Abstract
Cellulose-based materials, such as cellulose microspheres, have attracted enormous attention because of their widespread applications in water and protein purifications, chromatographic stationary phase, biocatalyst, drug delivery, electrode materials, etc. Here, homogenous and spherical porous regenerated cellulose microstructures (RCMSs) obtained from the agglomeration of micro/nanospheres were fabricated via a simple emulsion–coagulation–oven-drying process in pulp cellulose–tetraethylammonium hydroxide (TEAOH)/urea/H2O solution, and the formation mechanism of the RCMSs was investigated by controlling the synthesis time. The results revealed that the uniform micro/nanospheres with a narrow size distribution of 600 nm–6 μm were first synthesized, followed by the formation of the RCMSs via the continuous agglomeration of the micro/nanospheres with the increasing synthesis time. Additionally, the RCMSs exhibiting micro/nanoscale pores with an adjustable mean diameter (r) of 280–103 μm were readily prepared by controlling the stirring speed between 300 and 1200 rpm. The re-wetted RCMSs exhibited a swelling ratio (SR) of 690–1400%, indicating their excellent swelling performance. Furthermore, the RCMSs with the structure of cellulose II exhibited good physical properties, including high porosity (Pr, 90–93%), pore volume (Vp, 7.0–10.3 cm3/g), specific surface area (S, 40–70 m2/g), and chemical/thermal stabilities. These findings can contribute to the design and exploitation of highly functional cellulose-based materials exhibiting micro/nanostructures.






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References
Abe M, Fukaya Y, Ohno H (2012) Fast and facile dissolution of cellulose with tetrabutylphosphonium hydroxide containing 40 wt% water. Chem Commun 48:1808–1810. https://doi.org/10.1039/c2cc16203b
Álvarez A, Cachero S, González-Sánchez C, Montejo-Bernardo J, Pizarro C, Bueno JL (2018) Novel method for holocellulose analysis of non-woody biomass wastes. Carbohydr Polym 189:250–256. https://doi.org/10.1016/j.carbpol.2018.02.043
Azubuike CP, Rodríguez H, Okhamafe AO, Rogers RD (2012) Physicochemical properties of maize cob cellulose powders reconstituted from ionic liquid solution. Cellulose 19:425–433. https://doi.org/10.1007/s10570-011-9631-y
Buchtová N, Pradille C, Bouvard JL, Budtova T (2019) Mechanical properties of cellulose aerogels and cryogels. Soft Matter 15:7901–7908. https://doi.org/10.1039/c9sm01028a
Capek I (2004) Preparation of metal nanoparticles in water-in-oil (w/o) microemulsions. Adv Colloid Interfac 110:49–74. https://doi.org/10.1016/j.cis.2004.02.003
Druel L, Kenkel A, Baudron V, Buwalda S, Budtova T (2020) Cellulose aerogel microparticles via emulsion-coagulation technique. Biomacromol 21:1824–1831. https://doi.org/10.1021/acs.biomac.9b01725
French AD (2014) Idealized powder diffraction patterns for cellulose polymorphs. Cellulose 21:885–896. https://doi.org/10.1007/s10570-013-0030-4
Gericke M, Trygg J, Fardim P (2013) Functional cellulose beads: preparation, characterization, and applications. Chem Rev 113:4812–4836. https://doi.org/10.1021/cr300242j
Graham D (1955) Characterization of physical adsorption systems. III. The separate effects of pore size and surface acidity upon the adsorbent capacities of activated carbons. J Phys Chem 59:896–900. https://doi.org/10.1021/j150531a022
Gregg SJ, Sing KSW (1982) The physical adsorption of gases by microporous solids: the type II isotherm. In adsorption, surface area and porosity. Academic Press, London, pp 41–110
He M, Cho BU, Won JM (2016) Effect of precipitated calcium carbonate–cellulose nanofibrils composite filler on paper properties. Carbohydr Polym 136:820–825. https://doi.org/10.1016/j.carbpol.2015.09.069
He M, Yang G, Cho BU, Lee YK, Won JM (2017) Effects of addition method and fibrillation degree of cellulose nanofibrils on furnish drainability and paper properties. Cellulose 24:5657–5669. https://doi.org/10.1007/s10570-017-1495-3
Hua J, Meng R, Wang T, Gao H, Luo Z, Jin Y, Liu L, Yao J (2019) Highly porous cellulose microbeads and their Adsorption for methylene blue. Fibers Polym 20:794–803. https://doi.org/10.1007/s12221-019-8334-0
Idström A, Gentile L, Gubitosi M, Olsson C, Stenqvist B, Lund M, Bergquist KE, Olsson U, Köhnke T, Bialik E (2017) On the dissolution of cellulose in tetrabutylammonium acetate/dimethyl sulfoxide: a frustrated solvent. Cellulose 24:3645–3657. https://doi.org/10.1007/s10570-017-1370-2
Kaewprasit C, Hequet EF, Abidi N, Gourlot JP (1998) Application of methylene blue adsorption to cotton fiber specific surface area measurement: part I. methodology. J Cot Sci 2:164–173
Kane IA, Clare MA, Miramontes E, Wogelius R, Rothwell JJ, Garreau P, Pohl F (2020) Seafloor microplastic hotspots controlled by deep-sea circulation. Science 368:1140–1145. https://doi.org/10.1126/science.aba5899
Lau BBY, Luis ET, Hossain MM, Hart WES, Cencia-Lay B, Black JJ, To TQ, Aldous L (2015) Facile, room-temperature pre-treatment of rice husks with tetrabutylphosphonium hydroxide: enhanced enzymatic and acid hydrolysis yields. Bioresour Technol 197:252–259. https://doi.org/10.1016/j.biortech.2015.08.056
Li R, Wang S, Lu A, Zhang L (2015) Dissolution of cellulose from different sources in an NaOH/urea aqueous system at low temperature. Cellulose 22:339–349. https://doi.org/10.1007/s10570-014-0542-6
Li W, Luo X, Song R, Zhu Y, Li B, Liu S (2016) Porous cellulose microgel particle: a fascinating host for the encapsulation, protection, and delivery of lactobacillus plantarum. J Agric Food Chem 64:3430–3436. https://doi.org/10.1021/acs.jafc.6b00481
Luo X, Zhang L (2010) Creation of regenerated cellulose microspheres with diameter ranging from micron to millimeter for chromatography applications. J Chromatogr A 1217:5922–5929. https://doi.org/10.1016/j.chroma.2010.07.026
Luo X, Yuan J, Liu Y, Liu C, Zhu X, Dai X, Ma Z, Wang F (2017) Improved solid-phase synthesis of the phosphorylated cellulose microsphere adsorbents for highly effective Pb2+ removal from water: the batch and fixed-bed column performance and the adsorption mechanism. ACS Sustain Chem Eng 5:5108–5117. https://doi.org/10.1021/acssuschemeng.7b00472
Macarthur DE (2017) Beyond plastic waste. Science 358:843. https://doi.org/10.1126/science.aao6749
Malik MA, Wani MY, Hashim MA (2012) Microemulsion method: A novel route to synthesize organic and inorganic nanomaterials. Arab J Chem 5:397–417. https://doi.org/10.1016/j.arabjc.2010.09.027
Peng F, Ren JL, Xu F, Bian J, Peng P, Sun RC (2009) Comparative study of hemicelluloses obtained by graded ethanol precipitation from sugarcane bagasse. J Agric Food Chem 57:6305–6317. https://doi.org/10.1021/jf900986b
Sayyed AJ, Deshmukh NA, Pinjari DV (2019) A critical review of manufacturing processes used in regenerated cellulosic fibres: viscose, cellulose acetate, cuprammonium, LiCl/DMAc, ionic liquids, and NMMO based lyocell. Cellulose 26:2913–2940. https://doi.org/10.1007/s10570-019-02318-y
Segal L, Creely JJ, Martin AE Jr, 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. https://doi.org/10.1177/004051755902901003
Singh N, Prasad K (2019) Multi-tasking hydrated ionic liquids as sustainable media for the processing of waste human hair: a biorefinery approach. Green Chem 21:3328–3333. https://doi.org/10.1039/c9gc00542k
Sirviö JA, Heiskanen JP (2020) Room-temperature dissolution and chemical modification of cellulose in aqueous tetraethylammonium hydroxide–carbamide solutions. Cellulose 27:1933–1950. https://doi.org/10.1007/s10570-019-02907-x
Sixta H, Michud A, Hauru L, Asaadi S, Ma Y, King AWT, Kilpeläinen I, Hummel M (2015) Ioncell-F: a high-strength regenerated cellulose fibre. Nord Pulp Pap Res J 30:43–57. https://doi.org/10.3183/npprj-2015-30-01-p043-057
Swatloski RP, Spear SK, Hobrey JD, Rogers RD (2002) Dissolution of cellulose with ionic liquids. J Am Chem Soc 124:4974–4975. https://doi.org/10.1021/ja025790m
Tang X, Liu G, Zhang H, Gao X, Li M, Zhang S (2021) Facile preparation of all-cellulose composites from softwood, hardwood, and agricultural straw cellulose by a simple route of partial dissolution. Carbohydr Polym 256:117591. https://doi.org/10.1016/j.carbpol.2020.117591
TAPPI (2009) TAPPI-T-203-cm-09. Alpha, beta- and gamma-cellulose in pulp.
TAPPI (2012) TAPPI-T-212-om-12. One percent sodium hydroxide solubility of wood and pulp.
TAPPI (2012) TAPPI-T-211-om-12. Ash in wood, pulp, paper and paperboard: combustion at 525°C.
TAPPI (2015) TAPPI-T-222-om-15. Acid-insoluble lignin in wood and pulp.
Tu H, Zhu M, Duan B, Zhang L (2020) Recent progress in high-strength and robust regenerated cellulose materials. Adv Mater 33:2000682. https://doi.org/10.1002/adma.202000682
Wang Y, Liu L, Chen P, Zhang L, Lu A (2018) Cationic hydrophobicity promotes dissolution of cellulose in aqueous basic solution by freezing-thawing. Phys Chem Chem Phys 20:14223–14233. https://doi.org/10.1039/c8cp01268g
Wei W, Meng F, Cui Y, Jiang M, Zhou Z (2017) Room temperature dissolution of cellulose in tetra-butylammonium hydroxide aqueous solvent through adjustment of solvent amphiphilicity. Cellulose 24:49–59. https://doi.org/10.1007/s10570-016-1113-9
Wernersson E, Stenqvist B, Lund M (2015) The mechanism of cellulose solubilization by urea studied by molecular simulation. Cellulose 22:991–1001. https://doi.org/10.1007/s10570-015-0548-8
Wu S, Gong Y, Liu S, Pei Y, Luo X (2021) Functionalized phosphorylated cellulose microspheres: design, characterization and ciprofloxacin loading and releasing properties. Carbohydr Polym 254:117421. https://doi.org/10.1016/j.carbpol.2020.117421
Xiang X, Guo L, Wu X, Ma X, Xia Y (2012) Urea formation from carbon dioxide and ammonia at atmospheric pressure. Environ Chem Lett 10:295–300. https://doi.org/10.1007/s10311-012-0366-2
Xie L, Li X, Deng J, Gong Y, Wang H, Mao S, Wang Y (2018) Sustainable and scalable synthesis of monodisperse carbon nanospheres and their derived superstructures. Green Chem 20:4596–4601. https://doi.org/10.1039/c8gc02196a
Xie J, Xu J, Cheng Z, Chen J, Zhang Z, Chen T, Yang R, Sheng J (2020) Facile synthesis of fluorine-free cellulosic paper with excellent oil and grease resistance. Cellulose 27:7009–7022. https://doi.org/10.1007/s10570-020-03248-w
Xu D, Chen C, Xie J, Zhang B, Miao L, Cai J, Huang Y, Zhang L (2016) A hierarchical N/S-codoped carbon anode fabricated facilely from cellulose/polyaniline microspheres for high-performance sodium-ion batteries. Adv Energy Mater 6:1501929. https://doi.org/10.1002/aenm.201501929
Ye D, Lei X, Li T, Cheng Q, Chang C, Hu L, Zhang L (2019) Ultrahigh tough, super clear, and highly anisotropic nanofiber-structured regenerated cellulose films. ACS Nano 13:4843–4853. https://doi.org/10.1021/acsnano.9b02081
Yoo MK, Reza MS, Kim IM, Kim KJ (2015) Physical properties and fibrillation tendency of regenerated cellulose fiber dry jet-wet spun from high-molecular weight cotton linter Pulp/NMMO solution. Fiber Polym 16:1618–1628. https://doi.org/10.1007/s12221-015-5313-y
Zambrano F, Wang Y, Zwilling JD, Venditti R, Jameel H, Rojas O, Gonzalez R (2021) Micro- and nanofibrillated cellulose from virgin and recycled fibers: a comparative study of its effects on the properties of hygiene tissue paper. Carbohydr Polym 254:117430. https://doi.org/10.1016/j.carbpol.2020.117430
Zhang L, Zhou J, Yang G, Chen J (1998) Preparative fractionation of polysaccharides by columns packed with regenerated cellulose gels. J Chromatogr A 816:131–136. https://doi.org/10.1016/S0021-9673(98)00475-0
Zhang X, Liu X, Zheng W, Zhu J (2012) Regenerated cellulose/graphene nanocomposite films prepared in DMAC/LiCl solution. Carbohydr Polym 88:26–30. https://doi.org/10.1016/j.carbpol.2011.11.054
Zhang J, Wang M, Li W, Wei W, Li J, Jiang M, Wang Y, Zhou Z (2019) TBAH/urea/H2O solvent for room temperature wet-spinning of cellulose and optimization of drawing process. Cellulose 26:6959–6977. https://doi.org/10.1007/s10570-019-02536-4
Zheng C, Zheng H, Hu C, Wang Y, Wang Y, Zhao C, Ding W, Sun Q (2019) Structural design of magnetic biosorbents for the removal of ciprofloxacin from water. Bioresour Technol 296:122288. https://doi.org/10.1016/j.biortech.2019.122288
Zhong C, Cheng F, Zhu Y, Gao Z, Jia H, Wei P (2017) Dissolution mechanism of cellulose in quaternary ammonium hydroxide: Revisiting through molecular interactions. Carbohydr Polym 174:400–408. https://doi.org/10.1016/j.carbpol.2017.06.078
Zhu Y, Romain C, Williams CK (2016) Sustainable polymers from renewable resources. Nature 540:354–362. https://doi.org/10.1038/nature21001
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This research is financially supported by Basic Science Research Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Education (NRF-2019R1A2C2009284).
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Xu, F., Cho, BU. Preparation of porous regenerated cellulose microstructures via emulsion-coagulation technique. Cellulose 29, 1527–1542 (2022). https://doi.org/10.1007/s10570-022-04428-6
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DOI: https://doi.org/10.1007/s10570-022-04428-6


