All Issue

2025 Vol.57, Issue 4 Preview Page

Original Paper

Preparation and Characterization of Anion-Capturing Aerogel from Freeze-Dried Quaternary Ammonium Cellulose Nanofibers
Yoon-Hyuck Choi1
,
Seungmin Han1
,
Soo-Jeong Shin2†
,
Wanhee Im2‡
1Department of Forest Products and Engineering, College of Agriculture, Life & Environment Science, Chungbuk National University, Graduate Student
2Department of Wood and Paper Science, College of Agriculture, Life & Environment Science, Chungbuk National University, Professor
†Corresponding Author: E-mail: soojshin@cbnu.ac.kr (Address: Department of Wood and Paper Science, College of Agriculture, Life & Environment Science, Chungbuk National University, Cheongju, 28644, Republic of Korea)
‡Corresponding Author: E-mail: iwh1009@cbnu.ac.kr (Address: Department of Wood and Paper Science, College of Agriculture, Life & Environment Science, Chungbuk National University, Cheongju, 28644, Republic of Korea)
30 August 2025. pp. 43-53
PDF XML Citation
Abstract

Cellulose nanofibers (CNFs) are natural nanomaterials derived from cellulose with tunable surface properties, making them ideal candidates for water filtration applications. By adjusting the width and length of these fibers, the pore size of filters can be controlled. In this study, CNFs were functionalized with quaternary ammonium groups via a pre-treatment process to enhance their anion capture efficiency. The degree of quaternary amination was varied to systematically tune the charge density and anion adsorption capacity of the CNFs. Cellulose treated with different amounts of glycidyltrimethylammonium chloride (GMA) was processed through a high-pressure homogenizer to produce CNFs with quaternary ammonium groups. The properties of the functionalized CNFs, including zeta potential, particle size distribution, and viscosity, were analyzed. Zeta potential analysis revealed that increasing the degree of quaternary amination reduced the anionic nature of the fibers and confirmed substitution with cationic quaternary ammonium groups. Furthermore, higher degrees of amination resulted in shorter fibers and enhanced intermolecular interactions, leading to increased viscosity. The CNFs were processed into aerogels and evaluated for anion adsorption capacity. Energy-dispersive X-ray spectroscopy (EDS) demonstrated a higher distribution of nitrogen on the CNF surface with increased amination. Filters produced with these CNFs captured more Cl- and Br- ions from 500 ppm solutions, while effectively reducing the charge density of the filtered solutions. These findings demonstrate the potential of functionalized CNFs as sustainable and efficient materials for advanced water filtration systems. The results underscore the importance of tailoring surface functionalization to optimize performance in anion removal, highlighting applications in industrial and municipal wastewater treatment.

Keywords
Cellulose nanofibers (CNFs)
aerogel filter
cationic CNF
water treatment
freeze drying
References
1

Kargarzadeh, H., Mariano, M., Huang, J., Lin, N., Ahmad, I., Dufresne, A., and Thomas, S., Recent developments on nanocellulose reinforced polymer nanocomposites: A review, Polymer 132:368-393 (2017).

10.1016/j.polymer.2017.09.043
2

Aulin, C., Salazar-Alvarez, G., and Lindström, T., High strength, flexible and transparent nanofibrillated cellulose-nanoclay biohybrid films with tunable oxygen and water vapor permeability, Nanoscale 4(20):6622-6628 (2012).

10.1039/c2nr31726e
3

Xie, H., Du, H., Yang, X., and Si, C., Recent strategies in preparation of cellulose nanocrystals and cellulose nanofibrils derived from raw cellulose materials, International Journal of Polymer Science 2018(1):7923068 (2018).

10.1155/2018/7923068
4

Velásquez-Cock, J., Gañán, P., Posada, P., Castro, C., Serpa, A., Putaux, J. L., and Zuluaga, R., Influence of combined mechanical treatments on the morphology and structure of cellulose nanofibrils: Thermal and mechanical properties of the resulting films, Industrial Crops and Products 85:1-10 (2016).

10.1016/j.indcrop.2016.02.036
5

Lichtenstein, K. and Lavoine, N., Toward a deeper understanding of the thermal degradation mechanism of nanocellulose, Polymer Degradation and Stability 146:53-60 (2017).

10.1016/j.polymdegradstab.2017.09.018
6

Iwatake, A., Nogi, M., and Yano, H., Cellulose nanofiber-reinforced polylactic acid, Composites Science and Technology 68(9):2103-2106 (2008).

10.1016/j.compscitech.2008.03.006
7

Eichhorn, S. J., Dufresne, A., Aranguren, M., Marcovich, N. E., Capadona, J. R., Rowan, S. J., Weder, C., Thielemans, W., Roman, M., Renneckar, S., Gindl, W., Veigel, S., Keckes, J., Yano, H., Abe, K., Nogi, M., Nakagito, A. N., Mangalam, A., Simonsen, J., Benight, A. S., Bismarck, A., Berglund, L. A., and Peijs, T., Current international research into cellulose nanofibres and nanocomposites, Journal of Materials Science 45:1-33 (2010).

10.1007/s10853-009-3874-0
8

Barhoum, A., Li, H., Chen, M., Cheng, L., Yang, W., and Dufresne, A., Emerging applications of cellulose nano-fibers, Handbook of Nanofibers, pp.1131-1156 (2019).

10.1007/978-3-319-53655-2_53
9

Barhoum, A., Samyn, P., Öhlund, T., and Dufresne, A., Review of recent research on flexible multifunctional nanopapers, Nanoscale 9(40):15181-15205 (2017).

10.1039/C7NR04656A
10

Qua, E. H., Hornsby, P. R., Sharma, H. S., Lyons, G., and McCall, R. D., Preparation and characterization of poly(vinyl alcohol) nanocomposites made from cellulose nanofibers, Journal of Applied Polymer Science 113(4):2238-2247 (2009).

10.1002/app.30116
11

Missoum, K., Belgacem, M. N., and Bras, J., Nanofibrillated cellulose surface modification: A review, Materials 6(5):1745-1766 (2013).

10.3390/ma605174528809240PMC5452503
12

Nechyporchuk, O., Pignon, F., and Belgacem, M. N., Morphological properties of nanofibrillated cellulose produced using wet grinding as an ultimate fibrillation process, Journal of Materials Science 50:531-541 (2015).

10.1007/s10853-014-8609-1
13

Cervin, N. T., Andersson, L., Ng, J. B. S., Olin, P., Bergström, L., and Wågberg, L., Lightweight and strong cellulose materials made from aqueous foams stabilized by nanofibrillated cellulose, Biomacromolecules 14(2):503-511 (2013).

10.1021/bm301755u
14

Liu, J., Yang, R., Wang, Y., Hua, F., and Tong, S., Cationic cellulose nanofibers with efficient anionic dye adsorption: Adsorption mechanism and application in salt-free dyeing of paper, Cellulose 29(3):2047-2061 (2022).

10.1007/s10570-021-04406-4
15

Rossi, B. R., Pellegrini, V. O., Cortez, A. A., Chiromito, E. M., Carvalho, A. J., Pinto, L. O., Camila, A. R., Valmor, R. M., and Igor, P., Cellulose nanofibers production using a set of recombinant enzymes, Carbohydrate Polymers 256:117510 (2021).

10.1016/j.carbpol.2020.117510
16

Jo, H. M., Lee, J. Y., Kim, S. H., and Lee, Y. H., Effect of nanofibrillated cellulose made from enzyme-pretreated bamboo pulp on paper strength, BioResources 16(1):964-978 (2021).

10.15376/biores.16.1.964-978
17

Moberg, T., Sahlin, K., Yao, K., Geng, S., Westman, G., Zhou, Q., Oksman, K., and Rigdahl, M., Rheological properties of nanocellulose suspensions: Effects of fibril/particle dimensions and surface characteristics, Cellulose 24:2499-2510 (2017).

10.1007/s10570-017-1283-0
18

Balea, A., Merayo, N., De La Fuente, E., Negro, C., and Blanco, Á., Assessing the influence of refining, bleaching and TEMPO-mediated oxidation on the production of more sustainable cellulose nanofibers and their application as paper additives, Industrial Crops and Products 97:374-387 (2017).

10.1016/j.indcrop.2016.12.050
19

Kaffashsaie, E., Yousefi, H., Nishino, T., Matsumoto, T., Mashkour, M., Madhoushi, M., and Kawaguchi, H., Direct conversion of raw wood to TEMPO-oxidized cellulose nanofibers, Carbohydrate Polymers 262:117938 (2021).

10.1016/j.carbpol.2021.117938
20

Serra, A., González, I., Oliver-Ortega, H., Tarrès, Q., Delgado-Aguilar, M., and Mutjé, P., Reducing the amount of catalyst in TEMPO-oxidized cellulose nanofibers: Effect on properties and cost, Polymers 9(11):557 (2017).

10.3390/polym911055730965860PMC6418795
21

Im, W., Rajabi Abhari, A., Youn, H. J., and Lee, H. L., Morphological characteristics of carboxymethylated cellulose nanofibrils: The effect of carboxyl content, Cellulose 25:5781-5789 (2018).

10.1007/s10570-018-1993-y
22

Zahra, A., Gao, S., Park, J. M., and Shin, S. J., Impact of carboxymethylation pretreatment on the rheology of cellulose nanofiber from bleached rice hull, Journal of KAPPI 54(3):63-72 (2022).

10.7584/JKTAPPI.2022.06.54.3.63
23

Isogai, A., Saito, T., and Fukuzumi, H., TEMPO-oxidized cellulose nanofibers, Nanoscale 3(1):71-85 (2011).

10.1039/C0NR00583E
24

Benhamou, K., Dufresne, A., Magnin, A., Mortha, G., and Kaddami, H., Control of size and viscoelastic properties of nanofibrillated cellulose from palm tree by varying the TEMPO-mediated oxidation time, Carbohydrate Polymers 99:74-83 (2014).

10.1016/j.carbpol.2013.08.032
25

Olszewska, A., Eronen, P., Johansson, L. S., Malho, J. M., Ankerfors, M., Lindström, T., ruokolainen, J., Laine, J., and Österberg, M., The behaviour of cationic NanoFibrillar Cellulose in aqueous media, Cellulose 18(5):1213-1226 (2011).

10.1007/s10570-011-9577-0
26

Chaker, A. and Boufi, S., Cationic nanofibrillar cellulose with high antibacterial properties, Carbohydrate Polymers 131:224-232 (2015).

10.1016/j.carbpol.2015.06.003
27

Song, Y., Zhang, J., Gan, W., Zhou, J., and Zhang, L., Flocculation properties and antimicrobial activities of quaternized celluloses synthesized in NaOH/urea aqueous solution, Industrial & Engineering Chemistry Research 49(3):1242-1246 (2010).

10.1021/ie9015057
28

Jia, B., Zhou, J., and Zhang, L., Electrospun nano-fiber mats containing cationic cellulose derivatives and poly(vinyl alcohol) with antibacterial activity, Carbohydrate Research 346(11):1337-1341 (2011).

10.1016/j.carres.2011.04.040
29

Kono, H., Sogame, Y., Purevdorj, U. E., Ogata, M., and Tajima, K., Bacterial cellulose nanofibers modified with quaternary ammonium salts for antimicrobial applications, ACS Applied Nano Materials 6(6):4854-4863 (2023).

10.1021/acsanm.3c00616
30

Saini, S., Falco, Ç. Y., Belgacem, M. N., and Bras, J., Surface cationized cellulose nanofibrils for the production of contact active antimicrobial surfaces, Carbohydrate Polymers 135:239-247 (2016).

10.1016/j.carbpol.2015.09.002
31

Littunen, K., De Castro, J. S., Samoylenko, A., Xu, Q., Quaggin, S., Vainio, S., and Seppälä, J., Synthesis of cationized nanofibrillated cellulose and its antimicrobial properties, European Polymer Journal 75:116-124 (2016).

10.1016/j.eurpolymj.2015.12.008
32

Martins, N. C. T., Freire, C. S. R., Pinto, R. J. B., Fernandes, S. C. M., Pascoal Neto, C. P., Silvestre, A. J. D., Causio, J., Baldi, G., Sadocco, P., and Trindade, T., Electrostatic assembly of Ag nanoparticles onto nanofibrillated cellulose for antibacterial paper products, Cellulose 19:1425-1436 (2012).

10.1007/s10570-012-9713-5
33

Wang, R., Guan, S., Sato, A., Wang, X., Wang, Z., Yang, R., Hsiao, B. S., and Chu, B., Nanofibrous microfiltration membranes capable of removing bacteria, viruses and heavy metal ions, Journal of Membrane Science 446:376-382 (2013).

10.1016/j.memsci.2013.06.020
34

Karim, Z., Claudpierre, S., Grahn, M., Oksman, K., and Mathew, A. P., Nanocellulose based functional membranes for water cleaning: Tailoring of mechanical properties, porosity and metal ion capture, Journal of Membrane Science 514:418-428 (2016).

10.1016/j.memsci.2016.05.018
35

Zhou, Y., Fu, S., Zhang, L., Zhan, H., and Levit, M. V., Use of carboxylated cellulose nanofibrils-filled magnetic chitosan hydrogel beads as adsorbents for Pb(II), Carbohydrate Polymers 101:75-82 (2014).

10.1016/j.carbpol.2013.08.055
36

Singh, K., Arora, J. K., Sinha, T. J. M., and Srivastava, S., Functionalization of nanocrystalline cellulose for decontamination of Cr(III) and Cr(VI) from aqueous system: Computational modeling approach, Clean Technologies and Environmental Policy 16:1179-1191 (2014).

10.1007/s10098-014-0717-8
37

Voisin, H., Bergström, L., Liu, P., and Mathew, A. P., Nanocellulose-based materials for water purification, Nanomaterials 7(3):57 (2017).

10.3390/nano703005728336891PMC5388159
38

Abbott, A. P., Bell, T. J., Handa, S., and Stoddart, B., Cationic functionalisation of cellulose using a choline based ionic liquid analogue, Green Chemistry 8(9):784-786 (2006).

10.1039/b605258d
39

Baouab, M. H. V., Gauthier, R., Gauthier, H., and El Baker Rammah, M., Cationized sawdust as ion exchanger for anionic residual dyes, Journal of Applied Polymer Science 82(1):31-37 (2001).

10.1002/app.1820
40

Im, W., Park, S. Y., Yook, S., Goo, S., Lee, H. L., and Youn, H. J., Cationization of pulp fibers as pretreatment and preparation of cationic cellulose nanofibrils, Journal of Korea TAPPI 52(1):45-54 (2020).

10.7584/JKTAPPI.2020.02.52.1.45
41

Ru, J., Tong, C., Chen, N., Shan, P., Zhao, X., Liu, X. Chen, J., Li, Q., Liu, X., Liu, H., and Zhao, Y., Morphological and property characteristics of surface-quaternized nanofibrillated cellulose derived from bamboo pulp, Cellulose 26:1683-1701 (2019).

10.1007/s10570-018-2146-z
42

Lee, J. Y., Kim, K. M., Kim, S. H., Jo, H. M., and Kim, C. H., Study on the quaternization reaction conditions for cationic cellulose nanofibril, Journal of KAPPI 51(6):144-151 (2019).

10.7584/JKTAPPI.2019.12.51.6.144
43

Long, L. Y., Weng, Y. X., and Wang, Y. Z., Cellulose aerogels: Synthesis, applications, and prospects, Polymers 10(6):623 (2018).

10.3390/polym1006062330966656PMC6403747
44

Mendoza, D. J., Hossain, L., Browne, C., Raghuwanshi, V. S., Simon, G. P., and Garnier, G., Controlling the transparency and rheology of nanocellulose gels with the extent of carboxylation, Carbohydrate Polymers 245:116566 (2020).

10.1016/j.carbpol.2020.116566
45

Curvello, R., Mendoza, L., McLiesh, H., Manolios, J., Tabor, R. F., and Garnier, G., Nanocellulose hydrogel for blood typing tests, ACS Applied Bio Materials 2(6):2355-2364 (2019).

10.1021/acsabm.9b00080
46

Pääkkö, M., Ankerfors, M., Kosonen, H., Nykänen, A., Ahola, S., Österberg, M., Ruokolainen, J., Laine, J., Larsson, P. T., Ikkala, O., and Lindström, T., Enzymatic hydrolysis combined with mechanical shearing and high-pressure homogenization for nanoscale cellulose fibrils and strong gels, Biomacromolecules 8(6):1934-1941 (2007).

10.1021/bm061215p
47

Lee, S. H., Jo, H. M., Kim, D. H., Lee, J. Y., Han, J. H., and Yun, K. Y., Evaluation of the physical properties of carboxymethylated cellulose nanofiber derived from red algae pulp, Journal of Korea TAPPI 54(4):25-33 (2022).

10.7584/JKTAPPI.2022.08.54.4.25
48

Li, V. C., Mulyadi, A., Dunn, C. K., Deng, Y., and Qi, H. J., Direct ink write 3D printed cellulose nanofiber aerogel structures with highly deformable, shape recoverable, and functionalizable properties, ACS Sustainable Chemistry & Engineering 6(2):2011-2022 (2018).

10.1021/acssuschemeng.7b03439
49

Pei, A., Butchosa, N., Berglund, L. A., and Zhou, Q., Surface quaternized cellulose nanofibrils with high water absorbency and adsorption capacity for anionic dyes, Soft Matter 9(6):2047-2055 (2013).

10.1039/c2sm27344f
50

Lee, J. Y., Kim, E. H., Park, T. U., Jo, H. M., Kim, C. H., and Jeun, J. P., Development of metal ion absorbing filter using cellulose nanofibrils, Journal of Korea TAPPI 49(3):95-101 (2017).

10.7584/JKTAPPI.2017.06.49.3.95
51

Mo, L., Pang, H., Tan, Y., Zhang, S., and Li, J., 3D multi-wall perforated nanocellulose-based polyethylenimine aerogels for ultrahigh efficient and reversible removal of Cu(II) ions from water, Chemical Engineering Journal 378:122157 (2019).

10.1016/j.cej.2019.122157
52

Mautner, A., Kwaw, Y., Weiland, K., Mvubu, M., Botha, A., John, M. J., Matibe, A., Siqurira, G., and Bismarck, A., Natural fibre-nanocellulose composite filters for the removal of heavy metal ions from water, Industrial Crops and Products 133:325-332 (2019).

10.1016/j.indcrop.2019.03.032
Information
  • Publisher :Korea Technical Association of The Pulp and Paper Industry
  • Publisher(Ko) :한국펄프종이공학회
  • Journal Title :Journal of Korea TAPPI
  • Journal Title(Ko) :펄프종이기술
  • Volume : 57
  • No :4
  • Pages :43-53
  • Received Date : 2025-06-12
  • Revised Date : 2025-07-28
  • Accepted Date : 2025-08-03
  • DOI :https://doi.org/10.7584/JKTAPPI.2025.8.57.4.43
Journal Informaiton Journal of Korea TAPPI Journal of Korea TAPPI
Online Submission
  • scopus
  • NRF
  • KOFST
  • crossref crossmark
  • crossref cited-by
  • crosscheck
  • orcid
Journal Informaiton Journal Informaiton - close