materials

Article
Facile Synthesis of CeO2-LaFeO3 Perovskite
Composite and Its Application for
4-(Methylnitrosamino)-1-(3-Pyridyl)-1-Butanone
(NNK) Degradation
Kaixuan Wang 1 , Helin Niu 1, *, Jingshuai Chen 1 , Jiming Song 1 , Changjie Mao 1 ,
Shengyi Zhang 1 , Saijing Zheng 2 , Baizhan Liu 2 and Changle Chen 3, *
1 Anhui Province Key Laboratory of Environment-Friendly Polymer Materials,
School of Chemistry and Chemical Engineering, Anhui University, Hefei 230601, China;
wangkaixuan55@163.com (K.W.); cjshuai@126.com (J.C.); songjm@ustc.edu.cn (J.S.);
maocj2011@gmail.com (C.M.); syzhangi@126.com (S.Z.)
2 Key Laboratory of Cigarette Smoke Research of China National Tobacco Corporation, Shanghai 200082,
China; zhengsj@sh.tobacco.com.cn (S.Z.); liubz@sh.tobacco.com.cn (B.L.)
3 CAS Key Laboratory of Soft Matter Chemistry, Department of Polymer Science and Engineering,
University of Science and Technology of China, Hefei 230026, China
* Correspondence: niuhelin@ahu.edu.cn (H.N.); changle@ustc.edu.cn (C.C.); Tel.: +86-551-6386-1279 (H.N.);
+86-551-6360-1495 (C.C.)

Academic Editor: Anke Weidenkaff

Received: 23 February 2016; Accepted: 26 April 2016; Published: 29 April 2016

Abstract: A facile and environmentally friendly surface-ion adsorption method using CeCO3 OH@C
as template was demonstrated to synthesize CeO2 -LaFeO3 perovskite composite material.
The obtained composite was characterized by X-ray diffraction (XRD), fourier transform infrared
spectra (FT-IR), field-emission scanning electron microscopy (FE-SEM), transmission electron
microscopy (TEM), thermo-gravimetric analysis and differential scanning calorimetry (TG-DSC),
N2 adsorption/desorption isotherms and X-ray photoelectron spectra (XPS) measurements. The
catalytic degradation of nitrosamine 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK) was
tested to evaluate catalytic activity of the CeO2 -LaFeO3 composite. Much better activity was observed
for the CeO2 -LaFeO3 composite comparing with CeO2 and LaFeO3 . These results suggested that
perovskite composite materials are a promising candidate for the degradation of tobacco-specific
nitrosamines (TSNAs).

Keywords: CeO2 -LaFeO3 ; NNK; degradation; perovskite

1. Introduction
Perovskite materials can be described as ABO3 , with A and B being two cations and O being an
oxygen anion. Perovskite materials are well known for their advantageous physical and chemical
properties for various applications such as catalysts [1,2], multiferroic materials [3], energy conversion
materials [4,5], and gas sensors [6]. Recently, LaFeO3 and related materials have received increasing
attention [7,8]. CeO2 has been extensively studied as a catalyst to transform some environmentally
harmful substances into environmentally friendly materials, such as oxidation CO [9], selective
reduction of NO [10] and photocatalytic degradation of Rhodamine B [11]. Therefore, it is highly
fascinating to combine the advantages of LaFeO3 and CeO2 materials [12,13]. A variety of techniques
have been developed to fabricate the CeO2 -LaFeO3 composite materials, such as the solid-state
reaction method [14], solution combustion and co-precipitation method [15], low-temperature
thermal decomposition method [16] and ethylene diamine tetraacetic acid-citrate method [17].

Materials 2016, 9, 326; doi:10.3390/ma9050326 www.mdpi.com/journal/materials

Materials 2016, 9, 326 2 of 12

In this work, we reported a facile and environmentally friendly surface-ion adsorption method
to prepare perovskite-type LaFeO3 and a CeO2 -LaFeO3 composite. The formation mechanism was
also investigated.
Tobacco smoke contains more than 5000 kinds of compounds. Among these chemicals,
tobacco-specific nitrosamines (TSNAs) play a significant role in causing lung cancer and other diseases
for people who either use tobacco products or are exposed to secondhand smoke [18]. There are mainly
four kinds of tobacco-specific nitrosamines: 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK),
N’-nitrosonornicotine (NNN), N’-nitrosoanatabine (NAT) and N’-nitrosoanabasine (NAB) [19], of
which NNK has been identified as the most potent lung carcinogen [20,21]. In order to protect public
health, it is necessary to reduce the level of NNK in tobacco. Control of the storage environment,
reduction of leaf nitrate contents, and the scavenging of gaseous nitrosating agents could be especially
effective to reduce or inhibit NNK formation during the storage of cured tobacco [22]. Zeolites were
successfully applied to capture and degrade NNK in gas or liquid phases [19,23]. Nanostructured
titanates were also used as catalysts for selectively reducing NNK in mainstream cigarette smoke [24].
These results suggest that it is possible to efficiently degrade NNK contents with suitable catalysts.
Since all TSNA materials contain N-NO group, it was hypothesized that the catalytic breaking of the
chemical bond in the N-NO group by perovskite materials may be the key step for the decomposition of
these carcinogens [19]. In this work, we preformed systematic studies on the properties of CeO2 -LaFeO3
composite for the degradation of NNK.

2. Results and Discussion

Figure 1A shows the X-ray powder diffraction (XRD) patterns of (a) CeO2 ; (b) LaFeO3 ;
(c) CeO2 -LaFeO3 precursor; and (d) CeO2 -LaFeO3 . The samples were scanned from 2θ degrees
of 20˝ to 90˝ , using a Cu Kα radiation with a characteristic wavelength (λ) of 0.15405 nm. As shown in
Figure 1A-a, the main characteristic peaks located at 2θ = 28.55˝ , 47.48˝ , 56.34˝ are corresponding to
the (111), (220), (311) planes of CeO2 , which are in good agreement with the reported XRD data (JCPDS
Card No. 43-1002). All of these peaks are corresponding to a face-centered cubic (fcc) fluorite structure
CeO2 [25]. Figure 1A-b can be assigned to the orthorhombic perovskite LaFeO3 structure with the
Pbnm space group, and the diffraction peaks completely agree with those of JCPDS Card No. 37-1493.
No obvious peak could be observed in the XRD pattern of CeO2 -LaFeO3 precursor (Figure 1A-c),
indicating that neither LaFeO3 nor CeO2 were formed after ultrasonic-assisted surface-ion adsorption
treatment. In Figure 1A-d, the main diffraction peaks at 2θ = 22.61˝ , 32.19˝ , 39.67˝ , 46.14˝ and 57.39˝
belong to the LaFeO3 orthorhombic perovskite phase and the weak signals at 2θ = 28.55˝ , 47.48˝ , 56.34˝
correspond to the CeO2 phase concurrent with the major perovskite phase. These results indicate
the formation of a CeO2 -LaFeO3 composite. The main diffraction peak of the obtained CeO2 -LaFeO3
was almost the same as that of LaFeO3 . However, the peak slightly shifted to a lower angle (inset
of Figure 1A), indicating an enlarged dimension of unit cell caused by the cerium substitution [26].
The crystallite size of the catalysts was estimated using Scherrer’s method as follows [27]:

D “ Kλ{βcosθ (1)

where D is the average diameter of the calculated particles; K is the shape factor of the average grain
size (the expected shape factor is 0.89), λ is the wavelength characteristic in Å (in this particular case
λ = 1.5405 Å); and β is the width of the X-ray peak at half height. The average crystallite size of CeO2 ,
LaFeO3 and CeO2 -LaFeO3 samples was found to be 12, 24 and 17 nm, respectively. In the CeO2 -LaFeO3
composite, the diffraction peak for the CeO2 phase is extremely weak. Therefore, the average crystallite
size in the CeO2 -LaFeO3 composite was determined using the main reflections (2θ = 22.61˝ , 32.19˝ )
corresponding to the LaFeO3 phase.
The FT-IR spectra of CeCO3 OH@C, CeO2 -LaFeO3 precursor and CeO2 -LaFeO3 are shown in
Figure 1B. The absorption peak centered at ca. 3410 cm´1 was attributed to the structural O-H stretching
vibration modes of physically absorbed H2 O on the samples or the surface O-H group in the materials,
Materials 2016, 9, 326 3 of 12
Materials 2016, 9, 326 3 of 12

whereas
asymmetric the absorption
and symmetric peaks at ca. 2922
stretching cm´1 andThe
vibrations. ca. 2852 cm´1 were
absorption peaksattributed
at 1796 cm to−1C-H
were asymmetric
attributed
and symmetric stretching vibrations. The absorption peaks at 1796 cm ´1 were attributed to (COO´ ).
to (COO−). The absorption peaks at ca. 1628 cm−1 (Figure 1B-a,b) were attributed to C=C vibrations
The absorption
[28,29], peaks atweaker
which became cm´1calcination
ca. 1628after (Figure 1B-a,b) were
(Figure attributed
1B-c). to C=C vibrations
The absorption peaks at[28,29],
ca. 1384which
cm−1
became weaker after calcination (Figure 1B-c). The absorption peaks at ca. 1384 cm ´1 were attributed
were attributed to -CH3 symmetrical deformation vibration (Figure 1B-a,c). The peak being stronger
to -CH3 symmetrical
(Figure 1B-b) was due deformation vibration
to stretching (Figure of
vibration 1B-a,c).
nitrateTheanion
peak being stronger
adsorbed on the(Figure
CeO1B-b) was
2-LaFeO3
due to stretching
precursor vibration
surface, which of nitrate anion
overlapped withadsorbed on the CeO2deformation
-CH3 symmetrical -LaFeO3 precursor surface,
vibration. Thewhich
peak
overlapped with -CH
becoming weaker (Figure 3 symmetrical deformation vibration. The peak becoming
1B-c versus Figure 1B-b) was ascribed to the decomposing of nitrate weaker (Figure 1B-c
versus
anions.Figure 1B-b) was
The bands in the ascribed
504−730 tocmthe−1decomposing
region (Figure of1B-c)
nitrate anions.
were The bands
assigned to thein the 504´730
stretching cm´of1
modes
region (Figure 1B-c)
the octahedral FeO6were
groupsassigned to the stretching
in perovskite, modesthe
which were of most
the octahedral
important FeO 6 groups in
absorption perovskite,
bands of the
which
perovskite structure [30]. The band located at ca. 453 cm (Figure 1B-c) can be assigned toatthe
were the most important absorption bands of the perovskite
−1 structure [30]. The band located ca.
453 ´ 1
cm (Figure 1B-c)
deformation modes of can
the be
sameassigned
polyhedrato the[31].
deformation
However, modes
no peaksof theofsame
CeO2polyhedra
were detected. [31]. However,
Based on
no peaks of CeO
the FT-IR analysis, were detected. Based on the FT-IR analysis, it can be concluded
2 it can be concluded that CeCO3OH@C possesses hydrophilic negatively 3charged that CeCO OH@C
possesses hydrophilic negatively charged groups such as -OH and -COO ´ on its carbonaceous shell,
groups such as -OH and -COO− on its carbonaceous shell, and these groups can cause adsorption
and
metal these groups
cations can causesolution.
in aqueous adsorption metal the
Through cations in aqueous
subsequent solution.process,
calcination Through thethe subsequent
carbonaceous
calcination
shell could be eliminated and the composite formed. Therefore, CeCO3OH@C can be Therefore,
process, the carbonaceous shell could be eliminated and the composite formed. used as a
CeCO
template3 OH@C can be used
to synthesize as a template
perovskite to synthesize perovskite composites.
composites.

Figure 1. (A) XRD spectra of different samples: (a) CeO2; (b) LaFeO3; (c) CeO2-LaFeO3 precursor; and
Figure 1. (A) XRD spectra of different samples: (a) CeO2 ; (b) LaFeO3 ; (c) CeO2 -LaFeO3 precursor; and
(d) CeO
(d) -LaFeO3;; Inset:
CeO2-LaFeO X-ray diffraction peak around 32° ˝ of LaFeO3 and CeO2-LaFeO3; (B) FT-IR
2 3 Inset: X-ray diffraction peak around 32 of LaFeO3 and CeO2 -LaFeO3 ; (B) FT-IR
spectra of: (a) CeCO 3OH@C; (b) CeO2-LaFeO3 precursor; and (c) CeO2-LaFeO3; TG-DSC curves of
spectra of: (a) CeCO3 OH@C; (b) CeO2 -LaFeO3 precursor; and (c) CeO2 -LaFeO3 ; TG-DSC curves of
(C) LaFeO
(C) precursor; (D)
LaFeO3 precursor; (D) CeO
CeO2-LaFeO 3 precursor.
3 2 -LaFeO3 precursor.

The TG-DSC curves of LaFeO3 precursor and CeO2-LaFeO3 precursor were shown in Figure 1C
The TG-DSC curves of LaFeO3 precursor and CeO2 -LaFeO3 precursor were shown in Figure 1C,D.
and Figure 1D. The total weight loss of LaFeO3 precursor (Figure 1C) was 89.70%, indicating a
The total weight loss of LaFeO3 precursor (Figure 1C) was 89.70%, indicating a 10.30% LaFeO3 product
10.30% LaFeO3 product yield. The sharp exothermic peak at 298 °C in the DSC curve corresponds to
yield. The sharp exothermic peak at 298 ˝ C in the DSC curve corresponds to the heat generated by
the heat generated by the burning of the carbonaceous spheres’ template and decomposing of nitrate
the burning of the carbonaceous spheres’ template and decomposing of nitrate anions [32]. The broad
anions [32]. The broad exothermic peak at about 348 °C can be attributed to the crystallization
process of LaFeO3 [33]. The total weight loss of the as-prepared CeO2-LaFeO3 precursor was 76.92%.
Materials 2016, 9, 326 4 of 12

exothermic peak at about 348 ˝ C can be attributed to the crystallization process of LaFeO3 [33].
The total weight
Materials loss of the as-prepared CeO2 -LaFeO3 precursor was 76.92%. The broad exothermic
2016, 9, 326 4 of 12
Materials 2016, 9, 326˝ ˝
peak at about 320 C and the sharp exothermic peak at about 487 C correspond to the combustion 4 of 12 of
The broad exothermic peak at about 320 °C and
carbon-rich polysaccharide (GCP) and formation of CeO2 -LaFeO3 . the sharp exothermic peak at about 487 °C
The broad to
correspond exothermic
the peak at
combustion of about 320 °C
carbon-rich and the sharp
polysaccharide exothermic
(GCP) and peak of
formation at CeO
about 487 °C
2-LaFeO 3.
The representative SEM and TEM images of the carbonaceous spheres and CeCO3 OH@C
correspond to the combustion
The representative SEM of carbon-rich
and polysaccharide
TEM images (GCP) and formation
of the carbonaceous spheres andof CeO
CeCO2-LaFeO
3OH@C 3.
templates are shown in Figure 2. After hydrothermal treatment, carbonaceous spheres formed
The representative
templates SEM and
are shown in Figure TEMhydrothermal
2. After images of the carbonaceous
treatment, spheresspheres
carbonaceous and CeCO 3OH@C
formed and
and displayed good monodispersed spherical morphology with an average diameter of 150 nm
templates
displayed are good shown in Figure 2.spherical
monodispersed After hydrothermal
morphologytreatment, carbonaceous
with an average diameterspheres
of 150formed
nm (Figureand
(Figure 2A,B). Figure 2C,D are the SEM and TEM images of CeCO3 OH@C. The GCP-coated CeCO3 OH
displayed
2A,B). Figure good2C,Dmonodispersed
are the SEM spherical
and TEMmorphology
images ofwith
CeCO an3OH@C.
averageThe diameter of 150 nm
GCP-coated CeCO(Figure
3OH
nanospheres
2A,B).
were
Figurewere
well
2C,Dwell
retained.
are retained.
Figure
the SEM Figure
3D shows
and TEM
that CeCO OH@C.
OH@C The
of CeCO33OH@C
imagesthat
has a CeCO3 OH CeCO core; 3aOHGCP
nanospheres 3D shows has a GCP-coated
CeCO3OH core; a GCP
shell has been
nanospheres prepared
shell has beenwere by the hydrothermal
well retained.
prepared method.
Figure 3D shows
by the hydrothermal To
thatTo
method. some
CeCO degree,
some3OH@C
degree,hasthe structure
theastructure
CeCO3OH of GCP-coated
of core; a GCP
GCP-coated
CeCO
shell3
CeCOhasOH
3OH
nanospheres
been prepared by
nanospheres have overlapped
theoverlapped
have hydrothermal with
with the shell,
method. which
To some
the shell, is
whichdegree,a similar result
the structure
is a similar to
result toofourour previous
GCP-coated
previous
work
CeCO
work[27].
3OH nanospheres have overlapped with the shell, which is a similar result to our previous
[27].
work [27].

Figure 2. SEM and TEM images of (A,B) carbonaceous spheres; (C,D) CeCO3OH@C.
Figure 2. SEM and TEM images of (A,B) carbonaceous spheres; (C,D) CeCO3 OH@C.
Figure 2. SEM and TEM images of (A,B) carbonaceous spheres; (C,D) CeCO3OH@C.

Figure 3. Cont.
Figure 3. Cont.
Figure 3. Cont.
Materials 2016, 9, 326 5 of 12
Materials 2016, 9, 326 5 of 12

Figure 3. SEM and TEM images of (A,B) LaFeO3; (C,D) CeO2; (E,F) CeO2-LaFeO3.
Figure 3. SEM and TEM images of (A,B) LaFeO3 ; (C,D) CeO2 ; (E,F) CeO2 -LaFeO3 .

The representative SEM and TEM images of LaFeO3, CeO2 and CeO2-LaFeO3 are shown in Figure 3.
The representative SEM and TEM images of LaFeO3 , CeO2 and CeO2 -LaFeO3 are shown in
The SEM image of LaFeO3 (Figure 3A) obtained by calcining the LaFeO3 precursor possesses a small
Figure 3. The SEM image of LaFeO 3 (Figure 3A) obtained
branch-shape structure which consists of many small nanorods. The TEM by calcining the LaFeO precursor
result3 also possesses
indicates that
a small branch-shape
the LaFeO structure which consists of many small nanorods. The TEM result also indicates
3 (Figure 3B) nanostructure was stacking by smaller LaFeO3 nanorods with an average
that the LaFeO
diameter of 324(Figure 3B) nanostructure
nm (calculated by using was stacking
Scherrer by smaller
equation). In theLaFeO nanorods
SEM 3image with3D),
(Figure an average
CeO2
diameter of 24 exhibit
nanoparticles nm (calculated
uniform size by distribution
using Scherrer equation).
and spherical In the SEM
morphology. Theimage (Figure
TEM image 3D), 3D)
(Figure CeO2
nanoparticles
indicated that exhibit uniform
the sample size distribution
is composed of tiny and spherical morphology.
nanocrystallites Thecalculated
(about 12 nm, TEM image (Figure
by using the3D)
indicated that the sample is composed of tiny nanocrystallites (about
Scherrer equation). The SEM image of CeO2-LaFeO3 (Figure 3E) displays an irregular porous12 nm, calculated by using
thestructure.
ScherrerThe equation).
morphologyThe SEMof CeO image
2-LaFeOof 3CeO -LaFeO3an
also2displays (Figure 3E)porous
irregular displays an irregular
structure porous
in the TEM
structure. The morphology
image (Figure 3F). of CeO2 -LaFeO3 also displays an irregular porous structure in the TEM
Brunauer-Emmett-Teller
image (Figure 3F). (BET) analysis was used to investigate the specific surface area of the
samples.
Brunauer-Emmett-Teller (BET) of
The specific surface areas CeO2, LaFeO
analysis was used3 and
toCeO 2-LaFeO3 the
investigate are specific
47.3, 24.7surface
and 12.7 m2·g
area ,
of−1the
respectively.
samples. The N2surface
The specific isotherm of CeO
areas 2-LaFeO
of CeO 3 shown in Figure 4 is close to Type IV (according to´1
2 , LaFeO3 and CeO2 -LaFeO3 are 47.3, 24.7 and 12.7 m ¨ g ,
2
International
respectively. The Union of Pure and
N2 isotherm Applied
of CeO Chemistry classification) with a hysteresis loop observed
2 -LaFeO3 shown in Figure 4 is close to Type IV (according to
in the range of 0.4–1.0 p/p 0, indicating the mesoporous structure of the CeO2-LaFeO3 composite.
International Union of Pure and Applied Chemistry classification) with a hysteresis loop observed in
the range of 0.4–1.0 p/p0 , indicating the mesoporous structure of the CeO2 -LaFeO3 composite.
Materials 2016, 9, 326 6 of 12
Materials 2016, 9, 326 6 of 12

Figure 4. N2 adsorption and desorption isotherms of LaFeO3, CeO2 and CeO2-LaFeO3 composite.
Figure 4. N2 adsorption and desorption isotherms of LaFeO3 , CeO2 and CeO2 -LaFeO3 composite.

The oxidation states of principal elements of LaFeO3 were analyzed by XPS. All the binding
The oxidation states of principal elements of LaFeO3 were analyzed by XPS. All the binding
energy values obtained in the XPS analysis were calibrated using C 1s (284.8 eV) as the reference.
energy values obtained in the XPS analysis were calibrated using C 1s (284.8 eV) as the reference.
Figure 5A−E display the XPS spectra of La 3d5/2, Fe 2p, Ce 3d and O 1s and C 1s core levels for the
Figure 5A–E display the XPS spectra of La 3d5/2 , Fe 2p, Ce 3d and O 1s and C 1s core levels for the
as-prepared CeO2, LaFeO3 and CeO2-LaFeO3. The peaks of La 3d5/2 and La 3d3/2 for LaFeO3 in Figure
as-prepared CeO2 , LaFeO3 and CeO2 -LaFeO3 . The peaks of La 3d5/2 and La 3d3/2 for LaFeO3 in
5A are situated at 833.9 and 837.5 eV and at 851.1 and 854.6 eV, while the peaks of La 3d5/2 and La
Figure 5A are situated at 833.9 and 837.5 eV and at 851.1 and 854.6 eV, while the peaks of La 3d5/2 and
3d3/2 for CeO2-LaFeO3 in Figure 5A are situated at 833.6 and 837.4 eV and at 850.42 and 854.5 eV.
La 3d3/2 for CeO2 -LaFeO3 in Figure 5A are situated at 833.6 and 837.4 eV and at 850.42 and 854.5 eV.
These results confirm the presence of La3+3+ions [34]. In Figure 5B, the peaks at 710.8 and 724.1 eV of
These results confirm the presence of La ions [34]. In Figure 5B, the peaks at 710.8 and 724.1 eV
LaFeO3 are attributed to the binding energies of Fe 2p3/2 and 2p1/2, while the peaks at 710.6 and 724.2
of LaFeO3 are attributed to the binding energies of Fe 2p3/2 and 2p1/2 , while the peaks at 710.6 and
eV of CeO2-LaFeO3 are attributed to the binding energies of Fe 2p3/2 and 2p1/2, respectively. No
724.2 eV of CeO2 -LaFeO3 are attributed to the binding energies of Fe 2p3/2 and 2p1/2 , respectively.
noticeable shoulder peaks are found in the Fe 2p XPS spectrum, indicating that Fe ions are in the Fe3+
No noticeable shoulder peaks are found in the Fe 2p XPS spectrum, indicating that Fe ions are in
oxidation state [35]. The Ce 3d transition peaks of CeO2 and CeO2-LaFeO3 composites are shown in
the Fe3+ oxidation state [35]. The Ce 3d transition peaks of 3+CeO2 and CeO2 -LaFeO3 composites are
Figure 5C. The v0, v’, u0, and u’ peaks are attributed to Ce , whereas v, v’’, v’’’, u, u’’, and u’’’ are
shown in Figure4+5C. The v4+0 , v’,3+u0 , and u’ peaks are attributed to Ce3+ , whereas v, v”, v”’, u, u”, and
attributed to Ce . The Ce /Ce atomic ratio has been obtained from the area of the peaks obtained
u”’ are attributed to Ce4+ . The Ce4+ /Ce3+ atomic ratio has been obtained from the area of the peaks
by the deconvolution procedure [36]. In this way, a Ce3+/(Ce4+ + Ce3+3+ ) ratio of 0.32 has been obtained on
obtained by the deconvolution procedure [36]. In this way, a Ce /(Ce4+ + Ce3+ ) ratio of 0.32 has
the CeO2 sample, while the amount of Ce3+ species increases on 3+ the CeO 2-LaFeO3 composite (Ce3+/(Ce4+ +
been obtained on the CeO2 sample, while the amount of Ce species increases on the CeO2 -LaFeO3
Ce3+) atomic ratio of 0.39). Especially the state of O 1s indicated that there are two sorts of oxygen on
composite (Ce3+ /(Ce4+ + Ce3+ ) atomic ratio of 0.39). Especially the state of O 1s indicated that there are
the surface, the lattice oxygen (OL) and the adsorbed oxygen (Oads). For O ions in LaFeO3, the broad
two sorts of oxygen on the surface, the lattice oxygen (OL ) and the adsorbed oxygen (Oads ). For O ions
and asymmetric O 1s XPS spectra correspond to two kinds of oxygen chemical states according to
in LaFeO3 , the broad and asymmetric O 1s XPS spectra correspond to two kinds of oxygen chemical
the binding energy range. The peak at approximately 529.0 eV is attributed to OL and the other broad
states according to the binding energy range. The peak at approximately 529.0 eV is attributed to
peak at around 531.6 eV is attributed to Oads, indicating that it is attributed to the contribution of
OL and the other broad peak at around 531.6 eV is attributed to Oads , indicating that it is attributed
La-O and Fe-O in LaFeO3 crystal lattice for the OL signal [34]. For O ions in CeO2, Figure 5D shows that
to the contribution of La-O and Fe-O in LaFeO3 crystal lattice for the OL signal [34]. For O ions in
the O 1s spectra for the sample contain one band located at 529.1 eV and a shoulder at the higher
CeO2 , Figure 5D shows that the O 1s spectra for the sample contain one band located at 529.1 eV
binding energy of 531.5 eV. The former is originated from lattice oxygen (Ce-O) and the latter can be
and a shoulder at the higher binding energy of 531.5 eV. The former is originated from lattice oxygen
attributed to the adsorbed oxygen [25]. As for CeO2-LaFeO3, the O 1s spectra (Figure 5D) also shows a
(Ce-O) and the latter can be attributed to the adsorbed oxygen [25]. As for CeO2 -LaFeO3 , the O 1s
major peak at the 529.3 eV and a broad shoulder peak around 531.5 eV, attributed to the lattice oxygen
spectra (Figure 5D) also shows a major peak at the 529.3 eV and a broad shoulder peak around 531.5 eV,
O2− (La-O, Fe-O and Ce-O) and adsorbed oxygen species. The C1s peaks are presented in Figure 5E.
attributed to the lattice oxygen O2´ (La-O, Fe-O and Ce-O) and adsorbed oxygen species. The C1s
The atomic concentration ratios were also obtained by XPS. The different atomic concentration
peaks are presented in Figure 5E.
ratios on the surface of as-prepared catalysts were calculated and are listed in Table 1. In addition,
the Fe/La ratio of LaFeO3 (1.2, see Table 1) and CeO2-LaFeO3 (1.35, see Table 1) are slightly higher
than theoretical value indicating that excess amount of iron appears on the surface of LaFeO3, which
Materials 2016, 9, 326 7 of 12

The atomic concentration ratios were also obtained by XPS. The different atomic concentration
ratios on the surface of as-prepared catalysts were calculated and are listed in Table 1. In addition, the
Fe/La ratio of LaFeO3 (1.2, see Table 1) and CeO2 -LaFeO3 (1.35, see Table 1) are slightly higher than
theoretical value indicating that excess amount of iron appears on the surface of LaFeO3 , which is
different from the results of Wei et al. [37]. The reason is not clear and needs to be examined further.
We suspect that such a result is likely related to the different preparation methods employed compared
to those of Wei et al.

A B C u''' u
u0 Ce 3d
La 3d3/2 Fe 2p1/2 Fe 2p5/2
LaFeO3 CeO2 u'
u'' v'''
La 3d5/2 v'v
LaFeO3
Intensity (a.u.)

v'' v0

Intensity (a.u.)
CeO2-LaFeO3 Intensity (a.u.)
CeO2-LaFeO3
CeO2-LaFeO3

870 860 850 840 830 740 735 730 725 720 715 710 705 920 910 900 890 880
Binding energy (eV) Binding energy (eV)
Binding energy (eV)
D O 1s E C1s
Intensity (a.u.)

CeO2
Intensity (a.u.)

CeO2
LaFeO3
LaFeO3

CeO2-LaFeO3
CeO2-LaFeO3
284.8 eV

538 536 534 532 530 528 526 294 292 290 288 286 284 282 280
Binding energy (eV)
Binding energy (eV)

Figure 5. XPS spectra of (A) La 3d; (B) Fe 2p; (C) Ce 3d; (D) O 1s for LaFeO3 , CeO2 and CeO2 -LaFeO3 ;
(E) C 1s.

Table 1. Surface elemental composition/at % of as-prepared catalysts obtained from XPS.

Samples Fe Ce La O C
CeO2 - 22.14 - 52.01 25.85
LaFeO3 17.01 - 14.19 51.6 17.2
CeO2 -LaFeO3 13.58 9.3 10.1 49.47 17.55

The adsorption and catalytic degradation of nitrosamine 4-(methylnitrosamino)-1

-(3-pyridyl)-1-butanone (NNK) were investigated to evaluate catalytic activity of CeO2 -LaFeO3 . Liquid
adsorption results are listed in Figure 6A. Compared with the Blank experiment without any catalyst,
the adsorption performance of the three catalysts followed the order of CeO2 -LaFeO3 (33.85%) > CeO2
(28.85%) > LaFeO3 (23.35%). The degradation of NNK using different catalysts is displayed in
Figure 6A. Compared to the blank experiment without any catalyst, the catalytic performance
of the three catalysts followed a sequence of CeO2 -LaFeO3 > LaFeO3 > CeO2 . The degradation
ratio of NNK is 76.78% for CeO2 -LaFeO3 , 58.09% for CeO2 and 64.12% for LaFeO3 . In summary,
CeO2 -LaFeO3 composite trapped more NNK (33.85 µg¨ g´1 ) than CeO2 (22.85 µg¨ g´1 ) and LaFeO3
(23.35 µg¨ g´1 ), despite the former having the smallest specific surface area among the three catalysts.
The catalytic activity per surface area of CeO2 -LaFeO3 , CeO2 and LaFeO3 to NNK were tested to be
6.05, 1.23, 2.60 µg¨ m´2 , respectively. MCM-22 could adsorb 54% nitrosamines in solution [38], and
SBA-15 could catalytically degrade 65% nitrosamines [39]. However, the specific surface of zeolites
usually displays 1´2 orders of magnitude higher than perovskite materials. The actual adsorption
ability of per m2 surface area of CeO2 -LaFeO3 composite is superior to zeolites. What is more, the
preparation processes for zeolites consume a large amount of strong acid or base, which is harmful to
Materials 2016, 9, 326 8 of 12

the environment. Additionally, the high cost of zeolites is a disadvantage for industry application.
Conversely, the CeO2 -LaFeO3 composite possesses the advantages of being environmentally friendly,
easy to synthesize, inexpensive to prepare, thermally stable and potentially easy to industrialize.
The resonance structure of NNK is shown in Figure 6B and the possible adsorption and
degradation mechanism
Materials 2016, 9, 326 is shown in Figure 6C. NNK possesses the N-N=O functional group, which 8 of 12
could be adsorbed on CeO2 -LaFeO3 surface through electrostatic interaction. The catalytic degradation
degradation
of NNK probably of NNK probably
starts from the starts from of
rupture thethe
rupture
N-N bondof theinN-N
the bond
N-N=O in the
groupN-N=O[39]. group
Under[39].
the
Under the same conditions, the CeO -LaFeO composite showed superior
same conditions, the CeO2 -LaFeO3 composite showed superior properties to the other two catalysts.
2 3 properties to the other two
catalysts.
This This mayfrom
may originate originate from the effect
the synergistic synergistic
of CeO effect of CeO2-LaFeO3 for degradation of NNK. In
2 -LaFeO3 for degradation of NNK. In the nominal
the nominal
composite CeO composite CeO2-LaFeO3 perovskite structure, some Ce3+ ions may substitute
3+
2 -LaFeO3 perovskite structure, some Ce ions may substitute the La ion in the A-site
3+ the La3+ ion
inthe
of the LaFeO
A-site 3ofperovskite
the LaFeOstructure.
3 perovskite structure.
From the XPSFrom the (the
result XPS Ce
result (the
3+ /(Ce 4+ Ce 3+
+ Ce /(Ce 4+ + Ce3+)ratio
3+ ) atomic atomicon
ratio on the CeO 2 -LaFeO 3 composite is higher than pure CeO 2), it
the CeO2 -LaFeO3 composite is higher than pure CeO2 ), it was confirmed that the Ce ion existswas confirmed that the
3+ Ce3+ ion

exists
in La1´xinCeLa 1−xCexFeO3 crystal phases. Because of the introduction 3+
x FeO3 crystal phases. Because of the introduction of the Ce
ofion,
thestronger
Ce3+ ion, stronger
interactions
interactions occur between Fe ions and the adsorbed O 2. Correspondingly, O2 is activated and may
occur between Fe ions and the adsorbed O2 . Correspondingly, O2 is activated and may lead to higher
lead to higher
oxidative reactivity oxidative
than pure reactivity
LaFeO3 [12],thanresulting
pure LaFeO 3 [12], resulting in higher activity for the
in higher activity for the CeO2 -LaFeO3 composite.
CeO 2-LaFeO3 composite. Furthermore, CeO2 has high oxygen storage capacity, high oxygen mobility
Furthermore, CeO2 has high oxygen storage capacity, high oxygen mobility and facile reducibility [16].
andsynergistic
The facile reducibility
effect of[16]. The synergistic
the LaFeO effect of the LaFeO3 perovskite structure and CeO2 redox
3 perovskite structure and CeO2 redox property play a crucial role
property play a crucial role in
in enhancing the degradation efficiency of NNK. enhancing the degradation
Consequently, efficiency of NNK. Consequently,
the performance for degradationthe of
performance for degradation of NNK
NNK followed the order of CeO -LaFeO > LaFeO > CeO . followed the order of CeO 2-LaFeO3 > LaFeO3 > CeO2.
2 3 3 2

Figure6.6. (A)
Figure (A)Adsorbed
Adsorbed and
anddegradation
degradation percentage
percentage of
of NNK
NNKby byCeO
CeO22,, LaFeO
LaFeO33 and
and CeO
CeO22-LaFeO
-LaFeO33;;
(B) The resonance structure of NNK; (C) The possible adsorption and catalytic rupture manner
(B) The resonance structure of NNK; (C) The possible adsorption and catalytic rupture manner of NNK of
NNK
on CeOon CeO2-LaFeO
2 -LaFeO 3. 3.

3.3. Experimental Section

Section

3.1.
3.1.Materials
Materials
4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone
4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK)(NNK) were purchased
were purchased from Toronto
from Research
Toronto
Chemical Inc.
Research Chemical (Toronto, ON, Canada).
Inc. (Toronto, ON, Canada).La(NO 3 )3 ¨ 6H
La(NO 2 O,2O,
3)3·6H Ce(NO 3 )33)¨ 36H
Ce(NO ·6H22O,
O, glucose, urea,
urea,
Fe(NO ) ¨ 9H O were purchased from Shanghai Chemical Reagent Company (Shanghai,
Fe(NO33)33·9H22O were purchased from Shanghai Chemical Reagent Company (Shanghai, China). All China).
All
thethe chemicals
chemicals were
were analytical
analytical pure
pure grade
grade andwere
and wereused
usedasasreceived
receivedwithout
withoutfurther
furtherpurification.
purification.
Deionized
Deionizedwater
waterwas
wasused
usedthroughout
throughoutthe
theexperiments.
experiments.

3.2.
3.2.Synthesis
Synthesis
Based
Based on
on our
our previous
previous experiments
experiments [40],
[40], aa typical
typical synthesis
synthesis method was taken
method was taken after
after minor
minor
changes: 0.5 M glucose was sealed in a Teflon-lined stainless steel autoclave with 100 mL
changes: 0.5 M glucose was sealed in a Teflon-lined stainless steel autoclave with 100 mL capacity capacity
and ˝ C for 6 h. After cooling down naturally, the precipitate was harvested by
andmaintained
maintained at
at 180
180 °C for 6 h. After cooling down naturally, the precipitate was harvested by
centrifugation ˝C
centrifugation and washed thoroughly
and washed thoroughly with
with deionized
deionized water
water and
and ethanol. After drying
ethanol. After drying atat 60
60 °C
overnight, carbonaceous spheres were obtained. The amounts of 2.18 g La(NO3)3·6H2O and 2.02 g
Fe(NO3)3·9H2O were dissolved in 20 mL water. After magnetic stirring for 10 min, 1.00 g
carbonaceous spheres were added into the above solution. The solution was subsequently treated
ultrasonically at 600 W for 45 min. The resulting solution was aged at room temperature overnight to
achieve adsorption-desorption equilibrium between carbonaceous spheres with Fe3+ and La3+ ions
Materials 2016, 9, 326 9 of 12

overnight, carbonaceous spheres were obtained. The amounts of 2.18 g La(NO3 )3 ¨ 6H2 O and 2.02 g
Fe(NO3 )3 ¨ 9H2 O were dissolved in 20 mL water. After magnetic stirring for 10 min, 1.00 g carbonaceous
spheres were added into the above solution. The solution was subsequently treated ultrasonically
Materials 2016, 9, 326 9 of 12
at 600 W for 45 min. The resulting solution was aged at room temperature overnight to achieve
adsorption-desorption 3+ 3+
LaFeO 3 precursor. Theequilibrium
LaFeO3 precursor betweenwas carbonaceous
calcined at spheres
700 °C withforFe2 hand andLathe ions
LaFeO and3 then
was
˝
centrifuged. After drying at 60 C overnight, the obtained precursor was denoted as the LaFeO3
obtained.
precursor. The LaFeO
Uniform-sized 3 precursor
CeCO 3OH@Cwas calcined atwere
nanospheres 700 ˝synthesized
C for 2 h andby thea LaFeO 3 was obtained.
hydrothermal method. In a
Uniform-sized
typical synthesis, 0.63 CeCO 3 OH@C
g Ce(NO 3)3·6H nanospheres were synthesized
2O, 5.07 g glucose and 0.86 gby ureaa hydrothermal
were dissolved method.
in 100 In mLa
typical synthesis, 0.63 g Ce(NO ) ¨ 6H O, 5.07 g glucose and 0.86 g
water with magnetic stirring. The solution was transferred into a 100 mL Teflon-lined stainless steel
3 3 2 urea were dissolved in 100 mL
water with magnetic stirring. The solution was transferred into a 100
autoclave and hydrothermally treated at 180 °C for 2 h. After cooling down naturally, the precipitate mL Teflon-lined stainless steel
autoclave
was harvestedand hydrothermally
by centrifugation treated
and washedat 180 ˝ Cthoroughly
for 2 h. After cooling
with deionizeddownwaternaturally, the precipitate
and ethanol. After
drying at 60 °C overnight, CeCO3OH@C was obtained. A certain amount of CeCO3OH@C After
was harvested by centrifugation and washed thoroughly with deionized water and ethanol. was
drying atin60 ˝ C overnight, CeCO OH@C was obtained. A certain amount of CeCO OH@C was
calcined a muffle furnace at 550 °C 3 for 2 h to obtain CeO2 nanospheres. 3
calcined ˝ C for 2 h to obtain CeO nanospheres.
In a in a muffle
typical furnace
process, 2.18 atg550La(NO 3)3·6H2O and 2.02 g 2Fe(NO3)3·9H2O were dissolved in 20 mL
In a typical process, 2.18 g
water with magnetic stirring. Subsequently, La(NO 3 )3 ¨ 6H1.00
2 O and 2.02 3gOH@C
g CeCO Fe(NOwas 3 )3 ¨ 9H 2 O were
added dissolved
into the above in 20 mL
solution
waterevenly
and with magnetic
dispersed stirring.
with Subsequently,
the assistance 1.00ofg CeCO
magnetic3 OH@C was added
stirring. The into the above
solution was solution
treated
and evenly dispersed with the assistance of magnetic stirring. The solution
ultrasonically at 600 W for 45 min. The resulting solution was aged at room temperature overnight to was treated ultrasonically
at 600 W
achieve for 45 min. The resulting
adsorption-desorption equilibriumsolution was aged
between CeCOat 3room
OH@C, temperature
Fe3+ and Laovernight
3+ ions. The tosolution
achieve
adsorption-desorption equilibrium between 3+ 3+
was centrifuged and washed thoroughly with CeCO 3 OH@C,
deionized waterFeandand La The
ethanol. ions.obtained
The solution was
precursor
centrifuged and washed thoroughly with deionized water and ethanol.
was dried in an oven at 60 °C overnight and denoted as the CeO2-LaFeO3 precursor. The precursor The obtained precursor was
driedcalcined
in an oven ˝
at 60°C Cfor overnight
was at 700 2 h to and obtain denoted as the 3CeO
CeO2-LaFeO 2 -LaFeO3The
composite. precursor.
formation Theprocess
precursor of
was 2-LaFeO
CeO calcined at 700 ˝ C is
3 composite forillustrated
2 h to obtain CeO2 -LaFeO
in Scheme 3 composite.
1. First, La3+ and Fe The formation
3+ are process
incorporated of
into
CeO -LaFeO composite is illustrated in Scheme 1. First, La 3+ and Fe3+ are incorporated into
CeCO 2 3OH@C3 hydrophilic shell since the surface of CeCO3OH@C possesses hydrophilic groups.
CeCO3 OH@C
Second, hydrophilic
after calcination, theshell since theshell
hydrophilic surface of CeCO3 OH@C
was eliminated and CeO possesses
2-LaFeO3hydrophilic groups.
composite formed.
Second, after calcination, the hydrophilic shell was eliminated and
After calcination at 700 °C for 2 h, the spherical structure collapsed and a porous nanostructure CeO 2 -LaFeO 3 composite formed.
After calcination at 700 ˝ C for 2 h, the spherical structure collapsed and a porous nanostructure formed.
formed.

Scheme 1. Synthetic route to the CeO2-LaFeO3 perovskite composite.

Scheme 1. Synthetic route to the CeO2 -LaFeO3 perovskite composite.

3.3.
3.3. Degradation
Degradation of
of 4-(Methylnitrosamino)-1-(3-Pyridyl)-1-Butanone
4-(Methylnitrosamino)-1-(3-Pyridyl)-1-Butanone (NNK)
(NNK) by
by CeO
CeO22-LaFeO
-LaFeO33
The
The catalytic
catalytic activity
activity for
for the
the degradation
degradation of of NNK
NNK by CeO2-LaFeO
by CeO 3 was performed as follows:
2 -LaFeO3 was performed as follows:
50 mg catalyst was dispersed ultrasonically in 5 mL of 1 μg·mL −11NNK/methanol solution. After that,
´
50 mg catalyst was dispersed ultrasonically in 5 mL of 1 µg¨ mL NNK/methanol solution. After that,
all
all of
of the
the solutions
solutions were
were evenly
evenly dispersed
dispersed on
on the
the same
same mass
mass quantitative
quantitative filter
filter papers
papers several
several times
times
and
and dried at 30 C. Quantitative filter papers were made into cigarette shapes and smoked by using aa
dried at 30 °C.
˝ Quantitative filter papers were made into cigarette shapes and smoked by using
smoking
smoking machine.
machine. TheThesmoke
smokeandand the
the particles
particles after
after ignition
ignition were
were thoroughly
thoroughly absorbed,
absorbed, extracted,
extracted,
purified, and then transferred to a 25 mL volumetric flask and diluted with
purified, and then transferred to a 25 mL volumetric flask and diluted with methanol to volume. methanol to volume.
Finally,
Finally, the diluted methanol solution was analyzed by Agilent 6460 Triple
the diluted methanol solution was analyzed by Agilent 6460 Triple Quad Liquid chromatography-Mass Quad Liquid
chromatography-Mass
Spectrum (LC/MS, Agilent Spectrum (LC/MS, Santa
Technologies, Agilent Technologies,
Clara, CA, USA).Santa LaFeO Clara, CA, USA). LaFeO3 and
3 and CeO2 were also tested.
CeO were also
As a2control tested. As5 mL
experiment, a control experiment,
of 1 µg¨ 5 mL of 1 μg·mL
mL´1 NNK/methanol
−1
solution NNK/methanol
without catalyst solution without
was also tested.
catalyst was also tested.
Liquid adsorption of NNK was performed as follows: 20 mg LaFeO3, CeO2 and CeO2-LaFeO3
were added into 10 mL of 0.2 μg·mL−1 NNK/methanol solution, respectively. The solutions were
treated ultrasonically for 1 h and centrifuged at 5000 rpm for 10 min. As a control, 10 mL of
0.2 μg·mL−1 NNK/methanol solution without catalyst was also tested. The residual quantity of NNK
in absorbed methanol was carried out using Agilent 6460 Triple Quad LC/MS. The mass ratio of
Materials 2016, 9, 326 10 of 12

Liquid adsorption of NNK was performed as follows: 20 mg LaFeO3 , CeO2 and CeO2 -LaFeO3
were added into 10 mL of 0.2 µg¨ mL´1 NNK/methanol solution, respectively. The solutions were
treated ultrasonically for 1 h and centrifuged at 5000 rpm for 10 min. As a control, 10 mL of 0.2 µg¨ mL´1
NNK/methanol solution without catalyst was also tested. The residual quantity of NNK in absorbed
methanol was carried out using Agilent 6460 Triple Quad LC/MS. The mass ratio of catalyst to NNK
remained the same (catalyst: NNK = 10 mg:1 µg) in the catalytic and adsorption experiments.

3.4. Characterization
X-ray powder diffraction of the as-prepared materials were characterized by X-ray diffraction
(XRD, Rigaku D/max-RA, Tokyo, Japan, graphite monochromatized Cu Kα radiation, λ = 1.5406 Å, at
36 kV). FT-IR spectra were recorded with a Nicolet MAGNA-IR 750 instrument (KBr disks, Nicolet
Instrument, Madison, WI, USA) in the 4000–400 cm´1 regions. Morphologies of samples were
examined by field-emission scanning electron microscopy (FE-SEM, Hitachi S4800, Hitachi, Hitachi,
Japan). Transmission electron microscopy (TEM) was obtained by a JEM-2100 transmission electron
microscope (JEOL, Tokyo, Japan). Thermo-gravimetric analysis and differential scanning calorimetry
(TG-DSC) data was recorded with a thermal analysis instrument (WCT-1D, BOIF, Beijing, China) under
an airflow atmosphere at the heating rate of 10 ˝ C¨ min´1 from room temperature to 800 ˝ C. Specific
surface areas and sorption isotherms of the samples were measured via a nitrogen sorption system
at 77 K on a Micromeritics ASAP 2020 analyzer (Norcross, Atlanta, GA, USA). The specific surface
area was calculated by the Brunauer-Emmett-Teller (BET) method. The X-ray photoelectron spectra
(XPS) were taken on an ESCALab MKII X-ray photoelectron spectrometer (Thermo VG Scientific, West
Sussex, UK) to obtain further evidence for the purity and composition of the as-prepared products,
using Al Ka radiation as the exciting source.

4. Conclusions
In summary, LaFeO3 and CeO2 -LaFeO3 porous structured perovskite mixed oxides
were successfully synthesized by a novel surface-ion adsorption method using carbonaceous
microspheres and CeCO3 OH@C as templates. The surface-ion adsorption method could be a
promising method to synthesize various perovskite composite materials. The performance for
degradation of 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK) followed a sequence of
CeO2 -LaFeO3 > LaFeO3 > CeO2 . The CeO2 -LaFeO3 composite exhibited excellent catalytic activity
for NNK degradation, making it a promising candidate for environmentally friendly applications.
Based on these results, other catalysts with structures similar to CeO2 -LaFeO3 may also be used for
the degradation of tobacco-specific nitrosamines (TSNAs) such as NNK in tobacco. Furthermore, the
investigations of other Ce-doped perovskite materials, such as CeO2 -LaCoO3 and CeO2 -LaNiO3 for
the degradation of NNK, are in progress.

Acknowledgments: This work was supported by the Key Laboratory of Cigarette Smoke Research of
China National Tobacco Corporation (CF-ZJ2) and the National Natural Science Foundation of China (Grant
Nos. 21471001, 21275006 and 21575001), Key Project of Anhui Provincial Education Department (KJ2013A029) and
Natural Science Foundation of Anhui Province (1508085MB32).
Author Contributions: Kaixuan Wang, Jingshuai Chen, Jiming Song, Changjie Mao, Shengyi Zhang,
Saijing Zheng, Baizhan Liu performed the preparation of the samples, the characterizations and the catalytic
studies. Helin Niu and Changle Chen conceived and supervised the project. Helin Niu and Changle Chen wrote
the manuscript with contributions from all authors.
Conflicts of Interest: The authors declare no conflict of interest.

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