Abstract
In this work, we have applied, for the first time, solution plasma processing of cellulose-containing material to produce cellulose nanocrystals (CNC). The CNC samples produced in three different modes of solution plasma treatment were characterized using methods of dynamic light scattering, infrared spectroscopy, transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The proposed method of CNC production comprising the oxidation–hydrolysis strategy has proved to be effective and allowed us to reduce significantly the time of acid hydrolysis and to increase considerably the total CNC yield.
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Abbreviations
- CNC:
-
Cellulose nanocrystals
- MCC:
-
Microcrystalline cellulose
- FP:
-
Filter paper
- DC:
-
Direct current
- ζ-potential:
-
Electrokinetical potential
- IR-spectroscopy:
-
Fourier transform infrared spectroscopy
- DLS:
-
Dynamic light scattering
- TEM:
-
Transmission electron microscopy
- XRD:
-
X-ray diffraction
- XPS:
-
X-ray photoelectron spectroscopy
References
Araki J, Wada M, Kuga S, Okano T (1998) Flow properties of microcrystalline cellulose suspension prepared by acid treatment of native cellulose. Colloids Surf A 142:75–82. https://doi.org/10.1016/S0927-7757(98)00404-X
Beck-Candanedo S, Roman M, Gray DG (2005) Effect of reaction conditions on the properties and behavior of wood cellulose nanocrystal suspensions. Biomacromol 6:1048–1054. https://doi.org/10.1021/bm049300p
Bikales NM, Segal L (1971) Cellulose and cellulose derivatives. Wiley, New York
Bondeson D, Matthew A, Oksman K (2006) Optimization of the isolation of nanocrystals from microcrystalline cellulose by acid hydrolysis. Cellulose 13:171–180. https://doi.org/10.1007/s10570-006-9061-4
Braun B, Dorgan JR (2008) Single-step method for the isolation and surface functionalization of cellulosic nanowhiskers. Biomacromolecules 10(2):334–341. https://doi.org/10.1021/bm8011117
Camarero Espinosa S, Kuhnt T, Foster EJ, Weder C (2013) Isolation of thermally stable cellulose nanocrystals by phosphoric acid hydrolysis. Biomacromol 14(4):1223–1230. https://doi.org/10.1021/bm400219u
Carlsson CMG, Ström G (1991) Reduction and oxidation of cellulose surfaces by means of cold-plasma. Langmuir 7(11):2492–2497. https://doi.org/10.1021/la00059a016
Chávez-Guerrero L, Sepúlveda-Guzmán S, Silva-Mendoza J, Aguilar-Flores C, Pérez-Camacho O (2018) Eco-friendly isolation of cellulose nanoplatelets through oxidation under mild conditions. Carbohydr Polym 181:642–649. https://doi.org/10.1016/j.carbpol.2017.11.100
Chen L, Wang Q, Hirth K, Baez C, Agarwal UP, Zhu JY (2015) Tailoring the yield and characteristics of wood cellulose nanocrystals (CNC) using concentrated acid hydrolysis. Cellulose 22(3):1753–1762. https://doi.org/10.1007/s10570-015-0615-1
Chen L, Zhu JY, Baez C, Kitin P, Elder T (2016a) Highly thermal-stable and functional cellulose nanocrystals and nanofibrils produced using fully recyclable organic acids. Green Chem 18:3835–3843. https://doi.org/10.1039/C6GC00687F
Chen YW, Lee HV, Hamid SBA (2016b) Preparation and characterization of cellulose crystallites via Fe(III)-, Co(II)- and Ni(II)-assisted dilute sulfuric acid catalyzed hydrolysis process. J Nano Res 41:96–109. https://doi.org/10.4028/www.scientific.net/JNanoR.41.96
Cheng M, Qin Z, Chen Y, Hu S, Ren Z, Zhu M (2017) Efficient extraction of cellulose nanocrystals through hydrochloric acid hydrolysis catalyzed by inorganic chlorides under hydrothermal conditions. ACS Sustain Chem Eng 5(6):4656–4664. https://doi.org/10.1021/acssuschemeng.6b03194
Dong XM, Revol J-F, Gray DG (1998) Effect of microcrystallite preparation conditions on the formation of colloid crystals of cellulose. Cellulose 5(1):19–32. https://doi.org/10.1023/A:1009260511939
Espino-Pérez E, Domenek S, Belgacem N, Sillard C, Bras J (2014) Green process for chemical functionalization of nanocellulose with carboxylic acids. Biomacromol 15(12):4551–4560. https://doi.org/10.1021/bm5013458
Filson PB, Dawson-Andoh BE (2009) Sono-chemical preparation of cellulose nanocrystals from lignocellulose derived materials. Bioresour Technol 100(7):2259–2264. https://doi.org/10.1016/j.biortech.2008.09.062
Filson PB, Dawson-Andoh B, Schwegler-Berry D (2009) Enzymatic-mediated production of cellulose nanocrystals from recycled pulp. Green Chem 11:1808–1814. https://doi.org/10.1039/b915746h
French AD (2014) Idealized powder diffraction patterns for cellulose polymorphs. Cellulose 21(2):885–896. https://doi.org/10.1007/s10570-013-0030-4
Gaiolas C, Belgacem MN, Silva L, Thielemans W, Costa AP, Nunes M, Silva MJS (2009) Green chemicals and process to graft cellulose fibers. J Colloid Interf Sci 330(2):298–302. https://doi.org/10.1016/j.jcis.2008.10.059
Hamad WY, Hu TQ (2010) Structure-process-yield interrelations in nanocrystalline cellulose extraction. Can J Chem Eng 88(3):392–402. https://doi.org/10.1002/cjce.20298
Hirosawa S, Minato K, Nakatsubo F (2001) Influence of carboxyl group on the acid hydrolysis of cellulose. J Wood Sci 47(2):141–144. https://doi.org/10.1007/BF00780563
Hirota M, Furihata K, Saito T, Kawada T, Isogai A (2010a) Glucose/glucuronic acid alternating co-polysaccharides prepared from TEMPO-oxidized native celluloses by surface peeling. Angew Chem Int Ed 49(42):7670–7672. https://doi.org/10.1002/anie.201003848
Hirota M, Tamura N, Saito T, Isogai A (2010b) Water dispersion of cellulose II nanocrystals prepared by TEMPO-mediated oxidation of mercerized cellulose at pH 4.8. Cellulose 17(2):279–288. https://doi.org/10.1007/s10570-009-9381-2
Ioelovich M (2012) Optimal conditions for isolation of nanocrystalline cellulose particles. Nanosci Nanotechnol 2(2):9–13. https://doi.org/10.5923/j.nn.20120202.03
Ioelovich M (2013) Products of cellulose hydrolysis made by treatment of feedstock with concentrated solutions of sulfuric acid. Res Rev J Mater Sci 1(1):12–19. https://doi.org/10.4172/2321-6212.1000103
Ioelovich M (2017) Characterization of various kinds of nanocellulose. In: Kargarzadeh H, Ahmad I, Thomas S, Dufresne A (eds) Handbook of nanocellulose and cellulose nanocomposites, 1st edn. Wiley, New York, pp 51–100. https://doi.org/10.1002/9783527689972.ch2
Jiang F, Esker AR, Roman M (2010) Acid-catalyzed and solvolytic desulfation of H2SO4-hydrolyzed cellulose nanocrystals. Langmuir 26(23):17919–17925. https://doi.org/10.1021/la1028405
Johansson L-S, Campbell JM (2004) Reproducible XPS on biopolymers: cellulose studies. Surf Interface Anal 36:1018–1022. https://doi.org/10.1002/sia.1827
Julkapli NM, Bagheri S (2017) Progress on nanocrystalline cellulose biocomposites. React Funct Polym 112:9–21. https://doi.org/10.1016/j.reactfunctpolym.2016.12.013
Kargarzadeh H, Ioelovich M, Ahmad I, Thomas S, Dufresne A (2017) Methods for extraction of nanocellulose from various sources. In: Kargarzadeh H, Ahmad I, Thomas S, Dufresne A (eds) Handbook of nanocellulose and cellulose nanocomposites, 1st edn. Wiley, New York, pp 1–49. https://doi.org/10.1002/9783527689972.ch1
Karim MZ, Chowdhury ZZ, Hamid SBA, Ali ME (2014) Statistical optimization for acid hydrolysis of microcrystalline cellulose and its physiochemical characterization by using metal ion catalyst. Materials 7:6982–6999. https://doi.org/10.3390/ma7106982
Khelifa F, Ershov S, Habibi Y, Snyders R, Dubois P (2016) Free-radical-induced grafting from plasma polymer surfaces. Chem Rev 116(6):3975–4005. https://doi.org/10.1021/acs.chemrev.5b00634
Kontturi E, Meriluoto A, Penttilä PA, Baccile N, Malho J-M, Potthast A, Rosenau T, Ruokolainen J, Serimaa R, Laine J, Sixta H (2016) Degradationand crystallization of cellulose in hydrogen chloride vapor for high-yield isolation of cellulose nanocrystals. Angew Chem Int Ed 55(46):14455–14458. https://doi.org/10.1002/anie.201606626
Kuz’micheva LA, Titova YV, Maksimov AI (2011) Yields of hydroxyl radicals and hydrogen peroxide in a glow discharge system with a liquid cathode. Surf Eng Appl Elect 47(6):45–47. https://doi.org/10.3103/S106837551106010X
Kuz’micheva LA, Titova YV, Maksimov AI (2012) Accumulation of hydrogen peroxide at the long-term effect of an atmosphere pressure glow discharge on electrolyte solutions. Surf Eng Appl Elect 48(1):60–63. https://doi.org/10.3103/S1068375512010103
Leung ACW, Hrapovic S, Lam E, Liu Y, Male KB, Mahmoud KA, Luong JHT (2011) Characteristics and properties of carboxylated cellulose nanocrystals prepared from a novel one-step procedure. Small 7(3):302–305. https://doi.org/10.1002/smll.201001715
Li J, Zhang X, Zhang M, Xiu H, He H (2015) Ultrasonic enhance acid hydrolysis selectivity of cellulose with HCl–FeCl3 as catalyst. Carbohydr Polym 117:917–922. https://doi.org/10.1016/j.carbpol.2014.10.028
Li Y, Liu Y, Chen W, Wang Q, Liu Y, Li J, Yu H (2016) Facile extraction of cellulose nanocrystal from wood using ethanol and peroxide solvothermal pretreatment followed by ultrasonic nanofibrillation. Green Chem 18:1010–1018. https://doi.org/10.1039/C5GC02576A
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
Liu L, Sun J, Cai C, Wang S, Pei H, Zhang J (2009) Corn stover pretreatment by inorganic salts and its effects on hemicellulose and cellulose degradation. Bioresour Technol 100(23):5865–5871. https://doi.org/10.1016/j.biortech.2009.06.048
Liu D, Zhong T, Chang PR, Li K, Wu Q (2010) Starch composites reinforced by bamboo cellulosic crystals. Bioresour Technol 101(7):2529–2536. https://doi.org/10.1016/j.biortech.2009.11.058
Liu Y, Wang H, Yu G, Yu Q, Li B, Mu X (2014) A novel approach for the preparation of nanocrystalline cellulose by using phosphotungstic acid. Carbohyd Polym 110:415–422. https://doi.org/10.1016/j.carbpol.2014.04.040
Łojewski T, Zięba K, Knapik A, Bagniuk J, Lubańska A, Łojewska J (2010) Evaluating paper degradation progress. Cross-linking between chromatographic, spectroscopic and chemical results. Appl Phys A 100:809–821. https://doi.org/10.1007/s00339-010-5657-5
López-Linares JC, Romero I, Moya M, Cara C, Ruiz E, Castro E (2013) Pretreatment of olive tree biomass with FeCl3 prior enzymatic hydrolysis. Bioresour Technol 128:180–187. https://doi.org/10.1016/j.biortech.2012.10.076
Lu P, Hsieh Y-L (2010) Preparation and properties of cellulose nanocrystals: rods, spheres, and network. Carbohydr Polym 82:329–336. https://doi.org/10.1016/j.carbpol.2010.04.073
Lu Q, Tang L, Lin F, Wang S, Chen Y, Chen X, Huang B (2014) Preparation and characterization of cellulose nanocrystals via ultrasonication-assisted FeCl3-catalyzed hydrolysis. Cellulose 21(5):3497–3506. https://doi.org/10.1007/s10570-014-0376-2
Lu Q, Li X, Tang L, Lu B, Huang B (2015) One-pot tandem reactions for the preparation of esterified cellulose nanocrystals with 4-dimethylaminopyridine as a catalyst. RSC Adv 5:56198–56204. https://doi.org/10.1039/c5ra08690f
Man Z, Muhammad N, Sarwono A, Bustam MA, Kumar MV, Rafiq S (2011) Preparation of cellulose nanocrystals using an ionic liquid. J Polym Environ 19(3):726–731. https://doi.org/10.1007/s10924-011-0323-3
Mao J, Abushammala H, Brown N, Laborie M-P (2017) Comparative assessment of methods for producing cellulose I nanocrystals from cellulosic sources. In: Agarwal UP, Atalla RH, Isogai A (eds) Nanocelluloses: their preparation, properties, and applications, ACS symposium series, vol 1251. American Chemical Society, Washington, pp 19–53. https://doi.org/10.1021/bk-2017-1251.ch002
Miao J, Yu Y, Jiang Z, Zhang L (2016) One-pot preparation of hydrophobic cellulose nanocrystals in an ionic liquid. Cellulose 23(2):1209–1219. https://doi.org/10.1007/s10570-016-0864-7
Mondal S (2017) Preparation, properties and applications of nanocellulosic materials. Carbohyd Polym 163:301–316. https://doi.org/10.1016/j.carbpol.2016.12.050
Montanari S, Roumani M, Heux L, Vignon MR (2005) Topochemistry of carboxylated cellulose nanocrystals resulting from TEMPO-mediated oxidation. Macromolecules 38(5):1665–1671. https://doi.org/10.1021/ma048396c
Mosca Conte A, Pulci O, Knapik A, Bagniuk J, Del Sole R, Lojewska J, Missori M (2012) Role of cellulose oxidation in the yellowing of ancient paper. Phys Rev Lett 108:158301. https://doi.org/10.1103/PhysRevLett.108.158301
Nikitin D, Choukourov A, Titov V, Kuzmicheva L, Lipatova I, Mezina E, Aleksandriiskii V, Shelemin A, Khalakhan I, Slavinska D, Biederman H (2016) In situ coupling of chitosan onto polypropylene foils by an Atmospheric Pressure Air Glow Discharge with a liquid cathode. Carbohydr Polym 154:30–39. https://doi.org/10.1016/j.carbpol.2016.08.023
NIST Chemistry WebBook, http://webbook.nist.gov/chemistry. Accessed 01 Feb 2018
Niu M, Hou Y, Ren S, Wang W, Zheng Q, Wu W (2015) The relationship between oxidation and hydrolysis in the conversion of cellulose in NaVO3–H2SO4 aqueous solution with O2. Green Chem 17:335–342. https://doi.org/10.1039/c4gc00970c
Novo LP, Bras J, García A, Belgacem N, Curvelo AAS (2015) Subcritical water: a method for green production of cellulose nanocrystals. ACS Sustain Chem Eng 3(11):2839–2846. https://doi.org/10.1021/acssuschemeng.5b00762
Novo LP, Bras J, García A, Belgacem N, Curvelo AAS (2016) A study of the production of cellulose nanocrystals through subcritical water hydrolysis. Ind Crop Prod 93:88–95. https://doi.org/10.1016/j.indcrop.2016.01.012
Pertile RAN, Andrade FK, Alves C Jr, Gama M (2010) Surface modification of bacterial cellulose by nitrogen-containing plasma for improved interaction with cells. Carbohydr Polym 82:692–698. https://doi.org/10.1016/j.carbpol.2010.05.037
Peyre J, Pääkkönen T, Reza M, Kontturi E (2015) Simultaneous preparation of cellulose nanocrystals and micron-sized porous colloidal particles of cellulose by TEMPO-mediated oxidation. Green Chem 17:808–811. https://doi.org/10.1039/C4GC02001D
Piotto M, Saudek V, Sklenář V (1992) Gradient-tailored excitation for single-quantum NMR spectroscopy of aqueous solutions. J Biomol NMR 2(6):661–665. https://doi.org/10.1007/BF02192855
Prasertsunga I, Chutinate P, Watthanaphanit A, Saito N, Damrongsakkul S (2017) Conversion of cellulose into reducing sugar by solution plasma process (SPP). Carbohydr Polym 172:230–236. https://doi.org/10.1016/j.carbpol.2017.05.025
Rogovin ZA (1972) Chemistry of cellulose. Khimia, Moscow (in Russian)
Siqueira G, Tapin-Lingua S, Bras J, da Silva Perez D, Dufresne A (2010) Morphological investigation of nanoparticles obtained from combined mechanical shearing, and enzymatic and acid hydrolysis of sisal fibers. Cellulose 17(6):1147–1158. https://doi.org/10.1007/s10570-010-9449-z
Spectral Database for Organic Compound SDBS. National Institute of Advanced Industrial Science and Technology (AIST), http://sdbs.db.aist.go.jp. Accessed 01 Feb 2018
Spinella S, Maiorana A, Qian Q, Dawson NJ, Hepworth V, McCallum SA, Ganesh M, Singer KD, Gross RA (2016) Concurrent cellulose hydrolysis and esterification to prepare a surface-modified cellulose nanocrystal decorated with carboxylic acid moieties. ACS Sustain Chem Eng 4(3):1538–1550. https://doi.org/10.1021/acssuschemeng.5b01489
Titiova YV, Voronova MI, Maksimov AI (2008) Influence of gas-discharge plasma treatment in the electrolyte bulk on the cellulose properties. Russ J Appl Chem 81(5):854–857. https://doi.org/10.1134/s107042720805025x
Titova YV, Stokozenko VG, Aleksakhina EL, Maksimov AI (2012) Chemical interactions of a model lignin compound under plasma-solution treatment. Surf Eng Appl Elect 48(4):355–358. https://doi.org/10.3103/S1068375512040175
Torlopov MA, Udoratina EV, Maratov IS, Sitnikov PA (2017a) Cellulose nanocrystals prepared in H3PW12O40-acetic acid system. Cellulose 24(5):2153–2162. https://doi.org/10.1007/s10570-017-1256-3
Torlopov MA, Mikhaylov VI, Udoratina EV, Aleshina LA, Prusskii AI, Tsvetkov NV, Krivoshapkin PV (2017b) Cellulose nanocrystals with different length-to-diameter ratios extracted from various plants using novel system acetic acid/phosphotungstic acid/octanol-1. Cellulose 25(2):1031–1046. https://doi.org/10.1007/s10570-017-1624-z
Um BH, Karim MN, Henk LL (2003) Effect of sulfuric and phosphoric acid pretreatments on enzymatic hydrolysis of corn stover. Appl Biochem Biotechnol 105–108(1–3):115–125. https://doi.org/10.1385/ABAB:105:1-3:115
Voronova MI, Surov OV, Guseinov SS, Barannikov VP, Zakharov AG (2015) Thermal stability of polyvinyl alcohol/nanocrystalline cellulose composites. Carbohydr Polym 130:440–447. https://doi.org/10.1016/j.carbpol.2015.05.032
Wang QQ, Zhu JY, Reiner RS, Verrill SP, Baxa U, McNeil SE (2012) Approaching zero cellulose loss in cellulose nanocrystal (CNC) production: recovery and characterization of cellulosic solid residues (CSR) and CNC. Cellulose 19(6):2033–2047. https://doi.org/10.1007/s10570-012-9765-6
Yahya M, Lee HV, Hamid SBA (2015) Preparation of nanocellulose via transition metal salt-catalyzed hydrolysis pathway. BioResources 10(4):7627–7639. https://doi.org/10.15376/biores.10.4.7627-7639
Yan C-F, Yu H-Y, Yao J-M (2015) One-step extraction and functionalization of cellulose nanospheres from lyocell fibers with cellulose II crystal structure. Cellulose 22(6):3773–3788. https://doi.org/10.1007/s10570-015-0761-5
Yu H, Qin Z, Liang B, Liu N, Zhou Z, Chen L (2013) Facile extraction of thermally stable cellulose nanocrystals with a high yield of 93% through hydrochloric acid hydrolysis under hydrothermal conditions. J Mater Chem A 1(12):3938–3944. https://doi.org/10.1039/C3TA01150J
Zakharov AG, Maksimov AI, Titova YV (2007) Physicochemical properties of plasma–solution systems and prospects for their use in technology. Russ Chem Rev 76(3):235–251. https://doi.org/10.1070/RC2007v076n03ABEH003638
Zhang Y, Li Q, Su J, Lin Y, Huang Z, Lu Y, Sun G, Yang M, Huang A, Hu H, Zhu Y (2015) A green and efficient technology for the degradation of cellulosic materials: structure changes and enhanced enzymatic hydrolysis of natural cellulose pretreated by synergistic interaction of mechanical activation and metal salt. Bioresour Technol 177:176–181. https://doi.org/10.1016/j.biortech.2014.11.085
Zhang J, Wu J, Yu J, Zhang X, He J, Zhang J (2017) Application of ionic liquids for dissolving cellulose and fabricating cellulose-based materials: state of the art and future trends. Mater Chem Front 1(7):1273–1290. https://doi.org/10.1039/C6QM00348F
Zhou L, Yang X, Xu J, Shi M, Wang F, Chen C, Xu J (2015) Depolymerization of cellulose to glucose by oxidation–hydrolysis. Green Chem 17:1519–1524. https://doi.org/10.1039/c4gc02151g
Zhu H, Luo W, Ciesielski PN, Fang Z, Zhu JY, Henriksson G, Himmel ME, Hu L (2016) Wood-derived materials for green electronics, biological devices, and energy applications. Chem Rev 116:9305–9374. https://doi.org/10.1021/acs.chemrev.6b00225
Acknowledgments
This work was supported by the Russian Science Foundation (Grant Number 17-13-01240). The authors would like to thank The Upper Volga Region Centre of Physicochemical Research (Ivanovo, Russia) and Centre for collective use of scientific equipment of Ivanovo State University of Chemistry and Technology for some measurements carried out using the centers’ equipment.
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Surov, O.V., Voronova, M.I., Rubleva, N.V. et al. A novel effective approach of nanocrystalline cellulose production: oxidation–hydrolysis strategy. Cellulose 25, 5035–5048 (2018). https://doi.org/10.1007/s10570-018-1910-4
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DOI: https://doi.org/10.1007/s10570-018-1910-4