Received: 26 July 2018

| Revised: 14 October 2018

| Accepted: 10 November 2018

DOI: 10.1111/jace.16226

ORIGINAL ARTICLE

Synthesis, optical, and magnetic properties of six‐layered

Aurivillius bismuth ferrititanate

Yanlin Huang1 | Longqing Mi1 | Jie Qin1 | Shala Bi2 | Hyo Jin Seo2

1
College of Chemistry, Chemical
Engineering and Materials Science,
Soochow University, Suzhou, China
2
Department of Physics and
Interdisciplinary Program of Biomedical,
Mechanical & Electrical Engineering,
Pukyong National University, Busan,
Korea
Correspondence
Hyo Jin Seo, Department of Physics and
Interdisciplinary Program of Biomedical,
Mechanical & Electrical Engineering,
Pukyong National University, Busan,
Korea.
Email: hjseo@pknu.ac.kr
Funding information
Ministry of Science, ICT & Future
Planning, Grant/Award Number: NRF-
2013RA1A2009154
Abstract
This work reports on the preparation, structure, photochemical, and magnetic
properties of six‐layered Aurivillius bismuth ferrititanates, that is, Bi7Ti3Fe3O21,
Bi7(Ti2Nb)Fe3O21+δ, and Bi7(Ti2Mg)Fe3O21−δ nanoparticles. The samples were
prepared through the modified citrate complexation and precursor film process.
The XRD Rietveld refinements were conducted to study the phase formations and
crystal structure. The morphological and chemical component characteristics were
investigated using SEM, TEM, and EDX analyses. Bi7Ti3Fe3O21, Bi7(Ti2Nb)
Fe3O21+δ, and Bi7(Ti2Mg)Fe3O21−δ nanoparticles present an indirect allowed tran-
sitions with band energies of 2.04, 2.03, and 2.02 eV, respectively. The hybri-
dized (O2p+Fet2g+Bi6s) formed the valence band (VB) and electronic
components of (Ti–3d+Fe–eg) formed the conduction band (CB) of this six‐
layered Aurivillius bismuth ferrititanate. The three samples showed efficient pho-
tocatalytic degradation of Rhodamine B (RhB) dyes with the excitation wave-
length λ > 420 nm. The optical absorption, photodegradation, and magnetic
abilities were improved through microstructural modification on “B” site via par-
tial substitution of Mg2+ and Nb5+ for Ti4+. The photocatalytic results were dis-
cussed based on the layer structure and multivalent Fe ions. Fe3+/2+ in the
perovskite slabs (Bi5Fe3Ti3O19)2− could act as the catalytic mediators in the pho-
tocatalysis process. As a photocatalyst, Aurivillius Bi7(Ti2Mg)Fe3O21−δ nanoparti-
cle is advantageous due to its photocatalytic and magnetically recoverable
abilities.

KEYWORDS
Aurivillius phases, band structure, layered perovskites, nanoparticles, photocatalysis, semiconductors

1 | INTRODUCTION electrons of Bi3+ ere are often found to possess hybridized

It is well‐known that Bi3+ ion has a peculiar electronic
configuration of [Xe]4f145d106s2 with a 6s2 lone pair. Bi
oxides usually have strong polarization because of the
repulsive force from the peculiar lone pairs. Consequently,
the components have important electrical, magnetic, optical,
and photochemical applications.1–5 Bi‐based compounds
have drawn a lot of attention because for their potential
application as novel photocatalysts, in which the lone pair
band structures.5–9 Especially, Aurivillius compounds have
been widely reported because of its special layer perovskite
atom arrangements and favourable optical band struc-
ture.10–14 Also, many kinds of Aurivillius photocatalysts
have been intensively investigated in water splitting and
photocatalytic degradation of organic dyes.15–22
The general formula for Aurivillius compounds is
(Bi2O2)2+(An−1BnO3n+1)2−, where n is the number of per-
ovskite slabs, A ions (+1, +2, or +3 in valence) occupy in

J Am Ceram Soc. 2019;102:3555–3566. wileyonlinelibrary.com/journal/jace © 2018 The American Ceramic Society | 3555
3556
| HUANG
the cuboctahedral coordination, and B is a transition metal
ion in an octahedron site. The Aurivillius layers (Bi2O2)2+
and distorted perovskite slabs produce great polarization in
the structure.23 The most well‐known Aurivillius oxides are
BiFeO3 and Bi4Ti3O12.24 The combination between BiFeO3
and Bi4Ti3O12 results in different Aurivillius phases, which
is denoted by Bin+1Fen−3Ti3O3n+3 (n ≥ 4).22 This is a
typical sandwich structure constructed by
2−
(Bin−1Fen−3Ti3O3n+1) perovskite slabs and fluorite‐like
(Bi2O2)2+ layers in [001] direction.25
In this work, we reported the preparation and optical
properties of a higher order member (n = 6) of the Aurivil-
lius oxides, Bi7Ti3Fe3O21 [3(BiFeO3) + Bi4Ti3O12],
Bi7(Ti2Nb)Fe3O21+δ, and Bi7(Ti2Mg)Fe3O21−δ. The advan-
taged photocatlysts could be expected because its spe-
cialties. The main research motivations are as follows.
First, it could have a narrow band gap because the
hybridization of O2p with Bi6s can push up the valence
band edge, and the band energy could be reduced due to
the contribution of electronic transitions from Fe3+ ions.
The hybridized Bi6s–O2p has highly dispersed nature,
which can promote very high mobility of light‐created
charges.26 This is very advantageous for photocatalysis.
Second, this Aurivillius oxide containing Fe3+ ions have
magnetic properties at room temperature. This is highly
superior to the conventional photocatalysts because it can
be recovered magnetically after photocatalytic reactions.
Third, it is a common fact that both optical and magnetic
abilities of Aurivillius oxides have a strong dependence on
the structural distortion in the perovskite slab. Based on
this, Bi7(Ti2Nb)Fe3O21+δ (Nb–BTF) and Bi7(Ti2Mg)
Fe3O21−δ (Mg–BTF) were prepared and were compared
with the pure Bi7Ti3Fe3O21 (BTF). The structural modifica-
tion is expected to have influences on the band gap, recom-
bination of photogenerated charges, and magnetic
properties.
Three kinds of nanoparticles, that is Bi7Ti3Fe3O21
(BTF), Bi7(Ti2Nb)Fe3O21+δ (Nb–BTF), and Bi7(Ti2Mg)
Fe3O21−δ (Mg–BTF), were prepared through a modified
sol‐gel citrate complexation and precursor film process.
The phase formation together with the morphological char-
acteristics were studied. The optical absorption and band
gap structure were investigated. The photocatalytic and
magnetic abilities of the nanoparticles were discussed based
on the microstructural and defects characteristics.
2 | EXPERIMENTS
Bi7Ti3Fe3O21 (BTF), Bi7(Ti2Nb)Fe3O21+δ (Nb–BTF), and
Bi7(Ti2Mg)Fe3O21−δ (Mg–BTF) nanoparticles were pre-
pared through a modified sol‐gel citrate complexation and
precursor film process. The raw chemicals were Bi
ET AL.
(NO3)3·5H2O, Fe(NO3)3·9H2O, 4(MgCO3)·Mg(OH)2·5H2O,
Nb2O5, and Ti(OC4H9)4. First, the precursor solutions were
prepared. The chemical reagents (except for Nb2O5) were
completely dissolved in acetic acid solutions together with
methanol. Nb2O5 in stoichiometric components was put in
Teflon‐lined autoclaves filled with HF solutions, which
was heated treated at 180°C for 4 hours. The chelating
agent (citric acid) was added into each solution in double
molar amount of Bi3+, Fe3+, Nb5+, Mg2+, and Ti4+ ions.
The pH was adjusted to seven by adding ammonium
hydroxide to the precursor solutions. Figure 1 shows the
typical preparation process for Bi7Ti3Fe3O21 nanoparticles.
Second, the precursor sols were prepared. PVA aqueous
solution was used to adjust its viscosity. Third, the precur-
sor films were prepared. The sticky sols obtained in the
second step were spin‐coated on glass plate substrates.
After natural air drying for 2 hours, the precursor films
could be prepared. Finally, the dried precursor films could
be torn off from the glass substrates. The final nanoparti-
cles can be obtained after sintering at 850°C in air atmo-
sphere to decompose the organic components.
The XRD pattern of the nanoparticles was obtained on
a Rigaku D/Max‐2000 (Rigaku Corporation, Tokyo, Japan)
diffractometer (40 kV, 30 mA) with CuKα radiation. The
morphological and surface characteristics of as‐prepared
samples were investigated through TEM and SEM mea-
surements. EDX measurements were applied to detect the
chemical elements of the nanoparticles. The optical absorp-
tion was tested on a spectrophotometer (A Cary‐5000) in
the UV‐Vis wavelength region.
The photocatalysis experiments were conducted on Rho-
damine B (RhB) dye (300 mL, 10 mg/L). The incident
light was produced from an Xe‐lamp with 500 W power.
Air flow was pumped into a cylindrical reactor with a flow
rate of 500 mL/min. In the photocatalysis tests, the weight
of the sample was 0.05 g in 300 mL of RhB solutions. The
desorption/adsorption equilibrium was determined by plac-
ing the system in the dark place for 1 hour before photo-
catalytic tests. The photocatalytic effects were evaluated by
checking the optical absorption of RhB solution after a
time interval. The photodegradation was evaluated on the
base of the optical absorption on photocatalytic time.
3 | RESULTS
3.1 | Phase formation and structure
The phase formation and the experimental structures were
verified via the XRD patterns and the Rietveld refinements
as shown in Figure 2A‐C. The fitting qualities were kept
according to the good parameters of R‐factors (Rp, Rwp)
and fit (χ2). The structure pattern was well indexed to
PDF2 card No. 54‐1044 (Bi7Fe3Ti3O21) referred in the
HUANG ET AL.
F I G U R E 1 Schematic diagram of a
modified citrate complexation and precursor
film used for preparing Bi7Ti3Fe3O21
nanoparticles [Color figure can be viewed
at wileyonlinelibrary.com]
International Center for Diffraction Data database. No
impurity phase was detected. The pattern is completely
consistent to the six‐layered Aurivillius with orthorhombic
space group of Fm2m (No: 42).
The refinement gave an acceptable fit of the observed
pattern. The refined structure parameters are shown in
Table 1. The refined atomic position parameters and bond
lengths are given in Tables S1 and S2, respectively. The
substitution of Nb5+ and Mg2+ for Ti ions resulted in
the expansion of the unit cell as shown in Figure 2D.
The octahedral have great distortion in the perovskite
slabs. The favorable photochemical and photocatalysis
properties of the samples could be expected due to the
fact that the lattice distortion greatly influences the elec-
trical and optical properties of the layered Aurivillius
compounds.27
The experimental structures of Bi7Ti3Fe3O21 were
drawn according to the coordinate parameters as shown
in Table S1. The sandwich‐like structure viewed on the
[010] direction is shown in Figure 3A, which is built by
fluorite‐type (Bi2O2)2+ layers and six‐layered perovskite
slabs in an alternating arrangement. There are three kinds
of Bi3+ ions in the lattices. Bi(2,3) cations in perovskite
slabs occupy A‐site with the distorted eightfold coordina-
tion induced by the steric effects of 6s2 lone electron
| 3557
pairs. The six‐layered perovskite slabs are constructed by
the corner shared (Fe/Ti)O6 octahedra (Figure 3B). The
typical chains connected by [Bi2O2]2+ units are shown in
Figure 3C. The distorted square pyramid is formed by
(Bi(1)2O2)2+ unit. There is tremendous polarization in (Bi
(1)2O2)2+ layers due to lone electron pairs. The light‐cre-
ated electrons and holes could be efficiently separated
due to the inner electric field in the structure. The
recombination between light‐created electrons and holes
could be greatly prohibited by the (Bi2O2)2+ layer; how-
ever, the electrons and holes can move along (Bi2O2)2+
layers.28,29
3.2 | Morphological characteristics
All the three samples have similar morphological character-
istics. Figure 4A‐C shows the typical SEM graphs of
Bi7Ti2MgFe3O21 nanoparticles. The honeycomb‐like con-
struct was built by the particles aggregate (Figure 4A,B).
The uniform ball‐like crystals with a smooth surface in
high magnification (Figure 4C) could be observed. The size
was estimated as 50‐100 nm. Figure 4D displays the EDX
results. The elements Bi, Ti, Fe, Mg, and O were detected
in the nanoparticles. The atomic ratio is consistent with the
stoichiometric value in formula.
3558
| HUANG ET AL.

F I G U R E 2 Rietveld structure refinements of Bi7Ti3Fe3O21 (A), Bi7(Ti2Nb)Fe3O21+δ (B), and Bi7(Ti2Mg)Fe3O21−δ (C), and unit cell
volumes of the samples (D) [Color figure can be viewed at wileyonlinelibrary.com]

T A B L E 1 The structure refinement and the parameters of Bi7Ti3Fe3O21

Parameters Bi7Ti3Fe3O21 Bi7(Ti2Nb)Fe3O21+δ Bi7(Ti2Mg)Fe3O21−δ
Radiation CuKa CuKa CuKa
2θ (degree) 5‐110° 5‐110° 5‐110°
Symmetry Orthorhombic Orthorhombic Orthorhombic
Space group Fm2m (42) Fm2m (42) Fm2m (42)
a/Å 5.4511 (7) 5.4675 (7) 5.5126 (7)
b/Å 5.4129 (8) 5.5187 (8) 5.5456 (8)
c/Å 57.4161 (10) 57.7811 (7) 57.8571 (7)
α/° 90 90 90
Z 90 90 90
Rp 0.135 0.165 0.145
Rwp 0.0965 0.1201 0.1321
χ 2
7.15 7.42 8.32
V/Å3 1694.134 (50) 1743.4575 (50) 1768.732 (50)
HUANG ET AL.
The microstructural properties and morphologies of the
samples were detected via TEM tests. The plate‐like parti-
cles as shown in Figure 5A are in agreement with the
results in SEM. The sample has a size of around 100 nm.
Figure 5B displays the HRTEM results indicating a single‐
phased Bi7Ti2MgFe3O21. The space distance among the lat-
tice fringe was measured to be d = 0.275 nm, which corre-
sponded to (020) crystallographic plane. The SAED pattern
of the as‐grown Bi7Ti2MgFe3O21 is shown in Figure 5C,
F I G U R E 3 Unit cell (A), partial connection of perovskite slab
(B), and [Bi2O2]2+ (C) of Bi7Ti3Fe3O21 [Color figure can be viewed
at wileyonlinelibrary.com]
(A)
(C)
F I G U R E 4 SEM graphs (A, B, and C)
and EDX spectrum (D) of Bi7Ti2MgFe3O21
nanoparticles [Color figure can be viewed
at wileyonlinelibrary.com]
| 3559
which indicates the single crystal nature of the nanoparti-
cles. Figure 5D shows the N2desorption/adsorption curves
of the sample. The specific surface area of Bi7Ti2Mg-
Fe3O21 was 57.5 m2/g based on the Brunauer‐Emmett‐
Teller (BET) measurement. The pore size has a narrow dis-
tribution of about 6 nm. The big surface area is very bene-
ficial for the photocatalytic effects.
3.3 | Optical absorption and band structure
The optical absorption and the band structures of the semi-
conductors were investigated (Figure 6A). The difference is
a small red-shift of the absorption from Bi7Ti3Fe3O21 (Fig-
ure 6A) to Bi7(Ti2Nb)Fe3O21+δ (Figure 6B) and to
Bi7(Ti2Mg)Fe3O21−δ (Figure 6C). This indicates the band
gap narrow with the cation substitution in perovskite B‐
site.
Usually, a band energy (Eg) is estimated using the
Wood‐Tauc formula of αhν / ðhν  Eg Þk as displayed in
Figure 6A‐C, where h is Planck constant, α is absorbance,
ν is the light frequency, and k is related to the electronic
transition natures (k = 1/2, 2 for direct allowed, indirect
allowed, respectively). The optimum linear relations were
obtained for k = 2 indicating an indirect‐allowed type tran-
sition. The Eg value of Bi7Ti3Fe3O21, Bi7(Ti2Nb)Fe3O21+δ,
and Bi7(Ti2Mg)Fe3O21−δ were 2.04, 2.03 and 2.02 eV.
The absorption has a cut‐off edge created by the optical
transitions from Fe3+ ions. The band electronic structure of
the bismuth titanate ferric oxides have been well confirmed
by the experiments and the theoretical calculation, that is,
CB is formed by electronic components from Fe–eg and
(B)
(D)
3560
| HUANG
(A) (B)
(C) (D)
Ti3d, while the hybridized orbits of (Fe–t2g+O2p+Bi6s)
are formed from the VB band.22,30
The band structures are shown in Figure 6D. The
greatly dispersed CB and VB in this semiconductor are
critical for the immigration of photo‐induced electrons
and holes.28 Accordingly, the recombination between an
electron and a hole is greatly delayed. Usually, CB and
VB positions of a photocatalyst are theoretically deter-
mined by:
EVB ¼ X  E e þ 0:5Eg (1)
ECB ¼ X  E e þ 0:5Eg (2)
Here Ee is the free electron energy on hydrogen scale
(∼4.5 eV vs SHE) and X is the absolute electronegativity.
Using the equations, the energy levels for VB and CB of
three samples were determined (Figure 6D). The CB and
VB positions of the samples show a small shift due to the
changes in the cation on Ti sites.
3.4 | Photocatalytic activity
Figure 7A shows the photodegradation efficiencies of the
samples with the excitation wavelength of above 420 nm.
There are no obvious changes in the blank experiment.
Compared with the pure sample, the Nb‐ and Mg‐modified
samples promoted the degradation rate.
The kinetic characteristics of the photocatalytic reaction
is investigated using the pseudo‐first‐order rate equation of
ln(C0/Ct) = kt, where C0 is the original concentration, k is
ET AL.
F I G U R E 5 TEM images (A), HRTEM
result (B), selected area electron diffraction
(SAED) diffraction pattern (C), and N2
desorption/adsorption isotherms and the
distribution of pore size (D) of
Bi7Ti2MgFe3O21 nanoparticles [Color figure
can be viewed at wileyonlinelibrary.com]
a kinetic constant, and Ct is the concentration level after
photocatalysis. Figure 7B displays the relationship between
the reaction time and ln(C0/Ct). The pseudo‐first‐order type
for the photocatalytic reaction can be suggested according
to the linear as shown in Figure 7B. The kinetic constant
for the pure Bi7Ti3Fe3O21 is 9.85 × 10−3/min, while for
Bi7(Ti2Nb)Fe3O21+δ and Bi7(Ti2Mg)Fe3O21−δ, it is
1.16 × 10−2/min and 1.985 × 10−2/min, respectively. This
can be concluded that Mg‐modified Bi7Ti3Fe3O21 improved
the photocatalytic activities.
The reusability of photocatalyst was examined by recy-
cling photodegradation. The recycling tests for the photo-
catalytic degradation were carried out to investigate the
stability of the photocatalysts in Figure 7C. The photode-
gradation is relatively stable, and the stability of the sam-
ples before and after photocatalysis was tested using XRD
patterns. For example, the XRD patterns of Bi7(Ti2Mg)
Fe3O21−δ were measured (Figure 7D). The crystal forma-
tion before and after the experiments shows the same for-
mation. There are no other chemical changes
accompanying photocatalysis.
The real reactive species could be detected by adding
the corresponding scavengers into the photocatalytic reac-
tion system based on the changes in photocatalysis
effects. In this experiment, the scavengers ammonium
oxalate (AO), isopropanol (IPA), and benzoquinone (BQ)
were used for the removal of hole (h+), •OH, and radical
(•O2−), respectively.31 The photocatalysis effects of RhB
dye by Bi7(Ti2Mg)Fe3O21−δ with three scavengers are
shown in Figure 8. The photodegradation of RhB dye
HUANG ET AL. | 3561

F I G U R E 6 Optical absorption and band energy estimations for Bi7Ti3Fe3O21 (A), Bi7(Ti2Nb)Fe3O21+δ (B), and Bi7(Ti2Mg)Fe3O21−δ (C),
and valence band (VB) and conduction band (CB) energy levels of the three samples (D). Inset shows digital photo of the powders [Color figure
can be viewed at wileyonlinelibrary.com]

solutions is 31% without scavengers. The photocatalytic
efficiency decreases as the scavenger IPA was added into
the solutions, indicating the presence of radical (•HO), a
dominant active species, in Bi7(Ti2Mg)Fe3O21−δ‐RhB
solutions.
300 K. For the Mg‐substituted sample, the data show that
the magnetic behavior exhibit hysteresis loop with the
enhanced coercivity Hc = 121 Oe and saturation magneti-
zation Ms = 0.31 emu/g.

3.5 | Magnetic characteristics 4 | DISCUSSIONS

Figure 9 shows the magnetic hysteresis loop of three sam-
ples at 300 K from −50 to 50 kOe. The pure Bi7Ti3Fe3O21
exhibits a typical soft magnetic material with a thin hys-
teresis behavior as expected. Bi7Ti3Fe3O21 crystallizes in
Aurivillius with the orthorhombic perovskite‐type structure,
which contains the alternately arranged FeO6 octahedral
layers, which built the two‐dimensional magnetic structure.
The small saturation magnetization values (Ms) of Bi7Ti3-
Fe3O21 and Bi7(Ti2Nb)Fe3O21+δ were 0.045 emu/g at
The multivalence state of Fe ions in the lattices plays an
important role in the photocatalytic redox reactions. First, it
has been confirmed that the cations in perovskites slabs of
Aurivillius oxides, especially Fe (Fe3+/Fe2+), are usually
present in multivalent nature.32 The dominant reason is that
the cations in “B” site perovskite slabs create strong
hybridization resulting in multivalent states. For example,
the “B” sites in Bi5Ti3FeO15 were half occupied by
heterovalent Ti4+ and Fe3+ ions.19–21 Second, it has been
3562
| HUANG ET AL.

F I G U R E 7 A, Photocatalytic degradation of RhB dye by three samples; B, kinetics characteristics; C, the repeated effects; D, XRD before
and after photocatalysis [Color figure can be viewed at wileyonlinelibrary.com]

reported that the weak ferromagnetism in Aurivillius com-

ponents is usually induced by the Fe2+–O–Fe3+ clusters in
the lattices.33
The observed magnetic behavior observed in Figure 9
could follow this rule. The bond valence sum (Vi) calcula-
tions can be applied to study the heterovalent state. Vi is
the oxidation number of cation i coordinated by oxygen j,
which is determined according to the equation34:

Vi ¼ ∑j Vij (3)

 
Rij  dij
Vij ¼ exp (4)
b

where Rij is the bond‐valence parameter and dij is the bond

F I G U R E 8 Photocatalytic effects of Bi7(Ti2Mg)Fe3O21−δ under a
distance between atoms j and i. The two parameters are
series of scavengers with light illumination time of 60 min
expressed in Å. The value of constant b is 0.37. The
HUANG ET AL. | 3563

(A) 2p1/2 with a satellite peak. The asymmetry profiles were

given in two oxidation states of Fe3+/2+ with doublet peak
in the decomposition on referring to reports in the litera-
tures.36–38 In the same time, the multivalent characteristics
agree with the bond calculations. Fe2+/Fe3+ charge fluctua-
tion is a common complex in Aurivillius phases.32
The mixed valances of Fe3+/Fe2+ certainly need the
necessary charge compensation via O components. Fig-
ure 10B shows O‐1s XPS curves, which show a broad
curve with obvious asymmetry profile. The strong peak at
532.12 eV is certainly assigned to the characteristic signal
lattices of O. The sub‐bands at the shoulder were assigned
to the defects of O components such as oxygen vacancies
and adsorbed oxygen in the lattices.
As shown in Figure 6D, the band energies, CB, and VB
(B) positions are similar for three samples; however, the photo-
catalytic effects are different. Mg‐modified Bi7Ti3Fe3O21
showed the best photocatalytic activities. The differences in
photocatalytic activities could be also understood based on
the induced defects in the lattices. The big mismatch
between the valences of Mg2+ and Ti4+ ions could induce
rich oxygen vacancy defects in the lattices. In Bi7Ti3-
Fe3O21, substitution of Mg2+ with Ti4+ sites results in a
negative defect (MgTi)″. Generally, a charge compensation
is needed in a suggested mechanism: the defect site in
combination with an oxygen vacancy defect of ½VO2 ¨.
This phenomenon forms a dipole complex (MgTi)″‐ ½VO2 ¨
to maintain the charge balance, possibly resulting in a con-
figuration similar to Fe3+–□–Fe3+ in lattices (□ denotes
the oxygen vacancy). Similar results have been widely con-
firmed in magnetoelectric or Fe‐doped ferroelectric

F I G U R E 9 XPS results for Bi4f (A) and O‐1s (B) in Bi7(Ti2Mg)

Fe3O21-δ [Color figure can be viewed at wileyonlinelibrary.com]

following empirical formulae is used in the calculation33:

 
l0  lij
Vi ¼ ∑j Sij ¼ ∑j exp (5)
0:37
where Sij is bond valence and lij is interatomic distance.

The valence parameter l0 is 1.759  A for Fe3+ ion.35 The
bond valences of Fe(1), Fe(2), and Fe(3) in Bi7(Ti2Mg)
Fe3O21−δ are 2.911, 2.926, and 2.932, respectively. This
verifies the fact that the valence sums of Fe ions in this
Aurivillius oxide is lower than three. Therefore, it could be
suggested the mixed valence of Fe2+/Fe3+ in Bi7(Ti2Mg)
Fe3O21−δ nanoparticles.
The multivalence for the ions could be verified via the
XPS measurements. Three samples have the similar XPS F I G U R E 1 0 Magnetization‐magnetic field (M–H) hysteresis loops
profile as shown the typical result for Bi7(Ti2Mg)Fe3O21−δ of Bi7Ti3Fe3O21, Bi7(Ti2Nb)Fe3O21+δ, and Bi7(Ti2Mg)Fe3O21-δ at 300
nanoparticles. Figure 10A shows the XPS spectrum for Fe‐ K. Inset showing the enlarged curves of the M–H curves [Color figure
can be viewed at wileyonlinelibrary.com]
2p, which is expressed in two bands for Fe‐2p3/2 and Fe‐
3564
| HUANG
F I G U R E 1 1 Photocatalytic mediators of multivalent Fe ions on
photocatalysis
titanates.39 The intrinsic defects on the surface of a semi-
conductor could be reduced by oxygen vacancies. The sug-
gested dipole complexes of [(MgTi)″→VO••] can result in
high momentary polarizing fields which could accelerate
the separation between the photo‐induced hole‐electron and
the carrier transport,40 resulting in the fast photocatalytic
process.
The multivalent characteristics of Fe3+/2+ benefits the
catalytic reactions in a compound because they can act as
mediators in redox reactions. Fe3+/Fe2+ redox couples
enhance the efficiency of redox cycle and reduce catalytic
energy by prompting oxygen and electron transfer between
the bulk and the surface.
Figure 11 shows the mediator role of multivalent Fe3+/
2+
Fe ions on photocatalysis. The hybridized components
from Fe3+ ions contribute to the narrowed VB and CB
bands. This results in the enhanced optical absorption.
Moreover, Fe3+ ions could act as traps delaying the recom-
bination for electrons and to holes.41 In this way, Fe2+ ions
can be oxidized to Fe3+ via releasing an electron to
adsorbed‐O2, while Fe3+ ions could trap a hole because of
the induced energy level for Fe4+/Fe3+ above VB band. In
this way, the holes trapped on Fe4+ could immigrate to the
adsorbed hydroxyl species producing hydroxyl radical. The
reactive oxygen species, such as superoxide radicals and
hydroxyl radicals, have strong oxidative ability and take
crucial role in the photodegradation reactions.42–44 The
induced species improve the photocatalytic reactions for
dye degradation.
As shown in Figure 9, Mg2+‐doped sample shows a sig-
nificantly improved magnetization. Mg2+‐doping with Ti4+
ion can result in internal strain in the lattices of Aurivillius,
which can produce octahedral tilting and accordingly bring
in structural distortions in the lattices. The [FeO6]
ET AL.
octahedral with tilted orientation usually can induce the
multiferroic natures.45 Consequently, the ferromagnetism
can be used to magnetically recycle the photocatalysts after
its degradation in the dye solutions.
5 | CONCLUSIONS
Six‐layered Aurivillius oxides of Bi7Ti3Fe3O21, Bi7(Ti2Nb)
Fe3O21+δ, and Bi7(Ti2Mg)Fe3O21−δ have been synthesized
using a modified sol‐gel citrate complexation and precursor
film process. The nanoparticles have ball‐like crystals with
the size about 100 nm. Bi7Ti3Fe3O21, Bi7(Ti2Nb)Fe3O21+δ,
and Bi7(Ti2Mg)Fe3O21−δ nanoparticles have typically indi-
rect allowed transitions with band energy of 2.04, 2.03,
and 2.02 eV, respectively. The hybridized (O2p+Fet2g+
Bi6s) formed the valence band (VB) and electronic compo-
nents from (Ti–3d+Fe–eg) formed the conduction band
(CB) of this layered Aurivillius bismuth ferrititanates. The
Aurivillius oxides demonstrated an efficient degradation of
RhB dye with the excitation wavelength of λ > 420 nm.
The optical absorption, photocatalytic, and magnetic abili-
ties were improved through microstructural modification on
“B”‐site via partial substitution of Mg2+ and Nb5+ for
Ti4+. The photocatalytic results were discussed based on
the structural layers and multivalent Fe ions. The multiva-
lent Fe3+/2+ in the perovskite (Bi5Fe3Ti3O19)2− slabs could
act as the catalytic mediators in the photocatalysis process.
As a photocatalyst, Aurivillius Bi7(Ti2Mg)Fe3O21−δ
nanoparticle is advantageous due to its photocatalytic and
magnetically recoverable abilities.
ACKNOWLEDGMENTS
This work was supported by Basic Science Research Pro-
gram through the National Research Foundation of Korea
(NRF) funded by the Ministry of Science, ICT & Future
Planning (NRF‐2013RA1A2009154).
ORCID
Yanlin Huang https://orcid.org/0000-0002-7450-6050
Hyo Jin Seo https://orcid.org/0000-0002-0490-8484
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SUPPORTING INFORMATION
Additional supporting information may be found online in
the Supporting Information section at the end of the article.
How to cite this article: Huang Y, Mi L, Qin J, Bi
S, Seo HJ. Synthesis, optical, and magnetic
properties of six‐layered Aurivillius bismuth
ferrititanate. J Am Ceram Soc. 2019;102:3555–3566.
https://doi.org/10.1111/jace.16226