nanomaterials

Article
Enhanced Visible Light Driven Photocatalytic
Behavior of BiFeO3/Reduced Graphene
Oxide Composites
Yun-hui Si 1,† , Yu Xia 1,† , Shao-ke Shang 1 , Xin-bo Xiong 1 , Xie-rong Zeng 1 , Ji Zhou 2 and
Ya-yun Li 1, *
1 Shenzhen Key Laboratory of Special Functional Materials & Shenzhen Engineering Laboratory for Advance
Technology of Ceramics, College of Materials Science and Engineering, Shenzhen University,
Shenzhen 518060, China; 2161120218@email.szu.edu.cn (Y.S.); 2172341411@email.szu.edu.cn (Y.X.);
2172341466@email.szu.edu.cn (S.S.); xxbszdx@szu.edu.cn (X.X.); zengxier@szu.edu.cn (X.Z.)
2 State Key Laboratory of New Ceramics and Fine Processing, School of Materials Science and Engineering,
Tsinghua University, Beijing 100084, China; zhouji@tsinghua.edu.cn
* Correspondence: kittyli@szu.edu.cn; Tel.: +86-0755-86713945
† These authors contributed equally to this paper.




Received: 26 June 2018; Accepted: 9 July 2018; Published: 13 July 2018


Abstract: BiFeO3 /Reduced Graphene Oxide (BFO/RGO) composites have been fabricated by a
simple hydrothermal method. The X-ray diffraction (XRD), scanning electron microscopy (SEM),
Raman, and X-ray photoelectron spectroscopy (XPS) analysis reveal that graphene oxide was reduced
in hydrothermal process and BFO/RGO composites were successfully synthesized. UV-visible
absorption and photoluminescence properties show that the introduction of RGO can effectively
reduce the recombination of photogenerated electron and hole pairs. Compared to the pristine BFO,
the photocatalytic performance of BiFeO3 Graphene Oxide (BGO) composites is enhanced for the
degradation of Methylene blue (MB) solution under visible light irradiation, and the result shows
that the optimal amount of Graphene Oxide (GO) in the composites is 60 mg (BGO60). The excellent
photocatalytic performance is mainly ascribed to improved light absorption, increased reactive sites,
and the low recombination rate of electron-hole pairs. This work can provide more insights into
designing advanced photocatalysts for wastewater treatment and environmental protection.

Keywords: BiFeO3 ; reduced graphene oxide; photocatalytic; visible light

1. Introduction
In recent decades, with the rapid development of economic globalization, the energy crisis
and environmental pollution have become the two main challenges that restrict the sustainable
development of our society. The excessive exploitation and utilization of coal, oil, and other fossil
fuels has brought irreversible damage to the earth’s ecosystem. Industrial wasted water, gas and
residue exist widely in water, soil, and the atmosphere, which are difficult to decompose through
natural processes. In addition, the rapid development of industry is stimulating the demand of energy,
while conventional fossil fuels are limited and non-renewable. In 1972, A. Fujishima and K. Honda
reported that hydrogen and oxygen was produced by the decomposition of water on a TiO2 single
crystal electrode [1], this discovery confirms that clean energy hydrogen can be produced by using
ultraviolet light in the sunlight, which has a profound impact on the energy crisis. As an opportunity,
the era of photocatalytic technology has been opened. Semiconductor photocatalytic technology can
convert solar energy into electrical energy and chemical energy [2–4]. Many semiconductor materials,
such as TiO2 , ZnO, Fe2 O3 , and CdS, have a suitable band structure as a photocatalyst [5–8]. Among

Nanomaterials 2018, 8, 526; doi:10.3390/nano8070526 www.mdpi.com/journal/nanomaterials

Nanomaterials 2018, 8, 526 2 of 12

them, TiO2 has become the most widely used photocatalyst because of its stable chemical properties,
strong oxidation reduction, corrosion resistance, non-toxic, and low cost. However, TiO2 has a wide
band gap (3.2 eV), which can only be stimulated by ultraviolet light with wavelengths less than
387 nm [9]. The energy of ultraviolet light is only 4% of the total energy of the sun, which makes the
utilization of the sun light very low. In addition, TiO2 nanoparticles are often difficult to recycle and
reuse, this also seriously restricts its application and development.
Bismuth ferrite (BiFeO3 , BFO) is a kind of multiferroic material with ferroelectric and
ferromagnetic properties at room temperature at the same time [10]. Its high ferroelectric Curie
temperature and ferromagenicNéel temperature determine wide application prospects in memory,
sensors, and spintronic devices. Recently, studies have shown that BFO is a new generation of
photocatalyst with visible light response [11]. The experimental test shows that BFO has a narrow
band gap, and its band gap energy is about 2.2 eV [12]. The absorbance spectral response range of BFO
includes UV and visible light, which is expected to be an excellent visible light driven semiconductor
catalyst. Furthermore, it is easy to recover due to its magnetic property at room temperature [13].
A large number of experiments show that BFO has excellent degradation ability to organic pollutants
under visible light irradiation [14,15]. However, the high recombination rate of photogenerated
electron-hole and low quantum yield restrict the wider application of BFO in waste water treatment
industry. For the purpose of enhancing the photocatalytic activity of BFO, a lot of studies have been
carried out [16,17]. The enhancement of actual photocatalytic performance depends on reducing the
recombination of photo-generated electrons and holes, heightening the light absorption, and improving
the ability to absorb the target molecules. The most important thing is to rapidly separate the electrons
and holes excited in the conduction band, and reduce the recombination rate of the electron-hole pairs.
The recombination of photogenerated electron-hole pairs is usually suppressed by creating electron or
hole capture centers in the lattice of the catalyst, and the doping of foreign atoms in the BFO (A or
B position) has been proved to be an effective method [18,19]. In addition, the surface deposition of
noble metals and the construction of heterostructures with other semiconductor materials are also
considered feasible methods to enhance the photocatalytic activity of BFO [20].
Based on the novel physical and chemical properties and broad application prospects, two
dimensional (2D) materials have attracted much attention in the field of catalysis [21,22]. Graphene is
one of the most popular nano structure materials with a two dimensional honeycomb lattice structure
consisting of a carbon six membered ring [23]. In recent years, graphene has been used as an efficient
photocatalyst to improve the efficiency of an artificial photosynthesis system [24,25]. In spite of this,
graphene is nonpolar and difficult to dissolve in common polar solvents such as water and ethanol,
so it is difficult to compound with other materials. As one of the important derivatives of graphene,
graphene oxide (GO) is a new type of carbon material with excellent performance, with high surface
area and rich functional groups on the surface [26]. Due to its rich oxygen containing functional
groups on the surface, graphene oxide exhibits polarity and strong hydrophilicity, which makes it
easily dissolve in an aqueous solution. On account of the serious functionalization of the conjugated
network, the graphene oxide thin sheet has the characteristics of insulation. Highly conducting
graphene can be obtained by reduction of GO with various reducing agents [27]. Recent research
reveals that the reduction of graphene oxide by the hydrothermal method has greatly improved the
electron mobility and charge capacity of graphene oxide compared with chemically reduced graphene
oxide (RGO) [28,29]. More importantly, its surface oxygen-containing functional groups provide
rich binding sites for the photocatalytic materials. A large number of studies have reported that
many photocatalytic effect semiconductor materials are combined with reduced graphene oxide [30],
and can achieve enhancement in photocatalytic performance [31–34]. This strategy is of great interest
to us. Based on the reports that semiconductor/graphene composites have been able to improve
the photocatalytic performance of semiconductor photocatalysts, it is generally believed that the
mechanism of performance enhancement include the enhanced adsorption properties of composite
materials and the formation of carbon material/semiconductor interfaces to promote electron hole
Nanomaterials 2018, 8, 526 3 of 12

pair separation. Little work has been done to systematically study the effect of graphene addition on
the morphology and photocatalytic properties of BFO, and the corresponding mechanism is not clear.
In our study, it is found that a small amount of GO will increase the size of BFO particles and decrease
photocatalytic performance. Only a suitable amount of GO could obtain enhanced photocatalytic
properties in the composites. We explain this phenomenon and expect to provide ideas for the design
of new photocatalytic materials in the future.
In this work, we synthesized BFO/RGO composites through a one step hydrothermal method,
the RGO nanosheets were successfully immobilized to the surface of BFO particles. We have
systematically studied the influence of the addition amount of GO on the phase, morphology,
and photocatalytic properties of the BFO/RGO composite photocatalysts. The possible mechanism of
enhanced photocatalytic performance is proposed.

2. Experimental

2.1. Sample Preparation

Graphene oxide was synthesized by a modified Hummer’s method, which has been reported
by the literature [35]. Bi(NO3 )3 ·5H2 O and Fe(NO3 )3 ·9H2 O with 1:1 molar ration (5 mmol) were
dissolved in the 10 mL nitric acid (4 M).The mixture was stirred vigorously to get a clarified solution
at room temperature. 30 mL of KOH solution (12 M) was dripped into the above solution as slowly
as possible. Then the GO powder of different amounts was added to the mixture and continuously
stirred. The reddish brown precipitation was treated by ultrasonic treatment and transferred into a
50 mL teflon lined stainless vessel and heated at 180 ◦ C for 24 h. The obtained samples were repeatedly
washed with deionized water and absolute ethanol, and dried at 80 ◦ C in a vacuum oven for 8 h.
According to the difference in the amount of GO, the final samples are named as BGO10 (10 mg),
BGO30 (30 mg), BGO60 (60 mg), BGO100 (100 mg), and BGO150 (150 mg).

2.2. Characterization
The synthesized samples were characterized for structural analysis using X-ray powder diffraction
(D8Advance, Bruker, Karlsruhe, Germany) and chemical state analysis using X-ray photoelectron
spectroscopy (Escalab 250XI, ThermoFisher Scientific, Waltham, MA, USA). The grain morphology
was examined with scanning electron microscopy (SU70, Hitachi, Tokyo, Japan). Raman spectra of
BGO samples were taken with a Raman Microscope (inVia, Renishaw, Gloucester, Britain). The optical
characteristics using UV-visible absorption/diffuse reflectance spectroscopy on a UV-2650 (Shimadzu,
Kyoto, Japan). The photoluminescence spectroscopy (F-4500, Hitachi, Tokyo, Japan) of BFO and BGO
samples are operated at room temperature at the excitation wavelength at 325 nm.

2.3. Photocatalytic Experiment

The photocatalytic activities of the as-synthesized BFO and BGO samples were studied by the
decolorization of methylene blue (MB) solution under visible light irradiation (Xe lamp, 500 W;
cutoff filter, λ > 420 nm). In order to avoid the influence of thermal effect, the photocatalytic reaction
is kept at room temperature by the circulating water cooling. In a typical experimental experiment,
the photocatalytic reaction was performed through a 100 mL 20 mg/L MB solution suspended with a
25 mg photocatalyst in a reactor under continuous magnetic stirring, which was irradiated by xenon
lamp. As a comparison, the blank samplewasmeasured without any photocatalyst and other conditions
remained the same. The suspension was stirring for 30 min to reach the adsorption-desorption
equilibrium in a dark environment before irradiation. Subsequently, the degradation efficiency of MB
was evaluated by centrifuging the retrieved sample and measuring the intensity of the absorption peak
of MB (λ = 664 nm) relative to its initial intensity (C/C0 ) using a UV–V spectrophotometer (UV-2450,
Shimadzu, Kyoto, Japan). The stability of the photocatalyst was studied by washing and drying the
last used sample.
Nanomaterials 2018, 8, 526 4 of 12
Nanomaterials 2018, 8, x FOR PEER REVIEW 4 of 12

3. Results and Discussion

3. Results and Discussion
3.1. Structure
3.1. Structure and
and Phase
Phase Analysis
Analysis
The X-ray
The X-ray diffraction
diffraction(XRD)
(XRD)patterns
patternsofofthetheGO,GO,BFO,
BFO,andandBGOBGOcomposites
compositesare are shown
shown inin Figure
Figure 1.
1. The XRD patterns are in well agreement with JCPDS data (No. 86-1518),
The XRD patterns are in well agreement with JCPDS data (No. 86-1518), R3c space group, and the R3c space group, and the
perovskite based
perovskite based rhombohedral
rhombohedral structure.
structure. AllAll ofof the BGO samples
the BGO samples are indexed as
are indexed pure phase
as pure phase BFO,
BFO,
without other secondary or impurities. It can be considered that a proper amount
without other secondary or impurities. It can be considered that a proper amount of GO introduction of GO introduction
does not
does not change
change thethe phase
phase structure
structure of of BFO,
BFO, and
and shows
shows that
that the
the process
process adopted
adopted is is mature
mature and and stable.
stable.
There are no r-GO diffraction peaks detected in the BGO composites, this may be ascribed to fact
There are no r-GO diffraction peaks detected in the BGO composites, this may be ascribed to the the
that that
fact the the
r-GO concentration
r-GO concentration is too
is toosmall
small ininthethecomposites,
composites,leading
leadingtoto thethe disappearance
disappearance of the
of the
diffraction peaks of the r-GO. The diffraction peak at 12.7 degrees can be corresponding
diffraction peaks of the r-GO. The diffraction peak at 12.7 degrees can be corresponding to the (001) to the (001)
peak of
peak of graphene
graphene oxide,
oxide,and and the
the weak
weak peak
peak atat 42.5
42.5 degree
degree is
is indexed
indexed to to the
the (100)
(100) peak,
peak, it
it is
is considered
considered
that the graphene oxide was fully oxidized. It is worth noting that the characteristic
that the graphene oxide was fully oxidized. It is worth noting that the characteristic peak of graphene peak of graphene
oxide at
oxide at 12.7
12.7 degrees
degrees disappears
disappears in in the
the BGO
BGO composites,
composites, andand this
this confirms
confirms that
that graphene
graphene oxideoxide waswas
successfully reduced in the hydrothermal process. At the same time, the diffraction
successfully reduced in the hydrothermal process. At the same time, the diffraction peak intensity peak intensity of
the BGO composites decreases as compared with the pure phase BFO;
of the BGO composites decreases as compared with the pure phase BFO; this should be due to the this should be due to the
presence of
presence of reduce
reduce graphene
grapheneoxideoxidethat
thatreduces
reducesthe thecrystallinity
crystallinityof ofthe
theBGO
BGOcomposites.
composites.

Figure 1.
Figure 1. X-ray
X-ray diffraction
diffraction (XRD)
(XRD) patterns
patterns of
of Graphene
Graphene Oxide
Oxide (GO),
(GO), bismuth
bismuthferrite
ferrite(BFO)
(BFO)and
andBiFeO
BiFeO33
Graphene Oxide (BGO) composites.
Graphene Oxide (BGO) composites.

The morphology
The morphologyand and microstructure
microstructure of as-synthesized
of the the as-synthesized BFO and BFO BGO and BGO were
samples samples were
observed
by scanning electron microscopy (SEM), as shown in Figure 2a–f. Pure BFO (Figure 2a) shows2a)
observed by scanning electron microscopy (SEM), as shown in Figure 2a–f. Pure BFO (Figure a
spherical morphology with a uniform particle size. Compared with pure BFO, there is a significanta
shows a spherical morphology with a uniform particle size. Compared with pure BFO, there is
significant
change in thechange in the morphology
morphology of the BFO/RGO of the BFO/RGO
compositescomposites
due to the due to the introduction
introduction of GO, in
of GO, as shown as
shown in Figure 2b–f. The layered RGO were attached to the surface of BFO
Figure 2b–f. The layered RGO were attached to the surface of BFO particles and distributed randomly. particles and distributed
randomly.
Owing Owing
to the to the introduction
introduction of GO, the size of GO, theBFO
of the size particles
of the BFO particlessignificantly,
increased increased significantly, and
and the surface
the surface became more rough, as shown in Figure 2b. Due to the large
became more rough, as shown in Figure 2b. Due to the large longitudinal and transverse ratio of longitudinal and transverse
ratio
the of the graphene
graphene oxide nanoscale,
oxide nanoscale, the dispersion
the dispersion of grapheneof graphene
oxide inoxide in the amorphous
the amorphous precursor precursor
of BFO
of BFO leads to the formation of the interpenetrating network of RGO in
leads to the formation of the interpenetrating network of RGO in the composite of BFO and RGO [36].the composite of BFO and
RGO [36]. The growth of BFO was limited by the network of RGO, the final
The growth of BFO was limited by the network of RGO, the final particle size of the BFO was reduced particle size of the BFO
was reduced
compared withcompared
pure BFO. with pure
With BFO.
the With of
increase theGO
increase
content,of GO
the content,
size of BFO the size of BFO the
the particles particles
decreased,
decreased, and BGO60 showed the smallest particle size in both BFO and
and BGO60 showed the smallest particle size in both BFO and BGO samples (Figure 2d). The slight BGO samples (Figure 2d).
The slight introduction of GO would act as the aggregation center of BFO
introduction of GO would act as the aggregation center of BFO particles, which could be the reason particles, which could be
the the
for reason
larger forsize
the of
larger size of photocatalyst
BGO10.The BGO10.The photocatalyst
with smallerwith size smaller
has a largersize specific
has a larger
surfacespecific
area
surface area and increased reactive sites, which will contribute to the enhancement
and increased reactive sites, which will contribute to the enhancement of photocatalytic activity. It is of photocatalytic
activity. It is that
noteworthy noteworthy
when the that
GO when the GO
content contentto
continues continues
increase,tothe
increase,
size ofthe thesize
BFOof particles
the BFO particles
become
become larger and cannot be tightly combined with the RGO layer (Figure
larger and cannot be tightly combined with the RGO layer (Figure 2e,f). Because of the high content 2e,f). Because of the high
of
content of acidic oxygen functional groups in GO, the presence of excess GO leads to the decrease of
alkalinity in an aqueous solution [37], the lower alkaline concentration leads to the rapid growth of
Nanomaterials 2018, 8, 526 5 of 12

acidic oxygen functional groups in GO, the presence of excess GO leads to the decrease of alkalinity in
an aqueous solution [37], the lower alkaline concentration leads to the rapid growth of crystal rather
Nanomaterials 2018, 8, x FOR PEER REVIEW 5 of 12
than nucleation, which may be the reason for the increase of particle size in BGO100 and BGO150
Nanomaterials 2018, 8, x FOR PEER REVIEW 5 of 12
[12].
In order to further demonstrate the successful synthesis of BFO/RGO composites,
crystal rather than nucleation, which may be the reason for the increase of particle size in BGO100 the magnification
crystal
of BGO60 rather
was
and BGO150 thanIn
provided
[12]. nucleation,
(Figure
order which
3a). The
to further maytypical
be the morphology
demonstrate reason for the of
the successful increase
BFO and
synthesisofofparticle sizecomposites,
RGO could
BFO/RGO in be
BGO100
observed,
and
marked BGO150
the as [12].
magnification
Area 1 andofAreaIn order
BGO60to further demonstrate
was providedThe
2, respectively. (Figure the
energy successful
3a).dispersive synthesis
The typicalX-ray of
morphology BFO/RGO composites,
of BFO (EDS)
spectroscopy and RGO pattern
the
could
of BGO60 magnification
be observed,
confirmed of BGO60
thatmarked was provided
as Area
the composite (Figure
Area 3a).
1photocatalyst
and The composed
typical morphology
2, respectively.
was Theofenergy
Bi, Fe, of BFO and
dispersive
O, and RGO
CX-ray
elements.
could be observed, markedof as
spectroscopy
As seen in the insert(EDS) pattern
of Figure theArea
3b, BGO60 atomic1 and Area
confirmed
ratio of Bi,2,the
that respectively.
Fe,composite The energy was
and O in photocatalyst
Area 1 was closedispersive
composedX-rayof
to the theoretical
spectroscopy (EDS) pattern of BGO60 confirmed that the composite photocatalyst
Bi, Fe, O, and C elements. As seen in the insert of Figure 3b, the atomic ratio of Bi, Fe, and O in Area was composed of
value of BFO. EDS results showed that only two elements of C and O were found in Area 2 (Figure 3c),
Bi, Fe, close
1 was O, and toCtheelements. As seen
theoretical valueinofthe
BFO.insert
EDS of results
Figure showed
3b, the atomic ratio
that only of Bi,
two Fe, andofOCinand
elements AreaO
indicating
1were
that
wasfound
reduced
close to
graphene
the theoretical
oxide
value
was attached
of BFO. that
EDSreduced
to the
results showed
surface
that
of BFO.
onlywas
It can
twoattached
be
elements
summed up that
in Area 2 (Figure 3c), indicating graphene oxide to of
theCsurface
and O
the desired
were
of BFO. BFO/RGO
found in Area
It can composites
2 (Figureup
be summed 3c), are successfully
indicating
that synthesized
that reduced
the desired BFO/RGO during
graphene the
oxide
composites was
are hydrothermal process
surfacealong
attached tosynthesized
successfully the
with of
the introduction
BFO.the
during It can of
hydrothermal appropriate
be summed up that
process amount
the with
along of
desired GO.
the BFO/RGO
introduction composites are successfully
of appropriate amount of GO. synthesized
during the hydrothermal process along with the introduction of appropriate amount of GO.

Figure 2. Scanning electron microscope (SEM) images of (a) BFO; (b) BGO10; (c) BGO30; (d) BGO60;
Figure 2. Scanning electron microscope (SEM) images of (a) BFO; (b) BGO10; (c) BGO30; (d) BGO60;
Figure
(e) BGO2.100;
Scanning electron microscope (SEM) images of (a) BFO; (b) BGO10; (c) BGO30; (d) BGO60;
(f) BGO150.
(e) BGO 100; (f) BGO150.
(e) BGO 100; (f) BGO150.

Figure 3. The magnification of (a) BGO60 composite; energy dispersive X-ray spectroscopy (EDS)
Figure 3. The
spectrum magnification
of BGO60; (b) Area of (a) Area
1; (c) BGO602. composite; energy dispersive X-ray spectroscopy (EDS)
Figure 3. The magnification of (a) BGO60 composite; energy dispersive X-ray spectroscopy (EDS)
spectrum of BGO60; (b) Area 1; (c) Area 2.
spectrum of BGO60; (b) Area 1; (c) Area 2.
Raman spectroscopy is an effective method for detecting the structure of materials and the
Raman
vibration spectroscopyofismolecules.
characteristics an effective Themethod
structure forand
detecting
structuralthe phase
structure of materials
transition of BFOand canthe
be
Raman
vibration
determined spectroscopy
characteristics
by the positionis
of an
and effective
molecules.
strengthThemethod
ofstructure
the Ramanforanddetecting
structural
peaks. BFO the
hasstructure
phase of materials
transition
a perovskite of BFO can
structure and
be the
with
determined
distorted
vibration by the position
trapezoid
characteristics hexahedronand at
of molecules. strength
roomThe ofstructure
the Raman
temperature, peaks.
called
and theBFOR3chas
structural a perovskite
space
phasegroup [38].structure
transition According
of BFO with
to
can be
distorted
the trapezoid
literature, 10 hexahedron
atoms of the at room
crystal celltemperature,
of a perovskitecalled the R3c
structure
determined by the position and strength of the Raman peaks. BFO has a perovskite structure with space
can group
produce [38].
18 According
optical phononto
the
distorted literature,
modes: 4A1+5A10
trapezoid atoms
2+9E, of the
A1 and
hexahedron crystal
Eatmode
roomare cell
theofRaman
a perovskite
temperature, calledstructure
activationthemodes, can
R3c spaceA2produce
mode
group is 18 optical
inactive
[38]. tophonon
Ramanto the
According
modes:
[39]. In 4A 1+5A2+9E,
general, Bi-OA1 band
and E is mode are the Raman
corresponding to Aactivation
1, E1 andmodes, A2 mode
E2 vibration is inactive
modes, Fe-Otoband
Raman is
literature, 10 atoms of the crystal cell of a perovskite structure can produce 18 optical phonon modes:
[39]. In general,
corresponding Bi-O
to E 3 andband is corresponding
E4 vibration modes. In our to A 1, E1 4and
study, E2 vibration
A1 modes and 8 Emodes, Fe-O band
modes (100–700 cm−1is)
4A1 +5A +9E, A1 and Eand
mode are the Raman activation modes, A2 mode is inactive to Raman −1) [39].
are 2consistent
corresponding to E3 the
with E4 vibration
vibration mode modes.
in theInliterature
our study, 4 Athe
[40], 1 modes
Raman andpeaks
8 E modes
at 137,(100–700
169, 216,cmand
In general,
are Bi-O
430 consistent band
cm−1 for BFO with is corresponding
the be
could vibration
ascribedmode to A
to A1-1, ,
in 1theE
A1-2, and E
1literature vibration
A1-3,2and[40], modes,
thevibration
A1-4 Raman peaksFe-O
modes, band
at and
137,theis corresponding
169,remaining
216, and
to E3 430
andcm E4−1peaks
vibration modes. In 347,
our to study, −1 ) are consistent
Raman for BFO could
at 260, be 305,
275, ascribed 372, 468,4A1-2,
A1-1, A1 modes
526, A1-3,610
and and
andcm 8 could
A1-4
−1 Evibration
modes (100–700
modes, and
be corresponding cmthe remaining
to E2, E3, E4,
with the vibration mode in the literature −1 for BFO
Raman peaks at 260, 275, 305, 347, 372,[40], the Raman
468, 526, and 610 peaks at 137,
cm−1 could be 169, 216, and 430
corresponding cmE3,
to E2, E4,
Nanomaterials 2018, 8, 526 6 of 12

could be ascribed to A1-1, A1-2, A1-3, and A1-4 vibration modes, and the remaining Raman peaks at
260, 275, 305, 347, 372, 468, 526, and 610 cm−1 could be corresponding to E2, E3, E4, E5, E6, E7, E8,
Nanomaterials 2018, 8, x FOR PEER REVIEW 6 of 12
and E9 vibration modes. Raman results also confirm that the synthesized BFO is pure phase without
impurity formation.
E5, E6, E7, E8, and AsE9 shown in Figure
vibration modes.4,Raman
the coexistence
results alsoofconfirm
BFO and thatRGO has been confirmed
the synthesized BFO is pureby the
Raman phase without
spectra impuritytwo
for BGO60, formation.
discreteAspeaks
shownatin1278
Figure
cm4,−1the
and 1591 cm−of1 BFO
coexistence and RGOto
are assigned has
thebeen
D band
and Gconfirmed
band of RGO,by thethe Raman spectra peaks
remaining for BGO60,
are thetwo discrete
Raman peaks atof1278
spectrum the cm −1 and 1591 cm−1 are
perovskite structural BFO.
assigned to the D band and G band of RGO, the remaining peaks
D band represents the defects of the C atomic lattice, G band represents the stretchingare the Raman spectrum of the of C
vibration
perovskite structural BFO. D band represents the defects of the C atomic lattice, G band represents
atom sp2 hybrids. This can confirm that the BFO/RGO composites are successfully synthesized. In
the stretching vibration of C atom sp2 hybrids. This can confirm that the BFO/RGO composites are
general, the intensity ratio of D peak to G peak (ID /IG ) is used to characterize the defect density in
successfully synthesized. In general, the intensity ratio of D peak to G peak (ID/IG) is used to
graphene. The peak intensity ratio of GO is 0.81 in our study as shown in the inset of Figure 4, which
characterize the defect density in graphene. The peak intensity ratio of GO is 0.81 in our study as
is noteworthy
shown in theas the
insetcorresponding value
of Figure 4, which of the BGO60
is noteworthy as theiscorresponding
1.02, which isvalue
higher than
of the that of
BGO60 GO. It is
is 1.02,
provedwhich is higher than that of GO. It is proved that GO is reduced to RGO during the hydrothermal are
that GO is reduced to RGO during the hydrothermal process, and BFO/RGO composites
successfully
process, synthesized.
and BFO/RGO composites are successfully synthesized.

Figure
Figure 4. Raman
4. Raman spectra
spectra of of
BFOBFO andBGO60.
and BGO60. Inset
Inset shows
showsDDband
bandand
andGG
band of BGO60
band and and
of BGO60 GO. GO.

X-ray photoelectron spectroscopy (XPS) is performed to analyze the surface chemical

X-ray photoelectron
compositions and the spectroscopy
oxidation state(XPS)
of the is performed
elements to analyze
presented the surface chemical
in the as-synthesized BFO and compositions
BGO60
and the oxidation
samples. The fullstate of the
survey elements
spectrum presented
of the BGO60 sample in theisas-synthesized
shown in FigureBFO 5, theand BGO60peaks
dominant samples.
can survey
The full be assigned to Bi 4f,
spectrum ofBithe
4d,BGO60
Bi 5d, Fe 2p, O 1s,
sample and C 1s
is shown incore
Figurelevel5,states, the weak peaks
the dominant peaksare can be
attributed to Fe 2p and Bi 4s. The binding energy was obtained through correction
assigned to Bi 4f, Bi 4d, Bi 5d, Fe 2p, O 1s, and C 1s core level states, the weak peaks are attributed of charging effect
to Fe by
2pCand1s peak
Bi 4s.at 284.8 eV. Figure
The binding 6a,b show
energy wasthe high resolution
obtained through spectra of O 1sof
correction and Fe 2p core
charging levelby
effect of C 1s
BFO. The binding energy of O 1s in BFO appears at 530.2, 532.1, and 533.4 eV corresponding to lattice
peak at 284.8 eV. Figure 6a,b show the high resolution spectra of O 1s and Fe 2p core level of BFO.
oxygen, chemisorbed oxygen and physically absorbed oxygen, respectively. The doublet peak at
The binding energy of O 1s in BFO appears at 530.2, 532.1, and 533.4 eV corresponding to lattice oxygen,
711.0 eV and 724.6 eV for BFO can be corresponding to Fe 2p3/2 and Fe 2p1/2 core level states arising
chemisorbed
from the oxygen andsplitting,
spin-orbital physically absorbedThe
respectively. oxygen, respectively.
spin orbit The doublet
splitting energy of Fe 2ppeak at 711.0 eV and
3/2 and Fe 2p1/2 is
724.6calculated
eV for BFO caneV,
to 13.6 be which
corresponding
is consistent to with
Fe 2pthe and of
3/2value FeFe2p in the
3+ 1/2 core level states
literature [41]. In arising
addition,froma the
spin-orbital
satellitesplitting,
peak appearsrespectively.
at 719.0 eVThe spin orbit
between splitting
Fe 2p energy
3/2 orbit and Fe 2pof1/2Feorbit,
2p3/2 and 8FeeV2pabove
about 1/2 is the
calculated
Fe
to 13.6
2peV, which
3/2 orbit, is consistent
and this further with the value
confirms the +3of Fe3+ in
valence theof
state literature
the Fe iron [41].in Intheaddition, a satellite
as-synthesized BFOpeak
sample [42,43]. As shown in Figure 6c, the binding energies of O1s in BGO60
appears at 719.0 eV between Fe 2p3/2 orbit and Fe 2p1/2 orbit, about 8 eV above the Fe 2p3/2 orbit, composite are observed
at 530.3,
and this 532.2,
further and 533.6
confirms theeV+3for the positions
valence state ofofthe
lattice oxygen,
Fe iron in thechemisorbed
as-synthesized oxygenBFO and sample
physically [42,43].
As shown in Figure 6c, the binding energies of O1s in BGO60 composite are observed at 2p
absorbed oxygen, respectively. Compared with BFO (Figure 6b), the peak positions of Fe 3/2, Fe
530.3, 532.2,
2p1/2 and the satellite peak in BGO60 composite are shifted towards higher binding energy, located at
and 533.6 eV for the positions of lattice oxygen, chemisorbed oxygen and physically absorbed oxygen,
711.4, 724.9 and 719.4 eV (Figure 6d), the Fe 2p slight shift might be due to the interaction with many
respectively. Compared with BFO (Figure 6b), the peak positions of Fe 2p3/2 , Fe 2p1/2 and the satellite
oxygen containing groups in the RGO network. At the same time, O1s of BGO60 is also slightly
peak shifted
in BGO60to highcomposite are shifted
binding energy. towards
It should higher
attribute to thebinding
higher amountenergy, located
of C-O bonds at in
711.4,
BGO60. 724.9
As and
719.4 shown
eV (Figure 6d), the Fe 2p slight shift might be due to the interaction with
in Figure 6e, the C 1s for GO is deconvoluted into four peaks at 248.6, 285.4, 287.1, and 289.0 many oxygen containing
groupseV,incorresponding
the RGO network. to C-C, At
C-H,theC-Osame
andtime, O1s of groups,
COOH/C=O BGO60respectively.
is also slightly The shifted
binging to highofbinding
energy C
energy. It should
1s for BGO60attribute
(Figure 6f) tolocated
the higher amount
at 284.5, 285.3,of286.3
C-Oand bonds
288.3ineV,BGO60.
which As couldshown in Figure
be assigned 6e, the C
to C-C,
1s forC-H,
GO C-O, and COOH/C=O
is deconvoluted intogroups, respectively.
four peaks at 248.6, Compared with and
285.4, 287.1, GO, the 289.0relative area percentage to
eV, corresponding of C-C,
C-H, C-O and COOH/C=O groups, respectively. The binging energy of C 1s for BGO60 (Figure 6f)
Nanomaterials 2018, 8, 526 7 of 12

located at 284.5, 285.3, 286.3 and 288.3 eV, which could be assigned to C-C, C-H, C-O, and COOH/C=O
Nanomaterials 2018, 8, x FOR PEER REVIEW 7 of 12
groups, respectively.
Nanomaterials 2018, 8, x Compared with GO, the relative area percentage of C-O decreased 7inofBGO60,
FOR PEER REVIEW 12
whileC-O
the proportion
decreased inC-C increased.
BGO60, Thisproportion
while the change proves that GO was
C-C increased. This successfully reduced
change proves during
that GO was the
C-O decreased in BGO60, while the proportion C-C increased. This change proves that GO was
hydrothermal
successfullyprocess.
reduced during the hydrothermal process.
successfully reduced during the hydrothermal process.

Figure 5. Full survey spectrum of BGO60.

Figure5.5.Full
Figure Fullsurvey spectrumofofBGO60.
survey spectrum BGO60.

Figure 6. The high resolution spectrum of (a) O 1s for BFO; (b) Fe 2p for BFO; (c) O 1s for BGO60; (d)
Figure 6. The high resolution spectrum of (a)
(a)OO1s1s
forfor
BFO; (b) Fe
(b)2p
Fefor
2pBFO;
for (c) O 1s(c)
forOBGO60;
1s for (d)
FigureFe6.2pThe high
for BGO60; resolution
(e) C 1s forspectrum offor
GO; (f) C 1s BGO60. BFO; BFO; BGO60;
Fe 2p for BGO60; (e) C 1s for GO; (f) C 1s for
(d) Fe 2p for BGO60; (e) C 1s for GO; (f) C 1s for BGO60.BGO60.
Nanomaterials 2018, 8, 526 8 of 12

3.2. UV-Visible Absorption and Photoluminescence Properties

Nanomaterials 2018, 8, x FOR PEER REVIEW 8 of 12

The optical absorption of the as-synthesized BFO and BGO samples were characterized by
3.2. UV-Visible Absorption and Photoluminescence Properties
UV-visible diffuse
Nanomaterials reflectance
2018, 8, x FOR PEERspectroscopy
REVIEW (DRS), as shown in Figure 7. BFO has a 8strong of 12 light
The optical absorption of the as-synthesized BFO and BGO samples
absorption in the range of 200 to 550 nm and a sharp decline in absorption over 550 nm. The limited were characterized by UV-
3.2. UV-Visible
visible Absorption and
diffuse reflectance Photoluminescence
spectroscopy (DRS), asProperties
shown in Figure 7. BFO has a strong light absorption
visible light absorption restricts the application of BFO as an efficient visible light photocatalyst.
in the range of 200 to 550 nm and a sharp decline in absorption over 550 nm. The limited visible light
Compared toThe
theoptical
absorption pure absorption
restrictsBFO,the BGO
ofexhibited
the as-synthesized
application of BFO a as
better
an
BFO
lightand BGO samples
absorption andwere
can characterized
be extendedby to UV- visible
to the
visible diffuse reflectance spectroscopy (DRS), asefficient
shown invisible
Figurelight photocatalyst.
7. BFO has a strongCompared
light absorption the
light range
pure (420–800
BFO, BGO nm). In aall
exhibited of the
better light samples,
absorption BGO60
and can has
be the most
extended to theexcellent
visible optical
light range absorption
(420–
in the range of 200 to 550 nm and a sharp decline in absorption over 550 nm. The limited visible light
properties
800in both
nm).
absorption UV of and
Inrestricts
all thethevisible
samples, lightofregion.
BGO60
application has the
BFO as anStronger
most optical
excellent
efficient absorption
optical
visible lightabsorption means more
properties
photocatalyst. Compared photoelectron
in both
to UV
the
and
hole pairs visible
are light
produced, region.
which Stronger
will optical
effectively absorption
enhance means
the more photoelectron
photocatalytic
pure BFO, BGO exhibited a better light absorption and can be extended to the visible light range (420– hole
performance. pairs are
The light
produced, which will effectively enhance the photocatalytic performance. The light absorption of
absorption of BGO10
800 nm). In all ofis therelatively weak,has
samples, BGO60 this
thecould be attributed
most excellent optical to its larger
absorption particleinsize.
properties both UVAs shown
BGO10 is relatively weak, this could be attributed to its larger particle size. As shown in the inset of
and of
in the inset visible
Figure light7, region.
the band Stronger
gap valuesopticalof absorption
BFO andmeans more photoelectron
BGO composites could be holeestimated
pairs are on the
Figure 7, the band gap values of BFO and BGO composites could be estimated on the basis of the
basis of produced,
the equation
equation
which will effectively
=(αhν) −=Eg)
A(hν −enhance the photocatalytic
Eg)n/2 [11] . The band
performance.
(Eg)gap energy Theoflight
(Eg) BFO absorption
and BGO60 of were
is (αhν) A(hν this[11] . The band gap
be attributedenergy ofparticle
BFO and BGO60 were deduced to be
n/2
BGO10 relatively weak, could to its larger size. As shown in the inset of
deduced2.20to and
be 2.20 andrespectively.
1.78 eV, respectively. inThe decrease
gap ofin the band gap of should
the BGO composites
Figure 7,1.78
the eV,
band gap values The of BFOdecrease
and BGO thecomposites
band the
could BGO composites
be estimated on the basis be due
of the to
should bethe interaction
due to the of BFO and
interaction RGO.
of BFO and RGO.
equation (αhν) = A(hν − Eg)n/2 [11]. The band gap energy (Eg) of BFO and BGO60 were deduced to be
2.20 and 1.78 eV, respectively. The decrease in the band gap of the BGO composites should be due to
the interaction of BFO and RGO.

Figure 7. UV-visible absorption spectra of BFO and BGO samples. The inset shows the calculation of
Figure 7. UV-visible absorption spectra of BFO and BGO samples. The inset shows the calculation of
band gap.
band gap.
Figure 7. UV-visible absorption spectra of BFO and BGO samples. The inset shows the calculation of
Photoluminescence (PL) spectroscopy can be used as an effective probe to analyze the
band gap.
recombination rate of
Photoluminescence the electron
(PL) hole pairs
spectroscopy canin be
the used
semiconductors. As shownprobe
as an effective in Figure 8, the
to analyze the
emission intensity of the PL spectra for the BGO60 composites is lower than that of pure BFO, which
recombination rate of the electron
Photoluminescence (PL) hole pairs in the
spectroscopy cansemiconductors. As shown
be used as an effective in Figure
probe 8, thethe
to analyze emission
reveals the decrease of the recombination rate of photogenerated electron hole in BFO/RGO
intensityrecombination
of the PL rate of for
spectra
compositeintensity
photocatalysts.
the the
electron
BGO60 holecomposites
pairs in the issemiconductors.
lower than As shown
that of pureinBFO,
Figure 8, thereveals
which
emission of the PLThe closefor
spectra contact between
the BGO60 BFO and is
composites RGO enables
lower photogenerated
than that of pure BFO,carriers
which
the decrease of the
to migrate recombination rate of photogenerated electron hole in BFO/RGO composite
reveals theatdecrease
the interface, thereby
of the reducing
recombination the recombination
rate rate of electron-hole
of photogenerated pairs,
electron hole in which
BFO/RGOwill
photocatalysts. The
effectively close
enhance contact
the between
photocatalytic BFO and
performance RGO
of enables photogenerated
photocatalysts. carriers
composite photocatalysts. The close contact between BFO and RGO enables photogenerated carriers
to migrate at
the interface, thereby
to migrate reducingthereby
at the interface, the recombination rate of electron-hole
reducing the recombination pairs, which
rate of electron-hole will will
pairs, which effectively
enhanceeffectively
the photocatalytic
enhance theperformance of photocatalysts.
photocatalytic performance of photocatalysts.

Figure 8. Photoluminescence spectroscopy of BFO and BGO samples.

Nanomaterials 2018, 8, x FOR PEER REVIEW 9 of 12

Figure 8. Photoluminescence spectroscopy of BFO and BGO samples.

Nanomaterials 2018, 8, 526 9 of 12

3.3. Photocatalytic Activity

3.3. Photocatalytic Activityperformance of BFO and BGO samples are investigated by the degradation
The photocatalytic
of methylene blue (MB) aqueous
The photocatalytic performancesolution ofunder
BFO the and simulated
BGO samples visible light
are irradiation.
investigated Theby photo-
the
degradation of
degradation efficiency
methylene of organic
blue (MB) molecules
aqueous could be determined
solution under the by the equation:
simulated visible Degration (%) = (C
light irradiation.
− C0)photo-degradation
The /C × 100. Figure 9aefficiency
shows the photocatalytic
of organic molecules degradation efficiency by
could be determined characterized
the equation: byDegration
BFO and
BGO
(%) composites.
= (C − C0) /C × Under the irradiation
100. Figure 9a showsofthe visible light, MB degradation
photocatalytic solution is almost completely
efficiency degraded
characterized by
by BGO60
BFO and BGOwithin 100 min, and
composites. Underthe the
degradation
irradiation rate
of is 92%. Compared
visible with theispure
light, MB solution almostBFOcompletely
(34%), the
photocatalytic
degraded degradation
by BGO60 within 100efficiency
min, and is the
enhanced
degradationobviously.
rate isBGO30, BGO100 with
92%. Compared and the
BGO150
pure BFOalso
exhibited
(34%), excellent photocatalytic
the photocatalytic degradation properties,
efficiencyand the degradation
is enhanced obviously. rates wereBGO100
BGO30, 86%, 78%, andand 66%,
BGO150
respectively.
also exhibitedIn the blank
excellent sample measurements,
photocatalytic properties,the andMB thesolution
degradation degraded
rates 2% werewithin
86%,130 min,
78%, andwhich
66%,
should be due
respectively. In theto the
blankslight
sample thermal catalytic effect.
measurements, the MBIt solution
was obvious
degraded that2% thewithin
photocatalytic
130 min,
performances
which should be of BGO
due tocomposites
the slight were
thermalgreatly affected
catalytic by the
effect. content
It was of GO.
obvious thatWith the increase of
the photocatalytic
GO, the photodegradation
performances of BGO compositesefficiency of BGO
were composites
greatly affected first
by the increased
contentthen decreased.
of GO. With the Among them,
increase of
BGO60 showed the best photocatalytic activity, which was about 2.7 times
GO, the photodegradation efficiency of BGO composites first increased then decreased. Among them, than that of BFO. With the
increaseshowed
BGO60 of GO thecontent, the size of BFO
best photocatalytic particles
activity, decreased,
which was about resulting
2.7 timesin an
than increase
that of in contact
BFO. Witharea
the
with RGO. At the same time, the ability of light absorption and effective
increase of GO content, the size of BFO particles decreased, resulting in an increase in contact area photo-generated charge
separation
with RGO. At and thetransfer
same time,werethealso promoted,
ability and the photocatalytic
of light absorption activity was enhanced
and effective photo-generated charge
accordingly.
separation andHowever,
transfer wereas GO also continues
promoted, to andincrease, the excessactivity
the photocatalytic amount wasofenhanced
RGO will act as a
accordingly.
recombination
However, as GOof the photo-generated
continues electron-hole,
to increase, the excess amount of thereby
RGO willresulting
act as ain a decline in
recombination the
of the
photocatalytic activity.
photo-generated Based on
electron-hole, the experimental
thereby resulting inresults,
a declineBGO60 in thewas considered to
photocatalytic have an
activity. optimal
Based on
value of GO content. Remarkably, due to weak light absorption and larger
the experimental results, BGO60 was considered to have an optimal value of GO content. Remarkably, particle size, the number
of photo-generated
due carriers moving
to weak light absorption and larger to particle
the surfacesize,are
theless
numberand of easily recombine, resulting
photo-generated in poor
carriers moving
photocatalytic
to the surface are performance of BGO10,
less and easily this was
recombine, also associated
resulting with the results
in poor photocatalytic in the PL of
performance spectrum.
BGO10,
Additionally, the stability of the BGO60 photocatalyst was investigated in
this was also associated with the results in the PL spectrum. Additionally, the stability of the BGO60 three repeating cycles, as
shown in Figure
photocatalyst was9b. There was in
investigated a slight
three decrease
repeating(3%) cycles,in photocatalytic
as shown in Figure efficiency after three
9b. There was arecycle
slight
times, which may be due to the loss of catalyst in cycling experiments, and
decrease (3%) in photocatalytic efficiency after three recycle times, which may be due to the loss of the good cycle stability of
the photocatalyst was proved.
catalyst in cycling experiments, and the good cycle stability of the photocatalyst was proved.

Figure 9.9.(a)(a)
Figure Photocatalytic
Photocatalytic degradation
degradation efficiencies
efficiencies of methylene
of methylene blue
blue (MB) as a(MB) as aoffunction
function of
irradiation
irradiation
time time under
under visible visible
light for BFOlight for BFO
and BGO and BGO
samples; samples,
(b) Stability (b)
test ofStability test ofdegradation
photocatalytic photocatalytic
of
degradation of MB by BGO60 under visible
MB by BGO60 under visible light irradiation. light irradiation.

Compared with pure BFO, the photocatalytic performance of the synthesized BFO/RGO
Compared with pure BFO, the photocatalytic performance of the synthesized BFO/RGO
composites have been obviously improved. The proposed mechanism of enhanced photocatalytic
composites have been obviously improved. The proposed mechanism of enhanced photocatalytic
activity can be attributed to the following three aspects: (1) Enhanced optical absorption. In our study,
activity can be attributed to the following three aspects: (1) Enhanced optical absorption. In our
the BGO sample exhibited excellent optical absorption in both ultraviolet and visible region. At the
study, the BGO sample exhibited excellent optical absorption in both ultraviolet and visible region.
same time, the reduced band gap makes more absorbed photons form electron-hole pairs, resulting
At the same time, the reduced band gap makes more absorbed photons form electron-hole pairs,
in more reactive species on the catalyst surface and participating in the photocatalytic reaction; (2)
resulting in more reactive species on the catalyst surface and participating in the photocatalytic
Increased contact area with pollutants. Graphene has a large and smooth graphite layer, which
reaction; (2) Increased contact area with pollutants. Graphene has a large and smooth graphite layer,
Nanomaterials 2018, 8, 526 10 of 12

which produces π-π interaction. It is easy to adsorb organic pollutants with π electrons [44]. It has good
adsorption effect on methylene blue through the π-π and hydrogen bonds. A large number of RGO
nanosheets attach to the surface of the BFO particles, resulting in an increased contact area between
photocatalyst and organic pollutants; (3) A decrease in the recombination of the electron-hole pairs. The
close contact between BFO and RGO leads to the transport of photogenerated carriers at the interface,
and a semiconductor heterostructure may be formed locally [45]. It is believed that the delocalized
conjugated structure and superior electrical conductivity of RGO facilitate the photogenerated electrons
transferring from the conduction band of BFO to RGO, consequently suppressing the photogenerated
electron-hole recombination, and eventually leading to the enhanced photocatalytic performance;
(4) The affinity of graphene to dye molecules. RGO can in fact act as an entity to increase the affinity to
the molecules surrounding it and attract them near the grafted BFO photocatalyst [46].

4. Conclusions
In summary, BFO/RGO composite photocatalysts have successfully been synthesized by a facile
hydrothermal treatment. The XRD, SEM, Raman, and XPS characterizations confirm that graphene
oxide was reduced in hydrothermal process and compounded with BFO. The optical properties show
that the introduction of RGO can effectively enhance the optical absorption properties and reduce the
recombination of the electron hole pairs. Compared with pure BFO, the photocatalytic performance of
BGO composites is enhanced for degradation of MB solution under visible light irradiation, and the
result shows that the optimal amount of GO in the composites is 60 mg (BGO60). The enhanced
photocatalytic activity of the BGO composite photocatalysts should put down to the enhanced optical
absorption, increased contact area with pollutants, and the decreased recombination of photogenerated
electron-hole pairs. More importantly, BGO composites have the potential to be a highly efficient
visible light response photocatalyst for wastewater treatment and hydrogen production.

Author Contributions: Y.L. conceived and designed the experiments; Y.S. and Y.X. performed the experiments
and wrote the manuscript; S.S., X.X., X.Z. and J.Z. helped perform the analysis with constructive discussions.
Acknowledgments: This work was financially supported by the National Natural Science Foundation of China
(Grant No. 51702218), National Natural Science Foundation of Guangdong, China (Grant No. 2016A030310054
and 2017A030310009), Youth Foundation of Shenzhen University (Grant No. 2016004), and Opening Funding
of State Key Laboratory of New Ceramics and Fine Processing, School of Materials Science and Engineering of
Tsinghua University (Grant No. KF201601).
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Fujishima, A.; Honda, K. Electrochemical photolysis of water at a semiconductor electrode. Nature 1972, 238,
37–38. [CrossRef] [PubMed]
2. Hoffman, M.R.; Martin, S.T.; Choi, W.; Bahnemann, D.W. Environmental applications of semiconductor
photocatalysis. Chem. Rev. 1995, 95, 69–96. [CrossRef]
3. Chava, R.K.; Do, J.Y.; Kang, M. Hydrothermal growth of two dimensional hierarchical MoS2 nanospheres
on one dimensional CdS nanorods for high performance and stable visible photocatalytic H-2 evolution.
Appl. Surf. Sci. 2018, 433, 240–248. [CrossRef]
4. Chava, R.K.; Do, J.Y.; Kang, M. Fabrication of CdS-Ag3 PO4 heteronanostructures for improved visible
photocatalytic hydrogen evolution. J. Alloy. Compd. 2017, 727, 86–93. [CrossRef]
5. Konstantinou, I.K.; Albanis, T.A. TiO2 -assisted photocatalytic degradation of azo dyes in aqueous solution:
Kinetic and mechanistic investigations—A review. Appl. Catal. B Environ. 2004, 49, 1–14. [CrossRef]
6. Wang, S.; Kuang, P.Y.; Cheng, B.; Yu, J.G.; Jiang, C.J. ZnO hierarchical microsphere for enhanced
photocatalytic activity. J. Alloy. Compd. 2018, 741, 622–632. [CrossRef]
7. Xie, X.L.; Yang, H.Q.; Zhang, F.H.; Li, L.; Ma, J.H.; Jiao, H.; Zhang, J.Y. Synthesis of hollow microspheres
constructed with alpha-Fe2 O3 nanorods and their photocatalytic and magnetic properties. J. Alloy. Compd.
2009, 477, 90–99. [CrossRef]
Nanomaterials 2018, 8, 526 11 of 12

8. Zhang, Y.; Chen, Z.; Lu, Z. A facile method or the preparation of colored Bi4 Ti3 O12−x nanosheets with
enhanced visible-light photocatalytic hydrogen evolution activity. Nanomaterials 2018, 8, 261. [CrossRef]
[PubMed]
9. Asahi, R.; Morikawa, T.; Ohwaki, T.; Aoki, K.; Taga, Y. Visible-light photocatalysis in nitrogen-doped titanium
oxides. Science 2001, 293, 269–271. [CrossRef] [PubMed]
10. Kumar, A.; Scott, J.F.; Martinez, R.; Srinivasan, G.; Katiyar, R.S. In-plane dielectric and magnetoelectric
studies of BiFeO3 . Phys. Status Solidi A 2012, 209, 1207–1212. [CrossRef]
11. Gao, F.; Chen, X.Y.; Yin, K.B.; Dong, S.; Ren, Z.F.; Yuan, F.; Yu, T.; Zou, Z.G.; Liu, J.M. Visible-light
photocatalytic properties of weak magnetic BiFeO3 nanoparticles. Adv. Mater. 2007, 19, 2889–2892. [CrossRef]
12. Li, S.; Lin, Y.H.; Zhang, B.P.; Wang, Y.; Nan, C.W. Controlled fabrication of BiFeO3 uniform microcrystals
and their magnetic and photocatalytic behaviors. J. Phys. Chem. C 2010, 114, 2903–2908. [CrossRef]
13. Ederer, C.; Spaldin, N.A. Weak ferromagnetism and magnetoelectric coupling in bismuth ferrite. Phys. Rev. B
2005, 71, 060401. [CrossRef]
14. Cho, C.M.; Noh, J.H.; Cho, I.S.; An, J.S.; Hong, K.S. Low-temperature hydrothermal synthesis of pure BiFeO3
nanopowders using triethanolamine and their applications as visible-light photocatalysts. J. Am. Ceram. Soc.
2008, 91, 3753–3755. [CrossRef]
15. Wang, N.; Zhu, L.H.; Lei, M.; She, Y.B.; Cao, M.J.; Tang, H.Q. Ligand-Induced drastic enhancement of
catalytic activity of nano-BiFeO3 for oxidative degradation of bisphenol A. ACS Catal. 2011, 1, 1193–1202.
[CrossRef]
16. Huo, Y.N.; Jin, Y.; Zhang, Y. Citric acid assisted solvothermal synthesis of BiFeO3 microspheres with high
visible-light photocatalytic activity. J. Mol. Catal. A Chem. 2010, 331, 15–20. [CrossRef]
17. Liu, Y.; Zuo, R.Z.; Qi, S.S. Controllable preparation of BiFeO3 @carbon core/shell nanofibers with enhanced
visible photocatalytic activity. J. Mol. Catal. A Chem. 2013, 376, 1–6. [CrossRef]
18. Guo, R.Q.; Fang, L.; Dong, W.; Zheng, F.G.; Shen, M.R. Enhanced photocatalytic activity and ferromagnetism
in Gd doped BiFeO3 nanoparticles. J. Phys. Chem. C 2010, 114, 21390–21396. [CrossRef]
19. Xu, H.M.; Wang, H.C.; Shi, J.; Lin, Y.H.; Nan, C.W. Photoelectrochemical performance observed in Mn-doped
BiFeO3 heterostructured thin films. Nanomaterials 2016, 6, 215. [CrossRef] [PubMed]
20. Zhang, X.G.; Wang, B.; Wang, X.Z.; Xiao, X.H.; Dai, Z.G.; Wu, W.; Zheng, J.F.; Ren, F.; Jiang, C.Z. Preparation
of M@BiFeO3 nanocomposites (M = Ag, Au) bowl arrays with enhanced visible light photocatalytic activity.
J. Am. Ceram. Soc. 2015, 98, 2255–2263. [CrossRef]
21. Datta, R.S.; Ou, J.Z.; Mohiuddin, M.D.; Carey, B.J.; Zhang, B.Y.; Khan, H.; Syed, N.; Zavabeti, A.; Haque, F.;
Daeneke, T.; et al. Two dimensional PbMoO4 : A photocatalytic material derived from a naturally non-layered
crystal. Nano Energy 2018, 49, 237–246. [CrossRef]
22. Haque, F.; Daeneke, T.; Kalantar-Zadeh, K.; Ou, J.Z. Two-dimensional transition metal oxide and
chalcogenide-based photocatalysts. Nano-Micro Lett. 2018, 10, 23. [CrossRef]
23. Geim, A.K.; Novoselov, K.S. The rise of graphene. Nat. Mater. 2007, 6, 183–191. [CrossRef] [PubMed]
24. Xiang, Q.J.; Yu, J.G.; Jaroniec, M. Graphene-based semiconductor photocatalysts. Chem. Soc. Rev. 2012, 41,
782–796. [CrossRef] [PubMed]
25. Yadav, R.K.; Baeg, J.O.; Oh, G.H.; Park, N.J.; Kong, K.J.; Kim, J.; Hwang, D.W.; Biswas, S.K.
A photocatalyst-enzyme coupled artificial photosynthesis system for solar energy in production of formic
acid from CO2 . J. Am. Chem. Soc. 2012, 134, 11455–11461. [CrossRef] [PubMed]
26. Hummers, W.S.; Offeman, R.E. Preparation of graphitic oxide. J. Am. Chem. Soc. 1958, 80, 1339. [CrossRef]
27. Gao, X.F.; Jang, J.; Nagase, S. Hydrazine and thermal reduction of graphene oxide: Reaction mechanisms,
product structures, and reaction design. J. Phys. Chem. C 2010, 114, 832–842. [CrossRef]
28. Perera, S.D.; Mariano, R.G.; Nijem, N.; Chabal, Y.; Ferraris, J.P.; Balkus, K.J. Alkaline deoxygenated graphene
oxide for supercapacitor applications: An effective green alternative for chemically reduced graphene.
J. Power Sources 2012, 215, 1–10. [CrossRef]
29. Soltani, T.; Lee, B.K. Sono-synthesis of nanocrystallized BiFeo(3)/reduced graphene oxide composites for
visible photocatalytic degradation improvement of bisphenol A. Chem. Eng. J. 2016, 306, 204–213. [CrossRef]
30. Debabrata, M.; Chayan, A.; Barun, K.G.; Madhurya, C.; Narendra, N.G. One-Dimensional BiFeO3
nanowire-reduced graphene oxide nanocomposite as excellent supercapacitor electrode material. ACS Appl.
Energy Mater. 2018, 1, 464–474.
Nanomaterials 2018, 8, 526 12 of 12

31. Zhao, Q.; Liu, R.F.; Shen, Y.L.; Fang, M.L.; Dong, M.F. Highly efficient visible-light-driven graphene-CdS
nanocomposite photocatalysts. J. Nanosci. Nanotechnol. 2018, 18, 4755–4763. [CrossRef] [PubMed]
32. Xu, D.F.; Li, L.L.; He, R.A.; Qi, L.F.; Zhang, L.Y.; Cheng, B. Noble metal-free RGO/TiO2 composite nanofiber
with enhanced photocatalytic H2 -production performance. Appl. Surf. Sci. 2018, 434, 620–625. [CrossRef]
33. Hosseini, F.; Mohebbi, S. Photocatalytic oxidation based on modified titanium dioxide with reduced graphene
oxide and CdSe/CdS as nanohybrid materials. J. Clust. Sci. 2018, 29, 289–300. [CrossRef]
34. Liu, B.J.; Lin, L.; Yu, D.; Sun, J.; Zhu, Z.J.; Gao, P.; Wang, W. Construction of fiber-based BiVO4 /SiO2 /reduced
graphene oxide (RGO) with efficient visible light photocatalytic activity. Cellulose 2018, 25, 1089–1101.
[CrossRef]
35. Marcano, D.C.; Kosynkin, D.W.; Berlin, J.M.; Sinitskii, A.; Sun, Z.Z.; Slesarev, A.; Alemany, L.B.; Lu, W.;
Tour, J.M. Improved synthesis of graphene oxide. ACS Nano. 2010, 4, 4806–4814. [CrossRef] [PubMed]
36. Li, Z.X.; Shen, Y.; Yang, C.; Lei, Y.C.; Guan, Y.H.; Lin, Y.H.; Liu, D.B.; Nan, C.W. Significant enhancement
in the visible light photocatalytic properties of BiFeO3 -graphene nanohybrids. J. Mater. Chem. A 2012, 1,
823–829. [CrossRef]
37. Li, P.; Chen, Q.; Lin, Y.Y.; Chang, G.; He, Y.B. Effects of crystallite structure and interface band alignment on
the photocatalytic property of bismuth ferrite/(N-doped) graphene composites. J. Alloy. Compd. 2016, 672,
497–504. [CrossRef]
38. Fukumura, H.; Harima, H.; Kisoda, K.; Tamada, M.; Noguchi, Y.; Miyayama, M. Raman scattering study of
multiferroic BiFeO3 single crystal. J. Magn. Magn. Mater. 2007, 310, 367–369. [CrossRef]
39. Yang, Y.; Sun, J.Y.; Zhu, K.; Liu, Y.L.; Wan, L. Structure properties of BiFeO3 films studied by micro-Raman
scattering. J. Appl. Phys. 2008, 103, 093532. [CrossRef]
40. Jaiswal, A.; Das, R.; Vivekanand, K.; Abraham, P.M.; Adyanthaya, S.; Poddar, P. Effect of reduced particle
size on the magnetic properties of chemically synthesized BiFeO3 nanocrystals. J. Phys. Chem. C 2010, 114,
2108–2115. [CrossRef]
41. Fruth, V.; Popa, M.; Calderon-Moreno, J.M.; Anghel, E.M.; Berger, D.; Gartner, M.; Anastasescu, M.;
Osiceanu, P.; Zaharescu, M. Chemical solution deposition and characterization of BiFeO3 thin films.
J. Eur. Ceram. Soc. 2007, 27, 4417–4420. [CrossRef]
42. Wang, J.; Neaton, J.B.; Zheng, H.; Nagarajan, V.; Ogale, S.B.; Liu, B.; Viehland, D.; Vaithyanathan, V.;
Schlom, D.G.; Waghmare, U.V.; et al. Epitaxial BiFeO3 multiferroic thin film heterostructures. Science 2003,
299, 1719–1722. [CrossRef] [PubMed]
43. Hu, Z.J.; Chen, D.; Wang, S.; Zhang, N.; Qin, L.S.; Huang, Y.X. Facile synthesis of Sm-doped BiFeO3
nanoparticles for enhanced visible light photocatalytic performance. Mater. Sci. Eng. B 2017, 220, 1–12.
[CrossRef]
44. Liu, T.H.; Li, Y.H.; Du, Q.J.; Sun, J.K.; Jiao, Y.Q.; Yang, G.M.; Wang, Z.H.; Xia, Y.Z.; Zhang, W.; Wang, K.L.; et al.
Adsorption of methylene blue from aqueous solution by graphene. Colloids Surf. B 2012, 90, 197–203.
[CrossRef] [PubMed]
45. Ren, Y.; Nan, F.; You, L.; Zhou, Y.; Wang, Y.Y.; Wang, J.L.; Su, X.D.; Shen, M.R.; Fang, L. Enhanced
photoelectrochemical performance in reduced graphene oxide/BiFeO3 heterostructures. Small 2017, 13,
1603457. [CrossRef] [PubMed]
46. Atkin, P.; Daeneke, T.; Wang, Y.; Carey, B.J.; Berean, K.J.; Clark, R.M.; Ou, J.Z.; Arinchi, A.; Cole, I.S.;
Kalantar-zadeh, K. 2D WS2 /carbon dot hybrids with enhanced photocatalytic activity. J. Mater. Chem. A
2016, 4, 13563–13571. [CrossRef]

© 2018 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).