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com Current Opinion in
ScienceDirect
Preparation of cellulose nanofibers using green and
sustainable chemistry
Akira Isogai1 and Lennart Bergström1,2
The development of green and sustainable routes to liberate
crystalline cellulose microfibrils from plant cell walls is of
utmost importance to enable development of the large-scale
production of sustainable nanomaterials based on renewable
resources. The catalytic oxidation of cellulose using 2,2,6,6-
tetramethylpiperidine-1-oxyl radical (TEMPO) under aqueous
conditions at room temperature is a position-selective and
efficient chemical modification. TEMPO-mediated oxidation of
plant cellulose fibers, followed by gentle mechanical disinte-
gration of the oxidized celluloses in water, results in the for-
mation of TEMPO-oxidized cellulose nanofibers (TOCNs) with
homogeneous widths (~3 nm) and high aspect ratios. TOCNs
are characteristic bio-based materials with high tensile
strengths and elastic moduli. Sodium carboxylate groups are
densely present on the crystalline TOCN surfaces and can
undergo counterion exchange from sodium to other metal or
alkylammonium ions under aqueous conditions. The hydro-
philic/hydrophobic, stable/biodegradable, super deodorant,
catalytic, and other functionalities of TOCNs can be controlled
through counterion exchange.
Addresses
1 waste water, is formed during the isolation and purifi-
Department of Biomaterial Sciences, The University of Tokyo, 1-1-1
Yayoi, Bunkyo-ku, Tokyo 113-8657, Japan
2
Department of Materials and Environmental Chemistry, Stockholm
University, Svante Arrhenius Väg 16C, S-106 91 Stockholm, Sweden
Corresponding author: Isogai Akira (aisogai@mail.ecc.u-tokyo.ac.jp)
Current Opinion in Green and Sustainable Chemistry 2018,
12:15–21
This review comes from a themed issue on Green and Sustainable
Nanotechnology
Edited by Karen Edler, Janet L. Scott and Davide Mattia
Available online 19 April 2018
https://doi.org/10.1016/j.cogsc.2018.04.008
2452-2236/© 2018 Elsevier B.V. All rights reserved.
Introduction
The efficient utilization of plant biomass resources for
the production of energy and materials is indispensable
for a sustainable society. Wood biomass can provide a
persistent supply of renewable resources that do not
compete with food production. Plant cell walls consist of
cellulose, hemicelluloses, and lignin as predominant
components and cellulose fibers derived from wood have
been predominantly used as paper and board materials,
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Green and Sustainable Chemistry
as well as for cellulose-related products, such as viscose
rayon fibers and various cellulose derivatives.
The hierarchical structure of wood and the nano-
composite structures formed between cellulose, hemi-
celluloses, and lignin are responsible for the high
strength, stability, and durability of plants. Plant cellu-
lose walls contain crystalline and stable cellulose mi-
crofibrils with widths of w3 nm [1e3], each composed
of 20e40 fully extended cellulose chains. Cellulose
microfibrils are therefore bio-based nanofibers that are
continuously photosynthesized and accumulated in
plants, and are most abundantly present on earth.
Conventional routes for cellulose utilization include
effluent treatment, which may cause a significant envi-
ronmental burden. For example, the dissolution of cel-
lulose and cellulose derivatization, such as esterification
and etherification, usually require large amounts of sol-
vents and can involve toxic reagents [4e7]. As a
consequence, a significant amount of washing effluent,
which requires treatment before being discarded as
cation of regenerated cellulose fibers and cellulose
derivatives.
Nanocelluloses are defined as cellulose particles of
widths <100 nm. They originate from crystalline cel-
lulose microfibril structures and possess high strengths,
high elastic moduli, and large surface areas [8e13].
Nanocelluloses, produced by environmentally friendly
means, can therefore combine outstanding properties
with small or negligible carbon footprints compared with
inorganic and petroleum-based nanomaterials. The
efficient production of wood cellulose fibers using
modern pulping and bleaching technologies on an in-
dustrial scale can yield an inexpensive raw material for
nanocellulose production costing w60 cents per dry kg.
Pretreatments for preparation of cellulose
nanofibers
The outstanding stability of cellulose microfibrils,
resulting from numerous interfibrillar hydrogen bonds,
make completely separation of individual cellulose mi-
crofibrils from wood cellulose fibers impossible using
only mechanical disintegration in water. Cellulose
nanofibers (CNFs), as heterogeneous network struc-
tures with widths of 10e50 nm, can be prepared from
wood cellulose fibers suspended in water by repeated
high-pressure homogenization, but the production of
Current Opinion in Green and Sustainable Chemistry 2018, 12:15–21
16 Green and Sustainable Nanotechnology
such mechanically disintegrated CNFs requires large
amounts of energy (>200 kWh/kg) [10,11,13].
Recently, various mild pretreatments for wood cellulose
fibers before mechanical disintegration in water have
been developed, including endoglucanase treatment
[11,14], carboxymethylation [11,15], phosphorylation
[16], acetylation, and periodate oxidation with subse-
quent NaClO2-oxidation [17]. Catalytic oxidation with
2,2,6,6-tetramethylpiperidine-1-oxyl radical (TEMPO)
under aqueous conditions has been developed as a
pretreatment of plant cellulose fibers to efficiently
prepare new nanocelluloses [10,18e21].
de Nooy et al. first developed the TEMPO/NaBr/
NaClO oxidation of water-soluble polysaccharides in
water at pH 10, which converted primary hydroxy groups
of polysaccharides to sodium carboxylate groups [22].
This TEMPO-mediated oxidation was advantageous in
terms of reaction selectivity and efficiency, and
proceeded at lower temperatures than conventional
chemical reactions for introducing carboxy groups onto
cellulose. (Such conventional approaches include
carboxymethylation, N2O4 oxidation in chloroform, and
periodate oxidation with subsequent NaClO2 oxida-
tion.) The reaction used TEMPO and NaBr as catalysts,
with NaClO as the primary oxidant, leading to formation
of NaCl during oxidation [10]. Furthermore, a small
Figure 1
N-Hydroxy-TEMPO
TEMPO
TEMPO+
TEMPO-mediated oxidation
R-CH2OH + 2NaClO + NaOH
Mechanism of TEMPO-mediated oxidation for the conversion of primary hydroxy groups in cellulose into sodium C6-carboxylate groups using TEMPO/
NaBr/NaClO in water at pH 10 [10].
Current Opinion in Green and Sustainable Chemistry 2018, 12:15–21
amount of 0.5 M NaOH was simultaneously consumed
to neutralize carboxy groups formed during oxidation to
sodium carboxylate groups to keep the reaction medium
at pH 10 (Figure 1) [10].
When the TEMPO/NaBr/NaClO oxidation was applied
to water-insoluble wood cellulose fiber (or paper-grade
softwood bleached kraft pulp) suspended in water at
pH 10, the carboxylate contents of the cellulose
increased from 0.01 mmol/g to w1.7 mmol/g, depending
on the amount of NaClO added [10,20]. Importantly,
the reaction preserved the original fibrous morphology
of wood cellulose. The cellulose I crystal structure,
crystal widths, and crystallinities of the original wood
celluloses were unchanged by oxidation [10,18e
21]. TEMPO-mediated oxidation under optimized
conditions resulted in the selective and complete
oxidation of only C6-hydroxy groups exposed on the
crystalline cellulose microfibril surfaces [10,18e
21]. The TEMPO-mediated oxidation of native cel-
luloses can therefore be regarded as a green chemistry
route that proceeds under aqueous conditions at room
temperature and atmospheric pressure.
Alternatives to the above TEMPO/NaBr/NaClO oxida-
tion in water at pH 10 include TEMPO/NaClO/NaClO2
oxidation at higher temperatures (30e60  C) in water
under neutral or acidic conditions for 1e3 days
Sodium glucuronosyl unit
pH 8−10.5
Glucosyl unit
R-COONa + 2NaCl + 2 H2O
Current Opinion in Green and Sustainable Chemistry
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[10,23,24], and TEMPO electro-mediated oxidation
in water under neutral conditions [25,26]. In TEMPO/
NaClO/NaClO2 oxidation, TEMPO and NaClO behave
as catalysts and NaClO2 is the primary oxidant. TEMPO
electro-mediated oxidation is a chlorine-containing
oxidant-free system that generates TEMPO-oxidized
celluloses with high aldehyde contents [26].
Preparation of TEMPO-oxidized cellulose
nanofibers (TOCNs)
The gentle mechanical disintegration of aqueous sus-
pensions of fibrous wood TEMPO-oxidized celluloses
with sodium carboxylate contents of >1 mmol/g gener-
ates highly viscous and transparent gels. Transmission
electron microscopy (TEM) and atomic force microscopy
(AFM) observation showed that the gels consisted of
completely individualized TEMPO-oxidized cellulose
nanofibers (TOCNs) with homogeneous widths
(w3 nm). Osmotic effects and electrostatic repulsion
Figure 2
Conversion of wood cellulose fibers into TEMPO-oxidized cellulose nanofibers (TOCNs) ~3 nm in width through TEMPO-mediated oxidation and
subsequent gentle mechanical disintegration of oxidized cellulose in water.
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Cellulose nanofiber Isogai and Bergström 17
between the carboxylated TOCNs were responsible for
the complete individualization of wood cellulose micro-
fibrils in each cellulose fiber (Figure 2) [10,18e20].
TOCNs differ from other CNFs in several important
aspects: (i) Energy consumption for TOCN production
is low (<1 kWh/kg); (ii) TOCNs are completely indi-
vidualized in water and have small homogeneous widths
of w3 nm and high aspect ratios of >150; (iii) abundant
sodium carboxylate groups are densely present on the
crystalline TOCN surfaces and can be easily ion-
exchanged with other metal or alkylammonium ions;
and (iv) self-assembled, nematic ordered structures are
formed between TOCN elements, resulting in small
domains or clusters in water [10,13]. These attractive
preparation, morphology, surface nanostructure, and
self-assembly characteristics of TOCNs should be taken
into account in the processing and applications of this
renewable nanomaterial.
Current Opinion in Green and Sustainable Chemistry 2018, 12:15–21
18 Green and Sustainable Nanotechnology
Characteristics and surface modifications
of TOCNs
The tensile strengths of individual TOCN elements are
as high as w3 GPa when measured using the sonication-
induced fragmentation method [27], while the elastic
moduli of wood TOCNs are w140 GPa [28]. The ten-
sile strengths of TOCNs are similar to those of multi-
walled carbon nanotubes and polyamide fibers.
TOCN films, prepared from aqueous TOCN disper-
sions by casting and drying, are transparent, strong, and
flexible, and display high oxygen-barrier properties and
low coefficients of thermal expansion under dry condi-
tions [29,30]. The outstanding properties of TOCN
films have been related to the formation of self-
assembled domains with nanolayered, dense, and pore-
free structures [31]. Transparent, strong, and flexible
TOCN aerogels with excellent thermal insulation
properties can be prepared from TOCN-COOH
hydrogels through super critical point drying after sol-
vent exchange [32]. The network structure of TOCN
aerogels can be tuned using the drying method, which
Figure 3
Improvement of hydrophobic, water-resistant, and oxygen-barrier properties of TOCN films through counterion exchange of sodium carboxylate groups
with alkylammonium or metal ions [39,40]. Copyright 2014 and 2016. Reproduced with permission from the American Chemical Society and Elsevier Ltd.
Current Opinion in Green and Sustainable Chemistry 2018, 12:15–21
involves freeze-drying TOCN/water/tert-butanol mix-
tures, resulting in spider-web-like network structures
[33]. TOCN-containing composite films with excellent
mechanical, optical, electric, and oxygen-barrier prop-
erties can be prepared by casting and drying mixtures of
TOCN dispersions with aqueous solutions of poly(vinyl
alcohol) [34] and poly(acrylamide) [35], and aqueous
dispersions of nanoclays [36] and surface-hydrophilized
carbon nanotubes [37].
The sodium counterion of TOCN-COONa can be ion-
exchanged with protons by adding dilute HCl solution
to aqueous TOCN-COONa dispersions [31]. Figure 3
shows how counterion exchange from sodium to other
metal or alkylammonium ions can be efficiently
achieved under aqueous conditions. Counterion ex-
change with quaternary alkylammonium ions results in
TOCN-COONR4 films with hydrophobic properties
[38]. When TOCN-COONa films are soaked in various
aqueous metal chloride solutions, washed with water,
and dried, the resultant TOCN-COOM (M: metal ion)
films have high wet-tensile strengths [39]. TOCN-
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COONa films exhibit low oxygen permeabilities under
dry conditions, that significantly increase with
increasing relative humidity. In contrast, when the
counterions of TOCN films are exchanged with calcium
or iron ions, the oxygen-barrier properties are main-
tained, even at high relative humidities [39].
Aqueous TOCN-COOAg and TOCN-COOCu(II) dis-
persions spread onto filter paper exhibit super
deodorant properties toward H2S and CH3SH gases
[40]. The biodegradable/stable properties of TOCN
films and TOCN dispersions are also controllable using
counterion exchange [41,42]. Furthermore, TOCNs are
excellent binders for scaffolds of metal nanoparticles
and metal-organic frameworks with unique catalytic
functionalities [43e46].
Conclusions and perspectives
Since 2013, TOCNs have been commercialized as stable
ink dispersants for ballpoint pens with smooth writing
[47] and in disposable diapers with super deodorant
functionalities for adults [48]. In April 2017, Nippon
Figure 4
Concept of utilization cycle from wood biomass resources to advanced and commodity materials and devices using TEMPO-oxidized cellulose
nanofibers to establish a sustainable society.
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Cellulose nanofiber Isogai and Bergström 19
Paper Industries began TOCN production at a capacity
of 500 ton/year in the Ishinomaki Mill, Miyagi, Japan
[49]. Based on the characteristic properties and func-
tions of TOCNs relative to other materials, various
advanced and commodity materials containing wood
TOCNs are expected to be commercialized in the near
future. The establishment of such a material stream
from forestry to industry is promising for the establish-
ment of a sustainable society based on renewable wood
biomass resources (Figure 4).
However, as TOCNs were only first developed in 2006,
there remain fundamental problems that need to be
resolved to enable their practical applications. A deter-
mination method for the length and length distributions
of wood TOCNs should be established. Furthermore,
the thermal stability of TOCNs needs to be improved
for thermal molding processes with plastics. Additional
fundamental, experimental, and theoretical data should
be accumulated to apply TOCNs as reliable bio-based
nanomaterials, as in the case of conventional polymers,
glasses, metals, and papers.
Current Opinion in Green and Sustainable Chemistry 2018, 12:15–21
20 Green and Sustainable Nanotechnology
Acknowledgments
This research was supported by Core Research for Evolutional Science and
Technology (CREST, Grant number JPMJCR13B2) of the Japan Science
and Technology Agency (JST). LB wishes to thank the University of Tokyo
for funding a Visiting Professorship at the Graduate School of Agricultural
and Life Sciences. We thank Simon Partridge, Ph.D., from Edanz Group
(www.edanzediting.com/ac) and Professor Janet L. Scott, Guest Editor of
this journal, for editing a draft of this manuscript.
Conflicts of interest
There are no conflicts to declare.
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