Tailorable Cellulose II Nanocrystals (CNC II) Prepared in Mildly Acidic Lithium Bromide Trihydrate (MALBTH)

Li, Ning; Bian, Huiyang; Zhu, J. Y.; Ciesielski, Peter N.; Pan, Xuejun

doi:10.1039/D1GC00145K

Title: Tailorable Cellulose II Nanocrystals (CNC II) Prepared in Mildly Acidic Lithium Bromide Trihydrate (MALBTH)

Journal Article · Tue Mar 16 00:00:00 EDT 2021 · Green Chemistry

DOI:https://doi.org/10.1039/D1GC00145K· OSTI ID:1781611

Li, Ning; Bian, Huiyang; Zhu, J. Y.;

; Pan, Xuejun

Preparing cellulose II nanocrystals (CNC II) requires a polymorph transformation of natural cellulose I feedstocks. The transformation is usually achieved via a process such as mercerization or dissolution–regeneration. This study demonstrated a new method to prepare CNC II directly from bleached kraft pulp (BKP, a commercially available cellulose I feedstock) in a mildly acidic lithium bromide trihydrate (MALBTH) system, a concentrated (~61 wt%) solution of LiBr in water with a very low concentration (2.5 mM) of sulfuric acid. First, the BKP was treated in the MALBTH system to generate a cellulose II hydrolysis solid residue (CHR) with a yield of 64–86%, during which the selective hydrolysis of disordered cellulose and the polymorph transformation were completed simultaneously. Then, subsequent oxidation of the CHR by ammonium persulfate (APS, 0.1–0.6 M) resulted in the CNC II with high yield (up to 62%), high crystallinity (over 90%), rich surface carboxyl group (0.3–1.2 mmol g-1 cellulose), excellent colloidal stability (up to -59 mV zeta potential), and high thermal stability. The CNC II had a tunable length (26–57 nm), determined by the conditions of the MALBTH hydrolysis and the APS oxidation, but similar lateral dimension (8–10 nm). The characterization of the CHR by wide-angle X-ray diffraction and Fourier transform infrared spectroscopy verified the polymorphic transformation from cellulose I to II during the MALBTH treatment. The swelling of the BKP in the MALBTH enabled cellulose crystallites to slide and reassemble, which completed the rearrangement of cellulose chains from parallel to anti-parallel conformation (polymorph transformation from cellulose I to II). This study provided an efficient and green method to produce cellulose II nanocrystals with controllable aspect ratios via the simultaneous hydrolysis and polymorph transformation of cellulose I feedstocks.

Cite

Export

Save

Research Organization:: National Renewable Energy Lab. (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE)

DOE Contract Number:: DE-AC36-08GO28308

OSTI ID:: 1781611

Report Number(s):: NREL/JA-2800-79131; MainId:33357; UUID:f6fafe8b-5ef0-4961-a381-2f5d4b45beac; MainAdminID:19788

Journal Information:: Green Chemistry, Vol. 23, Issue 7

Country of Publication:: United States

Language:: English

References (53)

Cellulose: Fascinating Biopolymer and Sustainable Raw Material Klemm, Dieter; Heublein, Brigitte; Fink, Hans-Peter Angewandte Chemie International Edition, Vol. 44, Issue 22 https://doi.org/10.1002/anie.200460587	journal	May 2005
Wood-Derived Materials for Green Electronics, Biological Devices, and Energy Applications Zhu, Hongli; Luo, Wei; Ciesielski, Peter N. Chemical Reviews, Vol. 116, Issue 16 https://doi.org/10.1021/acs.chemrev.6b00225	journal	July 2016
Recent progress in cellulose nanocrystals: sources and production Trache, Djalal; Hussin, M. Hazwan; Haafiz, M. K. Mohamad Nanoscale, Vol. 9, Issue 5 https://doi.org/10.1039/C6NR09494E	journal	January 2017
Recent advances in regenerated cellulose materials Wang, Sen; Lu, Ang; Zhang, Lina Progress in Polymer Science, Vol. 53 https://doi.org/10.1016/j.progpolymsci.2015.07.003	journal	February 2016
Nanocellulose: a new ageless bionanomaterial Dufresne, Alain Materials Today, Vol. 16, Issue 6 https://doi.org/10.1016/j.mattod.2013.06.004	journal	June 2013
Nanocellulose–surfactant interactions Tardy, Blaise L.; Yokota, Shingo; Ago, Mariko Current Opinion in Colloid & Interface Science, Vol. 29 https://doi.org/10.1016/j.cocis.2017.02.004	journal	May 2017
Recent advances in the application of cellulose nanocrystals Grishkewich, Nathan; Mohammed, Nishil; Tang, Juntao Current Opinion in Colloid & Interface Science, Vol. 29 https://doi.org/10.1016/j.cocis.2017.01.005	journal	May 2017
Cellulose-Based Nanomaterials for Energy Applications Wang, Xudong; Yao, Chunhua; Wang, Fei Small, Vol. 13, Issue 42 https://doi.org/10.1002/smll.201702240	journal	September 2017
Critical insights into the reinforcement potential of cellulose nanocrystals in polymer nanocomposites Miao, Chuanwei; Hamad, Wadood Y. Current Opinion in Solid State and Materials Science, Vol. 23, Issue 4 https://doi.org/10.1016/j.cossms.2019.06.005	journal	August 2019
Optimization of the isolation of nanocrystals from microcrystalline cellulose by acid hydrolysis Bondeson, Daniel; Mathew, Aji; Oksman, Kristiina Cellulose, Vol. 13, Issue 2 https://doi.org/10.1007/s10570-006-9061-4	journal	April 2006
Tailoring the yield and characteristics of wood cellulose nanocrystals (CNC) using concentrated acid hydrolysis Chen, Liheng; Wang, Qianqian; Hirth, Kolby Cellulose, Vol. 22, Issue 3 https://doi.org/10.1007/s10570-015-0615-1	journal	April 2015
Characteristics and Properties of Carboxylated Cellulose Nanocrystals Prepared from a Novel One-Step Procedure Leung, Alfred C. W.; Hrapovic, Sabahudin; Lam, Edmond Small, Vol. 7, Issue 3 https://doi.org/10.1002/smll.201001715	journal	December 2010
Segal crystallinity index revisited by the simulation of X-ray diffraction patterns of cotton cellulose Iβ and cellulose II Nam, Sunghyun; French, Alfred D.; Condon, Brian D. Carbohydrate Polymers, Vol. 135 https://doi.org/10.1016/j.carbpol.2015.08.035	journal	January 2016
Highly thermal-stable and functional cellulose nanocrystals and nanofibrils produced using fully recyclable organic acids Chen, Liheng; Zhu, J. Y.; Baez, Carlos Green Chemistry, Vol. 18, Issue 13 https://doi.org/10.1039/C6GC00687F	journal	January 2016
Facile extraction of thermally stable cellulose nanocrystals with a high yield of 93% through hydrochloric acid hydrolysis under hydrothermal conditions Yu, Houyong; Qin, Zongyi; Liang, Banglei Journal of Materials Chemistry A, Vol. 1, Issue 12 https://doi.org/10.1039/c3ta01150j	journal	January 2013
Isolation of Thermally Stable Cellulose Nanocrystals by Phosphoric Acid Hydrolysis Camarero Espinosa, Sandra; Kuhnt, Tobias; Foster, E. Johan Biomacromolecules, Vol. 14, Issue 4 https://doi.org/10.1021/bm400219u	journal	March 2013
Cellulosic nanorods of various aspect ratios for oil in water Pickering emulsions Kalashnikova, Irina; Bizot, Herve; Bertoncini, Patricia Soft Matter, Vol. 9, Issue 3 https://doi.org/10.1039/C2SM26472B	journal	January 2013
Behavior of nanocelluloses at interfaces Capron, Isabelle; Rojas, Orlando J.; Bordes, Romain Current Opinion in Colloid & Interface Science, Vol. 29 https://doi.org/10.1016/j.cocis.2017.04.001	journal	May 2017
Unique Properties and Behavior of Nonmercerized Type-II Cellulose Nanocrystals as Carbon Nanotube Biocompatible Dispersants González-Domínguez, Jose M.; Ansón-Casaos, Alejandro; Grasa, Laura Biomacromolecules, Vol. 20, Issue 8 https://doi.org/10.1021/acs.biomac.9b00722	journal	June 2019
Understanding Longitudinal Wood Fiber Ultra-structure for Producing Cellulose Nanofibrils Using Disk Milling with Diluted Acid Prehydrolysis Qin, Yanlin; Qiu, Xueqing; Zhu, J. Y. Scientific Reports, Vol. 6, Issue 1 https://doi.org/10.1038/srep35602	journal	October 2016
Cellulose II nanoelements prepared from fully mercerized, partially mercerized and regenerated celluloses by 4-acetamido-TEMPO/NaClO/NaClO2 oxidation Hirota, Masayuki; Tamura, Naoyuki; Saito, Tsuguyuki Cellulose, Vol. 19, Issue 2 https://doi.org/10.1007/s10570-011-9642-8	journal	January 2012
Synthesis of redispersible spherical cellulose II nanoparticles decorated with carboxylate groups Beaumont, Marco; Nypelö, Tiina; König, Jakob Green Chemistry, Vol. 18, Issue 6 https://doi.org/10.1039/C5GC03031E	journal	January 2016
Characterization of cellulose II nanoparticles regenerated from 1-butyl-3-methylimidazolium chloride Han, Jingquan; Zhou, Chengjun; French, Alfred D. Carbohydrate Polymers, Vol. 94, Issue 2 https://doi.org/10.1016/j.carbpol.2013.02.003	journal	May 2013
Supramolecular Structure Characterization of Cellulose II Nanowhiskers Produced by Acid Hydrolysis of Cellulose I Substrates Sèbe, Gilles; Ham-Pichavant, Frédérique; Ibarboure, Emmanuel Biomacromolecules, Vol. 13, Issue 2 https://doi.org/10.1021/bm201777j	journal	February 2012
Cellulose dissolution in aqueous lithium bromide solutions Yang, Yeo-Jeong; Shin, Ji-Min; Kang, Tong Ho Cellulose, Vol. 21, Issue 3 https://doi.org/10.1007/s10570-014-0183-9	journal	February 2014
Preparation and Characterization of Regenerated Cellulose Film from a Solution in Lithium Bromide Molten Salt Hydrate Zhang, Xueqin; Xiao, Naiyu; Wang, Huihui Polymers, Vol. 10, Issue 6 https://doi.org/10.3390/polym10060614	journal	June 2018
Fabrication and Mechanistic Study of Aerogels Directly from Whole Biomass Liao, Yang; Pang, Zhiqiang; Pan, Xuejun ACS Sustainable Chemistry & Engineering, Vol. 7, Issue 21 https://doi.org/10.1021/acssuschemeng.9b04032	journal	September 2019
Cellulose II Aerogel‐Based Triboelectric Nanogenerator Zhang, Lei; Liao, Yang; Wang, Yi‐Cheng Advanced Functional Materials, Vol. 30, Issue 28 https://doi.org/10.1002/adfm.202001763	journal	May 2020
Comparative study of SPORL and dilute-acid pretreatments of spruce for cellulosic ethanol production Shuai, L.; Yang, Q.; Zhu, J. Y. Bioresource Technology, Vol. 101, Issue 9 https://doi.org/10.1016/j.biortech.2009.12.044	journal	May 2010
Mercury CSD 2.0 – new features for the visualization and investigation of crystal structures Macrae, Clare F.; Bruno, Ian J.; Chisholm, James A. Journal of Applied Crystallography, Vol. 41, Issue 2 https://doi.org/10.1107/S0021889807067908	journal	March 2008
Idealized powder diffraction patterns for cellulose polymorphs French, Alfred D. Cellulose, Vol. 21, Issue 2 https://doi.org/10.1007/s10570-013-0030-4	journal	August 2013
Comprehensive morphological and structural investigation of cellulose I and II nanocrystals prepared by sulphuric acid hydrolysis Flauzino Neto, Wilson Pires; Putaux, Jean-Luc; Mariano, Marcos RSC Advances, Vol. 6, Issue 79 https://doi.org/10.1039/C6RA16295A	journal	January 2016
A facile and fast method for quantitating lignin in lignocellulosic biomass using acidic lithium bromide trihydrate (ALBTH) Li, Ning; Pan, Xuejun; Alexander, Jane Green Chemistry, Vol. 18, Issue 19 https://doi.org/10.1039/C6GC01090C	journal	January 2016
Preparation of tough cellulose II nanofibers with high thermal stability from wood Wang, Haiying; Li, Dagang; Yano, Hiroyuki Cellulose, Vol. 21, Issue 3 https://doi.org/10.1007/s10570-014-0222-6	journal	March 2014
Production of cellulose nanofibrils from bleached eucalyptus fibers by hyperthermostable endoglucanase treatment and subsequent microfluidization Wang, Wangxia; Mozuch, Michael D.; Sabo, Ronald C. Cellulose, Vol. 22, Issue 1 https://doi.org/10.1007/s10570-014-0465-2	journal	October 2014
Isolation of cellulose nanocrystals from grain straws and their use for the preparation of carboxymethyl cellulose-based nanocomposite films Oun, Ahmed A.; Rhim, Jong-Whan Carbohydrate Polymers, Vol. 150 https://doi.org/10.1016/j.carbpol.2016.05.020	journal	October 2016
A Transition from Cellulose Swelling to Cellulose Dissolution by o -Phosphoric Acid: Evidence from Enzymatic Hydrolysis and Supramolecular Structure Zhang, Y. -H. Percival; Cui, Jingbiao; Lynd, Lee R. Biomacromolecules, Vol. 7, Issue 2 https://doi.org/10.1021/bm050799c	journal	February 2006
Periodic Disorder along Ramie Cellulose Microfibrils Nishiyama, Yoshiharu; Kim, Ung-Jin; Kim, Dae-Young Biomacromolecules, Vol. 4, Issue 4 https://doi.org/10.1021/bm025772x	journal	July 2003
Surface accessibility of cellulose fibrils studied by hydrogen–deuterium exchange with water Lindh, E. L.; Salmén, L. Cellulose, Vol. 24, Issue 1 https://doi.org/10.1007/s10570-016-1122-8	journal	November 2016
Direct Microwave-Assisted Hydrothermal Depolymerization of Cellulose Fan, Jiajun; De bruyn, Mario; Budarin, Vitaliy L. Journal of the American Chemical Society, Vol. 135, Issue 32 https://doi.org/10.1021/ja4056273	journal	July 2013
Structural FTIR analysis and thermal characterisation of lyocell and viscose-type fibres Carrillo, F.; Colom, X.; Suñol, J. J. European Polymer Journal, Vol. 40, Issue 9 https://doi.org/10.1016/j.eurpolymj.2004.05.003	journal	September 2004
Crystal Structure and Hydrogen-Bonding System in Cellulose Iβ from Synchrotron X-ray and Neutron Fiber Diffraction Nishiyama, Yoshiharu; Langan, Paul; Chanzy, Henri Journal of the American Chemical Society, Vol. 124, Issue 31 https://doi.org/10.1021/ja0257319	journal	August 2002
Mercerization of cellulose. II. Alkali–cellulose intermediates and a possible mercerization mechanism Okano, T.; Sarko, A. Journal of Applied Polymer Science, Vol. 30, Issue 1 https://doi.org/10.1002/app.1985.070300128	journal	January 1985
The relevance of structural features of cellulose and its interactions to dissolution, regeneration, gelation and plasticization phenomena Lindman, Björn; Medronho, Bruno; Alves, Luis Physical Chemistry Chemical Physics, Vol. 19, Issue 35 https://doi.org/10.1039/C7CP02409F	journal	January 2017
Mercerization of cellulose. I. X-ray diffraction evidence for intermediate structures Okano, T.; Sarko, A. Journal of Applied Polymer Science, Vol. 29, Issue 12 https://doi.org/10.1002/app.1984.070291247	journal	December 1984
Efficient extraction of carboxylated spherical cellulose nanocrystals with narrow distribution through hydrolysis of lyocell fibers by using ammonium persulfate as an oxidant Cheng, Miao; Qin, Zongyi; Liu, Yannan J. Mater. Chem. A, Vol. 2, Issue 1 https://doi.org/10.1039/C3TA13653A	journal	January 2014
Cellulose nanofibres by sonocatalysed-TEMPO-oxidation Rattaz, Aurélie; Mishra, Shree Prakash; Chabot, Bruno Cellulose, Vol. 18, Issue 3 https://doi.org/10.1007/s10570-011-9529-8	journal	March 2011
Extraction and comparison of carboxylated cellulose nanocrystals from bleached sugarcane bagasse pulp using two different oxidation methods Zhang, Kaitao; Sun, Peipei; Liu, He Carbohydrate Polymers, Vol. 138 https://doi.org/10.1016/j.carbpol.2015.11.038	journal	March 2016
Effect of Reaction Conditions on the Properties and Behavior of Wood Cellulose Nanocrystal Suspensions Beck-Candanedo, Stephanie; Roman, Maren; Gray, Derek G. Biomacromolecules, Vol. 6, Issue 2 https://doi.org/10.1021/bm049300p	journal	March 2005
Crystallite Width Determines Monolayer Hydration across a Wide Spectrum of Celluloses Isolated from Plants Driemeier, Carlos; Bragatto, Juliano The Journal of Physical Chemistry B, Vol. 117, Issue 1 https://doi.org/10.1021/jp309948h	journal	December 2012
Entire Surface Oxidation of Various Cellulose Microfibrils by TEMPO-Mediated Oxidation Okita, Yusuke; Saito, Tsuguyuki; Isogai, Akira Biomacromolecules, Vol. 11, Issue 6 https://doi.org/10.1021/bm100214b	journal	June 2010
Well defined thermostable cellulose nanocrystals via two-step ionic liquid swelling-hydrolysis extraction Lazko, Jevgenij; Sénéchal, Tangi; Landercy, Nicolas Cellulose, Vol. 21, Issue 6 https://doi.org/10.1007/s10570-014-0417-x	journal	September 2014
Comparative properties of cellulose nano-crystals from native and mercerized cotton fibers Yue, Yiying; Zhou, Chengjun; French, Alfred D. Cellulose, Vol. 19, Issue 4 https://doi.org/10.1007/s10570-012-9714-4	journal	May 2012

Similar Records

A study of TiO₂ nanocrystal growth and environmental remediation capability of TiO₂/CNC nanocomposites

Journal Article · Tue Jan 01 00:00:00 EST 2019 · RSC Advances · OSTI ID:1781611

Zhan, Chengbo; Li, Yanxiang; Sharma, Priyanka R.; +4 more

On the frequency shift of the C==O band in the infrared spectrum of gamma-irradiated cellulose I and cellulose II

Journal Article · Sat Jan 01 00:00:00 EST 1983 · J. Appl. Polym. Sci.; (United States) · OSTI ID:1781611

Bhama Iyer, P; Krishna Iyer, K R; Patil, N B

Chemical crosslinking of acrylic acid to form biocompatible pH sensitive hydrogel reinforced with cellulose nanocrystals (CNC)

Journal Article · Wed Sep 03 00:00:00 EDT 2014 · AIP Conference Proceedings · OSTI ID:1781611

Lim, Lim Sze; Ahmad, Ishak; Amin, Mohd. Cairul Iqbal Mohd

Related Subjects

29 EE - Bioenergy Technologies Office (EE-3B)
molten salt hydrate
nanocellulose
ammonium persulfate oxidation
amorphous cellulose hydrolysis
polymorph transformation

Title: Tailorable Cellulose II Nanocrystals (CNC II) Prepared in Mildly Acidic Lithium Bromide Trihydrate (MALBTH)

Citation Formats

References (53)

Similar Records

Related Subjects