Journal of Cleaner Production 148 (2017) 905e914

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Journal of Cleaner Production

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A comparative study of sodium/hydrogen titanate nanotubes/

nanoribbons on destruction of recalcitrant compounds and
sedimentation
Kunlanan Kiatkittipong a, *, Suttichai Assabumrungrat b
a
Department of Chemical Engineering, Faculty of Engineering, King Mongkut’s Institute of Technology Ladkrabang, Bangkok 10520, Thailand
b
Center of Excellence in Catalysis and Catalytic Reaction Engineering, Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn
University, Bangkok 10330, Thailand

a r t i c l e i n f o a b s t r a c t

Article history: The performances of sodium titanate nanotubes (Na-TT), hydrogen titanate nanotubes (H-TT), sodium
Received 6 August 2016 titanate nanoribbons (Na-TR) and hydrogen titanate nanoribbons (H-TR) on adsorption, photo-
Received in revised form degradation of methylene blue (MB) and sedimentability were investigated. The intrinsic property of Na-
6 February 2017
TT with high hydroxyl groups (anionic) provided a strong electrostatic interaction between the MB
Accepted 6 February 2017
Available online 6 February 2017
(cationic) under dark condition. The equilibrium and kinetic adsorption were fitted with Langmuir
isotherm models and the pseudo-second-order model, respectively. That is, Na-TT showed the best
maximum adsorption capacity of 178.6 mg/g and adsorption kinetics of 0.119 g/mg$min. When the light
Keywords:
Titanate
is turned on, H-TT showed advance its photocatalytic reaction rate of 1.16
102 min1 compared with
Nanotube Na-TT (the reaction rate of 1.02
102 min1). This attributed the saturated MB adsorption on Na-TT
Nanoribbon obstructed capacity to absorb photons, and thus the reaction gradually occurred. For the separation of
Adsorption photocatalysts from the suspension by adding alum as coagulant, Na-TT afforded the best sedimentability
Photocatalytic activity of which remaining Na-TT in water was approximately 5%. This study demonstrates that adsorption,
Sedimentation degradation and sedimentability were governed by the surface area and crystal structure, which revealed
increasing the performance in the order TiO2 < H-TR < Na-TR < H-TT < Na-TT.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction low concentrations, causing human health and environment

Wastewater treatment is based upon various physical, chemical
and biological processes. In fact, this consists of a combination of
many conventional operations such as coagulation, sedimentation,
precipitative softening, filtration, and chlorination which utilize
potentially hazardous or polluting materials. However, some haz-
ardous pollutants or chemical substances that persist in the envi-
ronment may not be eliminated in the conventional treatment
process (primary, secondary and tertiary treatment) (Gaya and
Abdullah, 2008). Many of them are very slowly degradable in
municipal wastewater treatment plants and they behave as
recalcitrant’. Bio-recalcitrant compounds, such as pharmaceuticals,
personal care products, surfactants, industrial chemicals, dyes, etc.,
contaminated in the environment are very dangerous even at very
* Corresponding author.
E-mail address: kunlanan.kia@kmitl.ac.th (K. Kiatkittipong).
problems. Therefore, the effective removal of bio-recalcitrant
compounds from wastewater effluent with cleaner technology is
of high interest. The approach for removal of recalcitrant organic
compounds is photocatalytic oxidation (Robertson, 1996). Photo-
catalytic oxidation relies upon the generation of highly reactive
short-lived hydroxyl radicals and generated holes to efficiently
degrade or even mineralize a wide range of organics or inorganic
molecules (Frank and Bard, 1977). The most widely-used catalyst
for water treatment applications such as pre-treated palm oil mill
effluent (Cheng et al., 2016), greywater (Chong et al., 2015), removal
of dye e.g. methylene blue (Momeni and Ghayeb, 2015) and
Rhodamine B (Momeni and Ahadzadeh, 2016) is titanium dioxide
(TiO2). An advancement of Ti-O nanostructures with controlled
architectures imparting advantageous physical and chemical
properties (e.g. surface area, crystal structure, greater percentage of
active crystal facets, porosity) can broaden the applications of TiO2
on photocatalysis in higher efficiency. For example, the dominate
crystal facet of {010} for titanate nanoribbons calcined at 800  C can

http://dx.doi.org/10.1016/j.jclepro.2017.02.043
0959-6526/© 2017 Elsevier Ltd. All rights reserved.
906 K. Kiatkittipong, S. Assabumrungrat / Journal of Cleaner Production 148 (2017) 905e914
be beneficial for photoactivity (Kiatkittipong et al., 2011). Na2Ti6O13
nanoribbons with tunnel-like structure provided better electron/
hole separation for the water splitting reaction (Kiatkittipong et al.,
2013). A high surface area of TiO2 nanotubes is a good nano-
structure for supporting metal to enhance the photocatalytic re-
action (Momeni et al., 2015). Moreover, nitrogen-doped TiO2
nanotubes showed a high mobility of electron on the catalyst sur-
face and efficient desorption of products, resulting in higher
product yield rates for photocatalytic CO2 conversion (Delavari
et al., 2016).
Nanostructures such as wire, rod, tube and ribbon-shaped
structures have been synthesized by various methods such as
template-assisted method, electrochemical anodic oxidation
method and hydrothermal method. The hydrothermal method is
reviewed and considered due to low cost, mass effective and high
product purity. Moreover, hydrothermal method is attractive for a
tight control of crystal growth and morphology (Kasuga et al.,
1998). In relation to photocatalysis, nanostructures with high sur-
face area have advantages in enhancing light absorption and more
active site numbers. This particular aspect is important for mole-
cules which can effectively adsorb onto the surface of the photo-
catalyst (Hu et al., 2011).
The product obtained from alkaline hydrothermal reaction was
proposed in the form of NaxH2-xTi3O7; where 0  x  2 (Chen et al.,
2002). As alkaline hydrothermal reaction following the acid
washing was proceeded, the NaxH2-xTi3O7 was exchanged the
cation with proton, forming hydrogen titanate (H2Ti3O7) (Tsai and
Teng, 2004). As comparing the photocatalytic activity between
non-acid washed sodium titanate and acid washed titanate, the
acid washed titanate (low Na content) was reported to promote
significantly higher activity of Brilliant-blue (KN-R) and rhodamine
6G degradation (Ribbens et al., 2008). Conversely, a higher activity
for photothionine degradation was found by using NaxH2-xTi3O7.
The intercalated Na atoms were suggested to trap the excited
electrons and facilitate separation of the photogenerated electrons
and holes (Pu et al., 2010).
Photocatalyst used in wastewater treatment should require post
treatment recovery, and separation of used photocatalyst from
water before releasing is also vital. In general, colloid photo-
catalysts provided a good performance in photocatalytic reaction,
but the effectiveness of their removal from suspension is limited.
TiO2 with graphite oxide has been proposed to impart an acceler-
ated sedimentation of catalyst slurry as compared to pure TiO2
despite the loss of catalytic activity (Szabo et al., 2013).
In the light of Ti-O nanostructured materials in photocatalytic
applications, many studies have been developed to fabricate Ti-O
nanostructured materials and to improve their properties for
photocatalytic degradation. However, limited direct assessment of
Ti-O nanostructures prepared under the different hydrothermal
condition on adsorption and photocatalytic abilities has been
attempted. Besides, the influence of morphology and phase com-
ponents as a photocatalyst on the separation from water before
releasing has been scarcely considered. A greater understanding of
these key aspects will be of value in developing photocatalyst and
apply to industrial applications.
The key objectives deriving from this work is to develop pho-
tocatalyst with controlled characteristics in diverse elongated
titanate nanostructures (including nanotubes and nanoribbons)
using alkaline hydrothermal synthesis. The effects of morphologies
and Naþ and Hþ ions intercalated in structure on adsorption and
photodegradation of methylene blue, as a model of recalcitrant
pollutants, are considered. Additionally, the sedimentation of tita-
nate nanostructures as shown in a term of suspended solid in water
is explored.
2. Experimental section
2.1. Chemicals
TiO2 (anatase 100%), sodium hydroxide (Ajax Finechem), hy-
drochloric acid (37 vol%, (J.T.Baker)), methylene blue (MB) (Sigma-
Aldrich Chemie GmbH) and alum were used without further
purification.
2.2. Titanate nanotubes and titanate nanoribbons synthesis
Titanate nanostructures were synthesized using a hydrothermal
procedure. Initially, 0.5 g of TiO2 and 20 mL of 10 M NaOH were
stirred for 1.5 h in a plastic bottle. The slurry was transferred to a
Teflon-lined autoclave, sealed and heat treated in an oven at (i)

150  C to produce the nanotubes or (ii) 200 C to produce the
nanoribbons. The resulting suspension was washed with 0.1 M HCl
to form hydrogen titanate while sodium titanate was washed with
water until the pH value of the wash solution reached approxi-
mately 6 (Kiatkittipong et al., 2011). The notation of synthesized
photocatalyst is shown in Table 1, and the synthesis pathways used
to produce photocatalysts is shown in Fig. 1.
2.3. Characterization
The crystal and structural characteristics of the products were
investigated by X-ray diffractometer (XRD). The surface
morphology of the samples was observed by scanning electron
microscope (SEM) including energy dispersive X-ray spectroscopy
(EDX) for measuring chemical composition, transmission electron
microscopy (TEM), and measured the specific surface area by using
the Brunauer-Emmett-Teller (BET) method. The surface bonding
states were analyzed by X-ray photoelectron spectroscopy (XPS)
analysis.
2.4. Adsorption and photodegradation
The adsorption performance and photocatalytic activity over
TiO2 starting material and all synthesized samples were performed
using aqueous MB under dark condition and UV light irradiation.
0.01 g of photocatalysts (TiO2, Na-TT, H-TT, Na-TR, H-TR) was added
to 200 mL of MB solution. The concentrations of MB were varied in
a range of 10e100 of mg/L for adsorption isotherm study. The
suspension was stirred at room temperature under dark condition.
The particles in sample solution were separated by micro-filter. The
MB concentrations in the sample solutions were analyzed by
absorbance measurement using UVevisible spectrometer. Photo-
catalyst stability test of all synthesized samples was studied. All
synthesized samples were recovered from the solution by micro-
filter, washed with distilled water and dried in an oven at 80  C.
The synthesized samples were then reused 3 times for MB
degradation.
2.5. Sedimentation
Jar test apparatus was conducted to perform the coagulation-
Table 1
The notations of all synthesized photocatalyst.
Synthesized samples Notations
Sodium titanate nanotubes Na-TT
Hydrogen titanate nanotubes H-TT
Sodium titanate nanoribbons Na-TR
Hydrogen titanate nanoribbons H-TR
 K. Kiatkittipong, S. Assabumrungrat / Journal of Cleaner Production 148 (2017) 905e914
1. Sample Preparation
Nanotubes
2. Hydrothermal Treatment
Temperature
Time
3. Washing
0.1 M HCl
H-TT
Fig. 1. Synthesis pathways used to produce sodium/hydrogen titanate nanotubes/nanoribbons.
flocculation. The 200 mL of suspension was stirred for 60 min in a
beaker. Then, 0.5 g of alum used as a coagulant was added in the
suspension, and the suspension was stirred for 20 min after which
it was allowed to rest and settle for a given period of time. After
coagulation-flocculation, the particles remaining in the water were
separated by filtration.
3. Results and discussion
3.1. Structures and morphology
The influences of reaction temperature and acid washing on
sample morphology were investigated by SEM and corresponding
TEM (inset) as shown in Fig. 2. Fig. 2(a) shows that morphology of
starting TiO2 is non-defining morphology. After hydrothermal re-
action of starting TiO2 and NaOH at 150  C for 72 h (Na-TT), the SEM
image in Fig. 2(b) reveals that the morphology of sample is a
defined tube-like structure having an outer diameter of approxi-
mately 9 nm and length in the order of microns. Similar
morphology was obtained for sample (H-TT) washed with acid after
the hydrothermal condition 150  C for 72 h in Fig. 2(c). The nano-
tube diameter is similar to that observed by other (Yu et al., 2006a).
At higher temperature (i.e. 200  C for 40 h) (Na-TR), nanoribbon
structure having a width of approximately 10e100 nm and length
in the order of microns is formed as shown in Fig. 2(d). At a shorter
hydrothermal time of 24 h, acid washing the sample after hydro-
thermal treatment accelerated nanoribbon formation (H-TR) in
Fig. 2(e). This was explained that the shorter hydrothermal time
needed to produce the interlayered architecture in the acid washed
907
0.5 g of TiO2 + 20mL of 10 M NaOH
Nanoribbons
150 °C 200 °C
72 h 24 h 40 h
Deionized water
H-TR Na-TT Na-TR
where hydrogen bond array (e.g., Ti-O-H) is faster than that of the
sodium bond array (e.g., Ti-O-Na) under milder conditions
(Kiatkittipong et al., 2010). However, the structures are slightly
fragmented may be because Naþ is replaced by Hþ during acid
wash.
The XRD patterns for all samples are shown in Fig. 3(a). 100%
anatase of TiO2 commercial used as starting material is confirmed.
With the alkaline hydrothermal reaction, the XRD pattern of Na-TT
corresponds to sodium titanate (Na2Ti3O7). The distinct peak
located at 9 indicates interlayer spacing of approximately 0.8 Å.
The pattern of acid washed sample (H-TT) can be indexed to
hydrogen titanate (H2Ti3O7). The decrease in interlayer spacing to
0.79 Å due to replacing Naþ ions with Hþ with a smaller ionic radius
compared with Naþ ions (Pu et al., 2010). The crystal structure of
H2Ti3O7 or Na2Ti3O7 was explained to be monoclinic, where is ar-
ranged in the form of TiO6 edge-sharing octahedron. Each slab is
connected at its corner to form layers that are separated by either
Naþ or Hþ ions (Kolen’ko et al., 2006). Fig. 3(a) indicates that the
XRD patterns for Na-TR and H-TR are sodium titanate (Na2Ti3O7)
and hydrogen titanate (H2Ti3O7), respectively which are similar to
those observed for Na-TT and H-TT. The distinct peak indicating
interlayer spacing of nanoribbons (Na-TR) is located at 2Ө z 11. A
distinct difference in interlayer spacing between nanotubes and
nanoribbons derives from structural formation. The nanoribbon
system comprises multilayered titanate sheets while bending of the
multilayered sheets addresses the nanotube formation
(Kleinhammes et al., 2005). Naþ and Hþ exchange process can be
confirmed by EDX analysis as shown in Fig. 3(b) and (c). EDX
analysis of the individual samples Na-TT and Na-TR showed a
908 K. Kiatkittipong, S. Assabumrungrat / Journal of Cleaner Production 148 (2017) 905e914

(a)

(b) (c)

50 nm 50 nm

(d) (e)

0.5 μm 0.5 μm

Fig. 2. SEM images of (a) TiO2 (starting material), (b) Na-TT, (c) H-TT, (d) Na-TR, (e) H-TR. Corresponding TEM (inset) showing the formation of Na-TT, H-TT, Na-TR and H-TR.

significant amount of sodium (Fig. 3(b)), while there was no sodium
ion present in both the H-TT and H-TR samples (Fig. 3(c)), indicating
that sodium was successfully exchanged with Hþ.
XPS spectra for the sodium titanate (Na-TT and Na-TR) and
hydrogen titanate (H-TT and H-TR) are provided in Fig. 4. The
spectra for sodium titanate appear the binding energy of the main
peaks Ti 2p, O 1s and Na 1s in Fig. 4(a). The peak of Ti 2p corre-
sponds to Ti 2p3/2 and Ti 2p1/2 of Ti (IV) oxidation state (Esparza
et al., 2013). The peak of O 1s attributes to Ti-O and -OH (Yu
et al., 2006b). The evidence of Na 1s located at 1072 in sodium
 K. Kiatkittipong, S. Assabumrungrat / Journal of Cleaner Production 148 (2017) 905e914 909

(a)

H-TR
(b)
Na-TR

H-TT

Na-TT Na-TT, Na-TR

(c)

TiO2

H-TT, H-TR

Fig. 3. (a) XRD patterns of TiO2 and all synthesized titanate, EDX analysis of (b) Na-TT, Na-TR and (c) H-TT, H-TR.

Table 2
O1S

BET surface area of TiO2 (starting material), Na-TT, H-TT, Na-

TR and H-TR.
Ti2P

Samples Surface area (m2/g)

O kill

TiO2 10
Intensity (a.u.)

C1S

Na-TT 138
H-TT 143
(b) Na-TR 32
Na1S

H-TR 35

(a) H-TR, 32e35 m2/g). When comparing the sodium titanate and
hydrogen titanate, it is apparent that the samples washed with HCl
have slightly higher surface area than the samples washed with
only water. That is, H-TT (143 m2/g) > Na-TT (138 m2/g), and H-TR
200
600

400
1,000

800

Binding Energy (eV)
Fig. 4. XPS spectra of (a) Na-TT, Na-TR and (b) H-TT, H-TR.
titanate was found, which agrees with the EDX analysis. The
hydrogen titanate in Fig. 4(b) is also obviously observed the pres-
ence of peaks Ti 2p and O 1s. However, the peak of Na 1s in
hydrogen titanate is not as intense as that in sodium titanate due to
Naþ and Hþ exchange process, corresponding to EDX analysis.
Table 2 shows that the formation of nanostructures is reflected
by the changes of surface area. The surface area of TiO2 (starting
materials) was 10 m2/g. It was found that alkaline hydrothermal
reaction can yield higher surface area products. The titanate
nanotubes (Na-TT and H-TT) have surface area of 138e143 m2/g
which is much higher than that of titanate nanoribbons (Na-TR and
(35 m2/g) > Na-TR (32 m2/g). This may due to the minor collapse of
samples after acid washing as was illustrated in Fig. 2. Fig. 5(a)
shows the adsorption-desorption isotherm of Na-TT. It was
observed that the N2 isotherm of Na-TT is type IV of hysteresis loop
according to IUPAC classification. The hysteresis loop of Na-TT was
located at relative pressure between 0.6 and 1, where the internal
pore of tube structure was presented at P/P0 < 0.8. The hysteresis
loop at 0.8 < P/P0 < 1 corresponded to the interspace pore between
tubes. This showed good agreement with the TEM represented in
Fig. 2. The pore distribution in Fig. 5(b) exhibits that the smaller
pores (pore diameter < 10 nm) corresponding to the pore inside
nanotubes, and the larger pores (pore diameter > 10 nm) attrib-
uting to voids occurring from overlap of nanotubes were both
found in Na-TT. In case of nanoribbons, the adsorption-desorption
isotherm of Na-TR in Fig. 6(a) is a small hysteresis loop at a high
relative P/P0. This is due to aggregation of ribbon structure resulting
in formation of macropores. This corresponded to the pore distri-
bution in Fig. 6(b) presenting only high pore diameters, which
ascribed to the secondary pore.
910 K. Kiatkittipong, S. Assabumrungrat / Journal of Cleaner Production 148 (2017) 905e914

(a) (b)

Fig. 5. Na-TT (a) Nitrogen adsorption-desorption, (b) Pore size distribution.

(a) (b)

Fig. 6. Na-TR (a) Nitrogen adsorption-desorption, (b) Pore size distribution.

3.2. Adsorption performance

Fig. 7 shows adsorption performance of TiO2, Na-TT, H-TT, Na-TR

and H-TR in MB solution under dark condition. MB adsorption
performance appears to increase in the order: TiO2 << H-TR < Na-
TR < H-TT << Na-TT. A typical of TiO2 shows little MB adsorption,
indicating poor adsorption of MB molecules onto surface. This is
similar with the work by other researcher who reported no dark
response onto the surface of TiO2 (Cheng et al., 2014). For com-
parison, titanate nanotubes (Na-TT and H-TT) are observed to a
comparatively higher MB adsorption than titanate nanoribbons
(Na-TR and H-TR) and TiO2. These findings attributed to (1) higher
surface area providing more MB adsorbed; (2) the formation of
nanotubes having high concentration of hydroxyl groups (anionic)
forming strong electrostatic interaction between the MB (cationic)
which favor the preferential MB adsorption (Natarajan et al., 2013).
However, the difference in MB adsorption between titanate nano-
ribbons (Na-TR and H-TR) was not significant due to a small in- Fig. 7. MB adsorption under dark using of TiO2 (starting material), Na-TT, H-TT, Na-TR
crease in surface area of H-TR. The best MB adsorption was and H-TR.
provided by Na-TT, whose C/C0 could achieve 0.4 (60% adsorption)
 K. Kiatkittipong, S. Assabumrungrat / Journal of Cleaner Production 148 (2017) 905e914 911

within 60 min. Na-TT adsorbs MB almost 2 times higher than H-TT Table 4
despite two samples exhibiting similar specific surface area. At this Freundlich isotherm parameters of methylene blue (MB) on TiO2 (starting material),
Na-TT, H-TT, Na-TR and H-TR.
point, it can be highlighted that Naþ ions in titanate exchanged
with a cationic dye of MB, which strongly adsorbed on the surface Photocatalyst KF nF R2
of titanate (Lee et al., 2007). This was similarly observed for titanate TiO2 starting material 2.01
102 0.52 0.985
nanoribbons, but not as much as on titanate nanotubes due to Na-TR 1.00
104 0.35 0.933
lower surface area of titanate nanoribbons. H-TR 3.04
105 0.28 0.910
Na-TT 6.97
1011 0.19 0.977
The equilibrium adsorption isotherm of MB in presence of all
H-TT 7.02
1014 0.12 0.988
samples was studied by Langmuir and Freundlich adsorption
models. The Langmuir adsorption models based on the assumption
of monolayer adsorption is expressed as
based structural materials and other classes of sorbents, the satu-
rated adsorption capacities are summarized in Table 5. The sorption
Ceq 1 Ceq performances of MB on Ti-O based material are very diverse. It
¼ þ
Qe Qm b Qm depends not only on their structures but also details of preparation
(concentration of reagent, ageing time, post treatment procedure).
where, Qe is the amount of MB adsorbed onto sample (mg/g), Ceq is Our sorption capacity in line with other researchers’ reported
MB concentration at equilibrium (mg/L), Qm is the maximum findings and the highlight is the importance of sodium incorpo-
amount of MB adsorbed per unit mass of sample (mg/g), and b is a rated in nanostructure without any further post treatment to ach-
constant related to the adsorption energy (L/mg). Table 3 shows Qm ieve high MB sorption capacity. Comparing to other classes of
and b, which were evaluated from the slope and intercept from sorbent materials, both TR and TT exhibit higher MB sorption ca-
plotting Ceq/Qe against Ceq, respectively. pacity than natural material e.g. kaolin while Na-TT is comparable
The Freundlich isotherm based on the assumption of a hetero- to bentonite and diatomaceous earth. However, the capacity is
geneous surface binding is expressed as much less than commercial activated carbon and biosorbent
(Marungrueng and Pavasant, 2007). Note that intensive review on
1 MB adsorption on natural materials, biosorbents, agricultural and
lnQe ¼ lnKF þ lnCe
nF industrial waste derived materials can be found in Rafatullah et al.
(2010).
where, KF is Freundlich constants (mg/g (L/mg)1/n) and dimen-
sionless nF suggests the favorability of adsorption. 3.3. Adsorption kinetics
Freundlich isotherm parameters of MB on different photo-
catalysts are provided in Table 4. The previous section demonstrated the highest adsorption
From Tables 3 and 4, it can be seen that the adsorption isotherms performance on Na-TT. Then, Na-TT was chosen to study adsorption
can be adequately described by Langmuir adsorption model kinetics. The adsorption kinetics of MB in presence of Na-TT was
because correlation coefficient R2 was found to be closer to unity studied by pseudo-first-order kinetic and pseudo-second-order
rather than Freundlich isotherm. This agreed with previous study kinetic. Pseudo-first-order is expressed as
(Natarajan et al., 2013). This indicates that the adsorption of MB on
TiO2 and titanate can be explained by monolayer adsorption; lnðQe  Qt Þ ¼ lnQe  k1 t
whereby a layer of MB molecules form over the surface of samples.
Pseudo second-order is expressed as
Na-TT provided the highest amounts of MB adsorption of 178.6 mg/
g with 0.39 L/mg constant related to the adsorption energy, which t 1 t
is slightly higher than the value reported by other (Xiong et al., ¼ þ
Qt k2 Qe 2 Qe
2010). The saturated adsorption capacities of MB for H-TT, Na-TR,
H-TR and TiO2 were reported as 111.1, 86.2, 80.7 and 4.7 mg/g,
where k1 is the rate constant of pseudo-first-order kinetic model
respectively. The order has been similarly observed by adsorption
(min1), k2 is rate constant of pseudo-second-order (g/mg min), Qe
performance in Fig. 7. It is worth to note that the amount of the MB
and Qt are the amounts of preferential adsorption of MB dye on Na-
adsorbed on Na-TT at equilibrium increased from 115 to 167 and
TT (mg/g) at equilibrium and at time t (min), respectively.
179 mg/g with the increase of initial MB concentration from 10 to
Table 6 showed kinetic data of the pseudo-first-order and
50 and 100 mg/L. This is due to the increase of driving force of the
pseudo-second-order kinetic models. It can be seen that the fitting
concentration gradient with increasing initial MB concentration. As
of experimental data exhibited a good compliance with pseudo-
constant sorbent loading, the removal efficiency decreased from
second-order kinetic equation, and linear plots of t/Qt versus t
59% to 17% and 9%. In order to increase removal efficiency, opti-
with correlation coefficients (R2) is closer to unity rather than
mizing amount of Na-TT loading is recommended for further
pseudo-first-order. The pseudo-second-order model can be
investigation.
explained that chemical sorption involving valency forces through
To compare the sorption performance of MB with other Ti-O
sharing or exchange of electrons between adsorbent and adsorbate
might be significant (Ho and McKay, 1999).
Table 3
Langmuir isotherm parameters of methylene blue (MB) on TiO2 (starting material), 3.4. Photocatalytic activity
Na-TT, H-TT, Na-TR and H-TR.

Photocatalyst Qm (mg/g) b (L/mg) R2 Fig. 8 presents the relative concentration of MB (C/C0) over time,
TiO2 starting material 4.7 0.06 0.999 where C and C0 are reaction concentrations at a specific time and
Na-TR 86.2 0.18 0.992 the initial concentrations of MB, respectively. Prior to photo-
H-TR 80.7 0.09 0.997 catalytic degradation, MB was adsorbed on the surface of photo-
Na-TT 178.6 0.39 0.999 catalyst for 60 min under the dark condition according to the
H-TT 111.1 0.12 0.994
aforementioned result illustrating the equilibrium adsorption
912 K. Kiatkittipong, S. Assabumrungrat / Journal of Cleaner Production 148 (2017) 905e914

Table 5
Maximum sorption capacity of MB on different Ti-O based structural materials and other class sorbents.

Sorbent Maximum sorption capacity (mg/g) References

Ti-O based materials

Sm3þ ions doped titania 2.9 Xiao et al., 2007

TiO2 nanotube 77.6 Natarajan et al., 2014
TiO2 nanotube calcined at 300  C 132 Jiang et al., 2012
Titanate/titania nanoparticles (solvothermal method) 162.2 Cheng et al., 2014
Hydrogen titanate nanowires (thin films) 80.2 Horvath et al., 2014
Hydrogen titanate nanowires (suspension) 133.9 Horvath et al., 2014
Hydrogen titanate nanoflower 147.1 Huang et al., 2012
Hydrogen titanate nanotubes 79.6 Huang et al., 2012
Hydrogen titanate nanowires 5.4 Huang et al., 2012
Sodium titanate nanotubes calcined at 400  C 133.3 Xiong et al., 2010
Sodium titanate nanotubes (Na-TT) 178.6 This study
Hydrogen titanate nanotubes (H-TT) 111.1 This study
Sodium titanate nanoribbons (Na-TR) 86.2 This study
Hydrogen titanate nanoribbons (H-TR) 80.7 This study
Other class materials
Kaolin 15.5 Ghosh and Bhattacharyya, 2002
Bentonite 150e175 Hong et al., 2009
Diatomaceous earth 198 Al-Ghouti et al., 2003
Commercial activated carbon 238, 297 Marungrueng and Pavasant (2007), Kannan and Sundaram (2001)
Macro alga Caulerpa lentillifera 417 Marungrueng and Pavasant (2007)

Table 6
Kinetic data of the pseudo-first-order and pseudo-second-order kinetic models at concentration ca. 10 mg/l.

Qe,exp (mg/g) pseudo-first-order pseudo-second-order

k1 (min1) Qe1,cal (mg/g) R2 k2 (g/(mg min)) Qe2,cal (mg/g) R2

115.0 0.079 146.9 0.938 0.075 133.3 0.973

Dark Condition UV Condition

TiO2
H-TR
Na-TR
H-TT
Na-TT

Fig. 8. Changes in the relative concentration (C/C0) of methylene blue over time by TiO2 (starting material), Na-TT, H-TT, Na-TR and H-TR.

(Fig. 6). As seen from the C/C0, a smaller degradation of MB on
typical TiO2 was obtained when compared to that of titanate
nanostructures. A significant decrease in approximate 80% MB
degradation was seen for the titanate nanotubes while titanate
nanoribbons exhibited approximate 60% MB degradation. This
indicated that the photocatalytic performance relied on the corre-
sponding surface area as shown in Table 2. At this point, the pho-
todegradation of MB on TiO2 and titanate nanostructures was found
to follow first order reaction, which was similarly observed by other
(Choudhury et al., 2016). The rate constant for TiO2 was 8.56
103
 K. Kiatkittipong, S. Assabumrungrat / Journal of Cleaner Production 148 (2017) 905e914
min1. For titanate nanotubes, the reaction rate constant (k) for Na-
TT (1.02
102 min1) was lower than that for H-TT (1.16
102
min1), despite a higher MB adsorption on Na-TT in dark condition.
The suppression of MB degradation on Na-TT may attribute that the
high amount of MB absorbed on Na-TT may block the active site for
light absorption. For nanoribbons, the reaction rates of Na-TR and
H-TR were 9.14
103 min1 and 9.32
103 min1, respectively.
The suppressed degradation of MB on Na-TR exhibited similar
behavior explained for titanate nanotubes, but the degradation of
MB between Na-TR and H-TR was not significantly different. This
behavior was also observed for oxalic degradation (Kiatkittipong
et al., 2013). This effect was not as pronounced for titanate nano-
ribbons because of their comparatively low surface area. Through
the results of this study, it was suggested that the adsorption pro-
cess and photodegradation should occur simultaneously. The
photocatalyst stability of all synthesized samples for MB degrada-
tion is illustrated in Fig. 9. The results reveal that the reaction rates
of Na-TT, H-TT, Na-TR, H-TR were not significantly different for at
least 3 cycles, indicating that all synthesized samples have photo-
catalytic stability.
3.5. Sedimentability
The sedimentability of suspension was studied by over the time
frame of 0e30 min. Their separability was presented in term of the
particle remaining in water as shown in Fig. 10. Their sedimentation
of particles was fast, and the particles remaining in water was
below 50% during the first 5 min. It is interesting that the sedi-
mentation of all synthesized titanates (particles remaining < 20%)
was more compared to TiO2 (particle remaining 30%) after 30 min.
The particles remaining in water for Na-TT and H-TT were
approximately 5% and 10%, respectively. Titanate nanotubes were
observed to provide a better settle down than titanate nanoribbons
(18% of Na-TR and 20% of H-TR remaining in water). This attributed
the higher negative charge on the surface of titanate nanotubes
which is more favourable surface for a high charge density of Al3þ
ion to form large particles and settle as sediment.
4. Conclusions
Titanate nanostructures were synthesized by reacting anatase
TiO2 (surface area of 10 m2/g) with 10 M NaOH under hydrothermal
condition. Sodium titanate nanotubes (Na-TT) having a surface area
of 138 m2/g were obtained at 150  C for 72 h. When Na-TT was
-2 -1
X 10 (min )
st
1 cycle
nd
k 2 cycle
rd
3 cycle
Fig. 9. Photocatalytic activity of TiO2 (starting material), Na-TT, H-TT, Na-TR and H-TR
for MB degradation with three times of cycling uses.
913
TiO2
H-TR
Na-TR
H-TT
Na-TT
Fig. 10. Particles remaining in water for suspensions over time.
immersed in HCl solution, Naþ is replaced by Hþ to form hydrogen
titanate nanotubes (H-TT). For titanate nanoribbons, a sodium
titanate nanoribbons (Na-TR) having surface area of 32 m2/g can be
obtained at temperature of 200  C for 40 h. When acid washing was
employed, hydrogen titanate nanoribbons (H-TR) were formed at
200  C for 24 h under hydrothermal condition. All synthesized
titanate nanostructures were more proficient for MB adsorption
performance as compared to starting material TiO2 due to higher
surface areas. The largest MB adsorption capacity was seen for Na-
TT which is found as one of the highest sorption capacity among Ti-
O structural materials from the literature. That is, the adsorption of
MB dye on Na-TT was explained by Langmuir adsorption model
with a maximum amount of 178.6 mg/g. The sodium incorporation
in titanate nanotubes is one of key parameters to achieve high MB
sorption capacity. The reaction of MB adsorption was pseudo-
second-order with the rate constant (k) of 0.075 g/mg min. This
was attributed to the high concentration of hydroxyl groups on the
surface, and negative charge of sodium titanate strongly adsorbed
cationic form of MB. Under light irradiation, the photocatalytic
activity increased in the order TiO2 < titanate
nanoribbons < titanate nanotubes, which can be explained in term
of their surface areas. However, the high amount of MB on sodium
titanate suppressed the reaction rate of degradation. This was
especially observed in the case for Na-TT due to comparatively high
surface area. That is, the reaction rate constant (k) for H-TT
(1.16
102 min1) was faster than that for Na-TT (1.02
102
min1). For sedimentability after photocatalytic reaction, the pre-
sent study clearly ascertained that all synthesized titanate nano-
structures provided better separation from water with alum when
compared with TiO2. The strong interaction between titanate
nanotubes and the Al3þ ion leads to preferential flocculation and
easy removal from the water, of which remaining Na-TT and H-TT in
water were approximately 5% and 10%, respectively.
Acknowledgement
This work was financially supported by the Thailand Research
Fund (TRF) (Grant No. TRG5780171) and King Mongkut’s Institute of
Technology Ladkrabang. The authors thank Mr.Kasidis Naktup,
Mr.Uaychai Risri, Mr.Wongskorn Itsaraporn and Miss Araya Chue-
bupa for their assistance.
914 K. Kiatkittipong, S. Assabumrungrat / Journal of Cleaner Production 148 (2017) 905e914

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