To Henri Chanzy, cellulose Master.
Abstract
Aerogels are lightweight open-pore nanostructured materials with high specific surface area. Till now, to obtain cellulose II aerogels, drying with supercritical CO2 was applied to preserve network morphology during drying and keep porosity open. In this work, we demonstrate that if dissolving cellulose in aqueous NaOH (with or without additive ZnO) and coagulating in ethanol and drying by evaporation in low vacuum from ethanol, cellulose II aerogel-like materials are obtained. In other words, hornification due to drying was avoided. No cellulose chemical modification or crosslinking was performed. Cellulose monoliths (after gelation of solutions) and beads (no gelation) with density 0.15–0.25 g/cm3 and specific surface area up to 250 m2/g were obtained avoiding using high-pressure (drying in supercritical conditions) or low-pressure (freeze-drying) technology. This discovery opens a new way of making meso- and small macroporous cellulose materials. In order to explore this phenomenon, various process parameters were tested. Other than ethanol cellulose non-solvents were probed, such as water, HCl, acetone and isopropanol. The influence of ZnO concentration and aging time of cellulose/NaOH/water gels on dry material properties was investigated. It was demonstrated that gelation step is not required to obtain aerogel-like cellulose as beads were made by dropping non-gelled cellulose/NaOH/water solution in ethanol. The hypotheses on the absence pores’ collapse during evaporative drying were suggested.
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References
Aegerter MA, Leventis N, Koebel M, Steiner IIISA (2023) Handbook of aerogels. In series Springer handbooks. Springer Nature, Switzerland (ISBN: 978-3-030-27321-7)
Aiello A, Cosby T, McFarland J, Durkin DP, Trulove PC (2022) Mesoporous xerogel cellulose composites from biorenewable natural cotton fibers. Carbohydr Polym 282:119040. https://doi.org/10.1016/j.carbpol.2021.119040
Ayadi F, Tourrette A (2015) Procédé de préparation d’un matériau poreux a base de cellulose, matériaux obtenus et utilisations. Patent FR 3 042 503 - A1
Borisova A, De Bruyn M, Budarin VL, Shuttleworth PS, Dodson Mateus JR, Segatto L, Clark JH (2015) A sustainable freeze-drying route to porous polysaccharides with tailored hierarchical meso- and macroporosity. Macromol Rapid Commun 36:774–779. https://doi.org/10.1002/marc.201400680
Buchtova N, Budtova T (2016) Cellulose aero-, cryo- and xerogels: towards understanding of morphology control. Cellulose 23:2585–2595. https://doi.org/10.1007/s10570-016-0960-8
Budtova T (2019) Cellulose II aerogels: a review. Cellulose 26:81–121. https://doi.org/10.1007/s10570-018-2189-1
Budtova T, Navard P (2016) Cellulose in NaOH–water based solvents: a review. Cellulose 23:5–55. https://doi.org/10.1007/s10570-015-0779-8
Ciolacu D, Ciolacu F, Popa VI (2011) Amorphous cellulose - Structure and characterization. Cell Chem Technol 45:13–21
Druel L (2019) Cellulose based aerogels: properties and shaping as beads. PhD thesis, Mines Paris, defended 10 May 2019. https://pastel.archives-ouvertes.fr/tel-02434794v1/document
Druel L, Budtova T (2019) Procedé de fabrication d’aerocellulose. FR3094009A1
Druel L, Niemeyer P, Milow M, Budtova T (2018) Rheology of cellulose-[DBNH][CO2Et] solutions and shaping into aerogel beads. Green Chem 20:3993. https://doi.org/10.1039/c8gc01189c
Druel L, Kenkel A, Baudron V, Buwalda S, Budtova T (2020) Cellulose aerogel microparticles via emulsion-coagulation technique. Biomacromolecules 21:1824–1831. https://doi.org/10.1021/acs.biomac.9b01725
Franchimont APN (1910) On sodium-alkyl carbonates. KNAW Proc 12:303–304
Gomollón-Bel F (2022) IUPAC top ten emerging technologies in chemistry. Chem Int 44:4–13. https://doi.org/10.1515/ci-2022-0402
Groult S, Budtova T (2018) Tuning structure and properties of pectin aerogels. Eur Polym J 108:250–261. https://doi.org/10.1016/j.eurpolymj.2018.08.048
Guerrero-Alburquerque N, Zhao S, Adilien N, Koebel MM, Lattuada M, Malfait MJ (2020) Strong, machinable, and insulating chitosan–urea aerogels: toward ambient pressure drying of biopolymer aerogel monoliths. ACS Appl Mater Interfaces 12:2037–22049. https://doi.org/10.1021/acsami.0c03047
Gunnarsson M, Theliander H, Hasani M (2017) Chemisorption of air CO2 on cellulose: an overlooked feature of the cellulose/NaOH(aq) dissolution system. Cellulose 24:2427–2436. https://doi.org/10.1007/s10570-017-1288-8
Gunnarsson M, Bernin D, Östlund A, Hasani M (2018) The CO2 capturing ability of cellulose dissolved in NaOH(aq) at low temperature. Green Chem 20:3279–3286. https://doi.org/10.1039/c8gc01092g
Gunnarsson M, Bernin D, Hasani M (2021) On the interference of urea with CO2/CO32 chemistry of cellulose model solutions in NaOH(aq). Carbohydr Polym 251:117059. https://doi.org/10.1016/j.carbpol.2020.117059
Isobe N, Kim U-J, Kimura S, Wada M, Kuga S (2011) Internal surface polarity of regenerated cellulose gel depends on the species used as coagulant. J Colloid Interface Sci 359(1):194–201
Jimenez-Saelices C, Seantier B, Cathala B (2017) Grohens Y spray freeze-dried nanofibrillated cellulose aerogels with thermal superinsulating properties. Carbohydr Polym 157:105–113. https://doi.org/10.1016/j.carbpol.2016.09.068
Liu Y, Piron DL (1998) Study of tin cementation in alkaline solution. J Electrochem Soc 145:186–190. https://doi.org/10.1149/1.1838233
Liu W, Budtova T, Navard P (2011) Influence of ZnO on the properties of dilute and semi-dilute cellulose–NaOH–water solutions. Cellulose 18:911–920. https://doi.org/10.1007/s10570-011-9552-9
Malakooti S, Qin G, Mandal C, Soni R, Taghvaee T, Tsao N, Shiao J, Kulkarni SS, Sotiriou-Leventis C, Leventis N, Lu H, Malakooti S (2019) Low-cost, ambient-dried, superhydrophobic, high strength, thermally insulating, and thermally resilient polybenzoxazine aerogels. ACS Appl Polym Mater 1:2322–2333. https://doi.org/10.1021/acsapm.9b00408
Negrier M, El Ahmar E, Sescousse R, Sauceau M, Budtova T (2023) Upcycling of textile waste into high added value cellulose porous materials, aerogels and cryogels. RSC Sustain. https://doi.org/10.1039/d2su00084a
O’Neil MJ (ed) (2006) The Merck index: an encyclopedia of chemicals, drugs, and biologicals. Merck and Co., Inc, Whitehouse Station, p 1485
Pour G, Beauger C, Rigacci A, Budtova T (2015) Xerocellulose: lightweight, porous and hydrophobic cellulose prepared via ambient drying. J Mater Sci 50:4526–4535. https://doi.org/10.1007/s10853-015-9002-4
Roy C, Budtova T, Navard P (2003) Rheological properties and gelation of aqueous cellulose-NaOH solutions. Biomacromolecules 4:259–264. https://doi.org/10.1021/bm020100s
Schwertfeger F, Frank D, Schmidt M (1998) Hydrophobic waterglass based aerogels without solvent exchange or supercritical drying. J Non-Cryst Solids 225:24. https://doi.org/10.1016/S0022-3093(98)00102-1
Sehaqui H, Zhou Q, Ikkala O, Berglund LA (2011) Strong and tough cellulose nanopaper with high specific surface area and porosity. Biomacromolecules 12:3638–3644
Sehaqui H, Zimmermann T, Tingaut P (2014) Hydrophobic cellulose nanopaper through a mild esterification procedure. Cellulose 21:367–382. https://doi.org/10.1007/s10570-013-0110-5
Sescousse R, Gavillon R, Budtova T (2011) Aerocellulose from cellulose–ionic liquid solutions: preparation, properties and comparison with cellulose–NaOH and cellulose–NMMO routes. Carbohydr Polym 83(4):1766–1774. https://doi.org/10.1016/j.carbpol.2010.10.043
Smith DM, Deshpande R, Brinke CJ (1992) Preparation of low-density aerogels at ambient pressure. MRS Symp Proc 271:567–572. https://doi.org/10.1557/PROC-271-567
Svensson A, Larsson PT, Salazar-Alvarez G, Wågberg L (2013) Preparation of dry ultra-porous cellulosic fibres: characterization and possible initial uses. Carbohydr Polym 92:775–783
Yamasaki S, Sakuma W, Yasui H, DaichoK Saito T, Fujisawa S, Isogai A, Kanamori K (2019) Nanocellulose xerogels with high porosities and large specific surface areas. Front Chem 7:316. https://doi.org/10.3389/fchem.2019.00316
Zou F, Budtova T (2023) Starch alcogels, aerogels, and aerogel-like xerogels: adsorption and release of theophylline. ACS Sustain Chem Eng 11:5617–5625. https://doi.org/10.1021/acssuschemeng.2c07762
Acknowledgments
This project has received funding from the European Union’s Horizon 2020 research and innovation program under grant agreement no. 685648. We are grateful to Nestlé for the determination of metal content, to Pierre Ilbizian (PERSEE, Mines Paris) for supercritical drying and to Suzanne Jacomet (CEMEF, Mines Paris) for guidance in SEM imaging.
Funding
This project has received funding from the European Union’s Horizon 2020 research and innovation program under grant agreement no. 685648.
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All authors contributed to the study conception and design. Material preparation, data collection and analysis were performed by LD; project management and results analysis was done by TB. The first draft of the manuscript was written by LD as a chapter of her PhD thesis; article version was written by TB. All authors read and approved the final manuscript.
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Druel, L., Budtova, T. Aerogel-like (low density and high surface area) cellulose monoliths and beads obtained without supercritical- or freeze-drying. Cellulose 30, 8339–8353 (2023). https://doi.org/10.1007/s10570-023-05349-8
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DOI: https://doi.org/10.1007/s10570-023-05349-8