Abstract
In this work, we report one-pot synthesis of free standing and porous hybrid cross-linked aerogels based on cellulose nanocrystals (CNCs) and polysilsesquioxane (PSS). The synthesis of the aerogel was carried out in two steps. The first was CNC surface modification, using a 3-isocyanatopropyltriethoxysilane, and the second, a sol–gel process, resulting in the formation of a PSS network which cross-linked with the nanoparticles. 29Si solid state NMR analysis revealed that this network was mostly made up of linear and three-dimensional PSS domains. Aerogels showed shape stability and high porosity (> 89%). The presence of macro and mesopores was confirmed by SEM and BET analyses, respectively, and the presence of the PSS network domains in the pore walls was characterized by TEM. In addition, these CNC/PSS aerogels were omniphilic, absorbing approximately the same amount of both water and toluene. These characteristics make these aerogels interesting material to be used as absorbents for a wide variety of spills.
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Abraham E, Weber DE, Sharon S et al (2017) Multifunctional cellulosic scaffolds from modified cellulose nanocrystals. ACS Appl Mater Interfaces 9:2010–2015. https://doi.org/10.1021/acsami.6b13528
Agustin MB, Ahmmad B, Alonzo SMM, Patriana FM (2014) Bioplastic based on starch and cellulose nanocrystals from rice straw. J Reinf Plast Compos 33:2205–2213. https://doi.org/10.1177/0731684414558325
Aulin C, Netrval J, Wågberg L, Lindström T (2010) Aerogels from nanofibrillated cellulose with tunable oleophobicity. Soft Matter 6:3298. https://doi.org/10.1039/c001939a
Brandão LR, Yoshida IVP, Felisberti MI, Gonçalves MDC (2013) Preparation and characterization of cellulose acetate/polysiloxane composites. Cellulose 20:2791–2802. https://doi.org/10.1007/s10570-013-0039-8
Brinker CJ (1988) Hydrolysis and condensation of silicates: effects on structure. J Non Cryst Solids 100:31–50. https://doi.org/10.1016/0022-3093(88)90005-1
Cai J, Liu S, Feng J et al (2012) Cellulose-silica nanocomposite aerogels by in situ formation of silica in cellulose gel. Angew Chem Int Ed 51:2076–2079. https://doi.org/10.1002/anie.201105730
Chatterjee S, Sen Gupta S, Kumaraswamy G (2016) Omniphilic polymeric sponges by ice templating. Chem Mater 28:1823–1831. https://doi.org/10.1021/acs.chemmater.5b04988
Chu G, Qu D, Zussman E, Xu Y (2017) Ice-assisted assembly of liquid crystalline cellulose nanocrystals for preparing anisotropic aerogels with ordered structures. Chem Mater 29:3980–3988. https://doi.org/10.1021/acs.chemmater.7b00361
Cunha AG, Freire CSR, Silvestre AJD et al (2010) Preparation and characterization of novel highly omniphobic cellulose fibers organic–inorganic hybrid materials. Carbohydr Polym 80:1048–1056. https://doi.org/10.1016/j.carbpol.2010.01.023
Dai D, Fan M (2011) Investigation of the dislocation of natural fibres by Fourier-transform infrared spectroscopy. Vib Spectrosc 55:300–306. https://doi.org/10.1016/j.vibspec.2010.12.009
De France KJ, Hoare T, Cranston ED (2017) Review of hydrogels and aerogels containing nanocellulose. Chem Mater. https://doi.org/10.1021/acs.chemmater.7b00531
de Junior ARO, Yoshida IVP, Ferrarezi MMF, do Gonçalves MDC (2012) Cellulose acetate/polysilsesquioxane composites: thermal properties and morphological characterization by electron spectroscopy imaging. J Appl Polym Sci 123:2027–2035. https://doi.org/10.1002/app34707
de Oliveira Taipina M, Ferrarezi MMF, Yoshida IVP, Gonçalves MDC (2013) Surface modification of cotton nanocrystals with a silane agent. Cellulose 20:217–226. https://doi.org/10.1007/s10570-012-9820-3
Eyley S, Thielemans W (2014) Surface modification of cellulose nanocrystals. Nanoscale 6:7764–7779. https://doi.org/10.1039/c4nr01756k
French AD (2014) Idealized powder diffraction patterns for cellulose polymorphs. Cellulose 21:885–896. https://doi.org/10.1007/s10570-013-0030-4
Gaspar D, Fernandes SN, de Oliveira AG et al (2014) Nanocrystalline cellulose applied simultaneously as the gate dielectric and the substrate in flexible field effect transistors. Nanotechnology 25:094008. https://doi.org/10.1088/0957-4484/25/9/094008
Heath L, Thielemans W (2010) Cellulose nanowhisker aerogels. Green Chem 12:1448. https://doi.org/10.1039/c0gc00035c
Hebeish A, Farag S, Sharaf S, Shaheen TI (2014) Thermal responsive hydrogels based on semi interpenetrating network of poly(NIPAm) and cellulose nanowhiskers. Carbohydr Polym 102:159–166. https://doi.org/10.1016/j.carbpol.2013.10.054
Jiang F, Hsieh Y-L (2014) Amphiphilic superabsorbent cellulose nanofibril aerogels. J Mater Chem C 2:6337–6342. https://doi.org/10.1039/c4ta00743c
Khanjanzadeh H, Behrooz R, Bahramifar N et al (2017) Surface chemical functionalization of cellulose nanocrystals by 3-aminopropyltriethoxysilane. Int J Biol Macromol. https://doi.org/10.1016/j.ijbiomac.2017.08.136
Kumaraswamy G, Chatterjee S, Sen Gupta S (2017) Macroporous omniphilic sponges. Patent number: US2017145179
Liao C, Zhao J, Yu P et al (2012) Synthesis and characterization of low content of different SiO2 materials composite poly (vinylidene fluoride) ultrafiltration membranes. Desalination 285:117–122. https://doi.org/10.1016/j.desal.2011.09.042
Lin N, Dufresne A (2014) Surface chemistry, morphological analysis and properties of cellulose nanocrystals with gradiented sulfation degrees. Nanoscale 6:5384–5393. https://doi.org/10.1039/c3nr06761k
Ly B, Thielemans W, Dufresne A et al (2008) Surface functionalization of cellulose fibres and their incorporation in renewable polymeric matrices. Compos Sci Technol 68:3193–3201. https://doi.org/10.1016/j.compscitech.2008.07.018
Madhusudana Rao K, Kumar A, Han SS (2017) Polysaccharide based bionanocomposite hydrogels reinforced with cellulose nanocrystals: drug release and biocompatibility analyses. Int J Biol Macromol 101:165–171. https://doi.org/10.1016/j.ijbiomac.2017.03.080
Mohammed N, Grishkewich N, Berry RM, Tam KC (2015) Cellulose nanocrystal–alginate hydrogel beads as novel adsorbents for organic dyes in aqueous solutions. Cellulose 22:3725–3738. https://doi.org/10.1007/s10570-015-0747-3
Oudiani E, Chaabouni Y, Msahli S, Sakli F (2011) Crystal transition from cellulose I to cellulose II in NaOH treated Agave americana L. fibre. Carbohydr Polym 86:1221–1229. https://doi.org/10.1016/j.carbpol.2011.06.037
Peng Y, Gardner DJ, Han Y et al (2013) Influence of drying method on the material properties of nanocellulose I: thermostability and crystallinity. Cellulose 20:2379–2392. https://doi.org/10.1007/s10570-013-0019-z
Prasad V, Kumar N, Mishra PR (2007) Amphiphilic gels as a potential carrier for topical drug delivery. Drug Deliv 14:75–85. https://doi.org/10.1080/10717540600642431
Reid MS, Villalobos M, Cranston ED (2017) Benchmarking cellulose nanocrystals: from the laboratory to industrial production. Langmuir 33:1583–1598. https://doi.org/10.1021/acs.langmuir.6b03765
Salon MCB, Gerbaud G, Abdelmouleh M et al (2007) Studies of interactions between silane coupling agents and cellulose fibers with liquid and solid-state NMR. Magn Reson Chem 45:473–483. https://doi.org/10.1002/mrc.1994
Segal L, Creely JJ, Martin A, 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
Thakur MK, Gupta RK, Thakur VK (2014) Surface modification of cellulose using silane coupling agent. Carbohydr Polym. https://doi.org/10.1016/j.carbpol.2014.05.041
Visanko M, Liimatainen H, Sirviö JA et al (2014) Amphiphilic cellulose nanocrystals from acid-free oxidative treatment: physicochemical characteristics and use as an oil–water stabilizer. Biomacromolecules 15:2769–2775. https://doi.org/10.1021/bm500628g
Wang G, He Y, Wang H et al (2015a) A cellulose sponge with robust superhydrophilicity and under-water superoleophobicity for highly effective oil/water separation. Green Chem 17:3093–3099. https://doi.org/10.1039/c5gc00025d
Wang S, Peng X, Zhong L et al (2015b) An ultralight, elastic, cost-effective, and highly recyclable superabsorbent from microfibrillated cellulose fibers for oil spillage cleanup. J Mater Chem A 3:8772–8781. https://doi.org/10.1039/c4ta07057g
Wang K, Nune KC, Misra RDK (2016) The functional response of alginate–gelatin–nanocrystalline cellulose injectable hydrogels toward delivery of cells and bioactive molecules. Acta Biomater 36:143–151. https://doi.org/10.1016/j.actbio.2016.03.016
Way AE, Hsu L, Shanmuganathan K et al (2012) PH-responsive cellulose nanocrystal gels and nanocomposites. ACS Macro Lett 1:1001–1006. https://doi.org/10.1021/mz3003006
Wu Y, Cao F, Jiang H, Zhang Y (2017) Preparation and characterization of aminosilane-functionalized cellulose nanocrystal aerogel. Mater Res Express 4:085303. https://doi.org/10.1088/2053-1591/aa8067
Xu Y-T, Dai Y, Nguyen T-D et al (2018) Aerogel materials with periodic structures imprinted with cellulose nanocrystals. Nanoscale. https://doi.org/10.1039/c7nr07719j
Yang X, Cranston ED (2014) Chemically cross-linked cellulose nanocrystal aerogels with shape recovery and superabsorbent properties. Chem Mater 26:6016–6025. https://doi.org/10.1021/cm502873c
Yang J, Han CR, Duan JF et al (2013) Mechanical and viscoelastic properties of cellulose nanocrystals reinforced poly(ethylene glycol) nanocomposite hydrogels. ACS Appl Mater Interfaces 5:3199–3207. https://doi.org/10.1021/am4001997
Yang X, Shi K, Zhitomirsky I, Cranston ED (2015) Cellulose nanocrystal aerogels as universal 3D lightweight substrates for supercapacitor materials. Adv Mater 27:6104–6109. https://doi.org/10.1002/adma.201502284
Zanini M, Lavoratti A, Lazzari LK et al (2016) Producing aerogels from silanized cellulose nanofiber suspension. Cellulose. https://doi.org/10.1007/s10570-016-1142-4
Zhang Z, Sèbe G, Rentsch D et al (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
Acknowledgments
This research was supported by Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP, Grants 2010/17804-7 and 2016/02414-5), Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq, Grant 136786/2015-4) and Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (Capes-PNPD, L. C. Battirola fellowship). The authors also gratefully acknowledge the National Institute for Complex Functional Materials (Inomat/INCT), the Brazilian Nanotechnology National Laboratory (LME/LNNano) and staff for the use of TEM facilities, MSc Laura C. E. da Silva and PhD Douglas S. da Silva for TEM measurements. The authors particularly thank Prof. Maria Isabel Felisberti for her assistance in compression tests and data analysis.
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de Morais Zanata, D., Battirola, L.C. & Gonçalves, M.C. Chemically cross-linked aerogels based on cellulose nanocrystals and polysilsesquioxane. Cellulose 25, 7225–7238 (2018). https://doi.org/10.1007/s10570-018-2090-y
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DOI: https://doi.org/10.1007/s10570-018-2090-y