Article

pubs.acs.org/cm

Macroporous Titanate Nanotube/TiO2 Monolith for Fast and Large-

Capacity Cation Exchange
Kenji Okada, Genki Asakura, Yasuaki Tokudome, Atsushi Nakahira, and Masahide Takahashi*
Department of Materials Science, Graduate School of Engineering, Osaka Prefecture University, Sakai, Osaka, 599-8531, Japan
*
S Supporting Information

ABSTRACT: Centimeter-scale monolithic composites con-

stituted of titanate nanotubes (TNTs) and titania nanoparticles
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were hydrothermally prepared from a concentrated aqueous

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emulsion of anatase TiO2 powder. The monolith was

composed of a nanotube-interconnected framework containing
micrometer-scale pores. Enhanced growth of TNTs in cavities
surrounded by TNT/TiO2 aggregated particles resulted in the
formation of entangled/interconnected TNT bridges between
TNT/TiO2 aggregates. The macroporosity depends on a
volume fraction of anatase to the aqueous solution. The
resulting monolithic TNT/TiO2 composite had sufficient
mechanical strength for various applications. The monolith exhibited a faster rate and a higher capacity of Li+ exchange than
simple compacted TNTs. The TNT monolith has potential in cation exchange and adsorption applications, because of its
macroporous flow channels.

■ INTRODUCTION
A titanate nanotube (TNT) is a 1D nanomaterial that has been
widely investigated since the first report in 1998.1 A tubular
TNT of 5−10 nm in diameter and tens to several hundreds of
nanometers in length exhibits n-type semiconductivity, photo-
catalytic activity, high specific surface area, and cation-exchange
behavior.2 Thus, TNT is a promising material for catalysts,3,4
hydrogen and Li storage,5−7 and electrodes for Li batteries.8
Controlling the nanostructure,9−12 macrostructure,13−15 and
orientation of TNTs can potentially enhance their proper-
ties,16,17 and promote their use in specific applications. For
example, vertically oriented TNTs are useful in field-emission
devices18 and superhydrophobic surfaces with switchable and
reversible water adhesion.19,20
TNTs are generally obtained as powders from the hydro-
thermal treatment of TiO2 with aqueous NaOH. Bulk-shaped
TNTs on the centimeter scale are usually preferred to powder
TNTs in catalysts, adsorbents, and hydrogen and Li+ storage
materials, because they are more easily handled and separated
from solution. Bulky TNTs can be formed from powdery
TNTs using polymer or amorphous binders. However, the
binders can obstruct cation-exchange sites in the interlayers of
the titanate structures, and active sites for adsorption of specific
ions and catalysts. Nakahira et al. prepared bulky TNTs without
using a binder; powdery TNTs were prepared and then shaped
by hydrothermal hot-pressing (HHP) treatment.21,22 HHP
treatment with a small amount of water induced compression
and cohesion between the TNTs. A high-density TNT pellet
was fabricated, without collapse of their tubular structures.
However, active sites are limited to the surfaces of bulk
materials, because of the absence of flow channels inside the
bulk materials for the rapid diffusion of adsorbate.23,24 Bulk
TNTs with macropores are, therefore, preferable in catalysts,
absorbents, and hydrogen and Li+ storage materials.
Herein, we prepared TNT monoliths with a hierarchical
architecture of nanopores and macropores, by a hydrothermal
reaction at much higher TiO2 concentration than conventional
conditions. Powdery TNTs are typically prepared by the
hydrothermal treatment of a small amount of TiO2 powder in
aqueous 10 M NaOH (e.g., 1 g of TiO2 in 50 mL of 10 M
NaOH aq) at 150 °C.14 The consumption of precursor TiO2
induces extensive TNT nucleation and growth, and powdery
TNTs are obtained after washing and drying the resulting white
suspension. Bavykin et al. reported the effect of TiO2/NaOH
molar ratio on TNT morphology.25 At high TiO2/NaOH ratio
(e.g., 9 g of TiO2 in 300 mL of 10 M NaOH aq), TNTs
aggregated into secondary particles larger than 10 μm. We
recently reported the use of a patterned TiO2 film as a TNT
precursor. TNTs grew faster and longer within micrometer-
scale grooves, than on the film surface.26 TNTs became
entangled and filled grooves in the early stage of reaction.
Introducing small cavities between TNT secondary particles is
expected to form entangled TNT bridges, and the TNT bridges
to then form a network within the entire monolith. In the
current study, a lower amount of NaOH aqueous solution and
correspondingly higher TiO2/NaOH ratio (e.g., 0.4 g of TiO2
in 2 mL of aqueous NaOH (5 M)) yielded TNT secondary
particles and intervening TNT bridges within small cavities.
The TNT bridges promoted the formation of three-dimen-
Received: January 15, 2015
Published: February 9, 2015

© 2015 American Chemical Society 1885 DOI: 10.1021/acs.chemmater.5b00184

Chem. Mater. 2015, 27, 1885−1891
Chemistry of Materials
sional TNT frameworks. The dense and entangled TNTs
formed in small cavities resulted in other more sparse TNT
areas. The TNT density variation yielded continuous macro-
pores, which were suitable for liquid transport within the
monolith. The porosity of a TNT monolith depends on a
volume fraction of anatase to NaOH aqueous solution. The
pore volume is controllable from porous (3.7 cm3/g) to dense
(0.6 cm3/g) states without any templating agents and porogens.
The monolith has potential as an adsorption media thanks to its
hierarchical architecture. The monolith exhibited a faster rate
and a higher capacity of Li+ exchange than a TNT pellet
fabricated by the HHP method. The exchange capacity is
comparable to that of the commercially available ion-exchange
resins.
■ EXPERIMENTAL SECTION
Preparation of TNT Monolith. To anatase powder (0.025−3.0 g;
ST-21, Isihara Sangyo, Co., Ltd., Japan), 5 M aqueous NaOH (2 mL)
was added in a polytetrafluoroethylene container (diameter: 30 mm,
height: 40 mm). The container was sealed in a stainless steel autoclave,
and heated at 130 °C for 2−168 h. After reaction, the monolithic
product in the bottom of the container was collected and washed with
aqueous HCl (pH 3) for 24 h. The products were slowly dried at 40
°C for 48 h.
Preparation of TNT Pellet. A TNT pellet without macropores
was prepared as a reference sample for comparing Li+ adsorption. The
TNT pellet was prepared by the HHP treatment of pure TNT powder
according to Nakahira et al.21,22 TNT powder was first prepared by the
hydrothermal treatment of anatase powder (1.0 g) with aqueous 10 M
NaOH (10 mL). The product was washed with aqueous HCl (pH 3)
for 24 h, and then collected by filtration. The TNT powder (1.0 g) was
then loaded into an HHP autoclave with deionized water (0.2 mL).
The sample was heated to 150 °C at 10 °C/min, under 40 MPa for 2
h. The autoclave was allowed to cool and then opened, and the TNT
pellet was collected.
Characterization. Macrostructures and nanostructures were
observed by a field emission SEM (S-4800, Hitachi, Japan).
Nanostructures and microstructures were observed by TEM (JEM-
2000FX; JEOL, Japan), operated at 200 kV. Crystal structures were
characterized by XRD, using CuKα radiation (λ = 0.154 nm) on a
Rigaku diffractometer (MultiFlex; Rigaku, Japan). The macroporosity
of samples was investigated by mercury intrusion porosimetry (Micro
Meritics Autopore IV 9520 type; Shimazu Co., Ltd., Japan). BET
surface areas were determined from N2 sorption measurements
(BELSORP-mini II; Bel Japan Inc., Japan). Samples were first
degassed under vacuum at 150 °C. Specific surface areas were
estimated by the BET method. The value of pore volume was
calculated by combining results of molar ratio (anatase:TNT) from
XRD and bulk density of the obtained monolith. The weight (Mbulk)
and volume (Vbulk) of the obtained bulk were measured by an electric
balance and a ruler, respectively. A volume of both components
(anatase and TNT) (Vmaterials) in the monolith was estimated by using
a molar ratio of anatase/TNT from XRD and a known density of
anatase (3.903 g/cm3) (JCPDS 84-1286) and TNT (3.164 g/cm3)
(JCPDS 47-0561). The estimated volume (Vmaterials) was subtracted
from the obtained bulk volume (Vbulk), and then the subtracted value
was divided by the weight of bulk (Mbulk) in order to calculate the pore
volume of obtained samples (calculated pore volume = (Vbulk −
Vmaterials)/Mbulk).
Li+ Adsorption Measurements. Li+ adsorption properties of the
TNT monolith obtained by 36 h of reaction, the TNT pellet and
strongly acidic cation-exchange resins (SK1B, Mitsubishi Chemical
Industry Ltd., Japan) were investigated. Prior to measurement, the
interlayer cations of both TNT-based samples and resin were
completely exchanged with protons, by washing with excess aqueous
HCl until a stable pH value of 3. Li+ adsorption measurement was
performed according to Bavykin et al.27 The protonated sample (0.1 g)
was immersed in water (10 mL), and aqueous 1 M LiOH (50 μL) was
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added. pH changes were recorded using a pH meter (D-72; HORIBA,
Japan) with glass electrodes at room temperature (20 ± 1 °C) under
stirring. The proton concentration of the solution was calculated from
its pH.
■
RESULTS AND DISCUSSION
Figure 1 shows a TNT monolith of 30 mm in diameter and
∼1.5 mm in thickness obtained by a hydrothermal treatment
Figure 1. TNT monolith synthesized by hydrothermal reaction for 36
h. (a) Optical image of the centimeter-scale monolith. (b, c) SEM
images showing the macropores and framework constructed of
interconnected and entangled TNTs. TNT secondary particles were
bridged by entangled TNTs. (d) TEM image showing the tubular
TNT structure.
with high TiO2/NaOH molar ratio of 0.4 g of TiO2 in 2 mL of
aqueous NaOH (5 M). Monoliths of centimeter scale could be
fabricated in various shapes using appropriate reaction
containers as molds (see Figure S1, Supporting Information).
The monolith was sufficiently robust that it could be handled
without special care. It should be noted that the monolith could
be obtained by a simple drying process without supercritical
drying. The scanning electron microscopy (SEM) image in
Figure 1b shows that the monolith possessed macropores of
which diameters are ranging from 1 to 10 μm. The monolith
consisted of interconnected and entangled TNTs, as shown in
Figure 1c. A few hundred nanometer pores formed between
entangled TNTs. The transmission electron microscopy
(TEM) image in Figure 1d indicated a tubular structure of
10 nm in diameter, which was consistent with reported
TNTs.1,3,8 The monolith had a specific surface area of 143 m2/
g.
The porosity of the TNT monolith depended on a volume
fraction of anatase to NaOH aq (VAnatase/VNaOH aq). Figure 2a
shows the effect of a volume fraction of anatase to NaOH aq on
the porosity and bulk density of the obtained TNT monoliths.
The pore volume is calculated by taking into account both the
molar fraction of TNT/anatase (see Figure S2, Supporting
Information) and the bulk density of the obtained monolith. An
increase of the volume fraction of anatase to NaOH aq resulted
in a decrease of the pore volume from 3.7 to 0.6 cm3/g. The
structural change observed by SEM is shown in Figure 2b−d
(details of the compositional dependence are shown in Figure
S3, Supporting Information). The frameworks of all the TNT
monoliths consisted of interconnected and entangled TNTs
with residual anatase particles. The pore volume became small
with an increase of a volume fraction of anatase. TNT
monoliths obtained from the volume fraction beyond 0.25
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Chemistry of Materials Article

Figure 2. (a) Calculated pore volume of the obtained TNT monolith versus a volume fraction of anatase to NaOH aqueous solution (VAnatase/
VNaOH aq). The value of pore volume is calculated by combining results of molar ratio from XRD and bulk density of the obtained monolith (see the
Experimental Section). (b−d) SEM images of the obtained TNT monolith prepared with VAnatase/VNaOH aq = 1.2 × 10−2, 4.9 × 10−2, and 25 × 10−2,
respectively. (e) Pore size distribution of monoliths prepared with VAnatase/VNaOH aq obtained by mercury intrusion porosimetry. (f) Schematic
illustration showing the relationship between the volume fraction and porosity of monolith; TNT monolith with higher porosity can be prepared
with lower anatase concentration (lower VAnatase/VNaOH aq value), while dense TNT monolith with lower porosity can be prepared with higher
anatase concentration (higher VAnatase/VNaOH aq value).

possessed dense macrostructures without macropores. The

porosity-volume fraction behavior can be divided into two
ranges: the formation of a macroporous TNT monolith at a low
and medium volume fraction range (from 0.003 to 0.25) and
the formation of a TNT monolith without macropores at a high
volume fraction range (from 0.25 to 0.37). Macropores
accommodated in the TNT monolith were characterized by
mercury intrusion porosimetry (Figure 2e). The pore volume
and pore size in the monoliths were identified from the
cumulative pore volume curves. An increase of VAnatase/VNaOH aq
results in a decrease of total pore volume and the size of
macropores. The monoliths prepared with VAnatase/VNaOH aq =
1.2 × 10−2, 4.9 × 10−2, and 25 × 10−2 have pore volumes of
1.75, 1.34, and 0.81 cm3/g, respectively. The maximum
macropore size is identified from an inflection point in the
micrometer range of the cumulative pore volume curve. The
maximum macropore size decreases from ∼10 μm to a few
hundred nanometers with increasing VAnatase/VNaOH aq value.
Gradual downward slopes from 10−2 to 100 ∼ 101 μm in
cumulative pore volume curves indicate that the monoliths have
a broad distribution of macropore sizes. The broad distribution
of macropore sizes reflects fabric-like morphologies of
entangled TNT. The relationship between a volume fraction
and porosity of monolith is schematically illustrated in Figure
2f. A TNT monolith of tunable macropore volume and size can
be prepared by the present processing without any templating
Figure 3. SEM images of products synthesized after hydrothermal
agents. The porosity can be adjusted from 3.7 to 0.6 cm3/g by
reaction for (a) 2, (b) 12, (c) 24, and (d) 72 h. Arrows in (a) indicate
simply varying a volume fraction of precursor to a reaction TNTs. The areas enclosed by orange lines and blue lines in (b)
solution. Hereafter, the volume fraction of 0.049 is chosen for indicate a few hundred nanometer pores and a few micrometer pores,
TNT monolith preparation to investigate the monolith respectively. (e) XRD patterns of products after increasing hydro-
formation mechanism, specific surface area, and Li+ adsorption thermal reaction times. Diffraction peaks of a titanate phase (at 2θ = 9,
measurement. 24.8, 28.4, 47.9°)19,20,28 appear after 2 h reaction time. (f) Pore size
The formation mechanism of monolithic TNT is discussed distribution of monoliths prepared with different reaction times.
by varying the hydrothermal reaction time. The time evolution
of the structure is shown in Figure 3a−d. The components and (Supporting Information), respectively. Longer reaction time
corresponding change of TNT/TiO2 ratio in the monolith led to an increase in the titanate phase,19,20,28 and an
prepared with increasing reaction time were investigated by X- elimination of the precursor anatase phase (an increase of the
ray diffraction (XRD), as shown in Figure 3e and Figure S4 TNT/anatase ratio). All the anatase particles were converted
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Chem. Mater. 2015, 27, 1885−1891
Chemistry of Materials Article

Figure 4. Formation mechanism of the hierarchically porous TNT monolith. (a−d) Evolution of nanometer-scale structures, where anatase
precursor nanoparticles and TNTs are shown as white spheres and yellow tubes, respectively: (a) aggregation of precursor; (b) formation of TNTs
on aggregates; (c) growth and entanglement of TNTs, and further growth and nucleation of TNTs with consumption of anatase; (d) TNT/anatase
secondary particles bridged by entangled TNTs. (e−f) Evolution of micrometer-scale structures, where secondary particles and TNT bridges are
shown as solid shapes and yellow lines, respectively: (e) dispersion of small and large secondary anatase particles; (f) TNT formation on the surface
of secondary particles while maintaining the macrostructure; (g) growth of larger secondary particles and consumption of smaller particles, and
formation of TNT bridges between large secondary particles; (h) further entanglement of TNTs within the framework. The density of TNTs is high
in small cavities between secondary particles.

into titanate by ∼168 h of reaction time. The anatase primary
particles used as a precursor aggregated to form secondary
particles (see Figure S5, Supporting Information). TNTs were
observed on the surface of TiO2 secondary particles after 2 h of
reaction, as indicated by arrows in Figure 3a. The TNT/TiO2
secondary particles of a few micrometers in size were formed, as
shown in the inset in Figure 3a. After 12 h of reaction, TNTs
got entangled to bridge TNT/TiO2 secondary particles for the
formation of the monolith framework (Figure 3b). A few
hundred nanometer pores were observed within the entangle-
ment of TNTs (orange lines in the figure). Macropores of a few
micrometers in diameter (blue lines) were formed between
TNT/TiO2 secondary particles. The small secondary particles
(< ∼2 μm) confirmed in Figure 3a were almost eliminated.
After 24 h of reaction, the entanglement of TNTs developed,
resulting in TNT bridges between TNT/TiO2 secondary
particles (Figure 3c). A TNT density varied throughout the
monolith, according to the size of cavities between secondary
particles. Cavities smaller than a few micrometers were filled
with high-density TNTs, while those larger than a few
micrometers were filled with low-density TNTs (see Figure
S6, Supporting Information). Macropores with various sizes
formed due to the TNT density fluctuation. The TNTs merged
with each other after 72 h of reaction to form titanate
nanowires (Figure 3d). The conversion of nanotubes to
nanowires was confirmed by TEM (Figure S7, Supporting
Information), which is reportedly induced by assembled TNT
bundles.29 A change of macropores in the monoliths was
investigated by mercury intrusion porosimetry (Figure 3f). The
total pore volume remained unchanged by the prolonged
hydrothermal treatments. The pore size distribution of the
monolith prepared for 12 h of reaction time (black line) has a
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gentle change in a range of a few hundred nanometers and a
steep decrease at around a few micrometers. This indicates the
existence of submicrometer pores with a largely distributed
diameter and relatively distinct macropores. After 36 h of the
reaction, the curve exhibited a gradual decrease from 10−2 to 10
μm without a steep decrease, meaning that the size of
macropores is evenly distributed. A proportion of a few
micrometer pores increases after 72 h because its cumulative
pore volume in the scale showed a higher value than that of 36
h reaction time.
A formation mechanism of the TNT monolith based on the
SEM, XRD, and mercury intrusion porosimetry results is shown
in Figure 4. The mechanism involves three stages: (1) TNT
formation while maintaining the anatase aggregate macro-
structure; (2) conversion of anatase to TNTs, and formation of
macropores through the consumption of small anatase
aggregates; (3) TNT framework extending throughout the
entire monolith while cavities between the secondary particles
are filled with entangled TNTs. During these stages, macro-
pores formed in less dense parts of the TNT framework. TNTs
formed on the surfaces of anatase aggregates during the first
stage (<6 h). The size of the anatase aggregates and
macrostructure were unchanged from those of the initial
aggregated anatase powder. The monolith was constituted of
almost 90% anatase. Slow TNT growth and undeveloped TNT
bridges resulted in poor connectivity between anatase
aggregates, making the monolith very fragile. During the
second stage (6−12 h), large TNT/TiO2 secondary particles
(>2 μm) grew, by the nucleation and growth of TNTs and
consumption of smaller anatase aggregates (<2 μm) leaving
macropores. TNT/TiO2 particles were bridged by entangled/
interconnected TNTs in which a few hundred nanometer pores
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Chemistry of Materials
were formed between each nanotubes. The resulting framework
made the monolith mechanically robust and easily handled.
Further TNT growth and entanglement strengthened the
framework during the third stage (12−36 h). The entangled
TNTs filled cavities between the secondary particles with
fluctuant TNT density. The rapid growth of TNTs in cavities
smaller than a few micrometers between TNT particles yielded
dense localized and entangled TNTs, while TNTs within
cavities larger than a few micrometers were sparse. This TNT
density fluctuation resulted in the formation of macropores
with widely distributed sizes from 10−2 to 10 μm. The product
after 36 h of reaction was mechanically stronger than that after
12 h due to a development of TNT networks. Further
increasing the reaction time above 36 h converted the TNTs
into titanate nanowires via their bundling, which formed a few
micrometer pores as interstices between the titanate nanowires.
The macropores of rigid inorganic monoliths are usually
formed by soft or hard template methods, where condensation
of the inorganic material strengthens the monolith frame-
work.30−33 The formation of the current macroporous
monolith differed significantly from this conventional mecha-
nism. We propose a new concept for fabricating rigid inorganic
macroporous monoliths composed of tangled 1D nanomateri-
als. Macropores are formed by inhomogeneous nanotube
growth, and the framework is strengthened by the bridging of
secondary particles. Although inorganic nanowire-based aero-
gels containing macropores reportedly fabricated and exhibited
high electrical conductivity and separation ability, the
approaches required templating agents (e.g., polymer,
ice)34−36 or supercritical drying using specialized equip-
ment.37,38 However, in the current study, macropores within
the TNT monolith were formed by the variation in TNT
density and controllable by simply varying a volume fraction of
precursor without any templating agents. In addition, robust
monoliths composed of 1D nanomaterials were obtained by a
simple drying process, which was possible because of its strong
framework of entangled TNTs.
The specific surface areas of the products were determined
according to Brunauer−Emmett−Teller (BET) analysis (Figure
5), and corresponding pore size distributions are shown in
Figure S8 (Supporting Information). The specific surface areas
of products obtained by reaction up to 36 h increased with
increasing reaction time. This was because of the formation of
TNTs and consumption of precursor anatase (∼70 m2/g). The
specific surface area of the product prepared after reaction for
Figure 5. BET surface areas of products prepared with different
hydrothermal reaction times.
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36 h was 143 m2/g. The specific surface area derived from
TNTs part in the composite monolith was calculated to be
∼175 m2/g by taking into account the TNT/anatase ratio
obtained by XRD measurements. The calculated value was
consistent with that of typical TNTs reported so far.29 The
specific surface area dramatically decreased with increasing
reaction time after 36 h despite the fraction of titanate content
increasing. Horváth et al. reported that the conversion of
titanate nanotubes into nanowires results in a lower specific
surface area.29 The SEM and TEM results in Figure 3 and
Figure S7 (Supporting Information) support this conclusion. In
summary, monoliths produced from reaction up to 36 h were
composed of anatase and TNTs, and the TNT/anatase ratio
increased with increasing reaction time.
An excellent cation-exchange behavior makes TNTs
promising materials for Li+ battery anodes, Li+ storage, and
capture of radioactive Cs+.39−41 We investigated the Li+
adsorption potential of the TNT monolith shown in Figure 1
(denoted “Monolith” in Figure 6). The monolith was prepared
Figure 6. Aqueous proton concentration with increasing immersion
time. Red: monolith containing macropores prepared by hydrothermal
reaction for 36 h. Blue: TNT pellet without macropores prepared by
HHP treatment.
from reaction for 36 h, and contained 1−10 μm pores (TNT/
anatase ratio: ∼0.6; BET specific surface area: 143 m2/g). Bulk
TNTs pellet without macropores was prepared by the HHP
treatment of pure TNT powder according to refs 21 and 22,
and their Li+ adsorption properties were investigated for
reference (denoted “Pellet” in Figure 6). The interlayer cations
of both samples were ion-exchanged with protons prior to the
Li+ adsorption test, by washing with acid. Li+ adsorption was
performed according to Bavykin et al.27 The change in aqueous
proton concentration with time was measured since 1 M
aqueous LiOH was added to the immersed protonated sample.
The Li+ adsorption capability was determined from the solution
proton concentration, because protons were released from
titanate interlayers upon exchanging with Li +. The Li+
adsorption measurements are shown in Figure 6, where the
proton concentration is plotted against immersion time. The
TNT monolith with macropores exhibited a faster rate and a
higher capacity of cation exchange than the TNT pellet without
macropores. It should be noted here that the prepared TNT
monolith shows excellent Li+ exchangeability, although the
product consisted of a composition of TNT (40%) with anatase
(60%) while the TNT pellet consisted of only TNT. The result
indicates that the Li+ exchangeability of bulky materials is
closely associated with their macroporosity rather than an
amount of cation-exchange material. This is because the
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Chemistry of Materials
macropores allow Li+ to rapidly access the cation-exchange sites
within the monolith. As a reference, a commercial acidic cation-
exchange resin (SK1B, Mitsubishi Chemical Industry Ltd.,
Japan) was also investigated using the same procedure. SK1B is
composed of polystyrene having sulfonic acid groups that can
exchange their protons for Li+ ions. The maximum cation-
exchange capacities of SK1B and the TNT monolith were
estimated as 1.2 × 10−9 and 3.4 × 10−9 mol/g for 16 days of
immersion time, respectively (see Figure S9, Supporting
Information). The TNT monolith showed a comparable or
higher cation-exchange capacity to the commercial ion-
exchange resin. In addition, the remarkable advantage of the
TNT monolith is the thermal and chemical stabilities. The
TNT monolith remained robust up to several hundred Celsius
and its cation-exchange capacity can be recovered. It could be
reused multiple times without a lack of the exchange ability
(Figure S10, Supporting Information). The acidic cation-
exchange resins consisting of polystyrene are generally instable
in a solution containing oxidant such as nitric acid and at high
temperature over ∼150 °C.42−44 In addition to Li+ exchange,
the product is useful for a capture and removal of Na+, K+ and
also radioactive Cs+ because Na+, K+, and Cs+ cations can be
reportedly intercalated between the layers of TNT similarly to
Li+.27
■
CONCLUSION
TNT monoliths containing hierarchical pores extending from
sub-nanometers to several tens of micrometers were hydro-
thermally prepared with conditions of a small amount of
aqueous NaOH and a high TiO2/NaOH ratio. The monolith
was formed from entangled and interconnected TNTs.
Macropores were formed by the spatial variation of TNT
density. The pore volume can be tubed by adjusting the TiO2/
NaOH ratio. Entangled TNTs and TNT bridges between
secondary particles made the monolith robust and easily
handled. The TNT monolith exhibited a high Li+ adsorption
rate and a large cation-exchange capacity.
■
ASSOCIATED CONTENT
*
S Supporting Information
Images of sample with varying shapes; titanate and anatase
molar concentrations; SEM images of TNT monolith prepared
with different volume fractions of anatase to NaOH aq
(VAnatase/VNaOH aq); SEM images of precursor anatase powder;
SEM image showing the macrostructure of a TNT monolith
prepared after 24 h of reaction; TEM images and
corresponding selected area electron diffraction patterns of
products, pore size distributions of products from different
hydrothermal reaction times; Li+ exchange measurements
showing exchange capacities of materials; and reusability of
TNT monolith. This material is available free of charge via the
Internet at http://pubs.acs.org.
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: masa@photomater.com. Phone: +81-72-254-9309
(M.T.).
Notes
The authors declare no competing financial interest.
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■ ACKNOWLEDGMENTS
The present work is partially supported by Grand-in-Aids from
the Ministry of Education, Culture, Sports, Science and
Technology (MEXT), administrated by Japan Society for the
Promotion of Science (JSPS) (No. 26288108, No. 26630322).
M.T. acknowledges financial support from The Murata
Scientific Foundation.
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1891 DOI: 10.1021/acs.chemmater.5b00184

Chem. Mater. 2015, 27, 1885−1891