CELLULOSE NANOFIBERS PREPARED

BY TEMPO-MEDIATED OXIDATION
UNDER ACID CONDITIONS
Saito, T.*, Fukuzumi H., Hirota M., Isogai, A.
Graduate School of Agricultural and Life Sciences, The
University of Tokyo, Japan
ABSTRACT
We found a route to disperse cellulose in water as
individual cellulose microfibrils by surface oxidation of
the fibrils using a stable nitroxyl catalyst under weakly
acidic conditions. The dispersed fibrils were 5 nm in width
and more than a few microns in length, and had high
degrees of polymerization of more than 900. A film
formed by drying the fibril dispersion was transparent and
flexible, and exhibited a quite-high tensile strength of 312
MPa.
BACKGROUND
Plant cellulose is synthesized in cell walls as
microfibrils consisting of dozens of directionally-aligned
molecular chains set in a highly crystalline arrangement
[1]. The cellulose microfibrils have extremely high aspect
ratios, and exhibit high stiffness, low thermal expansion
and yet lightness in weight. Thus, as suitable applications
of such nano-sized crystalline fibrils, reinforcement
components in flexible display panels [2] and oxygenbarrier layers in packaging films [3] have been recently
proposed. The individual fibrils, however, have hydroxyl
groups on their surfaces at high density and are firmly
assembled with one another in the cell walls by multiple
hydrogen bonds to support living bodies.
In our laboratory, we found a route to disperse plant
celluloses in water as crystalline nanofibers, namely
individual microfibrils, with regular widths of 3-5 nm and
average lengths of 0.5-1 microns [3-5]. The process relies
on a catalytic oxidation using 2,2,6,6tetramethylpiperidine-1-oxyl radical (TEMPO) in water.
The TEMPO-mediated oxidation can selectively oxidize
the primary hydroxyl groups on the fibril surfaces to
carboxyls, which develop anionic charges in water. The
repulsive effects work between the fibrils, and
consequently the oxidized celluloses disperse in water as
the individual fibrils, assisted by mild mechanical
disintegration.
The TEMPO-mediated oxidation has been applied to
celluloses, using NaBr and NaClO as an additional
catalyst and primary oxidant, respectively, at pH 9-11
[6,7]. However, side reactions including remarkable
depolymerization are inevitable in the
TEMPO/NaBr/NaClO system under alkaline conditions.
The degree of polymerization (DP) has a direct
relationship with the length of individual microfibrils and
mechanical properties of their applications [8]. To
*

Author for correspondence. E-mail: asaitot@mail.ecc.utokyo.ac.jp

maintain the structural potential of cellulose fibrils during

the oxidation, therefore, the catalytic oxidation system
should be applied to cellulose under weakly acidic
conditions. In addition, the aldehyde groups formed as
intermediate structures always remain to some extent in
the oxidized celluloses prepared by the
TEMPO/NaBr/NaClO system. These aldehyde groups are
thermally unstable and cause discoloration of the oxidized
celluloses when heated or dried at more than 80C.
Moreover, the residual aldehyde groups disturb the
dispersion of the oxidized celluloses as individual fibrils
in water by partial formation of hemiacetal linkages
between the fibrils.
In the present study, we applied the
TEMPO/NaClO/NaClO2 system [9] to cellulose under
aqueous conditions and characterized the oxidized
products. Here, sodium chlorite is used as the primary
oxidant, which immediately oxidizes aldehyde groups
formed as intermediate structures, to carboxyl groups
under weakly acidic conditions.
EXPERIMENTAL
Hardwood bleached kraft pulp (1 g) was suspended in
0.05 M sodium phosphate buffer (90 mL, pH 6.8)
dissolving TEMPO (0.016 g, 0.1 mmol) and sodium
chlorite (80%, 1.13 g, 10 mmol) in an airtight flask. The 2
M sodium hypochlorite solution (0.5 mL, 1.0 mmol) was
diluted to 0.1 M with 0.05M sodium phosphate buffer at
pH 6.8 and was added at one step to the flask. The flask
was immediately stoppered, and the suspension was
stirred at 60C for a designated time. After cooling the
suspension to room temperature, the oxidized celluloses
were thoroughly washed with water by filtration.
The TEMPO-oxidized cellulose with carboxylate
contents of more than 0.7 mmol/g was suspended in water
at a consistency of 1-3% (w/v), and the pH of the slurry
was set to 8 with 0.01 M NaOH. A blender (Excel Auto
Homogenizer, Nihonseiki, Japan) was first applied to the
slurry (20 mL) for 30 s, and sonication was then applied
for 60 s to the suspension (20 mL) diluted with water to a
consistency of 0.1%, using an ultrasonic homogenizer
(US-300T, Nihonseiki, Japan) at 19.5 kHz and an output
power of 300W. The suspension thus obtained was
centrifuged at 10,000 g to separate the supernatant from
the unfibrillated and partially fibrillated fraction, which
was then disintegrated again using mechanical and
ultrasonic homogenizers in water at pH 8. Almost all of
the TEMPO-oxidized celluloses were able to be converted
to the supernatant fraction by repetition of the above
treatments.
RESULTS AND DISCUSSION
In the oxidation of cellulose using the
TEMPO/NaClO/NaClO2 system, the pH of the reaction
medium was an important factor to effectively oxidize the
primary hydroxyls to carboxyl groups. The oxidation
successfully proceeded at pH 6.8, while nearly no
carboxylate groups were formed at pH 3.5. At pH 6.8, the
carboxylate content readily rose to 0.7 mmol/g, and then

Carboxylate content (mmol/g)

1200

0.6

900
0.4

Carboxylate content
Degree of polymerization

0.2

0.0

600

300

10

20

30

40

50

Degree of polymerization

1500

0.8

Reaction time (h)

Figure 1: Carboxylate content and degree of

polymerization of the celluloses oxidized by the
TEMPO/NaClO/NaClO2 system at pH 6.8.

500 nm

Figure 2: TEM image of the individual fibrils

dispersed in water by mechanical disintegration
of the oxidized cellulose and (inset) a highly
viscous and transparent gel of the fibrils at a
consistency of 0.3%.
gradually increased up to 0.8 mmol/g by the oxidation
(Figure 1). The 0.8 mmol/g of carboxylate contents
corresponds to about 15% of the entire primary hydroxyl
groups of the cellulose. No aldehyde groups were present
in the oxidized products. The oxidized products were
recovered at yields of 98-100% by filtration for all of the
conditions examined. In the case of the
TEMPO/NaBr/NaClO system, the yields of the oxidized
products generally decrease to 70-80% by side reactions.
The degrees of polymerization (DP) of the oxidized
celluloses were maintained at sufficiently high values of
more than 900 (Figure 1), and the substantial
depolymerization during the TEMPO-mediated oxidation
was found avoidable by using the TEMPO/NaClO/NaClO2
system at pH 6.8. In addition, the X-ray diffraction
patterns of both the original and oxidized celluloses were

almost identical and were typical for the cellulose I

allomorph forming native cellulose. Accordingly, the
crystal widths calculated from the diffraction pattern using
Scherrers equation were also unchanged before and after
the oxidation. These results show that the oxidation did
not proceed into the inside of crystalline structure forming
a cellulose fibril, and the carboxyl groups were formed by
the oxidation of primary hydroxyl groups exposed on the
fibril surfaces.
A highly viscous and transparent gel was obtained
from the oxidized cellulose having carboxyl groups of 0.8
mmol/g by mild mechanical disintegration in water. The
gel consisted of individual fibrils with widths of
approximately 5 nm and lengths of more than a few
microns (Figure 2). The electron diffraction diagram of the
gel constituents proved also that they were the crystalline
fibrils maintaining the cellulose I allomorph. Moreover, a
film formed by drying the fibril dispersion was transparent
and flexible. Because the DP values and the aspect ratios
of cellulose fibrils were sufficiently high, the transparent
film consisting of the crystalline fibrils alone exhibited a
quite-high tensile strength of 312 MPa.
CONCLUSIONS
Individualization of highly-crystalline and nano-sized
cellulose fibrils was achieved by surface oxidation of the
fibrils using a TEMPO catalyst at neutral pH and mild
mechanical disintegration of the oxidized cellulose in
water. The individual fibrils thus obtained were 5 nm in
width and more than a few microns in length, and had
high degrees of polymerization of more than 900.
Consequently, a film of such nano-sized fibrils had optical
transparency, high toughness and yet lightness in weight.
Moreover, because carboxyl groups are present on the
fibril surfaces at high density, further functionalizations of
the cellulose fibrils are also available by versatile
reforming technologies of carboxyl groups.
ACKNOWLEDGEMENTS
This research was supported as a Nanotech Challenge
Program from 2007 by the New Energy and Industrial
Technology Development Organization of Japan (NEDO,
Grant number 1023001) and by Grants-in-Aid for
Scientific Research (Grant number 18380102 and 1810902) from the Japan Society for the Promotion of
Science (JSPS).
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