016) Nanofluid of graphene-based amphiphilic Janus nanosheets for tertiary or enhanced oil recovery: high performance at low concentration. Proc Natl Acad Sci 113:7711–7716

  10. Yin T, Li H, Su L, Liu S, Yuan C, Fu D (2016) The catalytic effect of TiO2 nanosheets on extracellular electron transfer of Shewanella loihica PV-4. Phys Chem Chem Phys 18:29871–29878

  11. Behzadi A, Mohammadi A (2016) Environmentally responsive surface-modified silica nanoparticles for enhanced oil recovery. J Nanopart Res 18:1–19

    Article  CAS  Google Scholar 

  12. Liu Y, Liang F, Wang Q, Qu X, Yang Z (2015) Flexible responsive Janus nanosheets. Chem Commun 51:3562–3565

    Article  CAS  Google Scholar 

  13. Liang F, Shen K, Qu X, Zhang C, Wang Q, Li J et al (2011) Inorganic janus nanosheets. Angew Chem Int Ed 50:2379–2382

    Article  CAS  Google Scholar 

  14. Yi Y, Sanchez L, Gao Y, Yu Y (2016) Janus particles for biological imaging and sensing. Analyst 141:3526–3539

  15. Chevalier Y, Bolzinger M-A (2013) Emulsions stabilized with solid nanoparticles: Pickering emulsions. Colloids Surf A Physicochem Eng Asp 439:23–34

    Article  CAS  Google Scholar 

  16. Wang X, Xu J, Wang Q, Xu A, Zhai Y, Luo J et al (2017) Wet chemical synthesis of silica nanosheets via ethyl acetate-mediated hydrolysis of silica precursors and their applications. Small 13:1603369

  17. Iler RK (1955) The colloid chemistry of silica and silicates, vol 80. LWW

  18. Stone HA, Stroock AD, Ajdari A (2004) Engineering flows in small devices: microfluidics toward a lab-on-a-chip. Annu Rev Fluid Mech 36:381–411

  19. de Bellefon C (2004) Chemical micro-process engineering. Fundamentals, modelling and reactions. By Volker Hessel, Steffen Hardt and Holger Löwe. Angew Chem Int Ed 43:6583–6584

    Article  CAS  Google Scholar 

  20. Hönicke D (1999) Microchemical reactors for heterogeneously catalyzed reactions. Stud Surf Sci Catal 122:47–62

    Article  Google Scholar 

  21. Belliveau NM, Huft J, Lin PJ, Chen S, Leung AK, Leaver TJ et al (2012) Microfluidic synthesis of highly potent limit-size lipid nanoparticles for in vivo delivery of siRNA. Molecular Therapy—Nucleic Acids 1:e37

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  22. Dittrich PS, Manz A (2006) Lab-on-a-chip: microfluidics in drug discovery. Nat Rev Drug Discov 5:210–218

    Article  CAS  PubMed  Google Scholar 

  23. Zheng B, Tice JD, Ismagilov RF (2004) Formation of arrayed droplets by soft lithography and two-phase fluid flow, and application in protein crystallization. Adv Mater 16:1365–1368

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  24. Zhu Y, Power BE (2008) Lab-on-a-chip in vitro compartmentalization technologies for protein studies. In: Werther M, Seitz H (eds) Protein – Protein Interaction. Advances in Biochemical Engineering/Biotechnology, 110:81–114

  25. Sen A, Darabi J, Knapp D (2009) Design, fabrication and test of a microfluidic nebulizer chip for desorption electrospray ionization mass spectrometry. Sensor Actuat B-Chem 137:789–796

  26. Bhardwaj P, Bagdi P, Sen A (2011) Microfluidic device based on a micro-hydrocyclone for particle–liquid separation. Lab Chip 11:4012–4021

    Article  CAS  PubMed  Google Scholar 

  27. Tian W-C, Finehout E (2009) Microfluidics for biological applications, vol 16. Springer, New York

  28. Joensson HN, Andersson Svahn H (2012) Droplet microfluidics—a tool for single-cell analysis. Angew Chem Int Ed 51:12176–12192

    Article  CAS  Google Scholar 

  29. Zhao C-X, He L, Qiao SZ, Middelberg AP (2011) Nanoparticle synthesis in microreactors. Chem Eng Sci 66:1463–1479

    Article  CAS  Google Scholar 

  30. Hung L-H, Lee AP (2007) Microfluidic devices for the synthesis of nanoparticles and biomaterials. J Med Biol Eng 27:1

  31. Song Y, Hormes J, Kumar CS (2008) Microfluidic synthesis of nanomaterials. Small 4:698–711

    Article  CAS  PubMed  Google Scholar 

  32. Shestopalov I, Tice JD, Ismagilov RF (2004) Multi-step synthesis of nanoparticles performed on millisecond time scale in a microfluidic droplet-based system. Lab Chip 4:316–321

    Article  CAS  PubMed  Google Scholar 

  33. Wacker JB, Lignos I, Parashar VK, Gijs MA (2012) Controlled synthesis of fluorescent silica nanoparticles inside microfluidic droplets. Lab Chip 12:3111–3116

    Article  CAS  PubMed  Google Scholar 

  34. Pérez-Page M, Yu E, Li J, Rahman M, Dryden DM, Vidu R et al (2016) Template-based syntheses for shape controlled nanostructures. Adv Colloid Interf Sci 234:51–79

    Article  CAS  Google Scholar 

  35. Eun TH, Kim S-H, Jeong W-J, Jeon S-J, Kim S-H, Yang S-M (2009) Single-step fabrication of monodisperse TiO2 hollow spheres with embedded nanoparticles in microfluidic devices. Chem Mater 21:201–203

    Article  CAS  Google Scholar 

  36. Sebastian V, Basak S, Jensen KF (2016) Continuous synthesis of palladium nanorods in oxidative segmented flow. AIChE J 62:373–380

  37. Hassan N, Stocco A, Abou-Hassan A (2015) Droplet liquid/liquid interfaces generated in a microfluidic device for assembling Janus inorganic nanohybrids. J Phys Chem C 119:10758–10765

  38. Wojnicki M, Tokarski T, Hessel V, Fitzner K, Luty-Błocho M (2019) Continuous, monodisperse silver nanoparticles synthesis using microdroplets as a reactor. J Flow Chem 9:1–7

  39. Jundale R, Bari A, Thara C, Kulkarni A (2018) Continuous flow synthesis of micron size silica nanoparticles: parametric study and effect of dosing strategy. J Flow Chem 8:59–67

  40. Brinker CJ, Scherer GW (2013) Sol-gel science: the physics and chemistry of sol-gel processing. Academic press

  41. Cao Z, Wang G, Chen Y, Liang F, Yang Z (2015) Light-triggered responsive Janus composite nanosheets. Macromolecules 48:7256–7261

  42. Nguyen N-T, Wereley ST (2002) Fundamentals and applications of microfluidics. Artech House

  43. Veglio F, Trifoni M, Pagnanelli F, Toro L (2001) Shrinking core model with variable activation energy: a kinetic model of manganiferous ore leaching with sulphuric acid and lactose. Hydrometallurgy 60:167–179

    Article  CAS  Google Scholar 

  44. Levenspiel O (1999) Chemical reaction engineering. Ind Eng Chem Res 38:4140–4143

    Article  CAS  Google Scholar 

  45. Iles A, Oki A, Pamme N (2007) Bonding of soda-lime glass microchips at low temperature. Microfluid Nanofluid 3:119–122

  46. Mahadik SA, Kavale MS, Mukherjee S, Rao AV (2010) Transparent superhydrophobic silica coatings on glass by sol–gel method. Appl Surf Sci 257:333–339

    Article  CAS  Google Scholar 

  47. Zeibi Shirejini S, Mohammadi A (2017) Halogen–lithium exchange reaction using an integrated glass microfluidic device: an optimized synthetic approach. Org Process Res Dev 21:292–303

  48. Polak J, Lu BC-Y (1973) Mutual solubilities of hydrocarbons and water at 0 and 25 C. Can J Chem 51:4018–4023

    Article  CAS  Google Scholar 

  49. Metin CO, Baran JR, Nguyen QP (2012) Adsorption of surface functionalized silica nanoparticles onto mineral surfaces and decane/water interface. J Nanopart Res 14:1246

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  50. Rao KS, El-Hami K, Kodaki T, Matsushige K, Makino K (2005) A novel method for synthesis of silica nanoparticles. J Colloid Interface Sci 289:125–131

    Article  CAS  PubMed  Google Scholar 

  51. Qasim M, Ananthaiah J, Dhara S, Paik P, Das D (2014) Synthesis and characterization of ultra-fine colloidal silica nanoparticles. Adv Sci Eng Med 6:965–973

  52. Zhao M, Tang Z, Liu P (2008) Removal of methylene blue from aqueous solution with silica nano-sheets derived from vermiculite. J Hazard Mater 158:43–51

    Article  CAS  PubMed  Google Scholar 

  53. Kumar CS (2013) UV-VIS and photoluminescence spectroscopy for nanomaterials characterization. Springer

  54. Schmidt HK, Scholze H, Kaiser A (1984) Principles of hydrolysis and condensation reaction of alkoxysilanes. J Non-Cryst Solids 63:1–11

  55. Ro JC, Chung IJ (1989) Sol-gel kinetics of tetraethylorthosilicate (TEOS) in acid catalyst. J Non-Cryst Solids 110:26–32

    Article  CAS  Google Scholar 

  56. Schubert U (2015) The sol-gel handbook: synthesis, characterization, and applications. Wiley, Weinheim

    Google Scholar 

  57. Katepalli H, Bose A (2014) Response of surfactant stabilized oil-in-water emulsions to the addition of particles in an aqueous suspension. Langmuir 30:12736–12742

    Article  CAS  PubMed  Google Scholar 

  58. Vatanparast H, Shahabi F, Bahramian A, Javadi A, Miller R (2018) The role of electrostatic repulsion on increasing surface activity of anionic surfactants in the presence of hydrophilic silica nanoparticles. Sci Rep 8:7251

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  59. Hui Y, Zishang D, Zhonghua J, Xiaoping X (1989) Sol-gel process kinetics for Si(OEt)4. J Non-Cryst Solids 112:449–453

  60. Homma S, Ogata S, Koga J, Matsumoto S (2005) Gas–solid reaction model for a shrinking spherical particle with unreacted shrinking core. Chem Eng Sci 60:4971–4980

    Article  CAS  Google Scholar 

  61. Lee KT, Koon OW (2009) Modified shrinking unreacted-core model for the reaction between sulfur dioxide and coal fly ash/CaO/CaSO4 sorbent. Chem Eng J 146:57–62

  62. Missen RW, Mims CA, Saville BA (1999) Introduction to chemical reaction engineering and kinetics. J. Wiley

  63. Yagi S, Kunii D (1961) Fluidized-solids reactors with continuous solids feed—II: conversion for overflow and carryover particles. Chem Eng Sci 16:372–379

    Article  CAS  Google Scholar 

  64. Teh S-Y, Lin R, Hung L-H, Lee AP (2008) Droplet microfluidics. Lab Chip 8:198–220

    Article  CAS  PubMed  Google Scholar 

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  1. Department of Chemical and Petroleum Engineering, Sharif University of Technology, Tehran, Iran

    Mohsen Tamtaji & Aliasghar Mohammadi

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  1. Mohsen Tamtaji
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  2. Aliasghar Mohammadi
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Correspondence to Aliasghar Mohammadi.

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Tamtaji, M., Mohammadi, A. Continuous synthesis of plate-like silica microparticles using microfluidics. J Flow Chem 9, 161–174 (2019). https://doi.org/10.1007/s41981-019-00034-z

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