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Using a fully recyclable dicarboxylic acid for producing dispersible and thermally stable cellulose nanomaterials from different cellulosic sources

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Abstract

We fabricated cellulose nanocrystals (CNCs) and cellulose nanofibrils (CNFs) from different cellulose materials (bleached eucalyptus pulp (BEP), spruce dissolving pulp (SDP) and cotton based qualitative filter paper (QFP) using concentrated oxalic acid hydrolysis and subsequent mechanical fibrillation (for CNFs). The process was green as acid can be easily recovered, and the prepared cellulose nanomaterials were carboxylated and thermally stable. In detail, the CNC yield from the different materials was similar. After hydrolysis, the DP of the cellulose materials decreased substantially, whereas the mechanical fibrillation of the cellulosic solid residues (CSRs) did not dramatically reduce the DP of cellulose. CNCs with different aspect ratios were produced from different starting materials by oxalic acid hydrolysis. The CNCs and CNFs obtained from BEP and QFP possessed more uniform dimensions than those from SDP. On the other hand, CNFs derived from SDP presented the best suspension stability. FTIR analyses verified esterification of cellulose by oxalic acid hydrolysis. The results from both XRD and Raman spectroscopy indicated that whereas XRD crystallinity of CNCs from BEP and QFP did not change significantly, there was some change in Raman crystallinity of these samples. Raman spectra of SDP CNCs indicated that the acid hydrolysis preferably removed cellulose I portion of the samples and therefore the CNCs became cellulose II enriched. TGA revealed that the CNCs obtained from QFP exhibited higher thermal stability compared to those from BEP and SDP, and all the CNCs possessed better thermal stability than that of CNCs from sulfuric acid hydrolysis. The excellent properties of prepared cellulose nanomaterials will be conducive to their application in different fields.

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References

  • Agarwal UP (2014) 1064 nm FT-Raman spectroscopy for investigations of plant cell walls and other biomass materials. Front Plant Sci 5(490):1–12

    Google Scholar 

  • Agarwal UP, Reiner RS, Ralph SA (2010) Cellulose I crystallinity determination using FT-Raman spectroscopy: univariate and multivariate methods. Cellulose 17(4):721–733

    Article  CAS  Google Scholar 

  • Agarwal UP, Reiner RR, Ralph SA (2013) Estimation of cellulose crystallinity of lignocelluloses using near-IR FT-Raman spectroscopy and comparison of the Raman and Segal-WAXS methods. J Agric Food Chem 61(1):103–113

    Article  CAS  Google Scholar 

  • Agarwal UP, Ralph SA, Reiner RS, Baez C (2016) Probing crystallinity of never-dried wood cellulose with Raman spectroscopy. Cellulose 23(1):125–144

    Article  CAS  Google Scholar 

  • Beltramino F, Blanca Roncero M, Vidal T, Torres AL, Valls C (2015) Increasing yield of nanocrystalline cellulose preparation process by a cellulase pretreatment. Bioresour Technol 192:574–581

    Article  CAS  Google Scholar 

  • Bian H, Chen L, Dai H, Zhu JY (2017a) Integrated production of lignin containing cellulose nanocrystals (LCNC) and nanofibrils (LCNF) using an easily recyclable di-carboxylic acid. Carbohyd Polym 167:167–176

    Article  CAS  Google Scholar 

  • Bian H, Chen L, Wang R, Zhu JY (2017b) Green and low-cost production of thermally stable and carboxylated cellulose nanocrystals and nanofibrils using highly recyclable dicarboxylic acids. J Vis Exp. doi:10.3791/55079

    Google Scholar 

  • Biyani MV, Foster EJ, Weder C (2013) Light-healable supramolecular nanocomposites based on modified cellulose nanocrystals. Acs Macro Lett 2(3):236–240

    Article  CAS  Google Scholar 

  • Bondeson D, Mathew A, Oksman K (2006) Optimization of the isolation of manocrystals from microcrystalline cellulose by acid hydrolysis. Cellulose 13:171–180

    Article  CAS  Google Scholar 

  • Braun B, Dorgan JR (2009) Single-step method for the isolation and surface functionalization of cellulosic nanowhiskers. Biomacromolecules 10(2):334–341

    Article  CAS  Google Scholar 

  • Brito BSL, Pereira FV, Putaux J-L, Jean B (2012) Preparation, morphology and structure of cellulose nanocrystals from bamboo fibers. Cellulose 19(5):1527–1536

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • Chen L, Zhu JY, Baez C, Kitin P, Elder T (2016) Highly thermal-stable and functional cellulose nanocrystals and nanofibrils produced using fully recyclable organic acids. Green Chem 18:3835–3843

    Article  CAS  Google Scholar 

  • Cirtiu CM, Dunlop-Briere AF, Moores A (2011) Cellulose nanocrystallites as an efficient support for nanoparticles of palladium: application for catalytic hydrogenation and Heck coupling under mild conditions. Green Chem 13(2):288–291

    Article  CAS  Google Scholar 

  • de Castro DO, Bras J, Gandini A, Belgacem N (2016) Surface grafting of cellulose nanocrystals with natural antimicrobial rosin mixture using a green process. Carbohyd Polym 137:1–8

    Article  Google Scholar 

  • Deepa B, Abraham E, Cordeiro N, Mozetic M, Mathew AP, Oksman K, Faria M, Thomas S, Pothan LA (2015) Utilization of various lignocellulosic biomass for the production of nanocellulose: a comparative study. Cellulose 22(2):1075–1090

    Article  CAS  Google Scholar 

  • Dong XM, Revol JF, Gray DG (1998) Effect of microcrystallite preparation conditions on the formation of colloid crystals of cellulose. Cellulose 5(1):19–32

    Article  CAS  Google Scholar 

  • Eichhorn SJ, Dufresne A, Aranguren M, Marcovich NE, Capadona JR, Rowan SJ, Weder C, Thielemans W, Roman M, Renneckar S et al (2010) Review: current international research into cellulose nanofibres and nanocomposites. J Mater Sci 45(1):1–33

    Article  CAS  Google Scholar 

  • Espinosa SC, Kuhnt T, Foster EJ, Weder C (2013) Isolation of thermally stable cellulose nanocrystals by phosphoric acid hydrolysis. Biomacromolecules 14(4):1223–1230

    Article  Google Scholar 

  • Eyholzer C, Bordeanu N, Lopez-Suevos F, Rentsch D, Zimmermann T, Oksman K (2010) Preparation and characterization of water-redispersible nanofibrillated cellulose in powder form. Cellulose 17(1):19–30

    Article  CAS  Google Scholar 

  • Filson PB, Dawson-Andoh BE (2009) Sono-chemical preparation of cellulose nanocrystals from lignocellulose derived materials. Bioresour Technol 100(7):2259–2264

    Article  CAS  Google Scholar 

  • Ganan P, Cruz J, Garbizu S, Arbelaiz A, Mondragon M (2004) Stem and bunch banana fibers from cultivation wastes: effect of treatments on physico-chemical behavior. J Appl Polym Sci 94(4):1489–1495

    Article  CAS  Google Scholar 

  • Guru M, Bilgesu AY, Pamuk V (2001) Production of oxalic acid from sugar beet molasses by formed nitrogen oxides. Bioresour Technol 77(1):81–86

    Article  CAS  Google Scholar 

  • Hamad WY, Hu TQ (2010) Structure–process–yield interrelations in nanocrystalline cellulose extraction. Can J Chem Eng 88(3):392–402

    CAS  Google Scholar 

  • Jonoobi M, Oladi R, Davoudpour Y, Oksman K, Dufresne A, Hamzeh Y, Davoodi R (2015) Different preparation methods and properties of nanostructured cellulose from various natural resources and residues: a review. Cellulose 22(2):935–969

    Article  CAS  Google Scholar 

  • Kelly JA, Shukaliak AM, Cheung CCY, Shopsowitz KE, Hamad WY, MacLachlan MJ (2013) Responsive photonic hydrogels based on nanocrystalline cellulose. Angew Chem Int Ed 52(34):8912–8916

    Article  CAS  Google Scholar 

  • Kim J-H, Shim BS, Kim HS, Lee Y-J, Min S-K, Jang D, Abas Z, Kim J (2015) Review of nanocellulose for sustainable future materials. Int J Precis Eng Manuf Green Technol 2(2):197–213

    Article  Google Scholar 

  • Kurihara T, Isogai A (2014) Properties of poly(acrylamide)/TEMPO-oxidized cellulose nanofibril composite films. Cellulose 21(1):291–299

    Article  CAS  Google Scholar 

  • Lacerda TM, Zarnbon MD, Frollini E (2015) Oxalic acid as a catalyst for the hydrolysis of sisal pulp. Ind Crops Prod 71:163–172

    Article  CAS  Google Scholar 

  • Li B, Xu W, Kronlund D, Maattanen A, Liu J, Smatt J-H, Peltonen J, Willfor S, Mu X, Xu C (2015) Cellulose nanocrystals prepared via formic acid hydrolysis followed by TEMPO-mediated oxidation. Carbohydr Polym 133:605–612

    Article  CAS  Google Scholar 

  • Lin N, Dufresne A (2014) Surface chemistry, morphological analysis and properties of cellulose nanocrystals with gradiented sulfation degrees. Nanoscale 6(10):5384–5393

    Article  CAS  Google Scholar 

  • 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. Carbohydr Polym 110:415–422

    Article  CAS  Google Scholar 

  • Lu P, Hsieh Y-L (2010) Preparation and properties of cellulose nanocrystals: Rods, spheres, and network. Carbohydr Polym 82(2):329–336

    Article  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • Lu Q, Lin W, Tang L, Wang S, Chen X, Huang B (2015) A mechanochemical approach to manufacturing bamboo cellulose nanocrystals. J Mater Sci 50(2):611–619

    Article  CAS  Google Scholar 

  • Luzi F, Fortunati E, Puglia D, Lavorgna M, Santulli C, Kenny JM, Torre L (2014) Optimized extraction of cellulose nanocrystals from pristine and carded hemp fibres. Ind Crops Prod 56:175–186

    Article  CAS  Google Scholar 

  • Mansikkamaki P, Lahtinen M, Rissanen K (2005) Structural changes of cellulose crystallites induced by mercerisation in different solvent systems; determined by powder X-ray diffraction method. Cellulose 12(3):233–242

    Article  Google Scholar 

  • Mathew AP, Oksman K, Karim Z, Liu P, Khan SA, Naseri N (2014) Process scale up and characterization of wood cellulose nanocrystals hydrolysed using bioethanol pilot plant. Ind Crops Prod 58:212–219

    Article  CAS  Google Scholar 

  • Mendez J, Annamalai PK, Eichhorn SJ, Rusli R, Rowan SJ, Foster EJ, Weder C (2011) Bioinspired mechanically adaptive polymer nanocomposites with water-activated shape-memory effect. Macromolecules 44(17):6827–6835

    Article  CAS  Google Scholar 

  • Moon RJ, Martini A, Nairn J, Simonsen J, Youngblood J (2011) Cellulose nanomaterials review: structure, properties and nanocomposites. Chem Soc Rev 40:3941–3994

    Article  CAS  Google Scholar 

  • Peyre J, Paakkonen 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(2):808–811

    Article  CAS  Google Scholar 

  • Roman M, Winter WT (2004) Effect of sulfate groups from sulfuric acid hydrolysis on the thermal degradation behavior of bacterial cellulose. Biomacromolecules 5(5):1671–1677

    Article  CAS  Google Scholar 

  • Sacui IA, Nieuwendaal RC, Burnett DJ, Stranick SJ, Jorfi M, Weder C, Foster EJ, Olsson RT, Gilman JW (2014) Comparison of the properties of cellulose nanocrystals and cellulose nanofibrils isolated from bacteria, tunicate, and wood processed using acid, enzymatic, mechanical, and oxidative methods. ACS Appl Mater Interfaces 6(9):6127–6138

    Article  CAS  Google Scholar 

  • Schyrr B, Pasche S, Voirin G, Weder C, Simon YC, Foster EJ (2014) Biosensors based on porous cellulose nanocrystal-poly(vinyl alcohol) scaffolds. ACS Appl Mater Interfaces 6(15):12674–12683

    Article  CAS  Google Scholar 

  • Segal L, Creely JJ, Martin AE, Conrad CM (1959) An empirical method for estimating the degree of crystallinity of native cellulose using the X-ray diffractometer. Textile Res J 29(10):786–794

    Article  CAS  Google Scholar 

  • Sihtola H, Kyrklund B, Laamanen L, Palenius I (1963) Comparison and conversion of viscosity and DP-values determined by different methods. Paperi ja Puu 45:225–232

    Google Scholar 

  • Spinella S, Lo Re G, Liu B, Dorgan J, Habibi Y, Leclere P, Raquez J-M, Dubois P, Gross RA (2015) Polylactide/cellulose nanocrystal nanocomposites: efficient routes for nanofiber modification and effects of nanofiber chemistry on PLA reinforcement. Polymer 65:9–17

    Article  CAS  Google Scholar 

  • Taheri A, Mohammadi M (2015) The use of cellulose nanocrystals for potential application in topical delivery of hydroquinone. Chem Biol Drug Des 86(1):882–886

    Article  CAS  Google Scholar 

  • Tang L, Huang B, Lu Q, Wang S, Ou W, Lin W, Chen X (2013) Ultrasonication-assisted manufacture of cellulose nanocrystals esterified with acetic acid. Bioresour Technol 127:100–105

    Article  CAS  Google Scholar 

  • van den Berg O, Capadona JR, Weder C (2007) Preparation of homogeneous dispersions of tunicate cellulose whiskers in organic solvents. Biomacromolecules 8(4):1353–1357

    Article  Google Scholar 

  • Wang N, Ding EY, Cheng RS (2007) Thermal degradation behaviors of spherical cellulose nanocrystals with sulfate groups. Polymer 48(12):3486–3493

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • Wang QQ, Zhu JY, Considine JM (2013) Strong and optically transparent films prepared using cellulosic solid residue (CSR) recovered from cellulose nanocrystals (CNC) production waste stream. ACS Appl Mater Interfaces 5(7):2527–2534

    Article  CAS  Google Scholar 

  • Wang Q, Zhao X, Zhu JY (2014) Kinetics of strong acid hydrolysis of a bleached kraft pulp for producing cellulose nanocrystals (CNCs). Ind Eng Chem Res 53(27):11007–11014

    Article  CAS  Google Scholar 

  • Wang W, Mozuch MD, Sabo RC, Kersten P, Zhu JY, Jin Y (2015) Production of cellulose nanofibrils from bleached eucalyptus fibers by hyperthermostable endoglucanase treatment and subsequent microfluidization. Cellulose 22:351–361

    Article  CAS  Google Scholar 

  • Wang R, Chen L, Zhu JY, Yang R (2017) Tailored and integrated production of carboxylated cellulose nanocrystals (CNC) with nanofibrils (CNF) through maleic acid hydrolysis. ChemNanoMat. doi:10.1002/cnma.201700015

    Google Scholar 

  • Xiang ZY, Gao WH, Chen LH, Lan W, Zhu JY, Runge T (2016) A comparison of cellulose nanofibrils produced from Cladophora glomerata algae and bleached eucalyptus pulp. Cellulose 23(1):493–503

    Article  CAS  Google Scholar 

  • Xu XZ, Liu F, Jiang L, Zhu JY, Haagenson D, Wiesenborn DP (2013) Cellulose nanocrystals vs. cellulose nanofibrils: a comparative study on their microstructures and effects as polymer reinforcing agents. ACS Appl Mater Interfaces 5(8):2999–3009

    Article  CAS  Google Scholar 

  • Xu X, Wang H, Jiang L, Wang X, Payne SA, Zhu JY, Li R (2014) Comparison between cellulose nanocrystal and cellulose nanofibril reinforced poly(ethylene oxide) nanofibers and their novel shish-kebab-like crystalline structures. Macromolecules 47(10):3409–3416

    Article  CAS  Google Scholar 

  • Xu XZ, Zhou J, Jiang L, Lubineau G, Ng T, Ooi BS, Liao HY, Shen C, Chen L, Zhu JY (2016) Highly transparent, low-haze, hybrid cellulose nanopaper as electrodes for flexible electronics. Nanoscale 8(24):12294–12306

    Article  CAS  Google Scholar 

  • 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

    Article  CAS  Google Scholar 

  • Yu H-Y, Chen G-Y, Wang Y-B, Yao J-M (2015) A facile one-pot route for preparing cellulose nanocrystal/zinc oxide nanohybrids with high antibacterial and photocatalytic activity. Cellulose 22(1):261–273

    Article  CAS  Google Scholar 

  • Zhang S, Winestrand S, Guo X, Chen L, Hong F, Jonsson LJ (2014) Effects of aromatic compounds on the production of bacterial nanocellulose by Gluconacetobacter xylinus. Microb Cell Fact 13:62

    Article  Google Scholar 

  • Zhang K, Sun P, Liu H, Shang S, Song J, Wang D (2016a) Extraction and comparison of carboxylated cellulose nanocrystals from bleached sugarcane bagasse pulp using two different oxidation methods. Carbohydr Polym 138:237–243

    Article  CAS  Google Scholar 

  • Zhang Q, Bao W, Gong A, Gong T, Ma D, Wan J, Dai J, Munday JN, He JH, Hu L et al (2016b) A highly sensitive, highly transparent, gel-gated MoS2 phototransistor on biodegradable nanopaper. Nanoscale 8(29):14237–14242

    Article  CAS  Google Scholar 

  • Zhu JY, Sabo R, Luo X (2011) Integrated production of nano-fibrillated cellulose and cellulosic biofuel (ethanol) by enzymatic fractionation of wood fibers. Green Chem 13(5):1339–1344

    Article  CAS  Google Scholar 

  • Zhu H, Fang Z, Wang Z, Dai J, Yao Y, Shen F, Preston C, Wu W, Peng P, Jang N et al (2016) Extreme light management in mesoporous wood cellulose paper for optoelectronics. ACS Nano 10(1):1369–1377

    Article  CAS  Google Scholar 

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Acknowledgments

Chao Jia would like to thank the China Scholarship Council (CSC) for financial support. The authors thank Sally A. Ralph and Fred Matt, U.S. Forest Service, Forest Products Laboratory, for FT-Raman measurements, and carbohydrate analyses, respectively.

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Authors and Affiliations

  1. School of Materials Science and Engineering, Beijing Institute of Technology, Beijing, 100081, China

    Chao Jia & Ziqiang Shao

  2. Department of Materials Science and Engineering, University of Maryland College Park, College Park, MD, 20742, USA

    Chao Jia & Liangbing Hu

  3. Forest Products Laboratory, USDA Forest Service, Madison, WI, 53726, USA

    Chao Jia, Liheng Chen, Umesh P. Agarwal & J. Y. Zhu

  4. Key Laboratory of Biomaterials of Guangdong Higher Education Institutes, Department of Biomedical Engineering, Jinan University, Guangzhou, 510632, China

    Liheng Chen

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  1. Chao Jia
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Correspondence to J. Y. Zhu.

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Jia, C., Chen, L., Shao, Z. et al. Using a fully recyclable dicarboxylic acid for producing dispersible and thermally stable cellulose nanomaterials from different cellulosic sources. Cellulose 24, 2483–2498 (2017). https://doi.org/10.1007/s10570-017-1277-y

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