Journal of Hazardous Materials 243 (2012) 302310

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Journal of Hazardous Materials

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Hierarchically multifunctional K-OMS-2/TiO2 /Fe3 O4 heterojunctions for the

photocatalytic oxidation of humic acid under solar light irradiation
Tong Zhang, Xiaoli Yan, Darren Delai Sun
School of Civil and Environmental Engineering, Nanyang Technological University, Nanyang Avenue, 639798 Singapore, Singapore

h i g h l i g h t s
 Hierarchical K-OMS-2/TiO2 /Fe3 O4 heterojunctions are synthesized for the rst time.
 The synthesized material possesses excellent magnetic and photocatalytic properties.
 A proposed mechanism is used to illustrate the photocatalytic oxidation process.

a r t i c l e

i n f o

Article history:
Received 14 May 2012
Received in revised form 15 October 2012
Accepted 18 October 2012
Available online 26 October 2012
Keywords:
Fe3 O4
Heterojunctions
K-OMS-2
Photocatalytic
TiO2

a b s t r a c t
A multifunctional heterojunctioned K-OMS-2/TiO2 /Fe3 O4 (KTF) nanocomposite was successfully synthesized using a combination of hydrothermal and co-precipitation techniques. The resultant sample was
characterized by XRD, FESEM, TEM, N2 adsorption, XPS and VSM. Its photocatalytic activity was demonstrated in the photocatalytic degradation of humic acid (HA). Morphology characterization showed the
hierarchical structure of the synthesized material, and XRD results revealed that both the rutile and
anatase TiO2 structures are present in the sample. The average pore diameters and BET surface area of
the synthesized KTF heterojunctions were 40 nm and 134.42 m2 /g, respectively. XPS spectra conrmed
the presence of Fe3 O4 and TiO2 in the synthesized material, and the valences of Mn were kept at +3
and +4 after the grafting of Fe3 O4 and TiO2 . The synthesized material showed good magnetic response
and photocatalytic activity under simulated solar light irradiation, and 85.7% of HA was decomposed
after 120 min in the presence of KTF nanocomposites. The reusability study suggested that the magnetic
recovered material was stable enough for multiple recycling usages, verifying its potential application in
water purication.
2012 Elsevier B.V. All rights reserved.

1. Introduction
Photocatalytic oxidation (PCO) has been widely used in water
treatment due to its excellent performance on pollutants removal,
low cost, photochemical stability and without addition of toxic
chemicals [1,2]. As a typical semiconductor-based photocatalyst,
nanostructured TiO2 has been widely employed for water purication [35]. However, nanostructured TiO2 photocatalysts still
suffer some inherent drawbacks, such as aggregation in solution,
recombination of charge carriers (holeelectron pairs), and large
band gap. All of these properties impede the practical application
in photocatalytic process. Owing to the aggregation effect, nanosized TiO2 usually do not present individually in aqueous system.
For example, the aggregation of TiO2 nanoparticles can be up to
0.1 m, which would reduce the reaction sites on the surface and

Corresponding author. Tel.: +65 6790 6273; fax: +65 6791 0676.
E-mail address: DDSun@ntu.edu.sg (D.D. Sun).
0304-3894/$ see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.jhazmat.2012.10.037

thus lower the photocatalytic activity [6]. In a typical PCO process,

the photogenerated electrons and holes can migrate to the surface
of the photocatalyst, where they participate in redox reactions with
adsorbed species and form superoxide radical anion ( O2 ) and
hydroxyl radical ( OH), respectively. These reactive oxygen species
are mainly used for the degradation of pollutants in water [7,8].
However, some electrons and holes cannot participate in this process due to the recombination of the charge carriers, which leads
to the inhibition of photocatalytic activity [9]. In addition, in view
of the larger band gap [10], TiO2 requires UV light to excite and
thus lower the utilization of solar energy. To solve this problem,
photocatalysts with higher activity under visible light can be incorporated into TiO2 to form hybrid photocatalysts [11], which can
extend the photoresponse of the materials and make the photocatalysts utilizable under both UV light and visible light.
As a kind of ubiquitous transition metal oxides, manganese
oxides have been considered as promising materials due to their
vast applicabilities in batteries, molecular sieves, absorbents, and
catalysts [1214]. Cryptomelane-type manganese oxide (K-OMS2) is an octahedral molecular sieve composed of 2 2 edge-shared

T. Zhang et al. / Journal of Hazardous Materials 243 (2012) 302310

MnO6 octahedral chains, and mixed valences of manganese (Mn4+

and Mn3+ ) are situated in the octahedral sites of cryptomelane.
It is important to note that the presence of Mn4+ /Mn3+ can act
as an electron acceptor to prolong the lifetime of photogenerated
charge carriers [15,16]. Furthermore, current progress shows that
nanostructured manganese oxides (e.g. K-OMS-2), which possess
partially lled d-orbitals, can be effectively used as photocatalysts
under visible light [15,17]. It is predictable that materials based
on nanostructured K-OMS-2 would enhance the efciency of PCO
process under visible light. Moreover, the nanostructrued K-OMS-2
can be a template and control the morphology of the coated nanostructures on its surface, resulting in the increment of reaction sites.
Therefore, nanostructured manganese oxide is considered as an
ideal multifunctional support material to enhance the photocatalytic activity of the synthesized nanocomposites.
Separation of the nanocomposites in heterogeneous systems
is another steep challenge for practical applications. Many strategies such as free settling, centrifugation and membrane ltration,
have already been adopted to overcome this engineering problem
[18,19]. Nevertheless, these separation techniques always suffer
from prolong usage of equipment operation, complicated technical
requirements, and high operational costs, which severely restrict
many water treatment applications. In comparison with other separation techniques, magnetic separation exhibits excellent ability
in separation of nanosized materials with many advantages including easy operation and low cost [20,21]. Hence, it is desirable to
synthesize hybrid nanomaterials with efcient magnetic separation ability and PCO property under solar light irradiation.
In this work, a novel type of hierarchically magnetic K-OMS2/TiO2 /Fe3 O4 (KTF) heterojunctions was successfully synthesized
by a combination of hydrothermal and co-precipitation techniques.
Firstly, a hydrothermal method was employed to synthesize cryptomelane-type manganese oxide (K-OMS-2) nanowires
which served as substrates to guide the growth of secondary
TiO2 nanostructures. Subsequently, another hydrothermal process was carried out to form TiO2 nanostructures onto the
K-OMS-2 nanowires. Finally, magnetic Fe3 O4 nanoparticles were
grafted onto the synthesized K-OMS-2/TiO2 nanowires via a coprecipitation method. Laboratory-scale batch experiments were
conducted to investigate the degradation of humic acid (HA) under
solar light using the synthesized material as the photocatalyst,
which exhibits good photocatalytic activity. Moreover, the synthesized material is easy for recovery and recycling due to its magnetic
property.
2. Experimental
2.1. Synthesis of K-OMS-2 nanowires
K-OMS-2 nanowires were synthesized via a hydrothermal
method [22]. In a typical procedure, 12 mmol of K2 SO4 , 12 mmol
of K2 S2 O8 , and 8 mmol of MnSO4 H2 O were dissolved in 70 ml of
deionized water. The solution was then transferred to a 125 ml
Teon-lined stainless-steel autoclave. The autoclave was sealed
and heated in an oven at 250 C for 4 days. The resulting black
precipitate was suspended in 1000 ml deionized water, and stirred
vigorously for 12 h. After thorough washing with deionized water
to remove remaining ions present in the product, the sample was
dried at 105 C for 24 h.
2.2. Synthesis of hierarchical K-OMS-2/TiO2 nanostructures and
pure TiO2
To fabricate hierarchical K-OMS-2/TiO2 nanostructures, 100 mg
of the synthesized K-OMS-2 nanowires, 800 mg titanous sulfate,

303

and 0.4 ml concentrated H2 SO4 (98%) were dissolved in 70 ml

deionized water. After homogenization by an ultrasonic homogenizer (Sonics and Materials, CT, USA) for 10 min, the solution was
transferred to the 125 ml Teon-lined autoclave again and heated
at 105 C for 20 h. In order to remove all soluble ions in the solution, the product was washed several times before being separated
using a centrifuge. Then, the resulting product was dried in vacuum
for 48 h. Pure TiO2 was also synthesized via a hydrothermal process identical to that of hierarchical K-OMS-2/TiO2 nanostructures,
except without the addition of K-OMS-2 nanowires.

2.3. Synthesis of hierarchical KTF nanocomposites

To fabricate KTF nanocomposites, nanoparticles of Fe3 O4 were
deposited onto K-OMS-2/TiO2 nanostructures using a chemical coprecipitation method [21]. 10 ml of 0.02 mol/L ferric sulfate and
10 ml of 0.02 mol/L ferrous sulfate were vigorously stirred in a
beaker at room temperature. 5 mol/L KOH was then added dropwise into the solution. When pH of the solution was raised to 10,
0.5 g K-OMS-2/TiO2 was added into the system and continuously
stirred for 5 min. After that, pH value of the solution was adjusted
to 12 and stirred for another 20 min. The product was washed several times using deionized water before being separated using a
magnet.

2.4. Material characterization

The XRD data was collected on a Bruker D8 Advance X-ray
Morphologies of the syndiffractometer (Cu K  = 1.5406 A).
thesized materials were studied using a eld-emission scanning
electron microscope (FESEM) Jeol JSM-6340F (Japan) operated
at 5 kV, and transmission electron microscopy (TEM) was carried out on a Jeol JEM-2100F (Japan) operated at 200 kV.
BrunaurEmmettTeller (BET) surface area of the nanowires was
measured by N2 sorption using a Quantachrome Autosorb-1 instrument (USA). X-ray photoelectron spectroscopy (XPS) analysis was
carried out in an ultrahigh vacuum (UHV) chamber with a base
pressure below 2.66 107 Pa at room temperature. The room
temperature photoluminescence (PL) spectra were recorded on
a Fluorolog-3 spectrouorometer (Horiba Scientic, New Jersey,
USA) at an excitation wavelength of 300 nm.

2.5. Photocatalytic activity measurement

Photocatalytic activity of the synthesized nanocomposites was
evaluated by measuring the degradation rate of HA aqueous solution in a laboratory-scale batch photo-chemical reactor with 8
quartz at room temperature. A 500 W xenon lamp was used as the
simulated solar light source, surrounding with cool deionized water
at the outer wall through a quartz jacket. Before commencement of
irradiation, the reaction suspension containing HA solution (20 ml,
20 ppm) and synthesized nanocomposites (20 mg) was stirred in
the dark for 30 min to achieve equilibrium. The pH was maintained
at 5 with controlled addition of 0.01 mol/L HCl and 0.01 mol/L NaOH
solutions. The PCO process started once the lamp was lighted.
The quartz tubes were taken out from the photo-chemical reactor periodically, and samples were immediately ltered using glass
syringe lters (0.45 m) to separate the material for subsequent
analysis. Concentration of HA was determined by a UVvisible
spectrophotometer (Thermo Scientic Evolution 300) at a xed
wavelength of 436 nm. Total organic carbon (TOC) content was
measured using a total organic carbon analyzer (TOC-V CSH Shimadzu).

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T. Zhang et al. / Journal of Hazardous Materials 243 (2012) 302310

onto the synthesized hierarchical K-OMS-2/TiO2 nanocomposites

via a chemical co-precipitation process [21], as shown in Fig. 2C.
However, owing to the limited magnication of FESEM, it is difcult
to differentiate Fe3 O4 nanoparticles from the TiO2 nanostructures
in the image. In addition, the SEMEDX analysis in Fig. 2D reveals
that the external surface of the as-synthesized sample contains Mn,
Ti and Fe (atomic ratio is 16:29:5).
3.3. TEM observation

Fig. 1. XRD patterns of the synthesized K-OMS-2, K-OMS-2/TiO2 and KTF.

3. Results and discussion

3.1. XRD analysis
The X-ray diffraction (XRD) patterns of the synthesized nanostructured K-OMS-2, K-OMS-2/TiO2 and KTF are presented in Fig. 1.
All diffraction peaks of the upper curve in Fig. 1 can be perfectly
indexed to the K-OMS-2 crystalline phase (JCPDS 44-1386). The KOMS-2 phase is also observed in the other samples, indicating that
the crystal structure of the K-OMS-2 nanowires was not changed
in the coating processes of TiO2 and Fe3 O4 nanostructures. Interestingly, the grafted TiO2 on the K-OMS-2 nanowires showed both
diffraction peaks of anatase and rutile phases TiO2 . The peaks at
25 and 63 reveal the presence of anatase phase of TiO2 (JCPDS
21-1272) in the synthesized nanocomposites, while the peaks at
27 , 36 and 55 indicate the co-existence of rutile phase of TiO2
(JCPDS 21-1276). Moreover, the diffraction peaks of the synthesized
KTF showed slight changes after the grafting of Fe3 O4 nanoparticles and no marked Fe3 O4 diffraction peaks were observed in
the lower curve in Fig. 1, which can be attributed to the presence
of only a minimal amount of Fe3 O4 nanoparticles in the synthesized material. According to our previous study [21], the extent of
Fe3 O4 nanoparticles is controllable by the dosage of Fe3 O4 , and a
small quantity of Fe3 O4 is sufce in inducing magnetic separation
of the synthesized nanocomposites. Furthermore, the low extent
of Fe3 O4 nanoparticles on the surface of the synthesized K-OMS2/TiO2 nanocomposites would ensure the availability of surface
reactive sites without compromising PCO efciency.
3.2. FESEM observation and EDX analysis
Fig. 2 shows FESEM images of the synthesized K-OMS-2
nanowires, K-OMS-2/TiO2 heterojunctions, and hierarchical KTF
heterojunctions, respectively. As a primary substrate, the K-OMS-2
nanowires have diameters of about 4080 nm and are over several
hundreds of microns long, as shown in Fig. 2A. After a hydrothermal
process, the secondary TiO2 nanostructures were readily grafted
onto the surfaces of the K-OMS-2 nanowires, as shown in Fig. 2B.
Although it is difcult to determine an individual structure of
TiO2 from the FESEM image, it can be found that the K-OMS-2
nanowires were uniformly coated. To endow the synthesized material with magnetic property, Fe3 O4 nanoparticles were deposited

To further identify the surface morphology of the synthesized

materials, TEM characterization was conducted. TEM images of KOMS-2 nanowire and K-OMS-2/TiO2 hierarchical heterojunctions
are shown in Fig. 3A and B, respectively, which conrms the high
density secondary TiO2 hair-like structures anchored on surfaces
of the primary underlying K-OMS-2 nanowires. As a scaffold, KOMS-2 nanowires act as a dispersing template to downsize the TiO2
nanostructures and thus increase photoreactive sites for degradation of pollutants [23]. In addition, the hydrolysis of titanous sulfate
proceeded very slowly in the synthesis process. The slow hydrolysis process reduced the reaction and nucleation rate, which in turn
facilitate the growth of TiO2 on the surface of K-OMS-2. Previous
studies revealed that a mild and slow reaction would lead to the
formation of materials with well-organized morphologies [24,25],
which can explain the formation of evenly coated TiO2 nanostructures on the surface of K-OMS-2 nanowires. Comparing with other
fabrication methods (e.g. solgel), the morphology of TiO2 was controlled in this work, which increased the effective specic surface
area and thus enhanced the photocatalytic activity of the material.
Fig. 3D shows that the d-spacing of 0.48 nm corresponds to
{0 0 2} planes of monoclinic K2x Mn8 O16 , which further conrms
that the prepared nanowire is K-OMS-2. The HRTEM image of TiO2
shown in Fig. 3E reveals lattice fringes of the {1 1 0} with a dspacing of 0.32 nm, typical for tetragonal TiO2 . Fig. 3C veries that
Fe3 O4 nanoparticles were successfully deposited onto the synthesized K-OMS-2/TiO2 nanocomposites, and HRTEM image in Fig. 3F
shows that the size of the synthesized Fe3 O4 nanoparticle is about
5 nm. The Fe3 O4 nanoparticle is well crystallined with clear lattice fringes, and the width of 0.25 nm from inter-plane distance of
individual nanoparticle corresponds to (3 1 1) planes of Fe3 O4 [26],
which further conrms the existence of Fe3 O4 nanoparticles in the
synthesized nanocomposites.
3.4. BET surface area and pore structure
To examine the surface area, as well as the pore size distribution, nitrogen adsorption/desorption analysis was conducted on the
synthesized materials. As shown in Fig. 4, the BET surface area of
the synthesized K-OMS-2, K-OMS-2/TiO2 and KTF are recorded at
25.08 m2 /g, 111.58 m2 /g and 134.42 m2 /g, respectively, indicating
that the loading of TiO2 and Fe3 O4 nanostuctures on the K-OMS-2
nanowires has greatly increased the specic area of the material. It
can be attributed to the presence of K-OMS-2 scaffold, which acts as
a dispersing template to downsize the TiO2 and Fe3 O4 nanostructures during the synthesis process. An IV-type nitrogen isotherm
with H3-type hysteresis loops indicated that the synthesized KTF
heterojunctions were of mesoporous nature. According to the
IUPAC classication, mesoporous materials characterizing the Type
H3 loop are commonly observed with aggregates of plate-like particles, leading to formation of slit-shaped pores [27]. And the pores
were possibly from the interweaving of the TiO2 nanostructures
on the surface of K-OMS-2 nanowires. In addition, the mesoporosity of the KTF heterojunctions are well-justied based on the inset
of Fig. 4, where pore size distribution curve indicates a sharp peak
centered at the pore diameter of 40 nm, providing evidence that the
sample contains a majority of mesopores (2 nm < pore size < 50 nm).

T. Zhang et al. / Journal of Hazardous Materials 243 (2012) 302310

305

Fig. 2. (A) FESEM image of the K-OMS-2 nanowires; (B) FESEM image of the hierarchical K-OMS-2/TiO2 heterojunctions; (C) FESEM image of the hierarchical KTF heterojunctions; (D) EDX spectrum of the KTF.

Fig. 3. (A) TEM image of the K-OMS-2 nanowire, (B) TEM image of the hierarchical K-OMS-2/TiO2 heterojunctions, (C) TEM image of the hierarchical KTF heterojunctions,
(D) HRTEM image of the K-OMS-2 nanowire, (E) HRTEM image of the hierarchical K-OMS-2/TiO2 heterojunctions and (F) HRTEM image of the Fe3 O4 nanoparticles.

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T. Zhang et al. / Journal of Hazardous Materials 243 (2012) 302310

Fig. 4. N2 adsorption/desorption isotherm curve of the synthesized KTF heterojunctions; Inset is the pore size distribution of KTF heterojunctions.

The larger specic surface area and mesoporous structure would be

benecial to attract the organic pollutants onto the surface of the
photocatalyst for fast degradation.

states of Mn more specically. The peaks are centered at 641.7 eV

and 643.0 eV, indicating the presence of Mn3+ and Mn4+ , respectively [28]. Fig. 5B shows the high-resolution XPS spectra of Mn
2p taken on the surface of KTF, and the integrated tting peaks of
Mn 2p3/2 (641.8 eV and 643.3 eV) are very similar with the spectra in Fig. 5A [2931], indicating that there is no obvious change of
the valences of Mn after the TiO2 and Fe3 O4 grafting processes. It is
noteworthy that the mixed-valences of Mn is important in electron
transfer and lead to conductivity of resultant material [16], and thus
enhance the photocatalytic activity of the synthesized photocatalyst [15,32]. Moreover, the XPS spectra intensity of Mn declined
obviously after the coating processes, which can be attributed to
the surface of the K-OMS-2 nanowires being partially occupied by
TiO2 and Fe3 O4 nanostructures. Fig. 5C shows that the peaks for Ti
2p3/2 and Ti 2p1/2 are centered at 458.8 eV and 464.4 eV, representing the presence of a Ti4+ oxidation state in the sample [33], which
further conrmed the presence of TiO2 on the surface of K-OMS-2
nanowires. Fig. 5D shows the high-resolution XPS spectra of Fe 2p.
The respective binding energies of 710 eV and 724 eV indexed to Fe
2p3/2 and Fe 2p1/2 , are consistent with the reported values of Fe3 O4
[26], indicating the successful coating of Fe3 O4 onto the sample. It
is important to note that the presence of TiO2 and Fe3 O4 can endow
the synthesized nanocomposites with photocatalytic activity and
magnetic separation property.
3.6. Magnetism study

3.5. XPS analysis

The synthesized KTF heterojunctions were investigated by XPS
to identify the surface elemental compositions and binding energies, and the result indicates the sample contains K, Mn, O, Ti,
and Fe. The high-resolution XPS spectra of Mn 2p taken on the
surface of K-OMS-2 nanowires is shown in Fig. 5A and Gaussian
curve tting of Mn 2p3/2 was performed to describe the oxidation

The magnetic properties of KTF heterojunctions were measured

using a vibrating sample magnetometer (VSM) at room temperature with an applied eld of 10 kOe H 10 kOe, as shown in
Fig. 6. It can be seen that the magnetic saturation of the KTF
heterojunctions is 7.68 emu/g, which is much lower than that of
the corresponding pure Fe3 O4 nanoparticles (53.89 emu/g) [21],
resulting from the existence of K-OMS-2 and TiO2 . The material

Fig. 5. High-resolution XPS spectra of the Mn 2p taken on the K-OMS-2 nanowires (A); high-resolution XPS spectra of Mn 2p (B); Fe 2p (C) and Ti 2p region (D) taken on the
KTF heterojunctions.

T. Zhang et al. / Journal of Hazardous Materials 243 (2012) 302310

307

HA changes in Fig. 7, the residue of HA in 120 min was decreased

to 14.3% by using the KTF as a photocatalyst, which is more effective than the pure TiO2 and P25. Although the degradations of TOC
follow the similar trends with HA, the TOC removal rates are much
slower than HA due to the incompletely decomposition of HA at
the beginning of the PCO process.
Photocatalytic degradations for organic pollutants are often
described in terms of the LangmuirHinshelwood model, which
can be simplied as pseudo-rst order reaction as follows [1]:
r=

dC
= kC
dt

(1)

where k refers to the corresponding reaction rate kinetic constant

(h1 ). Hence, the pseudo rst-order reaction rate can be further
applied:
ln
Fig. 6. Magnetization curve of the synthesized KTF heterojunctions. Inset is the
photographs of a vial containing KTF heterojunctions in water (i) before and (ii)
after magnetic separation for 30 s.

exhibited remarkable magnetic selectivity, and can be rapidly separated under an applied magnetic eld. This magnetic separation
property is mainly accountable by the Fe3 O4 nanoparticles on the
surface of the material. Under an external magnetic eld, each individual Fe3 O4 nanoparticle contributes a portion of its traction on
moving the K-OMS-2/TiO2 nanostructures. Moreover, the nanostructures of K-OMS-2/TiO2 and Fe3 O4 can provide high surface
area of contact for the Fe3 O4 nanoparticles in transferring mechanical forces to the K-OMS-2/TiO2 . As shown in the inset of Fig. 6,
the material can be easily attracted and accumulated to a commercial magnet, indicating that the material can be recycled using a
magnetic separation method. The recycled materials can be further used in water treatment process and thus reduce secondary
pollution and lower the cost of materials.
3.7. Solar-light-induced catalytic activity studies
The photocatalytic activity of the synthesized KTF heterojunctions was evaluated by the degradation of HA under simulated solar
light irradiation, and the synthesized pure TiO2 and commercial
TiO2 P25 were also used for comparison. Fig. 7 shows the concentration changes of HA and TOC as a function of time, indicating that the
KTF heterojunctions exhibit higher photodegradation ability than
the pure TiO2 and P25 under the same conditions. As shown for the

Fig. 7. Changes of HA concentration and TOC during photolysis and photocatalytic

degradation in the presence of P25, the synthesized pure TiO2 and the KTF heterojunctions.

C
= kt
C0

(2)

where C (mg L1 ) is the HA concentration at time t, C0 (mg L1 ) is the

initial HA concentration measured after 30 min of dark adsorption
and t (h) is the reaction time.
Furthermore, the rst-order reaction model can be expended to
include the specic area of the synthesized material [34]:
ln

C
= ksa as m t = ksa a t
Co

(3)

where ksa is the specic reaction rate constant (L h1 m2 ), as is

the specic surface area of the materials (m2 /g), m is the mass of
concentration of the materials (g L1 ), and a is the surface area
concentration of the materials (m2 L1 ).
As shown in Fig. 8A, the reaction rate constants for the synthesized KTF and pure TiO2 are 0.882 h1 and 0.463 h1 , respectively.
The photocatalytic degradations of HA follow pseudo rst-order
kinetics in the studied concentration range, and thus the corresponding k constants indicate a good evaluation of the overall
photocatalytic reaction rates. Specic reaction rate constant values are more general descriptor of degradation of pollutants by
photocatalysts, and they allow the comparison of photocatalyts
with different specic surface areas [35]. As shown in Fig. 8B, the
ksa of 0.00657 L h1 m2 for the KTF (134.42 m2 /g) is higher than
0.00638 L min1 m2 of the pure TiO2 (72.74 m2 /g), indicating the
higher photocatalytic efciency of the synthesized KTF. This could
be explained by the following factors:
(1) The K-OMS-2 acts as a dispersing template to downsize the TiO2
nanostructures during the synthesis process and thus increase
the specic surface area of the synthesized material. The larger
surface area of the photocatalyst can directly enhance photocatalytic activity since PCO processes are predominantly driven by
surface reactions on the material. Moreover, with the increase
of specic surface area, there are more HA molecules adsorbed
onto the synthesized KTF heterojunctions than the pure TiO2
(Fig. 7). Previous report [36] revealed that more efcient oxidation can occur in the very vicinity of photocatalyst, thus the
photocatalyst with higher adsorption capacity would endow
the material with higher photocatalytic efciency. In addition,
it has been reported that K-OMS-2 doped TiO2 materials possess
good PCO efciency due to the presence of OH bonded groups
on the catalyst surface [32].
(2) The recombination rate of electrons and holes on the surface
of the photocatalyst can also affect photocatalytic efciency
[37,38]. As mixed valence in organic system leads to conductivity of the resultant materials, the Mn3+ /Mn4+ in the synthesized
KTF heterojunctions play a crucial role in electron transfer and
thus suppress the recombination of electron and hole pairs
[16,39].

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T. Zhang et al. / Journal of Hazardous Materials 243 (2012) 302310

Fig. 8. (A) Pseudo rst-order photocatalytic degradation of HA over the pure TiO2 and the KTF heterojunctions; (B) specic reaction rate rst-order photocatalytic degradation
of HA over the pure TiO2 and the KTF heterojunctions.

PL emission spectra are useful to study the efciency of charge

transfer behavior of photogenerated electrons and holes [40].
Fig. 9 shows the PL spectra of pure TiO2 and K-OMS-2/TiO2 ,
indicating that the PL intensity of pure TiO2 was substantially
quenched by the addition of K-OMS-2 nanowires. It is well
know that the intensity of PL emission is strongly dependent on
the recombination rate of photogenerated electrons and holes
[41]. In this study, K-OMS-2 nanowires act as trapping sites
to capture photogenerated electrons from the TiO2 conduction band, separating the photogenerated electron-hole pairs.
Thus, the presence of K-OMS-2 nanowires can retard the photogenerated charge carrier recombination rate of the synthesized
material, leading to the decline of PL spectrum intensity.
A proposed mechanism to illustrate the processes of light
activation, charge transfer and degradation of HA under solar
light is shown in Scheme 1. In a typical process, electrons are
excited from the valence band to the conduction band under
light absorption with energy equal to or greater than the band
gap of the TiO2 nanostructures in the synthesized material. KOMS-2 can act as an electron reservoir, which helps to trap the
photoinduced electrons emitted from the TiO2 photocatalyst
and thus retard the recombination of electron and hole pairs.
Consequently, more holes (h+ ) can migrate to the surface of
the photocatalyst, where the holes react with adsorbed water
or hydroxyl anions to form hydroxyl radicals ( OH) for the
oxidation of HA. To conrm the production of reactive oxygen

Fig. 9. PL spectra of the synthesized pure TiO2 and KTF heterojunctions.

species, photocatalytic degradation of HA via KTF was intervened by adding radical scavenging species, such as dimethyl
sulphoxide (DMSO), potassium iodide (KI) and benzoquinone
(BQ) to investigate contributory roles of the respective generated hydroxyl radical OH, photogenerated hole h+ and
superoxide radical O2 [42,43]. Fig. 10A shows that the
photodegradation rate of HA was declined with the increment
of DMSO concentration, indicating the production of OH in
the reaction system. Similarly, parallel to the increment of KI
concentration, an obvious decline in HA photodegradation was
observed (Fig. 10B), which can be attributed to the consumption
of h+ by the scavenger. In addition, the removal of HA can also be
suppressed by the introduction of BQ (Fig. 10C), which reveals
that the O2 was generated in the PCO process. These results
indicate that the presence of reactive oxygen species is crucial
for the degradation of HA in the system. Moreover, the degradation of HA was driven predominantly by OH, followed by h+
and O2 . When 1 mM of DMSO was added to quench OH in
the system, the residue of HA in 120 min was increased to 37.8%
as the consumed OH can no longer perform oxidative radical
attack on HA molecules. However, in the presence of 1 mM KI or
1 mM BQ, the residue of HA in 120 min was only 26.8% or 24.8%,
respectively. The result indicates that the hydroxyl radical OH
is the major active species in the degradation process.
(3) Current progress shows that K-OMS-2 can be directly used
as a photocatalyst to degrade organic pollutants under visible

Scheme 1. Proposed cycle of photo oxidation of HA on the surface of KTF heterojunctions under solar light irradiation.

T. Zhang et al. / Journal of Hazardous Materials 243 (2012) 302310

309

Fig. 10. Photocatalytic degradation of HA over KTF under the interference of (A) DMSO; (B) KI; (C) BQ.

light irradiation [15]. According to the XPS analysis in Fig. 5,

we could infer that K-OMS-2, TiO2 and Fe3 O4 are all exposed
on the external surface of the synthesized KTF. Although the
coating of TiO2 and Fe3 O4 may inhibit the light adsorption
onto K-OMS-2 to some extent, part of the light can still reach
to the surface of K-OMS-2 and lead to electron transfer in the
manganese oxide. Moreover, the excited electron from TiO2
can also be utilized in the K-OMS-2, as shown in Scheme 1.
Owing to the electron transfer in the manganese oxide, excited
oxygen species ( O2 ) can be formed and involved in the
oxidation of HA. Therefore, the degradation of HA can be
considered as a combination effect of h+ and O2 .
(4) In addition, Fe3 O4 nanoparticles can also affect the photocatalytic activity of the synthesized material. He et al.
[44] reported that the photocatalytic activity of magnetic
Fe3 O4 /TiO2 composites can be activated by visible light, which
can further enhance the efcacy of the synthesized material.
To investigate the photostability and reusability of the synthesized KTF, the material was collected using a commercial magnet
after the photodegaradation process of HA. After drying at 105 C,
the material was reused for 3 times under the same experimental conditions. The removal rate of HA in every cycle is shown in
Fig. 11, which indicates that the catalyst did not exhibit any signicant loss of the photocatalytic activity in the three successive
cycles. Moreover, the used KFT was further characterized after the
photocatalytic activity testing experiment. TEM images in Fig. 3C
and Fig. S1 show that the apparent morphologies of the synthesized KFT are very similar before and after the PCO process. XRD
result in Fig. S2 shows that the recycled KFT kept its original crystal
structure, and XPS spectra in Fig. S3 reveal that there is no obvious

Fig. 11. Cycling runs of photocatalytic degradation of HA in the presence of the

hierarchical KTF heterojunctions under solar light irradiation. The running time is
120 min for every cycle.

change of the valences of Mn, Ti and Fe after the reaction. The synthesized KTF possesses excellent stability, which is important to its
practical environmental applications.
4. Conclusions
In conclusion, a novel type of hierarchically multifunctional
KTF heterojunctions was successfully prepared using a combination of hydrothermal and co-precipitation methods. Although

310

T. Zhang et al. / Journal of Hazardous Materials 243 (2012) 302310

the proposed PCO mechanism needs to be further investigated,

it is without doubt that the synthesized material possesses good
magnetic response and photocatalytic properties under solar irradiation due to its higher surface area, lower recombination rate of
charge carriers, and the inherent photocatalytic activity of K-OMS2 under visible light. Moreover, the durability study showed that
the photocatalytic activity of the recovered KFT is stable enough
for multiple recycling, indicating the synthesized photocatalyst can
have potential in applications of environmental remediation.
Acknowledgements
We appreciate Mr. Benny Tan and Ms. Yixuan Wong for their
work on grammar check. We are grateful for the nancial support received from the Prime Ministers Ofce of Singapore via
an initiative called The Enterprise Challenge under award number P00579/1273, Singapore Environment & Water Industry (EWI)
Development Council under award number MEWR 621/06/166 and
the Public Utilities Board of Singapore.
Appendix A. Supplementary data
Supplementary data associated with this article can be
found, in the online version, at http://dx.doi.org/10.1016/
j.jhazmat.2012.10.037.
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