Superabsorbent Aerogels from Cellulose Nanofibril Hydrogels

  • Ossi LaitinenEmail author
  • Terhi Suopajärvi
  • Juho Antti Sirviö
  • Henrikki Liimatainen
Reference work entry
Part of the Polymers and Polymeric Composites: A Reference Series book series (POPOC)


Deep eutectic solvents (DESs) are promising green chemicals that can function as solvents, reagents, and catalysts in many applications because of their biodegradability, ready availability, and low toxicity. Here, a DES of choline chloride–urea was used as a non-hydrolytic pretreatment medium to obtain cellulose nanofibril (CNF) hydrogels from recycled cellulose pulps (boxboard, milk containerboard, and fluting) and virgin birch cellulose pulp using a mechanical Masuko grinder. The mechanical disintegration of DES-pretreated cellulose fibers resulted in highly viscous, gel-like cellulose nanofibril hydrogels with shear thinning behavior. According to transmission electron microscope (TEM) imaging, the nanofibrils had widths from 2 to 80 nm, possessed the initial cellulose I crystalline structure, and had a crystallinity index of 53–56%. The nanofibril hydrogels obtained were further used to produce low-cost, ultralight, highly porous, hydrophobic, and reusable superabsorbing aerogels that were used as efficient sponges to absorb oil and chemicals. The nanofibril sponges prepared by the consequent hydrophobic modification (silylation) of CNF hydrogels and freeze-drying had ultralow density (0.003 g/cm3) and high porosity (up to 99.8%). The sponges exhibited excellent oil/water absorption selectivity and ultrahigh oil (marine diesel oil, kerosene, gasoline, motor oil, castor oil, or linseed oil) and organic solvent (dimethyl sulfoxide, chloroform, n-hexane, toluene, acetone, or ethanol) absorption capacity. The nanofibril aerogels showed particular selectivity for marine diesel oil absorption from an oil–water mixture and possessed ultrahigh absorption capacities of up to 143 g/g, which were much higher than the commercial absorbent materials (i.e., polypropylenes) (9–27 g/g) used as references. Additionally, the absorbed oil could be recovered by means of simple mechanical squeezing, and the superabsorbent could be reused for at least 30 cycles.


Aerogel Cellulose nanofiber Deep eutectic solvent Nanocellulose hydrogel Oil removal Silylation Sponge 


  1. 1.
    Klemm D, Kramer F, Moritz S, Tom Lindström T, Ankerfors M, Gray D, Dorris A (2011) Nanocelluloses: a new family of nature-based materials. Angew Chem Int Ed 50:5438–5466. Scholar
  2. 2.
    Siró I, Plackett D (2010) Microfibrillated cellulose and new nanocomposite materials: a review. Cellulose 17:459–494. Scholar
  3. 3.
    Herrick FW, Casebier RL, Hamilton JK, Sandberg KRJ (1983) Microfibrillated cellulose: morphology and accessibility. J Appl Polym Sci Appl Polym Symp 37:815–827Google Scholar
  4. 4.
    Sirviö JA, Visanko M, Liimatainen H (2015) Deep eutectic solvent system based on choline chloride-urea as a pre-treatment for nanofibrillation of wood cellulose. Green Chem 17:3401–3406. Scholar
  5. 5.
    Singh BS, Lobo HR, Shankarling GS (2012) Choline chloride based eutectic solvents: magical catalytic system for carbon-carbon bond formation in the rapid synthesis of β-hydroxy functionalized derivatives. Catal Commun 24:70–74. Scholar
  6. 6.
    Liu H, Geng B, Chen Y, Wang H (2017) Review on the aerogel-type oil sorbents derived from nanocellulose. ACS Sustain Chem Eng 5:49–66. Scholar
  7. 7.
    Zanini M, Lavoratti A, Lazzari LK, Galiotto D, Pagnocelli M, Baldasso C, Zattera AJ (2016) Producing aerogels from silanized cellulose nanofiber suspension. Cellulose 24:769–779. Scholar
  8. 8.
    Zhang Z, Sèbe G, Rentsch D, Zimmermann T, Tingaut P (2014) Ultralightweight and flexible silylated nanocellulose sponges for the selective removal of oil from water. Chem Mater 26:2659–2668. Scholar
  9. 9.
    Korhonen JT, Kettunen M, Ras RHA, Ikkala O (2011) Hydrophobic nanocellulose aerogels as floating, sustainable, reusable, and recyclable oil absorbents. ACS Appl Mater Interfaces 3:1813–1816. Scholar
  10. 10.
    Cervin NT, Aulin C, Larsson PT, Wågberg L (2012) Ultra porous nanocellulose aerogels as separation medium for mixtures of oil/water liquids. Cellulose 19:401–410. Scholar
  11. 11.
    Zhou S, Liu P, Wang M, Zhao H, Yang J, Xu F (2016) Sustainable, reusable, and superhydrophobic aerogels from microfibrillated cellulose for highly effective oil/water separation. ACS Sustain Chem Eng 4:6409–6416. Scholar
  12. 12.
    Mulyadi A, Zhang Z, Deng Y (2016) Fluorine-free oil absorbents made from cellulose nanofibril aerogels. ACS Appl Mater Interfaces 8:2732–2740. Scholar
  13. 13.
    Wang Y, Yadav S, Heinlein T, Konjik V, Breitzke H, Buntkowsky G, Schneider JJ, Zhang K (2014) Ultra-light nanocomposite aerogels of bacterial cellulose and reduced graphene oxide for specific absorption and separation of organic liquids. RSC Adv 4:21553–21558. Scholar
  14. 14.
    Jiang F, Hsieh Y-L (2014) Amphiphilic superabsorbent cellulose nanofibril aerogels. J Mater Chem A 2:6337–6342. Scholar
  15. 15.
    Sai H, Xing L, Xiang J, Cui L, Jiao J, Zhao C, Lia Z, Li F (2013) Flexible aerogels based on an interpenetrating network of bacterial cellulose and silica by a non-supercritical drying process. J Mater Chem A 1:7963–7970. Scholar
  16. 16.
    Gupta S, Tai N-H (2016) Carbon materials as oil sorbents: a review on the synthesis and performance. J Mater Chem A 4:1550–1565. Scholar
  17. 17.
    Sabir S (2015) Approach of cost-effective adsorbents for oil removal from oily water. Crit Rev Environ Sci Technol 45:1916–1945. Scholar
  18. 18.
    Syed S, Alhazzaa MI, Asif M (2011) Treatment of oily water using hydrophobic nano-silica. Chem Eng J 167:99–103. Scholar
  19. 19.
    Santander M, Rodrigues RT, Rubio J (2011) Modified jet flotation in oil (petroleum) emulsion/water separations. Colloids Surf A Physicochem Eng Asp 375:237–244. Scholar
  20. 20.
    Feng J, Nguyen ST, Fan Z, Duong HM (2015) Advanced fabrication and oil absorption properties of super-hydrophobic recycled cellulose aerogels. Chem Eng J 270:168–175. Scholar
  21. 21.
    Yang S, Chen L, Mu L, Hao B, Ma P-C (2015) Low cost carbon fiber aerogel derived from bamboo for the adsorption of oils and organic solvents with excellent performances. RSC Adv 5:38470–38478. Scholar
  22. 22.
    Cortez JSA, Kharisov BI, Quezada TES, García TCH (2017) Micro- and nanoporous materials capable of absorbing solvents and oils reversibly: the state of the art. Pet Sci 14:84–104. Scholar
  23. 23.
    Al-Majed AA, Adebayo AR, Hossain ME (2012) A sustainable approach to controlling oil spills. J Environ Manag 113:213–227. Scholar
  24. 24.
    Banerjee SS, Joshi MV, Jayaram RV (2006) Treatment of oil spills using organo-fly ash. Desalination 195:32–39. Scholar
  25. 25.
    Rajaković-Ognjanović V, Aleksić G, Rajaković L (2008) Governing factors for motor oil removal from water with different sorption materials. J Hazard Mater 154:558–563. Scholar
  26. 26.
    Toyoda M, Aizawa J, Inagaki M (1998) Sorption and recovery of heavy oil by using exfoliated graphite. Desalination 115:199–201CrossRefGoogle Scholar
  27. 27.
    Okiel K, El-Sayed M, El-Kady MY (2011) Treatment of oil–water emulsions by adsorption onto activated carbon, bentonite and deposited carbon. Egypt J Pet 20:9–15. Scholar
  28. 28.
    Carmody O, Frost R, Xi Y, Kokot S (2007) Adsorption of hydrocarbons on organo-clays – implications for oil spill remediation. J Colloid Interface Sci 305:17–24. Scholar
  29. 29.
    Cho YK, Park EJ, Kim YD (2014) Removal of oil by gelation using hydrophobic silica nanoparticles. J Ind Eng Chem 20:1231–1235. Scholar
  30. 30.
    Wang D, McLaughlin E, Pfeffer R, Lin YS (2012) Adsorption of oils from pure liquid and oil–water emulsion on hydrophobic silica aerogels. Sep Purif Technol 99:28–35. Scholar
  31. 31.
    Lin C, Hong Y-J, Hu AH (2010) Using a composite material containing waste tire powder and polypropylene fiber cut end to recover spilled oil. Waste Manag 30:263–267. Scholar
  32. 32.
    Oh Y-S, Maeng J, Kim S-J (2000) Use of microorganism-immobilized polyurethane foams to absorb and degrade oil on water surface. Appl Microbiol Biotechnol 54:418–423CrossRefGoogle Scholar
  33. 33.
    Wei QF, Mather RR, Fotheringham AF, Yang RD (2003) Evaluation of nonwoven polypropylene oil sorbents in marine oil-spill recovery. Mar Pollut Bull 46:780–783. Scholar
  34. 34.
    Teas C, Kalligeros S, Zanikos F, Stournas S, Lois E, Anastopoulos G (2001) Investigation of the effectiveness of absorbent materials in oil spills clean up. Desalination 140:259–264CrossRefGoogle Scholar
  35. 35.
    Toyoda M, Inagaki M (2003) Sorption and recovery of heavy oils by using exfoliated graphite. Spill Sci Technol Bull 8:467–474. Scholar
  36. 36.
    Wang J, Zheng Y, Wang A (2012) Effect of kapok fiber treated with various solvents on oil absorbency. Ind Crop Prod 40:178–184. Scholar
  37. 37.
    Ali N, El-Harbawi M, Jabal AA, Yin C-Y (2012) Characteristics and oil sorption effectiveness of kapok fibre, sugarcane bagasse and rice husks: oil removal suitability matrix. Environ Technol 33:481–486. Scholar
  38. 38.
    Hussein M, Amer AA, Sawsan II (2011) Heavy oil spill cleanup using law grade raw cotton fibers: trial for practical application. J Pet Technol Altern Fuels 2:132–140Google Scholar
  39. 39.
    Sun X-F, Sun J-X (2002) Acetylation of rice straw with or without catalysts and its characterization as a natural sorbent in oil spill cleanup. J Agric Food Chem 50:6428–6433. Scholar
  40. 40.
    Khan E, Virojnagud W, Ratpukdi T (2004) Use of biomass sorbents for oil removal from gas station runoff. Chemosphere 57:681–689. Scholar
  41. 41.
    Annunciado TR, Sydenstricker THD, Amico SC (2005) Experimental investigation of various vegetable fibers as sorbent materials for oil spills. Mar Pollut Bull 50:1340–1346. Scholar
  42. 42.
    Wahi R, Chuah LA, Choong TSY, Ngaini Z, Nourouzi MM (2013) Oil removal from aqueous state by natural fibrous sorbent: an overview. Sep Purif Technol 113:51–63. Scholar
  43. 43.
    Nourbakhsh A, Ashori A (2010) Particleboard made from waste paper treated with maleic anhydride. Waste Manag Res 28(5):1–55. Scholar
  44. 44.
    Segal L, Creely JJ, Martin AE, Conrad CM (1959) An empirical method for estimating the degree of crystallinity of native cellulose using the X-ray diffractometer. Text Res J 29:786–794CrossRefGoogle Scholar
  45. 45.
    Xie Y, Hill CAS, Xiao Z, Militz H, Mai C (2010) Silane coupling agents used for natural fiber/polymer composites: a review. Compos A Appl Sci Manuf 41:806–819. Scholar
  46. 46.
    Li P, Sirviö JA, Haapala A, Liimatainen H (2017) Cellulose nanofibrils from nonderivatizing urea-based deep eutectic solvent pretreatments. ACS Appl Mater Interfaces 9:2846–2855. Scholar
  47. 47.
    Sharma M, Mukesh C, Mondal D, Prasad K (2013) Dissolution of α-chitin in deep eutectic solvents. RSC Adv 3:18149. Scholar
  48. 48.
    Abbott AP, Bell TJ, Handa S, Stoddart B (2005) O-Acetylation of cellulose and monosaccharides using a zinc based ionic liquid. Green Chem 7:705. Scholar
  49. 49.
    Zhang Q, Benoit M, De Oliveira Vigier K, Barrault J, Francois J (2012) Green and inexpensive choline-derived solvents for cellulose decrystallization. Chem Eur J 18:1043–1046. Scholar
  50. 50.
    Du C, Zhao B, Chen X-B, Birbilis N, Yang H (2016) Effect of water presence on choline chloride-2urea ionic liquid and coating platings from the hydrated ionic liquid. Sci Rep 6:29225. Scholar
  51. 51.
    Besbes I, Alila S, Boufi S (2011) Nanofibrillated cellulose from TEMPO-oxidized eucalyptus fibres: effect of the carboxyl content. Carbohydr Polym 84:975–983. Scholar
  52. 52.
    Lasseuguette E, Roux D, Nishiyama Y (2008) Rheological properties of microfibrillar suspension of TEMPO-oxidized pulp. Cellulose 15:425–433. Scholar
  53. 53.
    Iotti M, Gregersen ØW, Moe S, Lenes M (2011) Rheological studies of microfibrillar cellulose water dispersions. J Polym Environ 19:137–145. Scholar
  54. 54.
    Mohtaschemi M, Sorvari A, Puisto A, Nuopponen M, Seppälä J, Alava MJ (2014) The vane method and kinetic modeling: shear rheology of nanofibrillated cellulose suspensions. Cellulose 21:3913–3925. Scholar
  55. 55.
    Zhang Z, Tingaut P, Rentsch D, Zimmermann T, Sebe G (2015) Controlled silylation of nanofibrillated cellulose in water: reinforcement of a model polydimethylsiloxane network. ChemSusChem 8:2681–2690. Scholar
  56. 56.
    Materne T, de Buyl F, Witucki G (2004) Organosilane technology in coating applications: review and perspectives. Accessed 27 Feb 2017
  57. 57.
    Li Y-Q, Samad YA, Polychronopoulou K, Alhassan SM, Liao K (2014) Carbon aerogel from winter melon for highly efficient and recyclable oils and organic solvents absorption. ACS Sustain Chem Eng 2:1492–1497. Scholar
  58. 58.
    Sai H, Fu R, Xing L, Xiang J, Li Z, Li F, Zhang T (2015) Surface modification of bacterial cellulose aerogels’ web-like skeleton for oil/water separation. ACS Appl Mater Interfaces 7:7373–7381. Scholar
  59. 59.
    Zhao J, Ren W, Cheng H-M (2012) Graphene sponge for efficient and repeatable adsorption and desorption of water contaminations. J Mater Chem 22:20197–20202. Scholar
  60. 60.
    Liu F, Ma M, Zang D, Gao Z, Wang C (2014) Fabrication of superhydrophobic/superoleophilic cotton for application in the field of water/oil separation. Carbohydr Polym 103:480–487. Scholar
  61. 61.
    Bi H, Yin Z, Cao X, Xie X, Tan C, Huang X, Chen B, Chen F, Yang Q, Bu X, Lu X, Sun L, Zhang H (2013) Carbon fiber aerogel made from raw cotton: a novel, efficient and recyclable sorbent for oils and organic solvents. Adv Mater 25:5916–5921. Scholar
  62. 62.
    Bi H, Huang X, Wu X, Cao X, Tan C, Yin Z, Lu X, Sun L, Zhang H (2014) Carbon microbelt aerogel prepared by waste paper: an efficient and recyclable sorbent for oils and organic solvents. Small 10:3544–3550. Scholar
  63. 63.
    Hashim DP, Narayanan NT, Romo-Herrera JM, Cullen DA, Hahm MG, Lezzi P, Suttle JR, Kelkhoff D, Munoz-Sandoval E, Ganguli S, Roy AK, Smith DJ, Vajtai R, Sumpter BG, Meunier V, Terrones H, Terrones M, Ajayan PM (2012) Covalently bonded three-dimensional carbon nanotube solids via boron induced nanojunctions. Sci Rep 2:1–8. Scholar
  64. 64.
    Zhao Y, Hu C, Hu Y, Cheng H, Shi G, Liangti Q (2012) A versatile, ultralight, nitrogen-doped graphene framework. Angew Chem Int Ed 51:11371–11375. Scholar
  65. 65.
    Bi H, Xie X, Yin K, Zhou Y, Wan S, He L, Xu F, Banhart F, Sun L, Ruoff RS (2012) Spongy graphene as a highly efficient and recyclable sorbent for oils and organic solvents. Adv Funct Mater 22:4421–4425. Scholar
  66. 66.
    He Y, Liu Y, Wu T, Ma J, Wang X, Gong Q, Kong W, Xing F, Liu Y, Gao J (2013) An environmentally friendly method for the fabrication of reduced graphene oxide foam with a super oil absorption capacity. J Hazard Mater 260:796–805. Scholar
  67. 67.
    Wu Z-Y, Li C, Liang H-W, Chen J-F, Yu S-H (2013) Ultralight, flexible, and fire-resistant carbon nanofiber aerogels from bacterial cellulose. Angew Chem 125:2997–3001. Scholar
  68. 68.
    Zheng Q, Cai Z, Gong S (2014) Green synthesis of polyvinyl alcohol (PVA)–cellulose nanofibril (CNF) hybrid aerogels and their use as superabsorbents. J Mater Chem A 2:3110–3118. Scholar
  69. 69.
    Abraham E, Weber DE, Sharon S, Lapidot S, Shoseyov O (2017) Multifunctional cellulosic scaffolds from modified cellulose nanocrystals. ACS Appl Mater Interfaces 9:2010–2015. Scholar
  70. 70.
    Song C, Ding L, Yao F, Deng J, Yang W (2013) β-Cyclodextrin-based oil-absorbent microspheres: preparation and high oil absorbency. Carbohydr Polym 91:217–223. Scholar
  71. 71.
    Pan Y, Shi K, Peng C, Wang W, Liu Z, Ji X (2014) Evaluation of hydrophobic polyvinyl-alcohol formaldehyde sponges as absorbents for oil spill. ACS Appl Mater Interfaces 6:8651–8659. Scholar
  72. 72.
    Wang J, Wang A (2013) Acetylated modification of kapok fiber and application for oil absorption. Fibers Polym 14:1834–1840. Scholar

Copyright information

© Springer Nature Switzerland AG 2019

Authors and Affiliations

  • Ossi Laitinen
    • 1
    Email author
  • Terhi Suopajärvi
    • 1
  • Juho Antti Sirviö
    • 1
  • Henrikki Liimatainen
    • 1
  1. 1.University of Oulu, Fibre and Particle EngineeringOuluFinland

Personalised recommendations