Abstract
Cellulose nanofibers (CNFs) are becoming a topic of great interest due to their wide range of potential applications. The huge presence of carboxylic groups in TEMPO-oxidized CNFs indicate that this material could interact with cationic species in aqueous solution, such as metal ions. Nevertheless, the contact between nanofibers and water solutions requires a 3D structure to entrap and retain the nanofibers. In this sense, two different 3D structures were synthetized: CNF-calcium alginate beads and CNF-aerogels. After the synthesis and characterization of 3D structures, batch sorption studies were performed by using these sorbents to study their ability for metal removal. Equilibrium data fitted very well Langmuir and Freundlich isotherm models in the studied concentration range of copper(II) ions and confirmed that the copper sorption is a favorable process. Both new synthetized materials resulted to be effective for Cu(II) removal and maximum sorption capacity was higher for CNF-aerogels than CNF-calcium alginate beads. Finally, in this work it has been demonstrated that the synthetized 3D CNF-aerogel structure is an efficient sorbent for copper ion removal from aqueous solutions and the use of this synthetized structure for environmental decontamination opens a new opportunity to CNF applications.
Graphical abstract






Similar content being viewed by others
Explore related subjects
Discover the latest articles and news from researchers in related subjects, suggested using machine learning.References
Alves-Gurgel LV, Karnitz-Junior O, de Freitas-Gil RP, Gil LF (2008) Adsorption of Cu(II), Cd(II), and Pb(II) from aqueous single metal solutions by cellulose and mercerized cellulose chemically modified with succinic anhydride. Bioresour Technol 99:3077–3083. https://doi.org/10.1016/j.biortech.2007.05.072
Batmaz R, Mohammed N, Zaman M et al (2014) Cellulose nanocrystals as promising adsorbents for the removal of cationic dyes. Cellulose 21:1655–1665. https://doi.org/10.1007/s10570-014-0168-8
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
Bezbaruah AN, Krajangpan S, Chisholm BJ et al (2009) Entrapment of iron nanoparticles in calcium alginate beads for groundwater remediation applications. J Hazard Mater 166:1339–1343. https://doi.org/10.1016/j.jhazmat.2008.12.054
Bhatnagar A, Jain AK (2005) A comparative adsorption study with different industrial wastes as adsorbents for the removal of cationic dyes from water. J Colloid Interface Sci 281:49–55. https://doi.org/10.1016/j.jcis.2004.08.076
Delgado-Aguilar M, González I, Pèlach MA et al (2015) Improvement of deinked old newspaper/old magazine pulp suspensions by means of nanofibrillated cellulose addition. Cellulose 22:789–802. https://doi.org/10.1007/s10570-014-0473-2
Espinosa E, Tarrés Q, Delgado-Aguilar M et al (2016) Suitability of wheat straw semichemical pulp for the fabrication of lignocellulosic nanofibres and their application to papermaking slurries. Cellulose 23:837–852. https://doi.org/10.1007/s10570-015-0807-8
Fiol N, Poch J, Villaescusa I (2004) Chromium(VI) uptake by grape stalks wastes encapsulated in calcium alginate beads: equilibrium and kinetics studies. Chem Speciat Bioavailab 16:25–33. https://doi.org/10.3184/095422904782775153
Fiol N, Escudero C, Poch J, Villaescusa I (2006) Preliminary studies on Cr(VI) removal from aqueous solution using grape stalk wastes encapsulated in calcium alginate beads in a packed bed up-flow column. React Funct Polym 66:795–807. https://doi.org/10.1016/j.reactfunctpolym.2005.11.006
Fujisawa S, Okita Y, Fukuzumi H et al (2011) Preparation and characterization of TEMPO-oxidized cellulose nanofibril films with free carboxyl groups. Carbohydr Polym 84:579–583. https://doi.org/10.1016/j.carbpol.2010.12.029
Glover-Kerkvliet J (1995) Environmental assault on immunity. Environ Health Perspect 103:236–239. https://doi.org/10.1289/ehp.95103236
Henriksson M, Henriksson G, Berglund LA, Lindström T (2007) An environmentally friendly method for enzyme-assisted preparation of microfibrillated cellulose (MFC) nanofibers. Eur Polym J 43:3434–3441. https://doi.org/10.1016/j.eurpolymj.2007.05.038
Hii C, Gregersen Ø, Chinga-Carrasco G, Eriksen Ø (2012) The effect of MFC on the pressability and paper properties of TMP and GCC based sheets. Nord Pulp Pap Res J 27:388–396. https://doi.org/10.3183/NPPRJ-2012-27-02-p388-396
Hokkanen S, Repo E, Sillanpää M (2013) Removal of heavy metals from aqueous solutions by succinic anhydride modified mercerized nanocellulose. Chem Eng J 223:40–47. https://doi.org/10.1016/j.cej.2013.02.054
Hokkanen S, Bhatnagar A, Sillanpää M (2016) A review on modification methods to cellulose-based adsorbents to improve adsorption capacity. Water Res 91:156–173. https://doi.org/10.1016/j.watres.2016.01.008
Hsi C-KD, Langmuir D (1985) Adsorption of uranyl onto ferric oxhydroxides: application of the surface complexation site-binding model. Geochim Cosmochim Acta 49:1931–1941
Hubbe MA (2007) Paper’s resistance to wetting: a review of internal sizing chemicals and their effects. BioResources 2:106–145. https://doi.org/10.15376/biores.2.1.106-145
Isogai A, Saito T, Fukuzumi H (2011) TEMPO-oxidized cellulose nanofibers. Nanoscale 3:71–85. https://doi.org/10.1039/c0nr00583e
Jodra Y, Mijangos F (2001) Ion exchange selectivities of calcium alginate gels for heavy metals. Water Sci Technol 43:237–244. https://doi.org/10.2166/wst.2001.0095
Klemm D, Philipp B, Heinze T, Heinze U (1998) Comprehensive cellulose chemistry, vol 1. Wiley-VCH, Weinheim
Lay M, Méndez JA, Delgado-Aguilar M et al (2016) Strong and electrically conductive nanopaper from cellulose nanofibers and polypyrrole. Carbohydr Polym. https://doi.org/10.1016/j.carbpol.2016.06.102
Lin N, Dufresne A (2014) Nanocellulose in biomedicine: current status and future prospect. Eur Polym J 59:302–325. https://doi.org/10.1016/j.eurpolymj.2014.07.025
Lizundia E, Delgado-Aguilar M, Mutjé P et al (2016) Cu-coated cellulose nanopaper for green and low-cost electronics. Cellulose 23:1997–2010. https://doi.org/10.1007/s10570-016-0920-3
Low KS, Lee CK, Mak SM (2004) Sorption of copper and lead by citric acid modified wood. Wood Sci Technol 38:629–640. https://doi.org/10.1007/s00226-003-0201-9
Maatar W, Boufi S (2015) Poly(methacylic acid-co-maleic acid) grafted nanofibrillated celluloseas a reusable novel heavy metal ions adsorbent. Carbohydr Polym 126:199–207
Mahfoudhi N, Boufi S (2017) Nanocellulose as a novel nanostructured adsorbent for environmental remediation: a review. Cellulose 24:1171–1197
Mall ID, Srivastava VC, Agarwal NK, Mishra IM (2005) Adsorptive removal of malachite green dye from aqueous solution by bagasse fly ash and activated carbon-kinetic study and equilibrium isotherm analyses. Colloids Surfaces A Physicochem Eng Asp 264:17–28. https://doi.org/10.1016/j.colsurfa.2005.03.027
Maurya NS, Mittal AK, Cornel P, Rother E (2006) Biosorption of dyes using dead macro fungi: effect of dye structure, ionic strength and pH. Bioresour Technol 97:512–521. https://doi.org/10.1016/j.biortech.2005.02.045
Pidwirny M (2006) The hydrologic cycle. In: Fundamentals of physical geography, 2nd edn. http://www.physicalgeography.net/fundamentals/8b.html. Accessed 17 May 2018
Saito T, Kimura S, Nishiyama Y, Isogai A (2007) Cellulose nanofibers prepared by TEMPO-mediated oxidation of native cellulose. Biomacromol 8:2485–2491. https://doi.org/10.1021/bm0703970
Sehaqui H, Liu A, Zhou Q, Berglund LA (2010) Fast preparation procedure for large, flat cellulose and cellulose/inorganic nanopaper structures. Biomacromol 11:2195–2198. https://doi.org/10.1021/bm100490s
Serra A, González I, Oliver-Ortega H et al (2017) Reducing the amount of catalyst in TEMPO-oxidized cellulose nanofibers: effect on properties and cost. Polymers. https://doi.org/10.3390/polym9110557
Shinoda R, Saito T, Okita Y, Isogai A (2012) Relationship between length and degree of polymerization of TEMPO-oxidized cellulose nanofibrils. Biomacromol 13:842–849
Tarrés Q, Oliver-Ortega H, Llop M et al (2016) Effective and simple methodology to produce nanocellulose-based aerogels for selective oil removal. Cellulose 23:3077–3088. https://doi.org/10.1007/s10570-016-1017-8
Tarrés Q, Boufi S, Mutjé P, Delgado-Aguilar M (2017) Enzymatically hydrolyzed and TEMPO-oxidized cellulose nanofibers for the production of nanopapers: morphological, optical, thermal and mechanical properties. Cellulose. https://doi.org/10.1007/s10570-017-1394-7
Tarrés Q, Oliver-Ortega H, Ferreira PJ et al (2018) Towards a new generation of functional fiber-based packaging: cellulose nanofibers for improved barrier, mechanical and surface properties. Cellulose 25:683–695. https://doi.org/10.1007/s10570-017-1572-7
USGS (2013) The world’s water. http://ga.water.usgs.gov/edu/earthwherewater.html. Accessed 17 May 2018
Veglio F, Esposito A, Reverberi AP (2002) Copper adsorption on calcium alginate beads: equilibrium pH- related models. Hydrometallurgy 65:43–57
Vinícius L, Gurgel A, Gil LF (2009) Adsorption of Cu(II), Cd(II), and Pb(II) from aqueous single metal solutions by succinylated mercerized cellulose modified with triethylenetetramine. Carbohydr Polym 77:142–149. https://doi.org/10.1016/j.carbpol.2008.12.014
Wan Ngah WS, Hanafiah MAKM (2008) Removal of heavy metal ions from wastewater by chemically modified plant wastes as adsorbents: a review. Bioresour Technol 99:3935–3948. https://doi.org/10.1016/j.biortech.2007.06.011
Zhang Z, Sèbe G, Rendtsch D et al (2014) Ultralightweight and flexible silylated nanocellulose sponges for the selective removal of oil from water. Chem Mater 26:2659–2668
Acknowledgments
Authors wish to acknowledge the financial support of the Spanish Economy and Competitiveness Ministry to the project NANOPROSOST (reference CTQ2017-85654-C2-1-R) and MINNANO (CTM2015-68859-C2-1-R MINECO-FEDER), as well as CYTED for the support on networking and mobility of Mr. Matías G. Vásquez in the frame of the project P316RT0095–Red temática NANOCELIA.
Author information
Authors and Affiliations
Corresponding author
Electronic supplementary material
Below is the link to the electronic supplementary material.
Rights and permissions
About this article
Cite this article
Fiol, N., Vásquez, M.G., Pereira, M. et al. TEMPO-oxidized cellulose nanofibers as potential Cu(II) adsorbent for wastewater treatment. Cellulose 26, 903–916 (2019). https://doi.org/10.1007/s10570-018-2106-7
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10570-018-2106-7


