Powder Technology 254 (2014) 556562

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Powder Technology
journal homepage: www.elsevier.com/locate/powtec

Preparation, characterization and photocatalytic activity of Co-doped

LaMnO3/graphene composites
Jie Hu a,b, Jiahua Ma a, Lina Wang a, Hao Huang b,, Luwei Ma c
a
b
c

Hebei Key Laboratory of Applied Chemistry, Department of Environment and Chemistry, Yanshan University, Qinhuangdao 066004, PR China
State Key Laboratory of Metastable Materials Science & Technology, Yanshan University, Qinhuangdao 066004, PR China
Hebei Junsheng Occupational Health Evaluation Co. Ltd, Shijiazhuang 050061, PR China

a r t i c l e

i n f o

Article history:
Received 27 September 2013
Received in revised form 15 January 2014
Accepted 24 January 2014
Available online 3 February 2014
Keywords:
LaMn1 xCoxO3
Graphene
Composite
Photocatalyst

a b s t r a c t
A novel photocatalyst of LaMn1 xCoxO3/graphene composites had been synthesized by solgel process assisted
with chelating effect of citric acid. The structure, morphology and valence state of prepared samples were characterized by thermogravimetry-differential thermal analysis, X-ray diffraction, scanning electron microscopy,
transmission electron microscopy, X-ray photoelectron spectra and UVvis absorbance spectra. It was found
that LaMnO3 perovskite phase was successfully processed which anchored on the surface of graphene sheets,
and doping Co did not change the perovskite structure. The UVvis photocatalytic activity of the photocatalysts
was evaluated by the degradation of diamine green B. The results indicated that the photocatalytic activity of
composites depend strongly on the doping content of Co. LaMn1 xCoxO3/graphene composites prepared with
x = 0.15 had the greatest photocatalytic activity, and it displayed good stability during the photocatalytic and
recycling processes.
2014 Elsevier B.V. All rights reserved.

1. Introduction
Because of the increasing environmental pollution in recent years,
the degradation of organic pollutants has generated broad interest of
photocatalysis for both scientic understanding and potential applications [1]. To date, most investigations have focused on the photocatalyst
TiO2 resulting from its prominent characteristics, such as high photocatalytic activity, chemical stability, low cost and non-toxicity [2,3]. However, its practical application has not yet reached a satisfying extent
due to its wide band gap (3.2 eV) and high recombination of electron
hole pairs [4,5]. Therefore, nding a novel visible-light-driven semiconductor is of great interest.
Perovskite oxides have been known as an important kind of multifunctional material exhibiting a variety of interesting properties, such
as optical, electronic transport, and dielectric properties [3,6]. As a
typical ABO3-type perovskite structure material, LaMnO3 has many
special physical and chemical properties. Its crystal structure is stable,
especially when the A or B ions are partially substituted, crystal structure is not changed, but the performance is improved. In recent years,
much research has been done on the crystal structure, magnetic [7]
and electrical conductivity and electro-catalysis [8,9] for LaMnO3, but
the photocatalytic activity is rarely reported.
Recently, graphene has generated interest both in fundamental science and for wide potential applications due to its excellent electronic
properties, superior chemical stability and high specic surface area
Corresponding author. Tel.: +86 15369700375.
E-mail address: huanghao@ysu.edu.cn (H. Huang).
0032-5910/$ see front matter 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.powtec.2014.01.071

[10]. Graphene can absorb the dye molecules and also act as an excellent
electron-acceptor/transport material, and in addition, the surface
properties of graphene can be adjusted via chemical modication,
which facilitates its use in composite materials [11,12]. Fu and Wang
reported that a ZnFe2O4graphene nanocomposite showed enhanced
visible photocatalytic activity over pristine ZnFe2O4 in the presence of
H2O2 [13]. X.J. Bai et al. developed ZnWO4/graphene hybrid (GZW-X)
photo-catalysts via a facile in situ reduction of graphene oxide and
ZnWO4 in water and high efciency for the degradation of methylene
blue under both UV and visible light [14]. J.H. Li et al. conrmed
that a P25graphene nanocomposite prepared via a facile one-step
hydrothermal reaction exhibited UV and visible photocatalytic activity
that was superior to pristine P25 in the photodegradation of MB [11].
Xu et al. demonstrated ZnO/graphene nanocomposites exhibited a
higher UV light photocatalytic activity than pristine ZnO by taking advantage of the superior electrical conductivity and mechanical properties of graphene [15]. In order to enhance the semiconductors'
photocatalytic activity, there have been persistent efforts to load semiconductors on the structure of graphene [10,1618], but few studies
have focused on LaMnO3/graphene nanocomposite.
In this study, we used graphene as supporter that successfully deposited with LaMnO3 nanoparticles via solgel method. The graphene
sheets as charge transfer channel on LaMnO3 pholocatalyst easily
attracted electrons, retarding the charge pair recombination under
UVvis light irradiation. Doping rare-earth or other metal oxides into
the perovskite-type composites can increase their capability of trapping
and transferring electronhole pairs, which improves their photocatalytic activities. Accordingly, modication of LaMnO3/graphene by

J. Hu et al. / Powder Technology 254 (2014) 556562

doping Co ions with different contents was also prepared by the same
method. The photocatalytic activity of the LaMn1 xCoxO3/graphene
catalysts was tested on the degradation of diamine green B aqueous
solution under UVvis light. In order to investigate the reusable stability
of catalysts, the recycling experiments were carried out.
2. Experimental
2.1. Preparation of graphene
Commercial graphite powder was used as the starting reagent for
the synthesis of graphene oxide via a modied Hummers method [19]
in our experiment. In detail, graphite powder (5 g) was added to 98%
H2SO4 (115 mL) in an ice bath, KMnO4 (15 g) was added gradually
under continuous vigorous stirring and the temperature of the mixture
was kept below 20 C. Then, it was moved to a water bath, which was
kept at 35 C for 40 min with continuous stirring. This was followed
by adding distilled water (230 mL) to the mixture slowly and continuous stirring for 20 min, then the reaction was terminated by the addition
of distilled water (700 mL) and H2O2 solution (30%, 50 mL). After
stewing for 24 h at room temperature, the graphene oxide (GO) was
washed with 5% HCl solution and distilled water until SO24 anions
could not be detected. Small amounts of the dried GO were added into
a crucible, then, the crucible was calcined at 320 C for 15 min in the air.
2.2. Catalyst preparation
All the raw materials were analytically graded and used without further purication. The samples of LaMn1 xCoxO3/graphene composite
with various Co contents were prepared from La(NO3)3, Mn(NO3)2
and Co(NO3)2 by solgel method. In a typical experiment, the solgel
synthesis can be described in briefest terms as follows: 20 mL of
0.1 mol/L Mn(NO3)2, Co(NO3)2 solution (the molar ratio of Mn to Co
varied from 0.1 to 0.2) was mixed with 20 mL of 0.1 mol/L La(NO3)3 solution, with citric acid as the chelating agent and alkylphenols
polyoxyethylene (OP-10) as the dispersing agent were added to the
mixture solution, dispersed with the magnetic stirring, then mixed
with 100 mL of graphene water suspension (0.1 g/L) which was disposed by ultrasonic dispersing for 30 min. The obtained suspension
was adjusted to a pH value of ~9 with aqueous ammonia. It was aged
in the water-bath around 50 C until the xerogel had formed, and
then burned at 370 C for 5 h to remove extra organic compounds and
nitric acid. The burning remains were calcined at 650 C for 4 h in a vacuum furnace to form perovskite-type crystals. For comparison, the pure
LaMnO3 powders and LaMnO3/graphene composite were prepared
under the same condition.

light irradiation. And the UVvis light was obtained from a 300 W
xenon lamp. The distance between the light source and the surface of
dye solution was about 25 cm. In a typical photocatalysis measurement,
10 mg of photocatalyst powders was added to 50 mL of diamine green B
aqueous solution, the initial dye concentration was 20 mg/L. And prior
to irradiation, the suspension was magnetically stirred for 30 min to establish adsorption/degradation equilibrium in the dark. After every
30 min, 4 ml of suspension was continually taken from the reaction beaker and centrifuged at 3000 rpm/min for 5 min to remove the particles,
the upper transparent solution was measured at the range of 200
800 nm using the UVvis spectrophotometer (Shimadzu UV-2550).
Then the concentrations of the residual diamine green B were determined by measuring the absorbance at 612 nm, and the degradation
percentage was dened as (C0 Ct) / C0 100%, where C0 and Ct are
the concentrations of day before and after irradiation.
3. Results and discussion
In the process of sol preparation, the Zeta potential of the graphene
water suspension (0.1 g/L and 100 mL) in the initial sol was measured
by Nano ZS at 38.5 mV. Based on |Zeta potential| N30 mV [20],
graphene has good suspension stability in the sol. Epoxy, hydroxy, and
carboxyl hydrophilic groups can be found on the graphene surface and
edge because of the incomplete reduction of graphene oxide [21]. At approximately pH 9, the carboxyl group was ionized to produce hydrogen
ions, making the graphene surface carry a negative charge. Meanwhile,
the hydroxyl group of the graphene surface and the OH under alkaline
conditions generated hydrated anion. Hence, the graphene layers produced larger electrostatic repulsion, giving graphene good dispersion
stability. Then, the sol particles were adsorbed on the surface of
graphene by electrostatic adsorption and a formed complex gel in
solvent evaporation. The subsequent calcination process made the
perovskite particles grow and crystallize on the graphene surface.
In order to research the crystalline behavior and conrm the optimum calcining heat of LaMnO3/graphene, the precursor of the composite was characterized by using TG-DTA measurement, the result is
illustrated in Fig. 1. Corresponding to the weight loss between 100 C
to 200 C, there are two endothermal peaks in the DTA curve, which
can be mainly attributed to the evaporation of the free water and the
crystal water, respectively. The sharp exothermic peak at about 200 C
accompanied by a drastic weight loss may be caused by the decomposition of the superuous free citric acid. The following weight loss in the
temperature range of 230350 C was mostly due to the combustion
of the residual organic components, the decomposition of the nitrates
and the complexing citrate. It can be seen from the TG curve of
graphene, the slight weight loss between 400 and 600 C in the TG
curve of the LaMnO3/graphene may be mainly due to the combustion

2.3. Characterizations
The thermal decomposition behavior of the gel was characterized by
thermogravimetric and differential thermal analysis (DTA/TG, WCT-2A)
at a heating rate of 5 C/min in air. The catalyst structure was investigated by X-ray diffraction (XRD, Neo-3014 X-ray diffractometer) with Cu
K radiation ( = 1.5405 ), and diffraction patterns were recorded
over the range of 2080. A scanning electron microscope (FESEM,
Hitachi S-4800) with energy dispersive spectrometer (EDS) and a transmission electron microscope (TEM, JEOL-2010) were used to examine
the surface morphologies, the elements and the composition of the prepared sample. The electron binding energies for the elements were
measured by X-ray photoelectron spectroscopy (XPS, ESCALAB250)
with an Al K monochromatized source.
2.4. Photocatalytic activity testing
Photocatalytic activities of the as-prepared samples were evaluated
by the photocatalytic decomposition of diamine green B under UVvis

557

Fig. 1. TG-DTA curves of LaMnO3/graphene precursor and TG curves of graphene.

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of graphene in the air. An obvious endothermal peak appears on the

DTA curve at about 640 C, revealing that the perovskite was crystallized completely.
Fig. 2 shows the XRD patterns of graphite, graphene oxide, and
graphene. The strong diffraction peak of the graphite appeared at approximately 26 for C (0 0 2), which illustrates that the raw graphite
sheet layer is very regular. When graphite was oxidized, the XRD pattern of graphene oxide had a strong diffraction peak at approximately
2 = 6, which corresponds to water bound intercalated oxidized
graphene. This result suggests that the oxidized graphene sheet is
completely separated from the graphite. However, the XRD pattern of
graphene did not show the diffraction peak at 2 = 6, and the interlayer spacing changed from 1.16 nm in graphene oxide to 0.371 nm in
graphene, which is still slightly larger than the d-spacing of wellordered graphite (0.336 nm). The small amount of functional groups
and hydrogen remaining might be the main reason for this difference,
indicating incomplete reduction of graphene oxide to graphene. Compared with graphite, graphene has a low-intensity diffraction peak for
C (0 0 2), indicating the short-range order of graphene sheets [22].
The XRD patterns of LaMnO3, LaMnO3/graphene and Co doped
LaMnO3/graphene with different contents are shown in Fig. 3. The diffraction data of LaMnO3 can be indexed to perovskite-type structure,
without any miscellaneous peak, which agrees well with the reported
data (JCPDS No. 50-0297). From the XRD pattern of LaMnO3/graphene,
it can be seen that there are some small diffuse peaks, which have
lower intensity, appearing in the background. This may be due to the
low content of graphene in the composite and the disordered stacking
of the graphene sheets. Furthermore, the main diffraction peaks of
LaMnO3/graphene composites are similar to that of LaMnO3, which indicates that the presence of graphene dose not change the perovskitetype structure. Compared with LaMnO3/graphene, the diffraction
peaks of Co doped with different contents are all in good agreement
with it, therefore, it can be concluded that Mn ions that are partially
substituted by Co do not change the crystal structure of the composite.
The average grain size of the as-prepared samples were 22 nm,
22.6 nm, 24.6 nm, 17 nm, 15.4 nm, respectively, that is evaluated from
the FWHM of (2 0 0) peaks by using DebyeScherrer formula.
The FT-IR spectra of graphene, LaMnO3 and LaMnO3/graphene composite are shown in Fig. 4. It can be seen from the spectra of LaMnO3,
that there exist a strong absorption peak at about 593 cm1 which is attributed to Mn\O stretching vibration. As assertive evidence spectral line,
the absorption peak still exists in the spectra of LaMnO3/graphene composite. The characteristic absorption peak at approximately 1388 and
3446 cm1 correspond to the stretching vibration and deformation vibration of O\H, respectively [23]. The absorption peak near 1730 cm1 in
the spectra of graphene is attributed to C_O, which is also observed
in the spectra of LaMnO3/graphene. The absorption peak of the

Fig. 2. XRD patterns of graphite, graphene oxide and graphene.

Fig. 3. XRD patterns of a LaMnO3, b LaMnO3/graphene composite, c LaMn0.9Co0.1O3/

graphene composite, d LaMn0.85Co0.15O3/graphene composite, e LaMn0.8Co0.2O3/
graphene composite.

LaMnO3/graphene curve appearing at 1120 cm 1 clearly shows the

C\C skeletal vibration of the graphene sheets, indicating the formation
of graphene in LaMnO3/graphene.
Fig. 5(a) displays the FESEM image of graphene. As shown, the asprepared graphene has wrinkles and folds, which may be caused by
oxygen functionalization and the resultant defects during the preparation of graphene oxide [24]. Fig. 5(b) shows the FESEM image of
LaMn0.85Co0.15O3/graphene composite, it can be seen that graphene
is decorated homogeneously with perovskite nanoparticles, indicating
uniform growth of the LaMn0.85Co0.15O3 granules on the graphene.
This structure can enable the electron transfer from catalytic to
graphene sheets during photocatalytic process, and prevent the
photo-generated electronhole pairs from recombination. The TEM
image of LaMn0.85Co0.15O3/graphene composite is shown in Fig. 5(c),
it can be seen that the perovskite nanoparticles grew on the graphene
sheets, whose size is about 20 nm according to the result of XRD.
Fig. 5(d) shows the HRTEM image of LaMn0.85Co0.15O3/graphene
composite. LaMn0.85Co0.15O3 exhibited the same interlayer spacing
(0.274 nm), corresponding to the (2 0 0) crystal planes. This is consistent with the result calculated from XRD analysis. The area arranged
in a crisscross pattern is due to the overlapping of two particles. The selected area electron diffraction patterns (SAED) in Fig. 5(e) distinctly indicate some concentric rings arising from the diffractions of the (1 1 0),

Fig. 4. FT-IR spectra of graphene, LaMnO3 and LaMnO3/graphene composite.

J. Hu et al. / Powder Technology 254 (2014) 556562

559

Fig. 5. FESEM images of (a) graphene; (b) FESEM images, (c) TEM image, (d) HRTEM image, (e) SAED pattern and (f) EDS of LaMn0.85Co0.15O3/graphene composite.

(2 0 0) and (2 2 0) planes of LaMn0.85Co0.15O3/graphene composite,

which is in accordance with XRD analysis again. The EDS spectrum of
LaMn0.85Co0.15O3/graphene composite shown in Fig. 5(f) indicates the
presence of C, O, Mn, Co and La elements. The C signal should mainly
originate from graphene sheets, rather than the intensity of La signal,
of which the C signal seems to be much weaker. It may be result from
the low content of graphene. The content of O is higher than the theoretical value because of the residual oxygen-containing functional
groups in graphene [25]. The molar ratio of Co to Mn is about 1:5.7,
which indicates the amount of adulterating Co is substantially identical
with the theoretical value.
Fig. 6 shows the XPS spectrum of LaMn0.85Co0.15O3/graphene composite. As shown in Fig. 6(a), the peak contains C, O, Mn, Co, and La elements. Fig. 6(b) displays the O 1s spectra of LaMn0.85Co0.15O3/graphene
composite. It can be seen that the O 1s XPS signal was divided into two
peaks at 529.3 eV and 531.3 eV, indicating the existence of O in two
kinds of chemical states. The binding energy at 529.3 eV (designated
as OL) is attributed to the contribution of the crystal lattice oxygen,

and the binding energy at 531.3 eV (designated as OC) arises from the
chemisorbed oxygen species [26]. In Fig. 6(c), the peaks at 780.1 eV
and 795.6 eV correspond to binding energy of Co 2p3/2 and 2p1/2, respectively, and the spin energy is 15.5 eV, indicating that Co species
mainly exist in their +2 valence state. Fig. 6(d) shows the C 1s spectra
of LaMn0.85Co0.15O3/graphene composite. The peak located at 284.6 eV
is related to sp2 hybridized carbon in the graphene, which corresponds
to the C\C bond. The binding energies of 286.2 eV, 288.2 eV and
289.2 eV were assigned to the C\O bond, C_O bond and O\C_O
(\COO\) bond, respectively. The existence of the O\C_O \COO\)
band is the result from residual oxygenous groups in the graphene during the redox process.
Fig. 7 exhibits the degradation of the diamine green B in the presence
or absence of UVvis light irradiation and catalyst. From the pattern,
after lighting for 3 h without catalyst, the absorbance of the peak had
decreased slightly, it reveals the existence of photodecomposition of
dye. Resulting from the complex of graphene and its poriferous structure, the LaMnO3/graphene composite has signicant adsorption, and

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J. Hu et al. / Powder Technology 254 (2014) 556562

Fig. 6. XPS spectrum of LaMn0.85Co0.15O3/graphene composite. (a) Overall spectrum. (b) High-resolution curves of O 1s region. (c) High-resolution curves of Co 2p region. (d) C 1s core
levels.

60% of the dye was adsorbed. This adsorption process signicantly

increased the concentration of the dye molecules near the catalytic
surface, and it is also an important contributing factor for achieving
higher photocatalytic degradation. According to the pattern, the

Fig. 7. a Initial dye solution (20 mg/L), b light for 3 h without catalyst, c in the
dark environment with LaMnO3 powders for 3 h, d in the dark environment with
LaMnO3/graphene composite powders for 3 h, e light for 3 h with LaMnO3/graphene
composite powders, f light for 3 h with LaMn0.85Co0.15O3/graphene composite powders.

LaMn0.85Co0.15O3/graphene composite displays 10% higher photocatalytic efciency than the LaMnO3/graphene composite. It can be concluded that metal element doping is one of the typical approaches to improve
the performance of perovskite photocatalysts.
The degree of degradation of diamine green B solution with different
photocatalysts is shown in Fig. 8. It is clear that all of the catalysts

Fig. 8. The degree of degradation of diamine green B solution with the role of LaMnO3,
LaMnO3/graphene and LaMn1 xCoxO3/graphene composite (x = 0.1, 0.15, 0.2).

J. Hu et al. / Powder Technology 254 (2014) 556562

561

photocatalyst was used for the rst time. The removal rates of the
subsequent recycles were 95.6%, 93.5% and 92.3%, respectively.
After three cycles, the fourth time of the sample still retained good
photodegradation activity, illustrating that the catalyst was stable
during the photocatalytic and recycling processes.
3.1. Photocatalytic activity mechanism

Fig. 9. The photocatalytic cycles of LaMn0.85Co0.15O3/graphene composite.

modied by graphene exhibited higher photocatalytic activities than

those of pure LaMnO3. On the basis of the pattern, it is also observed
that the photocatalytic activities were enhanced with the increase of
Co doping (x was from 0 to 1.5). When the Mn3 + ion was displaced
by Co2 + ion, the donor centers and O vacancies were formed. When
the doping concentration of Co2+ ion was relatively low, the number
of the donor centers and O vacancies increased with the increase of doping concentration, leading to the increase in the number of photoinduced electronic coupling, which may prevent charge recombination.
Therefore, the photocatalytic activity increased. Subsequently, the photocatalytic activity was decreased with the further increasing of Co2+
ion content, because the redundant lattice defects may act as recombination centers for photoinduced electrons and holes, and consequently,
decreased the photocatalytic activity.
Stability of the photocatalyst is an important parameter to evaluate
the practical application. To research the stability of the photocatalyst,
the recycling experiments on LaMn0.85Co0.15O3/graphene composite
were actualized under the same reaction conditions. After the photocatalytic reaction, the catalyst was reclaimed by ltration and dried in the
oven. The recycling photocatalytic reaction of LaMn0.85Co0.15O3/graphene
composite is shown in Fig. 9. As shown in Fig. 9, 98.8% of diamine
green B was removed when the LaMn0.85Co0.15O3/graphene composite

The charge transfer mechanism that occurs in the LaMnO3/graphene

composite during photocatalytic process is shown in Fig. 10. During the
photocatalysis reaction, three processes are crucial, which are: the adsorption of contaminant molecules, the light absorption, and the charge
transportation and separation. Diamine green B molecules could transfer from the solution to the composites' surface and be adsorbed with
offset face-to-face orientation via conjugation between diamine
green B and aromatic regions of the graphene, therefore, due to its
giant -conjugation system and two-dimensional planar structure [27],
the adsorptivity of dyes improved compared to the bare LaMnO3. When
UVvis light is irradiated on the LaMnO3 surface, the photoexcited electrons can be transferred to the conduction band (CB) from the valence
band (VB) and while the holes form in the VB [28], then it generates a
couple of holes and electrons. In pure LaMnO3, electrons and holes
quickly recombine, resulting in low reactivity. By contrast, when
LaMnO3 is grown on the graphene, the exited electrons or holes can
quickly inject to graphene sheets and then reacted with adsorbed O2
or H2O on the graphene to produce OHor O22 radicals [23]. In this
way, LaMnO3/graphene composite could generate more holes and electrons, and generate more hydroxyl radicals and superoxide ions [29]. As
the result of production of above, dyes are fragmented to H2O, CO2 and
other mineralization. Due to these holes and electron transfers, charge
recombination is suppressed in LaMnO3/graphene composite and
hence largely enhances the efciency of photocatalytic properties.
4. Conclusions
In this work, LaMn1 xCoxO3/graphene composites with perovskite
structure were successfully synthesized by solgel process assisted with
chelating effect of citric acid. It was found that LaMnO3 perovskite phase
is successfully processed which anchored on the surface of graphene
sheets, and doping Co does not change the perovskite structure. In the

Fig. 10. Proposed mechanism for photocatalytic degradation of diamine green B over graphene based perovskite photocatalysts under light irradiation.

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J. Hu et al. / Powder Technology 254 (2014) 556562

photodegradation of diamine green B, after graphene was introduced to LaMnO3 as a photocatalytic, it can accelerate the adsorption
of the dye, while doping Co enhances the photocatalytic performance of
LaMnO3/graphene composites and LaMn0.85Co0.15O3/graphene composite has the best catalytic activity. In addition, the prepared catalyst
exhibited excellent stability during the photocatalytic and recycling
processes.
Acknowledgments
The authors gratefully acknowledge the support of the Natural
Science Foundation of Hebei Province (No. E2011203031), the Research
Program of the College Science & Technology of Hebei Province
(No. QN20131026) and the Technology Support Program of Hebei Province (No. 13214411).
Appendix A. Supplementary data
Supplementary data to this article can be found online at http://dx.
doi.org/10.1016/j.powtec.2014.01.071.
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