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Materials Chemistry
Cite this: J. Mater. Chem., 2011, 21, 7507
www.rsc.org/materials HIGHLIGHT
Ultra-fine cellulose nanofibers: new nano-scale
materials for water purification
Hongyang Ma, Christian Burger, Benjamin S. Hsiao* and Benjamin Chu*
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DOI: 10.1039/c0jm04308g

The major challenges in membrane technology for water filtration are the development of
new materials (e.g. high durability, low cost and low environmental concerns) and new
structures (e.g. directed water channels) that can produce high permeation flux (thus low
energy input) while maintaining a high selectivity or rejection rate. This highlight discusses the
utilization of ultra-fine cellulose nanofibers (UCN, diameter 5--10 nm), made by TEMPO/NaBr/
NaClO oxidation of natural cellulose (e.g. wood pulp), in different nanofibrous composite
formats that can meet this challenge for microfiltration (MF) and ultrafiltration (UF)
applications. The unique features of ultra-fine cellulose nanofibers include small diameter, high
surface-to-volume ratio, easy surface functionality, good mechanical properties and good
chemical resistance. The electrospun nanofibrous scaffolds with fine pore size defined by the
fiber diameter could be used to remove waterborne bacteria at two to three times higher flux
when compared to that of commercial MF membranes (e.g., Millipore GS9035). When UCN
were used as a functionalized adsorbent infused in the asymmetric two-layered non-woven
fibrous format, the membranes exhibited a high ability to remove bacteria (by size exclusion)
and viruses (by adsorption) simultaneously. When UCN were used as the barrier layer in an
asymmetric three-layered non-woven fibrous format containing fibers of different diameters
(from 5 nm to 20 mm), the membranes exhibited a two- to ten-fold increase in permeation flux
over commercial membranes for ultrafiltration of oil and water emulsions (e.g., for purification
of bilge water in ships or industrially produced water).

1. Introduction purify water.7,8 TFC membranes typically be improved by adopting a different struc-
consist of two or three layers, where the ture, consisting of asymmetric layers of
Due to the rapid population growth, bottom layer is a tough, non-woven fibrous non-woven fibers with different diameters,
mounting energy concerns and increasing material (e.g., non-woven mat of poly- which is the purpose as demonstrated in
environmental crisis, the development of ethylene terephthalate, PET) providing this highlight. In this structure, the top
new and more energy efficient membranes mechanical strength to support upper layer barrier layer as well as the mid-layer
for water purification is becoming an (s) with desired barrier or selective proper- support can have high porosity and inter-
important task for the materials commu- ties. Strategies for increasing the filtration connected pores, leading to high perme-
nity.1--3 The essential characteristics of efficiency are commonly associated with ation flux for both microfiltration (MF)
next generation membranes should be improvements in the top barrier layer or/ and UF applications.10--15
high efficiency, high durability, low and the mid-layer support. For example, For the top barrier layer in TFC
operating pressure (low energy), low cost, conventional barrier layers produced by membranes, the choice of polymer mate-
and the ability to fabricate using envi- phase inversion methods in ultrafiltration rials has thus far been limited to poly-
ronmentally friendly processes.4--6 (UF) membranes have a lower porosity acrylonitrile (PAN), polysulfone (PSU),
In the current technology, the use of thin- (approximately 50% bulk porosity and polyethersulfone (PES), polyvinylidene
film composite (TFC) membranes has been 20% surface porosity for the barrier).9,10 fluoride (PVDF), cellulose acetate (CA),
proven as a robust and efficient way to The cavities in such barriers are asymmetric and cross-linked polyamide (PA, prepared
and disconnected, thereby increasing the by interfacial polymerization (IP)).3--5,7 All
Department of Chemistry, Stony Brook resistance to water permeation as well as the aforementioned materials have their
University, Stony BrookNY, 11794-3400, USA. increasing the fouling of feeding advantages as well as limitations with re-
E-mail: [email protected]; bchu@
notes.cc.sunysb.edu; Fax: +1 (631) 632-6518; substances. The filtration efficiency (i.e., gards to applications for water filtration.
Tel: +1 (631) 632-7793; +1 (631) 632-7928 permeation flux) of TFC membranes can For example, PAN, PSU, PES, and PVDF,

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typically used for fabrication of MF and layer thickness was above a certain defined by only two parameters, the fiber
UF membranes, have good chemical threshold value (of about 50 mm), both diameter and the bulk porosity, and has
resistance, good mechanical properties and mean and maximum pore sizes (determined no other adjustable parameters. The exact
are cost-efficient. However, their hydro- by capillary flow porometry) reached definition of a ‘‘pore size’’ is non-trivial for
phobic nature can dramatically decrease a plateau. Fig. 1 illustrates the correlations the type of scaffold sketched in Fig. 2, but
the water permeability during filtration of between the maximum pore size, mean pore these figures provide some intuitive insight
wastewater due to the tendency of oil, size (also determined by SEM image anal- into the nature of the pores and their sizes,
particle or biomacromolecule fouling.10,15 ysis of some previously published data28--31) which is consistent with our experimental
Cellulose acetate is pH sensitive and can and fiber diameter in a non-woven layer of results in Fig. 1. Thus, the pore sizes can be
only be used within a narrow pH range, sufficient thickness. It was found that the adjusted by controlling the fiber diameter
while cross-linked PA has a low tolerance mean and maximum pore size can be scaled of the electrospun membrane, allowing
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for chlorine.16,17 Often, volatile and toxic linearly with the fiber diameter, indepen- them to satisfy the requirements for
solvents have to be used for the utilization dent of the polymer material. The mean various MF and UF applications.
of these materials for membrane fabrica- pore size was found to be about 3
1 times
tion, causing environmental concerns. the mean fiber diameter, and the maximum 3. High-flux nanofibrous MF
While some new materials exhibiting pore size was about 10
2 times the mean membranes
excellent properties for water filtration fiber diameter.
have been developed,18--22 their complex To guide our understanding of the One of the most important applications of
preparation process, high cost, and envi- membrane properties in a non-woven struc- this type of membrane is to eliminate
ronmental concerns make them difficult to ture, 3D simulated non-woven web models, bacteria and viruses from contaminated
implement on an industrial scale. having different fiber diameters, were created drinking water. As shown in Fig. 3, elec-
All the problems mentioned above to illustrate the relationship between the fiber trospun nanofibrous PAN scaffolds (B),
should be carefully addressed for the diameter and the pore size. Fig. 2 shows deposited onto PET non-woven
development of next generation three non-woven models at a constant substrates (C), have been fabricated and
membranes with high-flux, high retention, porosity (i.e., 80%) in a fixed volume with used as a base scaffold for such an MF
energy-saving, and durability.23,24 In this a relative fiber diameter ratio of 1 : 3 : 10, filter. The fiber diameter of the electro-
highlight, we demonstrate that the use of generated using a random arrangement of spun nanofibers (in the range of 100 nm) is
ultra-fine cellulose nanofibers allowed us cylinders which were fused together and about two orders of magnitude finer than
to reach this goal, where the different visualized using the cylinder blob model that of the PET non-woven substrate
membrane formats have exhibited very (POV-Ray ray-tracing software32). (in the range of 20 mm).
high-flux MF and UF performance.25--27 Assuming a monodisperse fiber diam- Typically, the diameter of most water-
eter, a random placement of fiber borne bacteria is larger than 0.2 mm. To
segments in the reference volume, and the test the bacterial retention capability of
2. Correlations between absence of felting (i.e., 3D entanglement, nanofibrous MF membranes, two
membrane pore size and fiber which is a valid assumption for electro- common water-borne bacteria, E. coli and
diameter in a non-woven spun fibers and a good approximation for B. diminuta, having dimensions of 0.5 
structure collapsed fiber suspensions), as well as 2.0 mm and 0.3  0.9 mm, respectively,
neglecting details on how fiber segments were used. According to Fig. 1, to design
The new nanofibrous membranes with high touching each other are fused together, the a non-woven scaffold with a mean pore
filtration efficiency were designed based on 3D non-woven structure can be fully size of 0.3 mm, the mean fiber diameter
the principle that the pore size distribution should be around 100 nm. This was
of a non-woven layer structure is correlated accomplished by electrospinning a PAN
with the fiber diameter and the bulk or polyvinyl alcohol (PVA) nanofibrous
porosity (i.e., the volume fraction of the layer (thickness of 45
5 mm, fiber
void phase). For example, in electrospun diameter of 110
30 nm) onto the PET
nanofibrous scaffolds, the mean fiber non-woven substrate.26 In these
diameter typically ranges from 50 nm to membranes, the log reduction value
over 1 mm. The bulk porosity of electrospun (LRV) against E. coli was found to be
scaffolds is typically around 75--85%, higher than 6.0 (the original concentration
which can be compacted further by calen- of E. coli was 107 plaque forming units per
daring or pressing for practical filtration millilitre (pfu mL1) in phosphate buffer
use, thus lowering the porosity to around Fig. 1 Correlations between maximum pore solution, PBS, pH ¼ 7.2. The LRV against
size, mean pore size and mean fiber diameter in
65%. In this porosity range B. diminuta (107 pfu mL-1) was over 4.0.
nanofibrous scaffolds, fabricated by means of
(i.e., 65%--85%), electrospun PAN and PES To evaluate the high-flux nature of these
electrospinning technology and using different
non-woven nanofibrous scaffolds (with polymeric materials. Data points were ob- membranes (e.g. PAN electrospun
layer thicknesses between 10 and 100 mm) tained from capillary flow porometry and SEM membranes in Fig. 3(G)), the water
can be used as models to correlate the of PAN and PES scaffolds electrospun for this permeability and pressure drop were
membrane pore size and fiber diameter. It study, as well as image analysis of previously investigated. When the water flow rate was
was discovered that, when the scaffold published SEM images.25,28--31 kept constant at 192 L m2 h1, the pressure

7508 | J. Mater. Chem., 2011, 21, 7507--7510 This journal is ª The Royal Society of Chemistry 2011
 View Article Online

adsorption. The adsorption capacity would

depend on the total surface area of cellulose
nanofibers and the charge density on the
surface. Ultra-fine cellulose nanofibers have
a very high surface-to-volume ratio of
600 m2 g1 and a relatively high surface
charge density of 1.0 mmol g1 cellulose.
To design a high-flux MF membrane with
simultaneous bacteria and virus retention
capability, an infusion method was used to
Fig. 2 Illustration of the correlations between pore size and fiber diameter at a constant porosity of
80% in a fixed volume.
load ultra-fine cellulose nanofibers (diame-
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ters  5 nm, lengths  200 nm) into the

connected cavities of an electrospun PAN
scaffold. It was found that by limiting the
loading amount of UCN to 10 mg cm3, the
pressure drop could be maintained at 0.4 psi
and the water/aqueous solution flux could
be maintained at 192 L m2 h1. Naturally,
the mean pore sizes of such a membrane
became smaller after the modification.
Upon infusion with 10 mg cm3 UCN, the
mean pore size of the electrospun PAN top-
layer decreased from 0.38 to 0.22 mm, and
the rejection ratio of 0.20 mm nanoparticles
(in 100 ppm) increased significantly from
13.8% to 97.7%. Most importantly, the log
reduction value (LRV) of this membrane
against the virus MS2 at pH 7 increased
from 0 to 2.0, which was higher than that of
the negatively charged commercial GS9035
microfilter (Millipore, 1.0 LRV under the
same conditions). Further modification of
Fig. 3 (A) TEM image of ultra-fine cellulose nanofibers with 5 nm fiber diameter. (B) and (C) are this membrane involving the coating of
SEM images of PAN electrospun nanofibers (100 nm fiber diameter) and PET non-woven mi- positively charged polymers, such as poly-
crofibers (20 mm fiber diameter), respectively. (D) A depiction of a two-layered fibrous structure ethylenimine (PEI), could increase the LRV
for microfiltration of bacteria ((B) + (C)). (E) A depiction of a two-layered fibrous structure infused to 4.0 against MS2, while only slightly
with ultra-fine cellulose nanofibers for microfiltration of both bacteria and viruses ((A) in (B) + (C)). increasing the pressure drop to 0.7 psi.
(F) A depiction of a three-layered fibrous structure with the barrier layer coated with ultra-fine
cellulose nanofibers for ultrafiltration of oil/water wastewater ((A) + (B) + (C)). (G)--(I) are SEM
images of the cross-sectional view of (D)--(F), with mean pore sizes of 300, 200 and 20 nm, 4. High-flux nanofibrous UF
respectively. membrane
Based on the dimensions and surface prop-
drop was only 0.2 psi; significantly lower cellulose sources (e.g., wood pulps or erties of cellulose nanofibers, another
(by about an order of magnitude) than that cotton pulps) using a TEMPO/NaBr/ important application is their utilization as
of commercial MF membranes. NaClO oxidation process in an aqueous a barrier layer for ultrafiltration.26,27
While the above two-layered non- solution and mild mechanical treat- According to Fig. 1, a non-woven scaffold
woven fibrous membranes are efficient to ment.26,33--35 The high surface-to-volume of UCN with 5 nm diameter would define
remove bacteria by size exclusion, ratio, highly hydrophilic and functional- a mean pore size of 15 nm in the barrier
their pore sizes are too large to retain ized surface, good chemical resistance, layer, which would be suitable for ultrafil-
viruses (e.g., MS2 bacteriophage with high crystallinity, good mechanical tration. A 3-layered asymmetric fibrous
dimensions of 27  32 nm). To maintain properties, and relative microbial inert- membrane (termed thin-film nanofibrous
the high-flux nature (i.e., avoid an ness of ultra-fine cellulose nanofibers have composite (TFNC) membrane), containing
increase in pressure drop), ultra-fine led to many interesting applications.34,35 a UCN barrier layer, an electrospun mid-
cellulose nanofibers (UCN) were infused From the TEMPO/NaBr/NaClO treat- layer support and a bottom non-woven
into the above membrane as adsorbents ment, C6-positioned hydroxyl groups in substrate, has been constructed for this
to remove viruses based on charge inter- cellulose molecules are partially oxidized purpose. Its schematic structure is shown in
actions with the nanofiber surface. The into carboxylate/aldehyde groups, resulting Fig. 3(F) and the SEM cross-sectional view
ultra-fine cellulose nanofibers (diameters in coverage of a negatively charged of the barrier layer is shown in Fig. 3(I). As
 5 nm) can be fabricated from various surface,33 which is suitable for virus the hydroxyl/carboxylate groups in the

This journal is ª The Royal Society of Chemistry 2011 J. Mater. Chem., 2011, 21, 7507--7510 | 7509
 View Article Online

barrier layer are hydrophilic, this TFNC their applicability. One problem is that the Eng. Chem. Res., 2010, 49(23), 11978–
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Acknowledgements
TFNC membranes was above 99.5%, 26 B. Chu, B. S. Hsiao and H. Y. Ma, WO
significantly higher than that of these two Financial support of this work was 2010042647, 2010.
27 H. Y. Ma, C. Burger, B. S. Hsiao and
commercial membranes (typically provided by the Office of Naval Research B. Chu, Biomacromolecules, 2011, DOI:
<98.5%). Moreover, the UCN-based (N000140310932) and the National 10.1021/bm1013316.
TFNC membranes exhibited superior Science Foundation (DMR-1019370). 28 K. Lin, K. N. Chua, G. T. Christopherson,
anti-fouling properties when compared to S. Lim and H. Q. Mao, Polymer, 2007, 48,
6384–6394.
PAN-based or PES-based UF 29 H. J. Jin, S. V. Fridrikh, G. C. Rutledge and
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7510 | J. Mater. Chem., 2011, 21, 7507--7510 This journal is ª The Royal Society of Chemistry 2011