Abstract
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.
Similar content being viewed by others
References
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. https://doi.org/10.1002/anie.201001273
Siró I, Plackett D (2010) Microfibrillated cellulose and new nanocomposite materials: a review. Cellulose 17:459–494. https://doi.org/10.1007/s10570-010-9405-y
Herrick FW, Casebier RL, Hamilton JK, Sandberg KRJ (1983) Microfibrillated cellulose: morphology and accessibility. J Appl Polym Sci Appl Polym Symp 37:815–827
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. https://doi.org/10.1039/C5GC00398A
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. https://doi.org/10.1016/j.catcom.2012.03.021
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. https://doi.org/10.1021/acssuschemeng.6b02301
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. https://doi.org/10.1007/s10570-016-1142-4
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. https://doi.org/10.1021/cm5004164
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. https://doi.org/10.1021/am200475b
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. https://doi.org/10.1007/s10570-011-9629-5
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. https://doi.org/10.1021/acssuschemeng.6b01075
Mulyadi A, Zhang Z, Deng Y (2016) Fluorine-free oil absorbents made from cellulose nanofibril aerogels. ACS Appl Mater Interfaces 8:2732–2740. https://doi.org/10.1021/acsami.5b10985
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. https://doi.org/10.1039/c4ra02168a
Jiang F, Hsieh Y-L (2014) Amphiphilic superabsorbent cellulose nanofibril aerogels. J Mater Chem A 2:6337–6342. https://doi.org/10.1039/c4ta00743c
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. https://doi.org/10.1039/c3ta11198a
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. https://doi.org/10.1039/C5TA08321D
Sabir S (2015) Approach of cost-effective adsorbents for oil removal from oily water. Crit Rev Environ Sci Technol 45:1916–1945. https://doi.org/10.1080/10643389.2014.1001143
Syed S, Alhazzaa MI, Asif M (2011) Treatment of oily water using hydrophobic nano-silica. Chem Eng J 167:99–103. https://doi.org/10.1016/j.cej.2010.12.006
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. https://doi.org/10.1016/j.colsurfa.2010.12.027
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. https://doi.org/10.1016/j.cej.2015.02.034
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. https://doi.org/10.1039/C5RA03701H
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. https://doi.org/10.1007/s12182-016-0143-0
Al-Majed AA, Adebayo AR, Hossain ME (2012) A sustainable approach to controlling oil spills. J Environ Manag 113:213–227. https://doi.org/10.1016/j.jenvman.2012.07.034
Banerjee SS, Joshi MV, Jayaram RV (2006) Treatment of oil spills using organo-fly ash. Desalination 195:32–39. https://doi.org/10.1016/j.desal.2005.10.038
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. https://doi.org/10.1016/j.jhazmat.2007.10.066
Toyoda M, Aizawa J, Inagaki M (1998) Sorption and recovery of heavy oil by using exfoliated graphite. Desalination 115:199–201
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. https://doi.org/10.1016/j.ejpe.2011.06.002
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. https://doi.org/10.1016/j.jcis.2006.09.032
Cho YK, Park EJ, Kim YD (2014) Removal of oil by gelation using hydrophobic silica nanoparticles. J Ind Eng Chem 20:1231–1235. https://doi.org/10.1016/j.jiec.2013.08.005
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. https://doi.org/10.1016/j.seppur.2012.08.001
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. https://doi.org/10.1016/j.wasman.2009.03.001
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 54:418–423
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. https://doi.org/10.1016/S0025-326X(03)00042-0
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 140:259–264
Toyoda M, Inagaki M (2003) Sorption and recovery of heavy oils by using exfoliated graphite. Spill Sci Technol Bull 8:467–474. https://doi.org/10.1016/S1353-2561(03)00131-2
Wang J, Zheng Y, Wang A (2012) Effect of kapok fiber treated with various solvents on oil absorbency. Ind Crop Prod 40:178–184. https://doi.org/10.1016/j.indcrop.2012.03.002
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. https://doi.org/10.1080/09593330.2011.579185
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 2:132–140
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. https://doi.org/10.1021/jf020392
Khan E, Virojnagud W, Ratpukdi T (2004) Use of biomass sorbents for oil removal from gas station runoff. Chemosphere 57:681–689. https://doi.org/10.1016/j.chemosphere.2004.06.028
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. https://doi.org/10.1016/j.marpolbul.2005.04.043
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. https://doi.org/10.1016/j.seppur.2013.04.015
Nourbakhsh A, Ashori A (2010) Particleboard made from waste paper treated with maleic anhydride. Waste Manag Res 28(5):1–55. https://doi.org/10.1177/0734242X09336463
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 29:786–794
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. https://doi.org/10.1016/j.compositesa.2010.03.005
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. https://doi.org/10.1021/acsami.6b13625
Sharma M, Mukesh C, Mondal D, Prasad K (2013) Dissolution of α-chitin in deep eutectic solvents. RSC Adv 3:18149. https://doi.org/10.1039/c3ra43404d
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. https://doi.org/10.1039/b511691k
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. https://doi.org/10.1002/chem.201103271
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. https://doi.org/10.1038/srep29225
Besbes I, Alila S, Boufi S (2011) Nanofibrillated cellulose from TEMPO-oxidized eucalyptus fibres: effect of the carboxyl content. Carbohydr Polym 84:975–983. https://doi.org/10.1016/j.carbpol.2010.12.052
Lasseuguette E, Roux D, Nishiyama Y (2008) Rheological properties of microfibrillar suspension of TEMPO-oxidized pulp. Cellulose 15:425–433. https://doi.org/10.1007/s10570-007-9184-2
Iotti M, Gregersen ØW, Moe S, Lenes M (2011) Rheological studies of microfibrillar cellulose water dispersions. J Polym Environ 19:137–145. https://doi.org/10.1007/s10924-010-0248-2
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. https://doi.org/10.1007/s10570-014-0409-x
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. https://doi.org/10.1002/cssc.201500525
Materne T, de Buyl F, Witucki G (2004) Organosilane technology in coating applications: review and perspectives. http://www4.dowcorning.com/content/publishedlit/26-1402-01.pdf. Accessed 27 Feb 2017
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. https://doi.org/10.1021/sc500161b
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. https://doi.org/10.1021/acsami.5b00846
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. https://doi.org/10.1039/c2jm34128j
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. https://doi.org/10.1016/j.carbpol.2013.12.022
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. https://doi.org/10.1002/adma.201302435
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. https://doi.org/10.1002/smll.201303413
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. https://doi.org/10.1038/srep00363
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. https://doi.org/10.1002/anie.201206554
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. https://doi.org/10.1002/adfm.201200888
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. https://doi.org/10.1016/j.jhazmat.2013.06.042
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. https://doi.org/10.1002/ange.201209676
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. https://doi.org/10.1039/c3ta14642a
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. https://doi.org/10.1021/acsami.6b13528
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. https://doi.org/10.1016/j.carbpol.2012.08.036
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. https://doi.org/10.1021/am5014634
Wang J, Wang A (2013) Acetylated modification of kapok fiber and application for oil absorption. Fibers Polym 14:1834–1840. https://doi.org/10.1007/s12221-013-1834-4
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2018 Springer International Publishing AG, part of Springer Nature
About this entry
Cite this entry
Laitinen, O., Suopajärvi, T., Sirviö, J.A., Liimatainen, H. (2018). Superabsorbent Aerogels from Cellulose Nanofibril Hydrogels. In: Mondal, M. (eds) Cellulose-Based Superabsorbent Hydrogels. Polymers and Polymeric Composites: A Reference Series. Springer, Cham. https://doi.org/10.1007/978-3-319-76573-0_20-1
Download citation
DOI: https://doi.org/10.1007/978-3-319-76573-0_20-1
Received:
Accepted:
Published:
Publisher Name: Springer, Cham
Print ISBN: 978-3-319-76573-0
Online ISBN: 978-3-319-76573-0
eBook Packages: Springer Reference Chemistry and Mat. ScienceReference Module Physical and Materials ScienceReference Module Chemistry, Materials and Physics