catalysts

Article
Perovskite-type LaFeO3: Photoelectrochemical
Properties and Photocatalytic Degradation of
Organic Pollutants Under Visible Light Irradiation
Mohammed Ismael and Michael Wark *
Institute of Chemistry, Chemical Technology 1, Carl von Ossietzky University Oldenburg,
Carl-von-Ossietzky-Str. 9-11, 26129 Oldenburg, Germany; mohammed.ismael1980@gmail.com
* Correspondence: michael.wark@uni-oldenburg.de; Tel.: +49-441-798-3675




Received: 15 February 2019; Accepted: 3 April 2019; Published: 8 April 2019


Abstract: Perovskite-type oxides lanthanum ferrite (LaFeO3 ) photocatalysts were successfully

prepared by a facile and cost-effective sol-gel method using La(NO)3 and Fe(NO)3 as metal
ion precursors and citric acid as a complexing agent at different calcination temperatures.
The properties of the resulting LaFeO3 samples were characterized by powder X-ray diffraction
(XRD), energy dispersive X-ray spectroscopy (EDXS), UV-Vis diffuse reflectance spectroscopy (DRS),
X-ray photoelectron spectroscopy (XPS), Fourier transform infrared spectra (IR), transmission electron
microscopy (TEM), N2 adsorption/desorption and photoelectrochemical tests. The photoactivity
of the LaFeO3 samples was tested by monitoring the photocatalytic degradation of Rhodamine B
(RhB) and 4-chlorophenol (4-CP) under visible light irradiation, the highest photocatalytic activity
was found for LaFeO3 calcined at 700 ◦ C, which attributed to the relatively highest surface area
(10.6 m2 /g). In addition, it was found from trapping experiments that the reactive species for
degradation were superoxide radical ions (O2 − ) and holes (h+ ). Photocurrent measurements and
electrochemical impedance spectroscopy (EIS) proved the higher photo-induced charge carrier
transfer and separation efficiency of the LaFeO3 sample calcined at 700 ◦ C compared to that
that calcined at 900 ◦ C. Band positions of LaFeO3 were estimated using the Mott-Schottky plots,
which showed that H2 evolution was not likely.

Keywords: sol-gel method; LaFeO3 ; visible light photocatalysis; perovskite-type structure;

Mott-Schottky plot

1. Introduction
Semiconductor-based catalysis is a green technology, which gained considerable attention owing
to its potential environmental applications, such as wastewater treatment, air purification and
degradation of different organic contaminants [1–3]. In the past few decades, titanium dioxide
(TiO2 ) as an n-type semiconductor has an attractive extensive interest as photocatalysts because of
its easy availability, inertness, low costs, nontoxicity and chemical stability [4]. However, the large
band gap energy for TiO2 (3.0–3.2 eV), requiring UV light that occupies around 5% of solar energy
for excitation, limits its applications to a great extent [5]. Another difficulty is the high recombination
rate of the photoexcited electron-hole pairs in TiO2 [6]. Many attempts have been developed to retard
this electron-hole recombination and to increase the photocatalytic efficiency of TiO2 , such as surface
modification using a suitable metal ion and nonmetal dopant to increase the visible light absorbance
and coupling with another semiconductor to enhance the charge separation efficiency [7,8]. Although
in some cases improved photocatalytic activities were reported, very often the doping increased the
number of structural defects acting as unwanted recombination centers. Therefore, the development of

Catalysts 2019, 9, 342; doi:10.3390/catal9040342 www.mdpi.com/journal/catalysts

Catalysts 2019, 9, 342 2 of 15

cost-effective, efficient and alternative photocatalysts with intrinsic narrow band gaps to increase the
visible light response has become a research focus [9,10]. Mixed metal oxides and oxynitrides attracted
interest since many of them are visible-light active, cheap, non-toxic and stable [11].
Iron is highly abundant in the earth crust and thus cheap. Many mixed metal oxides containing
iron, i.e., ferrites, offer suitable band gap energy for visible light absorption. Furthermore, the position
of their valence band edges is more positive than the oxidation potential of O2 /H2 O (1.23 V vs.
NHE) rendering them suitable for the photooxidation of water [12]. The high activity of ferrites for
degradation of pollutants has been proven in many studies [13–15]. Ferrites with a perovskite structure,
with a general formula of ABO3 with for example, A = rare-earth metal ion and B = Fe3+ ion, exhibit
a wide range of ferro-, piezo-, and pyro-electrical properties rendering them suitable as magneto-optical
material, electrode materials, structural materials, sensors and refractory materials [16]. The perovskite
LaFeO3 is employed as a catalyst, e.g., in solid oxide fuel cells, but also in devices using its good
dielectric properties and high piezoelectricity.
However, LaFeO3 has also been used as a photocatalyst; several studies focused on the synthesis
and the activity for photodegradation of several organic dyes under visible light irradiation [17–19].
Thirumalairajan et al. synthesized floral-like LaFeO3 by a surfactant-assisted hydrothermal technique
and found that the porous floral nanostructure led to higher photoactivity compared to bulk LaFeO3
for the degradation of different dyes, such as rhodamine B (RhB) and methylene blue (MB) [20]. Su et
al. prepared large surface area nanosized LaFeO3 particles by employing SBA-16 as a hard template
and compared its visible light activity for RhB degradation with that of LaFeO3 prepared by the citric
acid assisted sol-gel route [21]. Yang et al. prepared LaFeO3 by conventional co-precipitation and
enhanced its activity by post-treatment in molten salt [22]. Tijare et al. [23] formed nano-crystalline
LaFeO3 perovskite by the sol-gel route and claimed activity for photocatalytic hydrogen generation
under visible light irradiation.
In the present work, we applied the same synthetic route for LaFeO3 as Tijare et al. but altered
(i) the duration of the thermal treatment and (ii) used a pyrolysis step at 400 ◦ C instead of using
ultra-sonication or drying at 90 ◦ C in an oven. Citric acid assisted sol-gel was chosen as a synthesis route
because, in general, it is a suitable method for the synthesis of nanopowders with a well-developed
high specific surface area obtained at low calcination temperature and short times without employing
expensive sacrificial structure-directing agents or template structures. The visible light activity for
degradation of RhB and 4-chlorophenol (4-CP) as model organic pollutants was investigated. As for
Tijare et al., we also attempted hydrogen generation, however, failed with that and suspected it was
based on the Mott-Schottky plots calculating band positions that the conduction band edge of LaFeO3
was too positive than the reduction potential of H2 /H2 O (0 V vs. NHE) to create electrons which were
reductive enough to react with protons to hydrogen.

2. Results and Discussion

2.1. Structural and Optical Characterization of LaFeO3

The powder XRD patterns of the prepared LaFeO3 samples after calcination at various
temperatures are shown in Figure 1. All the diffraction peaks belong to the orthorhombic LaFeO3
with ABO3 -type perovskite structure (JCPDS card No. 88-0641) [24]. The main characteristic reflexes
are located at 2θ of 22.6◦ , 25.5◦ , 32.2◦ , 34.5◦ , 39.7◦ , 46.1◦ , 47.7◦ , 52.0◦ , 54.0◦ , 57.4◦ , 64.0◦ , 67.3◦ and
76.6◦ , being indexed to the (101), (111), (121), (210), (220), (202), (230), (141), (240), (115), (242) and (204)
diffraction planes, respectively [24]. This confirms the effective preparation of a single phase perovskite
LaFeO3 without any crystalline impurities like La2 O3 or Fe2 O3 . For calculating the crystallite sizes the
reflexes of highest intensity at 2θ = 32.2◦ were selected. With increasing calcination temperature the
diffraction peaks get sharper and more intense, indicating a better crystallization and growth of the
 Catalysts 2019, 9, 342 3 of 15

grains. The average crystallite sizes of LaFeO3 D have been determined by using the Debye-Scherer
formula [25]:
Kλ
Catalysts 2019, 9, x FOR PEER REVIEW D= 3 of 15
Catalysts 2019, 9, x FOR PEER REVIEW βcosθ 3 of 15

with with K being

K being the crystallite
the crystallite shape λ
shape factor, factor, λ thewavelength
the X-ray X-ray wavelength (1.5406
(1.5406 nm for Cu nm forβCu
Kα), Kα),
is the β is
width
with K being the crystallite shape factor, λ the X-ray wavelength (1.5406 nm for Cu Kα), β is
the width
of the of the diffraction
diffraction peak and θpeakis theand θ isangle.
Bragg the Bragg angle. Thesizes
The crystallite crystallite
were 27.4sizesnm,
were
and27.4
45.7nm,
nmand
for
the width of the diffraction peak and θ is the Bragg angle. The crystallite sizes were 27.4 nm, and
45.7 nm for S-700 and S-900, respectively. In the smaller particles, less time was needed for the
S-700 and S-900, respectively. In the smaller particles, less time was needed for the electrons and holes
45.7 nm for S-700 and S-900, respectively. In the smaller particles, less time was needed for the
electrons
to diffuse and
fromholes to diffuse
the inner part tofrom the inner
the surface part
of the to thewhere
catalyst, surface of could
they the catalyst, where
react. This they could
typically leads
electrons and holes to diffuse from the inner part to the surface of the catalyst, where they could
react. Thisphotocatalytic
to higher typically leadsefficiency.
to higher photocatalytic efficiency.
react. This typically leads to higher photocatalytic efficiency.

Figure 1. X-ray diffraction patterns of LaFeO3 obtained at different calcination temperatures.

Figure
Figure1.1.X-ray
X-raydiffraction
diffractionpatterns
patternsofofLaFeO
LaFeO3 obtained atat
3 obtained different
differentcalcination
calcinationtemperatures.
temperatures.

Figure
Figure2 22shows
shows the
showsthe scanning electron
thescanning
scanning micrographs of
electronmicrographs
micrographs the prepared
prepared LaFeO
LaFeO3 samples
samplesatat different
Figure electron ofofthe
the prepared LaFeO samples
33
atdifferent
different
calcination temperatures.
calcination temperatures. Scanning
temperatures. Scanning electron microscopy (SEM) was used to determine the
calcination Scanningelectron
electronmicroscopy (SEM)(SEM)
microscopy was usedwasto used
determine the morphology
to determine the
morphology of
of the perovskite the perovskite LaFeO 3 samples; as seen in Figure 2 both samples show a network
morphology of theLaFeO 3 samples;
perovskite LaFeO as3 samples;
seen in Figure 2 both
as seen samples
in Figure showsamples
2 both a networkshowstructure
a networkwith
structure withmorphology.
semi-spherical semi-spherical
It morphology.
was found that It was
the found
particle sizes that
of the were
S-700 particle sizes of smaller
significantly S-700 were
than
structure with semi-spherical morphology. It was found that the particle sizes of S-700 were
significantly
those of S-900, smaller than
consistent those
with ofof S-900,
theS-900, consistent
trendconsistent with
of the crystallite the
sizestrend of the
determined crystallite
from XRD. sizes determined
significantly smaller than those with the trend of the crystallite sizes determined
from XRD.
from XRD.

Figure 2.
Figure 2. SEM
SEM images
images of
of LaFeO
LaFeO33 calcined
calcined at
at different
different temperatures:
temperatures: (a)
(a) S-700,
S-700, (b)
(b) S-900.
S-900.
Figure 2. SEM images of LaFeO3 calcined at different temperatures: (a) S-700, (b) S-900.
Energy
Energy dispersive
dispersive X-ray
X-ray spectroscopy
spectroscopy (EDXS)
(EDXS) waswas used
used toto investigate
investigate thethe purity
purity and chemical
and chemical
Energy dispersive X-ray spectroscopy (EDXS) was used to investigate the purity and chemical
composition
composition of of synthesized LaFeO3 nanoparticles,
synthesized LaFeO nanoparticles, the the pattern
pattern of
of calcined LaFeO3 samples
calcined LaFeO samples areare shown
shown
composition of synthesized LaFeO 3 nanoparticles, the pattern of calcined LaFeO3 samples are shown
in Figure 3. Besides a carbon signal appearing at 0.277 keV and resulting from the latex of the SEM
in Figure 3. Besides a carbon signal appearing at 0.277 keV and resulting from the latex of the SEM
insample
Figureholder
3. Besides a carbon signal appearing at 0.277 keV and resulting from the latex of the SEM
sample holder due due to
to the
the incomplete
incomplete coverage
coverage of of the
the sample
sample [25],
[25], only
only lanthanum
lanthanum (La),(La), iron
iron (Fe)
(Fe) and
and
sample
oxygenholder due present,
to the incomplete coverage theofcitric
the sample [25], only lanthanum (La), toiron (Fe)purity
and
oxygen (O)
(O) were
were present, confirming
confirming that
that the citric acid
acid assisted
assisted sol-gel
sol-gel route
route leads
leads to high
high purity
oxygen
LaFeO3(O) were present,The confirming that the citric acid4.65
assisted sol-gelrelated
route to
leads to high
the purity
LaFeO 3 photocatalyst.
photocatalyst. The peaks
peaksatataround
around 0.83
0.83andand 4.65 keV
keV were
were related to La
La and
and the ones
ones at
at
LaFeO 3 photocatalyst. The peaks at around 0.83 and 4.65 keV were related to La and the ones at
around
around 6.399
6.399 and
and 0.704
0.704 keV
keV to
toFe;
Fe;they
theyproved
provedthatthatthe
theformation
formationofofthe theLaFeO
LaFeO photocatalyst
3 3 photocatalyst had
hada
around 6.399 and 0.704 keV to Fe; they proved that the formation of the LaFeO3 photocatalyst had a
1:1 molar ratio of metal ions as the atomic percentage obtained from EDXS was 0.35% for Fe and
1:1 molar ratio of metal ions as the atomic percentage obtained from EDXS was 0.35% for Fe and
0.34% for La in sample S-700 and 1.13% for Fe and 1.21% for La in S-900, respectively.
0.34% for La in sample S-700 and 1.13% for Fe and 1.21% for La in S-900, respectively.
Catalysts 2019, 9, 342 4 of 15

a 1:1 molar ratio of metal ions as the atomic percentage obtained from EDXS was 0.35% for Fe and
0.34% for
Catalysts La9,in
2019, sample
x FOR PEERS-700 and 1.13% for Fe and 1.21% for La in S-900, respectively.
REVIEW 4 of 15
Catalysts 2019, 9, x FOR PEER REVIEW 4 of 15

Figure
Figure 3. 3.Energy
Energydispersive
dispersive X-ray
X-ray (EDX)
(EDX) spectra
spectra of
ofLaFeO
LaFeO3 3atatdifferent calcination
different temperatures
calcination temperatures
Figure 3. Energy dispersive X-ray (EDX) spectra of LaFeO3 at different calcination temperatures
(S-700, S-900). (S-700, S-900).
(S-700, S-900).
Figure 44 presents
Figure presents the
the IR
IR spectra
spectra ofof different
different LaFeO samples prepared
LaFeO33 samples prepared atat different
different calcination
calcination
Figure 4 presents
temperatures in the the IR spectra
wavenumber range of 400–4000
different cmLaFeO−1 in 3 samples
order to prepared
determine at different
the possible calcination
functional
temperatures in the wavenumber range 400–4000 cm-1-1 in order to determine the possible functional
temperatures
groups inin the in the
the sample.wavenumber
sample. The
The FT-IR range
FT-IR spectra 400–4000
spectra were
were quite cm in order
quite featureless, to determine
featureless, confirming the
confirming again possible
again the functional
the purity
purity ofof the
the
groups
groups in thesamples.
synthesized sample. The
Thepeak
FT-IRatspectra
556 cm −were
1 canquite
be featureless,
attributed to confirming
the Fe–O again the
stretching purity of
vibration the
being
synthesized samples. The peak at 556 cm-1 can be attributed to the Fe–O stretching vibration being
-1
synthesized
characteristicsamples.
of the The octahedrons
the FeO peak at 556 cm in can be attributed to the Fe–O stretching vibration being
−1 can
characteristic of FeO66 octahedrons in perovskite-type
perovskite-type LaFeO LaFeO33 [26].
[26]. The
The band
band at at 716
716cm
cm-1-1 can be
be
characteristic
assigned bendingof the FeO 6
bending vibrations octahedrons
vibrations of
of the in perovskite-type LaFeO 3 [26]. The band− 1 at 716 cm can be
assigned the La-O
La-O bonds
bonds [11];
[11]; the
the small
small peak
peak atat2905
2905cm as well
cm-1-1 as well as
as the
the small
small
assigned
peak at bending
around vibrations
1600 cm of the
−1 resulted La-O
from bonds
small [11];
amounts the small
of citricpeak
acid at 2905 cm
residues, they as well
were as the
accountedsmallto
peak at around 1600 cm-1-1 resulted from small amounts of citric acid residues, they were accounted to
peak at around
C-H vibrations 1600
vibrations and cm
and the resulted
the symmetric from small
symmetric stretching
stretching of amounts
of the of
the carboxyl citric
carboxyl groups, acid residues, they were accounted to
C-H groups, respectively.
respectively.
C-H vibrations and the symmetric stretching of the carboxyl groups, respectively.

Figure 4. FT-IR spectra of LaFeO3 nanoparticles calcined at different temperatures.

Figure
Figure 4.
4. FT-IR
FT-IR spectra
spectra of
of LaFeO
LaFeO33 nanoparticles
nanoparticles calcined
calcined at
at different
different temperatures.
temperatures.

The
The specific
specific surface
surface areas
areas of
of the
the synthesized LaFeO
LaFeO333 samples
samples were
were determined
determined from
from aaa nitrogen
The specific surface areas of the synthesized LaFeO
synthesized samples were determined from nitrogen
nitrogen
adsorption-desorption isothermusing
using the BET approach. The isotherms of the samples can be
adsorption-desorption isotherm using the BET approach. The isotherms of the samples can be
adsorption-desorption isotherm the BET approach. The isotherms of the samples can be classified
classified into type III behavior (Figure 5), which is attributed to a weak adsorbate-adsorbent
classified
into type IIIinto type III(Figure
behavior behavior (Figure
5), which 5), which to
is attributed is aattributed to a weak adsorbate-adsorbent
weak adsorbate-adsorbent interaction [27].
interaction [27]. The surface areas decreased with increasing calcination temperature.the Although the
interaction
The surface[27]. The
areas surface areas
decreased with decreased
increasingwith increasing
calcination calcination Although
temperature. temperature. Although the
surface areas
surface areas were in general quite small, the area of S-700 exceeded even slightly the highest value
surface areas were in general quite
were in general quite small, the small, the area of S-700 exceeded even slightly the highest value
area of S-700 exceeded even slightly the highest value reported
reported
by Tijare by Tijare et al.
m2of/g9.5 m22In
/g [23]. In general, higher areas
surface areas facilitated adsorption of
reported by Tijare
et al. et al.
of 9.5 of 9.5 m /g general,
[23]. [23]. In general, higher surface
higher surface areas facilitated
facilitated adsorptionadsorption
of organicof
organic pollutants, promoted chargeseparation
carrier separation and enabled more light harvesting, resulting
organic pollutants,
pollutants, promoted promoted charge carrier separation
charge carrier and enabled
and enabled more
more light light harvesting,
harvesting, resultingresulting
in total
in total photocatalytic
higher photocatalytic
activity.activity.
in total higher photocatalytic
higher activity.
 Catalysts 2019, 9, 342 5 of 15
Catalysts2019,
Catalysts 2019,9,9,x xFOR
FORPEER
PEERREVIEW
REVIEW 5 5ofof1515

Figure5.
Figure
Figure 5.5.N
NN adsorption-desorptionisotherms
adsorption-desorption
22 2adsorption-desorption isotherms
isothermsforfor LaFeO
LaFeO
for samples
3 samples
LaFeO and
3 3samples and theresulting
the the
and resulting
resulting BETsurface
BET BET surface
surface areas
areas
of theofof
areas thedifferent
different
the different samples.
samples.
samples.

Diffuse reflectance UV-Vis spectroscopy was employed to characterize the optical properties of the
Diffusereflectance
Diffuse reflectanceUV-Vis
UV-Visspectroscopy
spectroscopywas wasemployed
employedtotocharacterize
characterizethe theoptical
opticalproperties
propertiesofof
LaFeO3 nanoparticles, as shown in Figure 6a. In the perovskite-type oxide, the strong absorption edge
theLaFeO
the LaFeO3 3nanoparticles,
nanoparticles,asasshownshownininFigure
Figure6a.6a.InInthetheperovskite-type
perovskite-typeoxide, oxide,the thestrong
strongabsorption
absorption
at 520 nm was ascribed to the electronic transition from the O 2p orbitals forming the valence band
edge at 520 nm was ascribed to the electronic transition from the O 2p
edge at 520 nm was ascribed to the electronic transition from the O 2p orbitals forming the valence orbitals forming the valence
to the Fe 3d orbitals in the conduction band [28]. The data showed that the sol-gel prepared LaFeO3
bandtotothe
band theFe Fe3d 3dorbitals
orbitalsininthetheconduction
conductionband band[28].[28].The
Thedata
datashowed
showedthat thatthethesol-gel
sol-gelprepared
prepared
photocatalyst could serve as a potential visible-light-driven photocatalyst. In addition, the band gap
LaFeO3 3photocatalyst
LaFeO photocatalystcould couldserve
serveasasaapotential
potentialvisible-light-driven
visible-light-drivenphotocatalyst.
photocatalyst.InInaddition,addition,the the
energy of LaFeO3 catalysts can be determined from Kubelka−Munk equation [29] via a Tauc plot:
band gap energy of LaFeO3 catalysts can be determined from Kubelka−Munk equation [29] via aa
band gap energy of LaFeO 3 catalysts can be determined from Kubelka−Munk equation [29] via
Taucplot:
Tauc plot:
n
α = B hv − Eg /hv
αα ==BB(ℎ𝑣 (ℎ𝑣−−𝐸𝐸) ) /ℎ𝑣 /ℎ𝑣
with α being the absorption coefficient, ν the irradiation frequency, Eg the band gap, B being a constant
(being with
with ααbeing
usually being the
the
1 for absorptioncoefficient,
absorption
semiconductors), coefficient,
h is theννPlanck
theirradiation
the irradiation frequency,
constantfrequency, Eg gthe
and n is a Econstant theband
band gap,BBbeing
gap,
depending being
on theaa
constant
constant (being
(being usually
usually 11 for
for semiconductors),
semiconductors), h hisis the
the Planck
Planck constant
constant and
and n
type of semiconductor (direct transition: n = 1/2; indirect transition: n = 2). For the direct transition n is
is a a constant
constant depending
depending
ononthe
thetype
typeofofsemiconductor
semiconductor semiconductor
LaFeO (directtransition:
(direct transition:nn==1/2; 1/2;indirect
indirecttransition:
transition:nn==2). 2).For
Forthe
thedirect
direct
3, the band gap energy values were estimated by extrapolation of the linear part
transition
transition
of the curves semiconductor
semiconductor LaFeO3,3,the
LaFeO
of the Kubelka–Munk the bandgap
band
function gap energy
energy
(αhv) valueswere
values
1/2 against were
the estimated
estimated
photon energy byextrapolation
by extrapolation
(hv), ofofthe
as displayed the
in
linear
linear part
part ofof the
the curves
curves of
of the
the Kubelka−Munk
Kubelka−Munk function
function (αhv)
(αhv) 1/2 against the photon energy (hv), as
1/2 against
Figure 6b. The S-700 sample absorbed slightly more light energy than the other ones showing that the photon energy (hv), as
adisplayed
displayed
decreasing ininFigure
Figure6b.
particle 6b.
size The
The S-700
andS-700 sampleabsorbed
sample
an increased absorbed
surface slightly
slightly
area amore
led tomore light
light
slight energy
redenergy
shift. than thanthetheother
otheronesones
showingthat
showing thataadecreasing
decreasingparticle
particlesize
sizeand
andan anincreased
increasedsurface
surfacearea arealedledtotoaaslight
slightredredshift.
shift.

Figure6.
Figure
Figure 6.6.Kubelka-Munk
Kubelka-Munkdiffuse
Kubelka-Munk diffusereflectance
diffuse reflectance
reflectance UV-Vis
UV-Vis
UV-Vis spectra
spectra (a)and
(a)(a)
spectra and and resulting
resulting band
resulting band gaps
gapsgaps
band from
fromfrom Tauc
TaucTauc
plots
plots(b)
(b)
plotsof (b)ofofthe
the thestudied
studiedstudiedLaFeO
LaFeO LaFeO
3 samples.
samples.
3 3samples.

X-ray photoelectron spectroscopy (XPS) was performed on the most promising LaFeO3 S-700 to
X-rayphotoelectron
X-ray photoelectronspectroscopy
spectroscopy(XPS)
(XPS)was
wasperformed
performedon onthe
themost
mostpromising
promisingLaFeO
LaFeO3 3S-700
S-700toto
determine the elemental composition and the chemical oxidation state of the sample surface. Figure 7
determinethe
determine theelemental
elementalcomposition
compositionand andthe
thechemical
chemicaloxidation
oxidationstate
stateofofthe
thesample
samplesurface.
surface.Figure
Figure
shows the X-ray photoelectron (XP) survey spectrum (Figure 7a) and the detailed spectra of the La
77shows
showsthe
theX-ray
X-rayphotoelectron
photoelectron(XP)(XP)survey
surveyspectrum
spectrum(Figure
(Figure7a)
7a)and
andthe
thedetailed
detailedspectra
spectraofofthe
theLa
La
3d, Fe 2p and O 1s. In addition to different La, Fe and O lines, Figure 7a shows also the C 1s signal,
3d,Fe
3d, Fe2p
2pand
andOO1s.1s.InInaddition
additiontotodifferent
differentLa,
La,Fe
Feand
andOOlines,
lines,Figure
Figure7a7ashows
showsalso
alsothe
theCC1s1ssignal,
signal,
which resulted from adventitious surface carbon and which was also referenced to a binding energy
whichresulted
which resultedfrom
fromadventitious
adventitioussurface
surfacecarbon
carbonand
andwhich
whichwaswasalso
alsoreferenced
referencedtotoaabinding
bindingenergy
energy
(284.8eV)
(284.8 eV)ininorder
ordertotoexclude
excludesurface
surfacecharge
chargeeffects
effectsfor
forall
allthe
theother
othersignals.
signals.TheThebinding
bindingenergies
energies
 Catalysts 2019, 9, 342 6 of 15

Catalysts 2019, 9, x FOR PEER REVIEW 6 of 15

(284.8 eV) in order to exclude surface charge effects for all the other signals. The binding energies
found in
found in the
the XP
XPspectra
spectraofofLaLa3d (Figure 7b) and
3d (Figure 7b) Fe
and2p Fe
(Figure 7c) revealed
2p (Figure that the iron
7c) revealed that and
the lanthanum
iron and
lanthanum ions were both present in the chemical valence state +III [30,31]. Figure 7d shows the Owith
ions were both present in the chemical valence state +III [30,31]. Figure 7d shows the O 1s signal 1s
binding
signal withenergies
binding ofenergies
about 529.9 eV, 531.1
of about 529.9eVeV,and 532.0
531.1 eVeV which
and 532.0corresponded as the mainas
eV which corresponded signal
the
to thesignal
main contribution of the La-Oof
to the contribution and
theFe-O
La-Ocrystal lattice
and Fe-O bonds,
crystal some
lattice surface
bonds, hydroxyl
some surfacegroups and
hydroxyl
chemisorbed
groups water, respectively
and chemisorbed [32,33]. In line
water, respectively with In
[32,33]. theline
expected composition
with the between La, between
expected composition Fe and O,
an atomic ratio of about 1:1:3 was found by comparing the relative signal intensities
La, Fe and O, an atomic ratio of about 1:1:3 was found by comparing the relative signal intensities in the different
in
XP spectra.
the different XP spectra.

X-rayphotoelectron
Figure7.7.X-ray
Figure photoelectronspectroscopy
spectroscopy(XPS)
(XPS)for
forthe
theS-700
S-700sample
samplesurvey
survey(a),
(a),and
andcore
corelevel
levelXPS
XPS
of La 3d (b), Fe 2p (c) and O1s (d).
of La 3d (b), Fe 2p (c) and O1s (d).

In order to investigate the energy band structure including the conduction band (CB) and
In order to investigate the energy band structure including the conduction band (CB) and
valence band (VB) position of LaFeO3 S-700 and S-900 photocatalysts, electrochemical flat potential
valence band (VB) position of LaFeO3 S-700 and S-900 photocatalysts, electrochemical flat potential
measurements were performed, and the resulting data are plotted in Figure 8a,b using the
measurements were performed, and the resulting data are plotted in Figure 8a and b using the Mott–
Mott–Schottky (MS) relation in the dark [34]:
Schottky (MS) relation in the dark [34]:
  
11 22 𝑘𝑇kT
= E − E
𝐸 − 𝐸 f b−−
C𝐶2 𝜀𝜀 eN
εεОo𝑒𝑁 𝑒e

withwith C being
C being the capacitance
the capacitance of space
of space charge,
charge, 𝜀 the dielectric
ε the dielectric constant,constant, 𝜀О the permittivity
ε o the permittivity of
of free space,
free space, N the electron donor density, E the applied potential and E the
N the electron donor density, E the applied potential and Efb the flat band potential. Plotting 1/C2
fb flat band potential.
Plotting
against E1/C 2 against E yields a straight line from which the slope of the donor density can be
yields a straight line from which the slope of the donor density can be calculated and Efb can
calculated and E
be determined as thefb can intercept
be determined as the intercept
of the abscissa of the abscissa
by extrapolation to C = 0.byTheextrapolation
positive slopes to C of = 0.
theThe
MS
positive slopes of the MS plots confirmed LaFeO 3 being an n-type semiconductor
plots confirmed LaFeO3 being an n-type semiconductor with electrons as the majority charge carriers. with electrons as
the
Themajority
flat bandcharge carriers.
potentials The(Figure
of S-700 flat band potentials
8a) and of S-700
S-900 (Figure 8b)(Figure 8a) andofS-900
at frequencies 100 Hz (Figure 8b) Hz
and 1000 at
frequencies of 100 Hz and 1000 Hz were calculated to be –0.3 and –0.25 V ( E
were calculated to be −0.3 and −0.25 V (EAg/AgCl(sat-KCl) ) referenced to the KCl-saturated Ag/AgCl
Ag/AgCl(sat-KCl) ) referenced
toelectrode,
the KCl-saturated
respectively.Ag/AgCl electrode,
Thus, using respectively.
the following Thus, using the following equation:
equation:
𝐸 =𝐸 / ( )+ 𝐸 / ( ) + 0.059 × 𝑝𝐻
ENHE = E0 Ag/AgCl (sat−KCl ) + E Ag/AgCl (sat−KCl ) + 0.059 × pH
with E0Ag/AgCl(sat-KCl) = 0.199. For the pH value of 5.6 of the 0.1 M Na2SO4 electrolyte solution,
potentials were 0.23 and 0.28 V versus the normal hydrogen electrode (NHE) result. For n-type
semiconductors the Efb was strongly related to the bottom of the conduction band (CB); typically, it is
assumed that CB is 0.1 V more negative than Efb [35], resulting in CB edges at about 0.13 V and 0.18 V
vs. NHE, respectively. These values are close to the position of the conduction band edge for YFeO3
Catalysts 2019, 9, 342 7 of 15

with E0 Ag/AgCl(sat-KCl) = 0.199. For the pH value of 5.6 of the 0.1 M Na2 SO4 electrolyte solution,
potentials were 0.23 and 0.28 V versus the normal hydrogen electrode (NHE) result. For n-type
semiconductors the Efb was strongly related to the bottom of the conduction band (CB); typically, it is
assumed that CB is 0.1 V more negative than Efb [35], resulting in CB edges at about 0.13 V and 0.18 V
Catalysts
vs. NHE, 2019, 9, x FOR PEERThese
respectively. REVIEW
values are close to the position of the conduction band edge for YFeO 7 of 15
3
calculated by Ismael et al. [36]. The slightly positive CB potential explains that the LaFeO3 was not
calculated
able to formbyhydrogen
Ismael etviaal. water
[36]. The slightly
splitting positive
under lightCB potential This
irradiation. explains that the LaFeO
was confirmed 3 was not
by respective
able to form hydrogen via water splitting under light irradiation. This was
experiments attempting photocatalytic H2 formation with our LaFeO3 samples on which platinum confirmed by respective
experiments attempting
nanoparticles (0.5 wt. %, photocatalytic
particle size <2Hnm)2 formation with our LaFeO3 samples on which platinum
were photodeposited as a co-catalyst. Even by the use
nanoparticles (0.5 wt. %, particle size <2 nm)
of light with λ ≥ 320 nm and methanol as a sacrificial were photodeposited as a co-catalyst.
agent, no hydrogen Evenwith
was detected by the
all use
the
of light with λ ≥ 320 nm and methanol as a sacrificial agent, no hydrogen was detected
Pt/LaFeO3 samples. This result stands in contrast to H2 formation reported earlier by Tijare et al. [23], with all the
Pt/LaFeO 3 samples. This result stands in contrast to H2 formation reported earlier by Tijare et al. [23],
Parida et al. [37] and Vaiano et al. [38], who, however, performed no analysis on conduction band
Parida et al.
positions. [37]some
Thus, and Vaiano et al. [38], the
doubts regarding who,H2however,
production performed
reported no analysis
in their on exist.
papers conduction band
positions.
Xu et Thus,
al. [39] some doubts
reported regarding
hydrogen the H2 production
production reported
activity over in their
a LaFeO papers exist.
3 /g-C3 N4 composite in the
Xu et al. [39] reported hydrogen production activity over a LaFeO3/g-C3N4 composite in the
presence of TEOA as a sacrificial reagent and Pt as a co-catalyst. Their results show that LaFeO3 alone
presence
had of TEOA
no activity as the
due to a sacrificial reagent and
positive conduction Pt edge
band as a co-catalyst. Their results
(0.11 V); hydrogen was onlyshow that
found LaFeO
if g-C 3
3 N4
alone had no activity due to the positive conduction band edge (0.11 V); hydrogen was only found if
(conduction band potential at −0.85 V vs. NHE) was added, which is in agreement of our results.
g-C3N4 (conduction
Hydrogen production band
waspotential
observedatfor–0.85
otherV ferrites,
vs. NHE) wasasadded,
such CuFe2 O which is in agreement of our
4 and NiFe2 O4 ; for those the
results. Hydrogen production was observed for other ferrites, such as CuFe2O4 and NiFe2O4; for
conduction band positions were found to be negative enough [40,41].
those the conduction band positions were found to be negative enough [40,41].
By taking into account the band gap energies of our LaFeO3 samples from the Tauc plots
By taking into account the band gap energies of our LaFeO3 samples from the Tauc plots (Figure
(Figure 6b), the valence band (VB) positions for S-700 and S-900 can be calculated according to
6b), the valence band (VB) positions for S-700 and S-900 can be calculated according to the
the equation Evb = Ecb + Eg [42], resulting in about Evb = 2.51 V and 2.68 V respectively.
equation 𝐸 = 𝐸 + 𝐸 [42], resulting in about Evb = 2.51 V and 2.68 V respectively.

Figure 8. Mott-Schottky
Figure 8. Mott-Schottkyplots
plotsatat100
100HzHzandand1 kHz of (a)
1 kHz of S-700 and and
(a) S-700 (b) S-900, (c) Nyquist
(b) S-900, plots of
(c) Nyquist S-700
plots of
and S-900 in 0.1 M Na SO (pH = 5.6) at 0.4 V vs. Ag/AgCl and (d) transient photocurrent
S-700 and S-900 in 0.12 M4 Na2SO4 (pH = 5.6) at 0.4 V vs. Ag/AgCl and (d) transient photocurrent responses
in 0.1 M Nain2 SO
responses /0.1
0.14M NaM Na2 SOM
2SO4/0.1 3 solution
Na2SO3 (pH = 5.6)
solution under
(pH white
= 5.6) underLED illumination.
white LED illumination.

Electrochemical impedance spectroscopy (EIS) and transient photocurrent experiments were

Electrochemical impedance spectroscopy (EIS) and transient photocurrent experiments were
performed to investigate the electron-hole separation efficiency in the LaFeO3 photocatalysts.
performed to investigate the electron-hole separation efficiency in the LaFeO3 photocatalysts. The
The electrode of S-700 shows the smaller arc size (Figure 8c). In general, a smaller arc size observed in
electrode of S-700 shows the smaller arc size (Figure 8c). In general, a smaller arc size observed in EIS
EIS semicircular Nyquist plots documents smaller charge-transfer resistance on the electrode surface
semicircular Nyquist plots documents smaller charge-transfer resistance on the electrode surface
and accelerated interface transport of charge carriers, which results in an effective photo-induced
and accelerated interface transport of charge carriers, which results in an effective photo-induced
charge carrier mobility and separation [43,44]. Figure 8d indicates the transient photocurrent
responses of S-700 and S-900. The photocurrent of S-700 sample was much higher than that of S-900
indicating the greatly improved charge transfer and separation ability [45,46]. The onset potential of
the photocurrent indicates the flat band potential of the electrode [47]. In this case, the sulfate/sulfite
Catalysts 2019, 9, 342 8 of 15

charge carrier mobility and separation [43,44]. Figure 8d indicates the transient photocurrent responses
of S-700 and S-900. The photocurrent of S-700 sample was much higher than that of S-900 indicating the
greatly improved charge transfer and separation ability [45,46]. The onset potential of the photocurrent
indicates the flat band potential of the electrode [47]. In this case, the sulfate/sulfite electrolyte solution
lowered the kinetic barrier for charge transport by trapping the photogenerated holes. Moreover,
the onset of the photocurrent lies at about 0.2 V vs. NHE for S-700, being in good agreement with the
flat band
Catalysts potential
2019, obtained
9, x FOR PEER from the Mott-Schottky plot.
REVIEW 8 of 15

2.2. Photocatalytic Properties

2.2. Photocatalytic Properties
Photocatalytic activities of the prepared LaFeO3 samples were evaluated by degradation of
Photocatalytic activities of the prepared LaFeO3 samples were evaluated by degradation of RhB
RhB and 4-CP in aqueous solution under visible light irradiation using a 420 nm cut-off filter.
and 4-CP in aqueous solution under visible light irradiation using a 420 nm cut-off filter. Before
Before irradiation, the suspensions were magnetically stirred in the dark for 40 min to ensure
irradiation, the suspensions were magnetically stirred in the dark for 40 min to ensure
adsorption-desorption equilibrium between the organic substrate and the photocatalyst, after visible
adsorption-desorption equilibrium between the organic substrate and the photocatalyst, after visible
light irradiation the absorbance of RhB was noticeably reduced (Figure 9a), although there was very
light irradiation the absorbance of RhB was noticeably reduced (Figure 9a), although there was very
little decrease in absorption before irradiation. This indicates that RhB degradation occurred instead of
little decrease in absorption before irradiation. This indicates that RhB degradation occurred instead
further adsorption. Since the intensity of the absorption peaks gradually decreased without any change
of further adsorption. Since the intensity of the absorption peaks gradually decreased without any
in their wavelength, it can be concluded that the degradation reaction takes place by an aromatic ring
change in their wavelength, it can be concluded that the degradation reaction takes place by an
opening without formation of stable de-ethylated intermediates [48,49].
aromatic ring opening without formation of stable de-ethylated intermediates [48,49].
Figure 9b shows that without LaFeO3 being present the dye RhB was quite stable and no significant
Figure 9b shows that without LaFeO 3 being present the dye RhB was quite stable and no
self-degradation under visible light took place. Also in the presence of SnO , a semiconductor with
significant self-degradation under visible light took place. Also in the2 presence of SnO2, a
a band gap of 3.0 eV, which can, thus, not be excited by light with λ ≥ 420 nm, only negligible
semiconductor with a band gap of 3.0 eV, which can, thus, not be excited by light with λ ≥ 420 nm,
degradation was found. Thus, sensitization effects can be ruled out as well. In the presence of
only negligible degradation was found. Thus, sensitization effects can be ruled out as well. In the
the photocatalyst LaFeO3, the photodegradation efficiency decreased with increasing calcination
presence of the photocatalyst LaFeO3, the photodegradation efficiency decreased with increasing
temperature of the LaFeO due to the decreasing surface area and increasing particle size. Besides the
calcination temperature of3the LaFeO3 due to the decreasing surface area and increasing particle size.
highest surface area sample facilitating the adsorption of the organic dyes and possibly trapping more
Besides the highest surface area sample facilitating the adsorption of the organic dyes and possibly
electrons and holes on the surface, the sample S-700 might also benefit from the slightly narrower
trapping more electrons and holes on the surface, the sample S-700 might also benefit from the
optical band gap allowing for more visible light absorption.
slightly narrower optical band gap allowing for more visible light absorption.

Figure 9. (a) UV-Vis spectra for the degradation of rhodamine B (RhB) under visible light irradiation
Figure 9. (a) UV-Vis spectra for the degradation of rhodamine B (RhB) under visible light irradiation
(λ ≥ 420 nm) on the LaFeO3 S-700 sample ([RhB] = 10−5 M, catalyst weight = 0.1 g) at 25 ◦ C.
(λ ≥ 420 nm) on the LaFeO3 S-700 sample ([RhB] = 10-5 M, catalyst weight = 0.1 g) at 25 °C. (b)
(b) Degradation of RhB as a function of irradiation time with visible light (λ ≥ 420 nm) in the presence
Degradation of RhB as a function of irradiation time with visible light (λ ≥ 420 nm) in the presence of
of different LaFeO3 catalysts or SnO2 for comparison.
different LaFeO3 catalysts or SnO2 for comparison.
The degradation of RhB obeys a pseudo-first-order kinetics law of the type [50]:
The degradation of RhB obeys a pseudo-first-order kinetics law of the type [50]:
ln c /c = kt
ln 𝑐 0⁄𝑐 t = 𝑘𝑡
withwith c0 being
c0 being the initial
the initial concentration
concentration of RhB,of RhB,
ct the ct the concentration
concentration of RhB at of
anyRhB
timeatt,any
t thetime t, t the
illumination
illumination time (min) and k is the first order rate −constant
1 (min -1). Figure 10 shows the linear
time (min) and k is the first order rate constant (min ). Figure 10 shows the linear relationships
relationships between ln(c0/ct) and t, the rate constant for S-700, S-750, S-850 and S-900 were 0.0062,
0.0032, 0.0026 and 0.0013 min-1, respectively.
In general, it is known that the photocatalytic degradation reaction of organic contaminants
proceeds mainly by the contribution of oxygen-containing reactive species such as superoxide (.O2-)
and hydroxyl radicals (.OH) [51,52]. Thus, in order to explore the reactive species for RhB
degradation different scavengers were tested in the photocatalytic process. The hydroxylation test
Catalysts 2019, 9, 342 9 of 15

between ln(c0 /ct ) and t, the rate constant for S-700, S-750, S-850 and S-900 were 0.0062, 0.0032,
0.0026 and 0.0013 min−1 , respectively.
In general, it is known that the photocatalytic degradation reaction of organic contaminants
proceeds mainly by the contribution of oxygen-containing reactive species such as superoxide (. O2 − )
and hydroxyl radicals (. OH) [51,52]. Thus, in order to explore the reactive species for RhB degradation
different scavengers were tested in the photocatalytic process. The hydroxylation test was done using
terephthalic acid (TA) as a probe molecule, in this test TA reacts with OH to produce highly fluorescent
Catalysts 2019, 9, x FOR PEER
2-hydroxyterepthalic REVIEW
acid (fluorescence maximum at 426 nm [53]). 9 of 15

Figure 10. Kinetics curves of LaFeO perovskites calcined at different temperatures.

Figure 10. Kinetics curves of LaFeO33perovskites calcined at different temperatures.
As seen from Figure 11a for S-700 very low fluorescence intensity at 426 nm was observed after
As seen from Figure 11a for S-700 very low fluorescence intensity at 426 nm was observed after
6 h of visible light irradiation suggesting very low hydroxyl radical formation on the surface of
6 h of visible light irradiation suggesting very low hydroxyl radical formation on the surface of the
the catalyst. Usually, the photoluminescence (PL) intensity at about 425 nm is proportional to the
catalyst. Usually, the photoluminescence (PL) intensity at about 425 nm is proportional to the
amount of the produced hydroxyl radical on the surface of the catalyst. In good agreement to that,
amount of the produced hydroxyl radical on the surface of the catalyst. In good agreement to that,
isopropanol (0.01 M), a known hydroxyl radical (. OH) quencher [54], showed only little effect on
isopropanol (0.01 M), a known hydroxyl radical (.OH) quencher [54], showed only little effect on the
the RhB degradation reaction (Figure 11b). However, the addition of benzoquinone (0.01 M) [55]
RhB degradation reaction. (Figure. 11b). However, the addition of benzoquinone (0.01 M) [55] as a
as a superoxide radical ( O− 2 ) quencher strongly decreased the degradation of RhB, indicating that
superoxide radical (.O-2) quencher strongly decreased the degradation of RhB, indicating that
degradation proceeds via superoxide radicals, which can only be produced via the reduction of
degradation proceeds via superoxide radicals, which can only be produced via the reduction of
dissolved oxygen by the excited electrons in the conduction band (CB) of LaFeO3 . This is surprising
dissolved oxygen by the excited electrons in the conduction band (CB) of LaFeO3. This is surprising
since the CB of LaFeO3 S-700 was detected to be at about 0.1 V, being more positive than the standard
since the CB of LaFeO3 S-700 was detected to be at about 0.1 V, being more positive than the
potential for the superoxide radical formation from adsorbed oxygen E0 (O2 /•O2 − ) = −0.046 V [56].
standard potential for the superoxide radical formation from adsorbed oxygen E0(O2/•O2-) = –0.046 V
Thus, the superoxide radical formation should not be possible. However, in the photocatalytic
[56]. Thus, the superoxide radical formation should not be possible. However, in the photocatalytic
experiment, the electrochemical standard conditions were not given, thus due to potential shifts
experiment, the electrochemical standard conditions were not given, thus due to potential shifts
depending on the Nernst law, the superoxide radical formation might become possible to some extent.
depending on the Nernst law, the superoxide radical formation might become possible to some
An indication for potential changes during the photocatalysis experiment might become visible in the
extent. An indication for potential changes during the photocatalysis experiment might become
increasing degradation of RhB in the presence of benzoquinone, which occurs with longer irradiation
visible in the increasing degradation of RhB in the presence of benzoquinone, which occurs with
time (Figure 11b). Approximately the same decrease in activity for RhB degradation is obtained when
longer irradiation time (Figure 11b). Approximately the same decrease in activity for RhB
10 vol. % methanol [57] were added as a hole (h+ ) quencher. The photogenerated holes can oxidize
degradation
− is
. obtained when 10 vol. % methanol [57] were added as a hole (h+) quencher. The
OH ions to OH radicals because the valence band position of S-700 (2.46 V) is more positive than the
photogenerated holes can oxidize OH- ions to .OH radicals because the valence band position of
redox potential of . OH/− OH (E0 = 1.99 V) [58]. These results for the active species being responsible
S-700 (2.46 V) is more positive than the redox potential of .OH/-OH (E0 = 1.99 V) [58]. These results for
for degradation agree with the results for the perovskite YFeO3 studied earlier by us [36]. In that paper,
the active species being responsible for degradation agree with the results for the perovskite YFeO3
it was concluded that superoxide radicals (. O2 ) and (. OH) have an effect but the holes (h.+ ) are the .main
studied earlier by us [36]. In that paper, it was concluded that superoxide radicals ( O2) and ( OH)
species on catalyst surfaces responsible for the photocatalytic activities.
have an effect but the holes (h+) are the main species on catalyst surfaces responsible for the
photocatalytic activities.
photogenerated holes can oxidize OH- ions to .OH radicals because the valence band position of
S-700 (2.46 V) is more positive than the redox potential of .OH/-OH (E0 = 1.99 V) [58]. These results for
the active species being responsible for degradation agree with the results for the perovskite YFeO3
studied earlier by us [36]. In that paper, it was concluded that superoxide radicals (.O2) and (.OH)
have an2019,
Catalysts effect but the holes (h+) are the main species on catalyst surfaces responsible for10 the
9, 342 of 15

photocatalytic activities.

Figure
Figure 11.
11. (a) Fluorescence
Fluorescencespectra
spectraofof
thethe 2-hydroxyterepthalic
2-hydroxyterepthalic acidacid solution
solution in theinpresence
the presence of3
of LaFeO
Catalysts
LaFeO3 S-700 and (b) the reactive species in trapping experiments during the degradation of RhB. 10 of 15
2019,
S-700 and9, x(b)
FORthePEER REVIEW
reactive species in trapping experiments during the degradation of RhB.

Figure
Figure 12 12 shows
shows that
that the
the LaFeO
LaFeO33 S-700
S-700 was
was not not only
only able
able to
to degrade
degrade dyesdyes like
like RhB
RhB under
under
visible-light
visible-light irradiation
irradiation at
at λ >> 420
420 nm,
nm, but
but also
also compounds
compounds like like 4-CP
4-CP which
which does
does not
not absorb
absorb lights
lights
themselves in that spectral range. Thus, a light-induced self-degradation can be
themselves in that spectral range. Thus, a light-induced self-degradation can be ruled out. With LaFeO ruled out. With3
LaFeO
S-700 the degradation efficiency on 4-CP was lower than that on RhB, but still more than 60% of60%
3 S-700 the degradation efficiency on 4-CP was lower than that on RhB, but still more than the
of
4-CPthewere
4-CPtransformed
were transformed by destroying
by destroying the aromatic
the aromatic ringwhich
ring system, system, which is responsible
is responsible for the
for the absorption
absorption at 315 nm,
at 315 nm, which was which
recorded wasandrecorded
followed and followed
with time inwith time12.
Figure inInFigure
a HPLC 12. analysis
In a HPLC analysis
performed
performed with mixture
with the reaction the reaction
after 5mixture after 5 hours
h of illumination, of illumination,
no significant amountsno significant amounts
of decomposition of
products
decomposition
were found. Totalproducts were found.
organic content Total organic
(TOC) analysis after fivecontent (TOC) analysis
hours illumination after fivethehours
time confirmed 4-CP
illumination
degradation;time confirmed
a reduction theTOC
of the 4-CPbydegradation;
55% was found. a reduction of the3 TOC
Our LaFeO by 55% was
photocatalyst found.
showed Our
higher
LaFeO
activity3 photocatalyst showedcompared
for 4-CP degradation higher activity
to that for 4-CP degradation
reported by Pirzada etcompared
al. [59] andtoHuthat reported
et al. [60]. by
Pirzada et al. [59] and Hu et al. [60].

Figure
Figure 12.
12. Degradation
Degradation ofof 4-CP
4-CP as
as aa function
function of
of irradiation
irradiation time
time without
without aa photocatalyst
photocatalyst and
and in
in the
the
presence of the LaFeO33 catalyst S-700.
presence of the LaFeO catalyst S-700.

3. Experimental
3. Experimental
3.1. Materials
3.1. Materials
All the reactants were commercial products. Iron (III) nitrate nonahydrate (Fe(NO3 )3 ·9H2 O, 99%),
citric acidthe
All (C6reactants were
H8 O7 , 99%) andcommercial
lanthanumproducts. Iron
(III) nitrate (III) nitrate
hexahydrate nonahydrate
(La(NO (Fe(NO3)39H2O,
3 )3 ·6H2 O, 99.999%) were
99%), citricfrom
purchased acid Sigma-Aldrich.
(C6H8O7, 99%) and lanthanum (III)
4-chlorophenol nitrate
(4-CP, ClC6hexahydrate
H4 OH, ≥99%) (La(NO 3)36H2O, 99,999%)
and Rhodamine B (RhB,
were purchased from Sigma-Aldrich. 4-chlorophenol (4-CP, ClC 6H4OH, ≥99%) and Rhodamine B
C28 H31 ClN2 O3 ) were bought from Merck. All chemicals were analytically pure and were used as
(RhB, C28without
received H31ClN2O 3) were bought from Merck. All chemicals were analytically pure and were used
further purification. Deionized water (>18 MΩ cm) obtained from a Sartorius water
as received without
purification system was further
usedpurification.
during the Deionized water procedure
whole synthetic (>18 MΩ cm) obtained
to prepare thefrom a Sartorius
required metal
water purification
ion solutions. system was used during the whole synthetic procedure to prepare the required
metal ion solutions.

3.2. Synthesis of LaFeO3 by the Citric Acid Assisted Sol-gel Method

The lanthanum ferrite perovskite was synthesized by the citric acid assisted sol-gel method [23].
In a typical synthesis, Fe(NO3)39H2O (0.0041 moles), La(NO3)36H2O (0.0041 moles) and citric acid
were separately dissolved in deionized water under continuous stirring in a 1:1:4 molar ratio. A high
Catalysts 2019, 9, 342 11 of 15

3.2. Synthesis of LaFeO3 by the Citric Acid Assisted Sol-gel Method

The lanthanum ferrite perovskite was synthesized by the citric acid assisted sol-gel method [23].
In a typical synthesis, Fe(NO3 )3 ·9H2 O (0.0041 moles), La(NO3 )3 ·6H2 O (0.0041 moles) and citric acid
were separately dissolved in deionized water under continuous stirring in a 1:1:4 molar ratio. A high
surplus of citric acid was required to chelate the metal cations and to prevent aggregation. The obtained
dark yellow, clear and transparent solution was obtained after the powders were completely dissolved
in the solution. From that, the viscous gel was formed by heating at 300 ◦ C for 2–3 h under continuous
magnetic stirring. Subsequently, the solvent was evaporated by combustion in a pyrolysis setup at
400 ◦ C for 1 h. The resulting fluffy powder, which was used as a precursor for LaFeO3 , was crushed
to a fine powder and subsequently calcined at different temperatures for 4 h in air. After cooling,
the obtained samples were characterized and tested in the photocatalytic degradation. They were
named S-700, S-750, S-850 and S-900 according to the calcination temperature applied.

3.3. Characterization
The crystalline phase and size of the obtained LaFeO3 nanoparticles were checked with
a Empyrean theta-theta X-ray diffraction system (PANalytical, Almelo, The Netherlands) operating
with Cu Kα radiation (λ = 1.540598 nm) at 40 kV and 40 mA in the 2θ range of 20–80◦ .
The Brunauer-Emmett-Teller (BET) surface areas were calculated from nitrogen adsorption-desorption
isotherms measured on a Tri Star II (Micromeritics GmbH, Aachen, Germany). All the samples were
degassed at 150 ◦ C overnight prior to the adsorption measurements.. The diffuse reflectance spectra
(DRS) and UV-Vis absorption spectra of the dye solutions were measured with a Varian Cary 4000
(Mulgrave, Australia). This spectrometer could also be equipped with an Ulbricht sphere allowing
the recording of UV-Vis diffuse reflectance spectra (DRS) in the region 200–800 nm using the white
standard MgO as a reference. The photoluminescence (PL) spectra were recorded using a Varian Cary
Eclipse fluorescence spectrophotometer (Mulgrave, Australia) at room temperature, with excitation
by incident light of 380 nm. The Fourier transform infrared spectra (FT-IR) were recorded using
a Bruker FT-IR Tensor 27 Spectrometer with a platinum ATR unit. The morphology of the prepared
samples and the content of the elements were studied using scanning electron microscopy (Hitachi,
S-3200N, Krefeld, Germany) and energy-dispersive X-ray spectroscopy (EDX Oxford INCAx-act,
Abingdon, UK), respectively. Since the photocatalytic properties of the LaFeO3 strongly depend on
the surface chemical state of the samples this was analyzed by X-ray photoelectron spectroscopy
(XPS) with an ESCALAB 250 Xi (Thermo Fisher, East Grinstead, UK) equipped with a monochromatic
Al Kα X-ray source (hν = 1486.6 eV) as the excitation source under ultrahigh vacuum conditions.
The high-resolution spectra for the C 1s, O 1s, La 3d and Fe 2p photoelectron lines were recorded
with a bandpass energy of 20 eV and a step size of 0.1 eV. The spectra were analyzed using Avantage
software (version 5.951). Binding energies in the high-resolution spectra were calibrated by setting the
C 1s signal to 284.8 eV. Electrochemical impedance spectroscopy (EIS), photocurrent measurement
and Mott Schottky plots were performed on an IM6e potentiostat (Zahner Elektrik, GmbH, Kronach,
Germany) and evaluated with the Thales (version 4.12) software. A standard three-electrode cell
configuration with Ag/AgCl (saturated KCl), coiled Pt-wire and LaFeO3 coated FTO were used as
the reference, counter and working electrodes, respectively. The working electrodes were prepared
on the conductive fluorine-doped tin oxide (FTO) glass slides (Pilkington, Weiherhammer, Germany)
of 2 × 6 cm size, which were sonicated before by applying in a sequence 0.1 M HCl, 0.1 M NaOH,
acetone and ethanol in an ultrasonic bath, then rinsed with deionized water and dried in an air stream.
Then 0.1 g of the respective LaFeO3 sample was dispersed in 500 µl of ethanol in an ultrasonic bath for
30 min and 200 µl of the obtained suspension were coated on the FTO glass substrate using the doctor
blade method. Finally, the FTO substrate was dried in a furnace for 30 min at 353 K and calcined for 3 h
at 873 K. An electrolyte 0.1 M Na2 SO4 aqueous solution was used for the Mott-Schottky measurements
and a 0.1 M Na2 SO4 /0.1 M Na2 SO3 aqueous solution was used as the supporting electrolyte for
photocurrent and electrochemical impedance measurements, respectively.
Catalysts 2019, 9, 342 12 of 15

3.4. Photocatalytic Degradation Activity and Hydrogen Evolution Measurements

The photocatalytic activity of the LaFeO3 samples was tested on one hand by the photocatalytic
decomposition of RhB and 4-CP as organic model pollutants under visible light irradiation (λ ≥ 420 nm)
and on the other hand by attempting hydrogen evolution using light of λ ≥ 320 nm and Pt nanoparticles
as a co-catalyst.
For the degradation experiments the visible light irradiation was obtained from a 150 W Xe
lamp equipped with a 420 nm cut-off filter. This optical cut-off filter was placed between the reactor
and the xenon lamp to cut off the UV light and to ensure visible light irradiation only; the distance
between the light source and the reactor containing solution was about 10 cm. Since for dyes, such as
RhB, self-excitation by the visible light could not be ruled out (although we found there was not
much indication for that, compare Figure 9b), 4-CP was used as a control substrate, which is not
absorbing in the vis-light range. In a typical test, 0.1 g of LaFeO3 and 100 mL of aqueous solutions
(10−5 M) of RhB or 4-CP were initially mixed under continuous magnetic stirring in a water-cooled
(10 ◦ C) double-wall 250 mL Pyrex reactor for 40 min in the dark to establish the adsorption-desorption
equilibrium between the photocatalyst and substrate (RhB or 4-CP). The cooling system was used to
cool down the double-wall Pyrex reactor to prevent the effect of the thermal catalytic reaction. Then the
samples were illuminated under visible light. Every one hour, a part of the suspension was taken out,
filtered to remove the particles and analyzed by the UV-Vis absorption measurement, the degree of
degradation was evaluated from the decrease of absorption at the RhB and 4-CP maxima at 554 nm
and 315 nm, respectively.
Photocatalytic H2 evolution was attempted in a double-walled quartz reaction vessel connected
to a closed gas circulation, using a 500 W Hg mid-pressure immersion lamp (Peschl UV-Consulting)
as a light source. Argon gas was used as the carrier gas with a flow of 50 NmL min−1 . The evolved
hydrogen gas was quantitatively analyzed by a multichannel analyzer (Emerson) equipped with
a thermal conductivity detector. In a typical photocatalytic reaction, 0.5 g of LaFeO3 photocatalysts
were suspended in a mixture of 550 mL water and 50 mL of the sacrificial agent methanol prior to the
irradiation. The solution was kept at 10 ◦ C by flushing cold water from a thermostat (LAUDA) through
a double-wall reactor made of normal glass. The normal glass mantle was tested to absorb all the light
with wavelengths shorter than about 320 nm. Thus, one can assume that the LaFeO3 samples are only
irradiated by light of λ ≥ 320 nm. The co-catalyst 0.5 wt. % Pt (particle size < 2 nm) was deposited
on the LaFeO3 powder via reductive photodeposition from H2 PtCl6 ·6H2 O. Upon light irradiation,
metallic Pt nanoparticles were photodeposited onto the photocatalyst surface sites preferentially
accessible for electrons, while CO2 was formed from methanol being employed as a sacrificial reagent
as qualitatively detected with our multichannel analyzer (Emerson). The standard redox potential for
the reduction of Pt2+ ions to metallic Pt is +1.2 V vs. NHE, thus the electrons in the CB of LaFeO3 are
able to initiate this reduction.

4. Conclusions
A perovskite-type LaFeO3 photocatalyst was synthesized using the quite simple citric acid
assisted sol-gel route. The prepared samples were characterized using different methods. The most
photocatalytically active sample for decomposition of RhB and 4-CP under visible light was the one
calcined at the lowest temperature of 700 ◦ C due to the highest surface area and the lowest band
gap energy. At temperatures lower than 700 ◦ C the crystallinity of the LaFeO3 samples was not
sufficient. Mott-Schottky plots revealed a positive potential of the CB at around 0.1 V explaining
the observed inactivity of LaFeO3 for the photocatalytic hydrogen evolution via water splitting and
methanol dehydrogenation. The photocatalytic degradation reaction of the pollutants occurred mainly
via direct reaction of the photogenerated holes, but to some extent especially in the starting period of
the degradation experiments also via superoxide radical formation. To sum up, LaFeO3 is a promising
photocatalytic material for degradation of organic pollutants under visible light irradiation.
Catalysts 2019, 9, 342 13 of 15

Author Contributions: M.I. performed the catalyst preparation, structural and electrochemical characterization
and the photocatalytic test experiments. He also prepared the first draft of the manuscript. This work was carried
out under the supervision of M.W., who also structured the discussion of the data and prepared the final version
of the manuscript.
Acknowledgments: We thank Dereje H. Taffa (University of Oldenburg) for his assistance in recording XP spectra
and fruitful discussions XPS and photoelectrochemical results. Financial support by the Phoenix Scholarship
program (PX14DF0164) for MI, and by the German Science Foundation (Deutsche Forschungsgemeinschaft, DFG)
under contracts WA 1116/28-1 and INST 184/154-1 for the X-ray diffractometer are gratefully acknowledged.
Conflicts of Interest: The authors declare no conflict of interest.

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