Journal of Alloys and Compounds 816 (2020) 153227

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Journal of Alloys and Compounds

journal homepage: http://www.elsevier.com/locate/jalcom

Photo-Fenton catalytic ability of iron-containing aluminosilicate glass

prepared by sol-gel method
I. Khan a, *, K. Nomura a, E. Kuzmann b, Z. Homonnay b, K. Sinko

b, M. Risti

c c, S. Krehula c,
S. Musi
c c, S. Kubuki a
a
Department of Chemistry, Graduate School of Science, Tokyo Metropolitan University, 1-1 Minami-Osawa, Hachi-Oji, Tokyo, 192-0397, Japan
b €tvo
Institute of Chemistry, Eo
nd University, Pa
€s Lora
zma
ny P. s., 1/A, Budapest, 1117, Hungary
c
Division of Materials Chemistry, RuCer Boskovi
c Institute, Bijenicka Cesta 54, 10000, Zagreb, Croatia

a r t i c l e i n f o a b s t r a c t

Article history: Glass samples with composition xFe2O3・yAl2O3・(100-x-y)SiO2 abbreviated as xFyAS for photo-Fenton
Received 25 June 2019 catalyst were prepared by a sol-gel method and heat-treated at 1000
C for 100 min. It was found that
Received in revised form when alumina was added to the Fe2O3 þ SiO2 glass matrix, the photo-Fenton activity tested with
16 November 2019
methylene blue degradation increased, so did the photoactivity with visible light. From Mo € ssbauer and
Accepted 30 November 2019
Available online 2 December 2019
XRD results, it was noticed that hercynite phase appeared that showed higher photoactivity even for the
samples having lower hematite content and that the Feþ3 (Td) content increased with Al2O3 content. In
these samples, the more Feþ3 (Td) found, the more effective was the photo-Fenton degradation.
Keywords:
57
Fe-Mo€ ssbauer spectroscopy © 2019 Elsevier B.V. All rights reserved.
Sol-gel method
Iron aluminosilicate glass
Photocatalytic activity
Photo-Fenton reaction

1. Introduction splitting, decomposition of various organic substances and waste-

In today’s world, more and more attention focuses on preserving
and protection of our environment by novel green chemical tech-
niques. One of the major problems is handling and cleaning the
wastewater polluted with organic compounds. The treatment of
these actual wastewaters by conventional technologies is compli-
cated. The complex mixture of compounds usually hampers the
recuperation of the organics [1e3]. Glasses and ceramics with
photocatalytic properties could be applied to degrade the organic
component of the contamination. The photocatalytic effect was
first discovered by Fujishima and Honda in TiO2 which was acti-
vated by UV light [4]. The TiO2-based photocatalytic process has
shown a great potential as a low-cost, non-toxic, environmentally
friendly and sustainable treatment technology to remove persistent
organic pollutants (POPs) from sewage to overcome the short-
comings of the conventional technologies. The preparation of this
material has a relatively low cost, it is non-toxic and inert, which
means it could be easily used for many applications just like water
* Corresponding author.
E-mail address: khan-irfan@ed.tmu.ac.jp (I. Khan).
water treatment [5e7]. However, this technology suffers from some
substantial technical barriers that impede its commercialization,
i.e., large band gap energy (3.2 eV) which means that it can only be
activated by UV light with the wavelength (l) of shorter than
388 nm, the inefficient exploitation of visible light, low adsorption
capacity for hydrophobic contaminants, the need for uniform dis-
tribution in aqueous suspension, and post-recovery of the TiO2
particles after water treatment. In order to enhance the photo-
catalytic activity and to reduce the energy band gap of TiO2, recent
research gave credence to catalysts doped with transition and noble
metals such as Pt, Pd, Au and Ag. The other approach is to prepare
photocatalysts with a narrower optical band gap that brings pho-
tocatalytic activity down to the visible light region. Hematite (a-
Fe2O3) is a suitable material, due to its photocatalytic properties,
chemical stability, nontoxicity and natural availability [6,8e11]. It
was reported that iron-containing materials could be prepared as
photocatalysts [12]. FeeCu/TiO2 [8], FeIII-TiO2 [13], Fe-WO3 [14], and
a-Fe2O3/Ca2Fe2O5 [15] showed remarkable photocatalytic activity
under visible light. Our previous study showed that the precipita-
tion of a-Fe2O3 from heat treated iron-containing silicate glass
prepared by the sol-gel method [16] and melt-quenching method
[17] results in photocatalytic activity. It showed high rate constants

https://doi.org/10.1016/j.jallcom.2019.153227
0925-8388/© 2019 Elsevier B.V. All rights reserved.
2 I. Khan et al. / Journal of Alloys and Compounds 816 (2020) 153227
(k) of 1.8  104 s1 [16] and 2.87  102 h1 [17] for Methylene
Blue (MB) decomposition under visible light. The glasses prepared
by either sol-gel or melt-quenching method have a good chemical
homogeneity and purity. Nonetheless, the sol-gel method provides
better control of structural properties and the composition.
Another advantage is that gel-derived glass-ceramics can be ob-
tained at lower temperature and therefore at lower energy con-
sumption which is very beneficial for a potential industrial
application [18].
Aluminate glass has broad optical transparency in the visible to
the infrared region [19]. Due to the remarkable IR light-
transmittance observed in aluminate glass, it is anticipated that
visible light-activated catalytic effect could be enhanced when
alumina (Al2O3) is added to iron-containing silicate glass. Alumina
is an excellent support for catalysts containing a-Fe2O3. This system
was found to degrade model compound orange II with the rate
constant of 3.54  104 min1 [20]. It could be seen that the pore
volume and surface area strongly depended on the alumina con-
tents and it increased with a larger amount of alumina. Photo-
catalytic degradation experiments indicate that the iron oxides
with 10% alumina had the highest activity [21].
Recently, enormous research interest has been focused on
numerous Advanced Oxidation Processes (AOPs). Among various
AOPs, heterogeneous Fenton and photo-Fenton processes by adding
H2O2 are one of the most widely studied processes as they give
promising results in the removal of toxic organic materials from
contaminated wastewater [22]. The Fenton process is an efficient
way to produce highly oxidizing species (hydroxyl radicals) from
hydrogen peroxide and Fe2þ ions. But the formation of large
amounts of iron-containing sludge (that contains Fe3þ ions) limits
the application of this reaction [23e25]. This limitation could be
overcome by using the photo-Fenton process as in this process
regeneration of ferrous ions takes place by photo-reduction of ferric
ions cyclically [26,27]. Another advantage of this process is that the
catalyst can be easily separated from the liquid phase after the
reaction.
In this study, we report the relationship between the structure
and photo-Fenton catalytic ability of iron-containing aluminosili-
cate glass prepared by the sol-gel method using 57Fe-Mo €ssbauer
spectroscopy, X-ray diffractometry (XRD), Diffuse reflectance
spectroscopy (DRS), and UltravioleteVisible light absorption spec-
troscopy (UV-VIS).
2. Experimental
2.1. Sample preparation
Iron-containing aluminosilicate glass with the composition of
xFe2O3 yAl2O3 (100xy)SiO2 (in mass%, x ¼ 30, 40 and 50, y ¼ 0,
10, 15 and 20), abbreviated as xFyAS was prepared by sol-gel
method. Chemical reagents of 1-propanol (Wako 162-04816),
7.8 M HNO3 (Wako 141-03166) and Si(OC2H5)4 (Wako 053-03476)
were stirred for 2 h at 80
C. After the stirring, designated amounts
of Fe(NO3)3$9H2O (Wako 095-00995) and Al(NO3)3$9H2O (Wako
015-01955) were added and dissolved in the mixture. As a gelation
agent, propylene oxide (Wako 165-05026) was added to the solu-
tion and the mixture was stirred at room temperature for 2 h. After
the gelation was completed, the mixture was aged at 80
C for 2 h
and dried at 60
C for 24 h. Finally, the dried gel was heat-treated at
1000
C for 100 min.
2.2. Characterization methods
Structure of the prepared xFyAS before and after heat-treatment
was characterized using 57Fe-Mo €ssbauer spectroscopy and X-ray
diffractometry (XRD). 57Fe-Mo €ssbauer spectra were measured in
constant acceleration mode at room temperature, using a source of
925 MBq 57Co(Rh) and a-Fe as a reference of zero velocity and
velocity scale calibration. The source was mounted on the MVT-
1000 transducer, which is connected by MDU-1200 driving unit.
The driving unit was connected to DFG-1200 digital function
generator. The g-ray transmitted through the sample was detected
by a Xe gas proportional counter at a voltage of 2 kV provided by an
ORTEC 556 High Voltage Power Supply unit. The signals were
amplified by ORTEC 142 preamplifier and ORTEC 570 amplifier and
then recorded by a multi-channel analyzer (MCA-7700, Seiko
EG&G). The samples with a weight of 40 mg were homogeneously
dispersed in disc of 10 mm in diameter. Mo €sswinn 3.0i XP program
was used to analyze the spectra obtained. XRD patterns were
recorded between 2Q of 10 and 80
with the precision and scan rate
of 0.02
and 5
min1, respectively. Cu-Ka rays (l ¼ 0.1541 nm) were
generated under the voltage and current of 50 kV and 300 mA,
respectively. The BrunauerEmmettTeller (BET) specific surface
area was estimated from N2 isotherms obtained using a BELSORP-
mini II (BEL Japan, Osaka, Japan) at 77 K. The analyzed samples
were evacuated at 573 K for 3 h prior to the measurement.
Photocatalytic activity of the heat-treated samples were evalu-
ated by adding 40 mg of well-pulverized glass samples into 10 mL
of Methylene Blue aqueous solution (MBaq) with a concentration of
20 mM. An appropriate amount of 0.2 M H2O2 was also added later
for evaluating photo-Fenton properties. UV-VIS spectra of MBaq
before and after the photocatalytic reaction were measured by
GENESYS™ 10S UVeVis spectrophotometer in which the visible
light emitted by a metal-halide lamp with the wavelength region
from 200 to 800 nm, the output power of 100 W and the intensity of
6 mWcm2 on the sample surface. Diffuse reflectance spectra with
reference barium sulfate were recorded by UV-3600 (Shimadzu) in
between the wavelengths of 190 and 1500 nm using the UV-VIS
spectrometer attached with an integrated spherical. Sampling
pitch and slit-width were set at 1.0 nm and 20 nm, respectively.
3. Results
3.1. Structural characterization
3.1.1. XRD patterns
XRD patterns of the 40FyAS samples after heat treatment at
1000
C for 100 min are shown in Fig. 1. Crystalline structure with
sharp peaks ascribed to quartz (SiO2, PDF No.: 96-901-0145, 2Q:
20.62
, 26.41
, 49.80
, 64.36
, 67.66
, 68.02
), fayalite (Fe2SiO4, PDF
No.: 96-900-0472, 2Q: 25.0
, 31.58
, 34.90
, 51.39
, 61.07
), he-
matite (a-Fe2O3, PDF No.: 96-901-5066, 2Q: 24.15
, 33.27
, 35.77
,
40.92
, 54.20
, 62.61
, 78.83
) and hercynite (FeAl2O4, PDF No.: 96-
900-1988, 2Q: 30.86
, 36.41
, 64.36
) phase could be detected for
this 40FyAS glass with ‘y’ of 0, 10, 15, 20. The samples with ‘y’ of ‘0’
contained a large amount of fayalite, which is in good correspon-
dence with a large amount of Fe2þ content assigned in the
Mo € ssbauer spectra as described later. By adding alumina to the
system, the amount of Fe2SiO4 amount decreased. For ‘y’ of 15 and
20, it completely disappeared, leaving hematite as the only iron
containing crystalline phase. Thus, the amount of a-Fe2O3 increases
and the amount of fayalite decreases with the increase of alumina
content. Hercynite phase was only observed in 40F10AS. These
results indicated that the precipitation of fayalite, hematite and
hercynite in heat-treated 40FyAS glass could be controlled by
changing the Al2O3 content. In the XRD spectra, the hematite and
the iron oxides with low magnetic field are not distinguishable
because of the structural similarities [28]. The crystalline peaks of
quartz, fayalite, hematite and hercynite were also observed in heat-
treated samples of 30FyAS and 50FyAS.
 I. Khan et al. / Journal of Alloys and Compounds 816 (2020) 153227 3

€ssbauer spectra of 40FyAS with ‘y’ of (a) 0, (b) 10, (c) 15 and (d) 20 after
Fig. 2. 57Fe-Mo
heat-treatment at 1000
C for 100 min.
Fig. 1. XRD patterns of 40FyAS samples with ‘y’ of (a) 0, (b) 10, (c) 15 and (d) 20 after
heat-treatment at 1000
C for 100min.
Table 1
57 € ssbauer spectra of 40FyAS samples with ‘y’ of 0, 10, 15 and 20 with heat-
Fe-Mo
When comparing the results of 30FyAS, 40FyAS and 50FyAS treatment at 1000
C for 100 min.
samples, the ratio of the crystalline phase was in good correspon- sample 40FyAS
dence with the initial amount of iron. 40FyAS and the 50FyAS
y Assignment A (%) d (mm s1) D (mm s1) Н int (Τ)
samples had the maximum amount of hematite crystalline phase.
In the case of 30FyAS and 50FyAS, the intensity of the diffraction 0 Fayalite 85 1.12 2.82 e
Hematite 15 0.37 0.20 51.6
peaks is relatively lower compared with 40FyAS, which showed 10 Fayalite 36 1.14 2.84 e
only a smaller fraction of the sample in the crystalline states. It is Fe2þ (Td) 24 0.92 1.45 e
noteworthy that in all the heat-treated samples, amorphous phase Hematite 40 0.37 0.20 51.2
persists due to the SiO2 matrix, in which the microstructure is 15 Fe3þ (Td) 18 0.24 1.00 e
Hematite 45 0.37 0.19 51.3
tetrahedrally oxygen coordinated Si4þ. The tetrahedra can be linked
FeIIIO 37 0.33 0.17 40.7
to each other through corner-shared oxygens, and the poly- 20 Fe3þ (Td) 25 0.24 0.91 e
crystalline matrix is composed of zigzag structures of these tetra- Hematite 38 0.37 0.19 51.4
hedra. This leads to long-range periodical disorder. One can FeIIIO 37 0.33 0.17 40.5
conclude from these XRD results that, interestingly, the alumina A: absorption area, d: isomer shift, D: quadrupole splitting, Hint: internal magnetic
containing phase stays amorphous even after heat treatment at field.
1000
C. Similar results were obtained as described in the literature
where the matrix phase stays amorphous [29,30].
treatment [32]. Adding alumina to the system Fe2þ content dras-
tically decreased. Fe2þ(fayalite) was only found in the case of
3.1.2. 57
Fe-Mo€ssbauer results 40F10AS, but was not observed in the other alumina-containing
57
Fe-Mo €ssbauer spectra and the parameters of heat-treated samples. In the case of heat-treated 40F10AS, the Mo €ssbauer
40FyAS samples with ‘y’ of 0, 10, 15 and 20, are shown in Fig. 2 spectrum includes a sextet due to hematite with d of
and Table 1, respectively. In the absence of Al3þ (y ¼ 0), the 0.37±0.01 mm s1, D of 0.20±0.01 mm s1 and two doublets due to
spectra showed a paramagnetic doublet with the isomer shift (d) of fayalite with d of 1.14±0.02 mm s1, D of 2.84±0.02 mm s1 and A of
1.12±0.02 mm s1, quadrupole splitting (D) of 2.82±0.02 mm s1 and 36% and to hercynite (FeAl2O4) with d of 0.92±0.01 mm s1, D of
absorption area (A) of 85% indicating the olivine crystal structure of 1.45±0.02 mm s1 and A of 24%. On the other hand, the Mo €ssbauer
the Fe2SiO4 material known as fayalite, similar to earlier mea- spectrum of heat-treated 40F15AS and 40F20AS included one
surements [16,31]. Alongside, there is a sextet due to hematite (a- doublet due to Feþ3 (Td) with constant d of 0.24±0.01 mm s1,
Fe2O3) with d of 0.37±0.1 mm s1, internal magnetic field (Hint) of decreasing D from 1.0±0.01 to 0.91±0.01 mm s1 and increasing A
51.6±0.1 T and A of 15%. It is noted that without Al3þ (y ¼ 0), the from 18 to 25%. In addition to the above-mentioned components,
sample contained a large amount of Fe2þ species due to the organic two magnetic sextets ascribed to regular hematite (d:
compounds, which have reductive properties through heat
4 I. Khan et al. / Journal of Alloys and Compounds 816 (2020) 153227

0.37±0.01 mm s1, D: 0.19±0.01 mm s1, Hint: 51.3±0.01 T) and iron Table 2(A)
57 €ssbauer spectra of 30FyAS samples with ‘y’ of 0, 10 and 20 after heat
oxides with the smaller magnetic field than a-Fe2O3 (d: Fe-Mo
treatment.
0.33±0.01 mm s1, D: 0.17±0.02 mm s1, Hint: 40.7±0.6 T) were
observed. The structural characterization of the iron oxides with sample 30FyAS
the low magnetic field (Hint) requires further studies. It is noted that y Assignment A (%) d (mm s1) D (mm s1) Н int (Τ)
the A value for hematite (a-Fe2O3) varied from 15 to 40 to 45 to 38%
0 Fayalite M1 43 1.12 2.82 e
with an increase of alumina ‘y’ from 0 to 10, 15 and 20. These results Fayalite M2 57 1.08 2.69
indicated that the precipitated crystalline phase changes its 10 Fayalite 24 1.16 2.84 e
composition from hematite (a-Fe2O3) to hercynite (FeAl2O4) when Fe2þ (Td) 20 0.92 1.40
€ssbauer Hematite 18 0.37 0.17 51.4
the Al2O3 content ‘y’ reaches 10 or exceeds it. The 57Fe-Mo
FeIIIO 38 0.32 0.13 41.8
spectra of heat treated 30FyAS and 50FyAS with ‘y’ of 0, 10, 20 were 20 Fe3þ (Td) 22 0.20 0.91 e
also measured as shown in Fig. 3(A) and (B) respectively. Precipi- Fe2þ (Td) 14 0.92 1.45 e
tation of fayalite, hercynite, hematite (a-Fe2O3) along with iron- Hematite 29 0.37 0.21 51.3
oxides of the low magnetic field was confirmed as shown in FeIIIO 35 0.42 0.21 35.2

Table 2(A) and (B). From the Mo€ssbauer spectra and XRD patterns, it A: absorption area, d: isomer shift, D: quadrupole splitting, Hint: internal magnetic
was proved that by adding alumina to the system, hercynite field.
(FeAl2O4) phase appeared.
Table 2(B)
3.2. Photocatalytic properties 57
Fe-Mo€ssbauer spectra of 50FyAS samples with ‘y’ of 0, 10 and 20 with heat
treatment at 1000
C for 100 min.
3.2.1. Photodegradation
sample 50FyAS
The MB concentration measured for xFyAS annealed glass
y Assignment A (%) d D Н int (Τ)
samples with ‘y’ of 0, 10, 15, 20 after visible light irradiation for 3 h is
(mm s1) (mm s1)
shown in Fig. 4. Measurements were made without visible light-
exposure as well. In these measurements, there is also a signifi- 0 Fayalite 69 1.12 2.82 e
Hematite 31 0.37 0.17 51.6
cant change in the MB decomposition constant for each sample as
10 Fe2þ (Td) 12 0.91 1.50 e
shown in Table 3. As shown in Table 4, the BET surface areas, Hematite 50 0.37 0.20 51.3
average pore volumes, and average pore radii are calculated from FeIIIO 38 0.32 0.21 40.6
isotherm data. It can be seen from the results that heat-treated 20 Fe3þ (Td) 13 0.26 1.00 e
Fayalite 23 1.16 2.84 e
40FyAS glass samples have low surface area which declines high
Fe2þ (Td) 22 0.92 1.50 e
porosity. All of the samples showed the decomposition of MB in the Hematite 42 0.35 0.20 50.7
photocatalytic reaction tests under visible light-exposure. In our
A: absorption area, d: isomer shift, D: quadrupole splitting, Hint: internal magnetic
previous study, we reported that visible light photocatalytic activity
field.
of iron-containing soda lime silicate glass after heat-treatment was
associated with precipitated a-Fe2O3 phase [17] and several other
papers reveal photocatalytic activity properties of the hematite degradation. However, due to the complicated structure, the
phase [8e12]. The Spinel type like hercynite (FeAl2O4) is rich in iron mechanism of photocatalytic activity of hercynite is still unidenti-
and aluminum and is presumed to be a promising candidate as fied. Hui-Ying Mu et al., proved that hercynite as an inexpensive
photocatalyst. Also, it showed higher pseudo-first-order rate con- visible-light-driven photocatalyst with a low energy band gap of
stants of 2.61  103 [33] and 13.6  102 [34] for phenol

Fig. 3. 57 €ssbauer spectra of xFyAS samples with ‘x’ of (A) 30 and (B) 50, and ‘y’ of (a) 0, (b) 10 and (c) 20 after heat-treatment at 1000
C for 100 min.
Fe-Mo
 I. Khan et al. / Journal of Alloys and Compounds 816 (2020) 153227 5

more by introducing hercynite (FeAl2O4) along with a-Fe2O3.

Similar results were also obtained in the case of 30FyAS and
50FyAS, where the hematite phase was less in the amount. In Fig. 5,
the pseudo-first-order rate constant is plotted against alumina
content. From this trend, it was observed that hematite (a-Fe2O3)
along with hercynite (FeAl2O4) was obtained at 10% of Al2O3, leads
to highest pseudo-first-order rate constant. The k value of
3.81  103 min1 was obtained, which is larger than the previ-
ously reported value of 3.5  104 min1 for annealed alumina-
dispersed a-Fe2O3 [20].

Fig. 4. Photocatalytic degradation of Methylene Blue in aqueous solution (MBaq)

reacted with 40FyAS glass with ’y’ of (a) 0 (green), (b) 10 (red), (c) 15 (yellow), (d) 20
3.2.2. Photo-Fenton properties
(black) and (e) blank (blue). (For interpretation of the references to colour in this figure The photo-Fenton catalytic activity of heat-treated 40FyAS with
legend, the reader is referred to the Web version of this article.) ‘y’ of 0, 10, 15, 20 was investigated under visible-light irradiation. All
the samples showed almost complete degradation within 30 min as
shown in Fig. 6. The best sample was 40F20AS, which have the
largest Feþ3 (Td) of 25% in the absorption area of Mo
Table 3 €ssbauer spec-
The pseudo-first-order rate constant (k) for photocatalytic degradation of methylene
blue (MB) with and without visible light irradiation (3 h). trum content yielding the highest pseudo-first-order rate constant
of 8.61  102 min1. The sample 40F0AS had a large amount of
k (x 103 min1)
Feþ2 in the form of fayalite (Fe2SiO4), which does not help in the
blank 30FyAS 40FyAS 50FyAS enhancement of the photo-Fenton reaction [31]. The samples
y 0 10 20 0 10 15 20 0 10 20 without visible-light irradiation were also measured but their
kirr 1.08 1.26 2.49 2.01 1.92 3.81 3.35 2.19 1.78 1.91 2.21 degradation rates were very low in comparison to the light-on
knoirr 0.71 0.57 1.08 0.97 0.28 1.56 1.20 1.05 0.89 0.78 1.13 experiments as shown in Fig. 7. This further proves the photo-
kirr: with irradiation knoirr: without irradiation. catalytic activity in 40FyAS. Similar results were obtained in the
samples of 30FyAS and 50FyAS. Under the irradiation, the photo-
catalytic activity in 40FyAS is highest among these samples.
Table 4
Surface Areas, Average pore volume, and average Pore radii of 40FyAS samples with
‘y’ of 0, 10, 15 and 20 with heat-treatment at 1000
C for 100 min.

Catalyst SBET (m2 Average pore volume  102 Average pore radii
g1) (cm3 g1) (nm)

40F0AS 3.29 0.81 1.64

40F10AS 7.98 2.09 1.85
40F15AS 5.22 2.23 1.21
40F20AS 7.24 1.78 1.85

1.77 eV [33]. In 40FyAS with y ¼ 0, it can be seen that the decom-

position rate was the lowest because of the large amount of Feþ2 in
the form of fayalite. Kobzi et al., showed that iron-silicate glass with
a large amount of fayalite is not photocatalytically active [31].
Photocatalytic activity of iron-containing silicate glass was
enhanced by introducing alumina. These results indicate that the Fig. 5. The pseudo-first-order rate constant (k) recorded for the degradation of MBaq
under the visible-light irradiation plotted against alumina content for 40FyAS glass
addition of alumina into iron silicate glass causes an increase in the after heat treatment at 1000
C for 100 min.
rate constant for MB decomposition. In our previous study of
similar compositional samples prepared with the melt-quenching
method, the same trend was observed as a function of alumina
content [35].
Pseudo-first-order rate constant (k) of the MB decomposition
was estimated using the following equation, i.e.,

ln(Ct/C0) ¼ kt, (1)

where, C0 is the concentration of MBaq before photocatalytic reac-

tion test (¼20 mM). Values of k for MB decomposition calculated for
the blank sample, annealed 40F0AS, 40F10AS, 40F15AS and
40F20AS glasses were found to be 1.92  103, 3.81  103,
3.35  103 and 2.19  103 min1, respectively. Let us note that on
the basis of the Mo € ssbauer spectra the amount of a-Fe2O3 phase
was a bit less in 40F10AS than in 40F15AS, but the former showed a Fig. 6. Kinetic degradation under the photo-Fenton reaction of MBaq and 40FyAS glass
higher decomposition rate. These results proved that visible light with ’y’ of (a) 0 (green), (b) 10 (black), (c) 15 (yellow), (d) 20 (red) and (e) blank (blue).
(For interpretation of the references to colour in this figure legend, the reader is
photocatalytic activity of aluminosilicate glass could be increased
referred to the Web version of this article.)
6 I. Khan et al. / Journal of Alloys and Compounds 816 (2020) 153227

Fig. 8. Tauc’s plot for heat-treated samples of 40FyAS with ’y’ of (a) 0 (red), (b) 10
(blue), (c) 15 (green), (d) 20 (black). (For interpretation of the references to colour in
this figure legend, the reader is referred to the Web version of this article.)

Fig. 7. The k values evaluated under the MBaq photo-Fenton degradation using
40FyAS sample with ’y’ of (a) 0, (b) 10, (c) 15, (d) 20 and (e) blank. Fig. 9, illustrates the relationship between degradation efficiency
percentage and cycle times. A three percent loss in the catalytic
degradation has been observed till seven cycles from the first-run
4. Discussion
suggesting high stability and recycling ability of 40F20AS catalyst
for the degradation of Methylene Blue under the irradiation of
Comparing the three series of iron aluminosilicate glasses with
visible light.
respect to their photocatalytic effect, it can be said that the series
containing 40% Fe2O3 had the best degradation rate (Table 3) which
was at y ¼ 10 in the case of 40FyAS. There was a slight decrease in 5. Summary
the pseudo-first-order rate constant for heat-treated 40F20AS. This
decline was also observed in 30F20AS. To explain this phenome- Photo-Fenton catalytic ability of iron-containing aluminosilicate
non, we measured the band gap energies of the glass samples by glass was investigated on sol-gel synthesized and heated 30FyAS,
diffuse reflectance spectroscopy. 40FyAS and 50FyAS samples utilizing 57Fe MS, XRD and UV-VIS. The
The band gap energy (Eg) for annealed iron-containing alumi- samples with ‘y’ of 10, 15, and 20 heat treated at 1000
C for
nosilicate glass samples was estimated by the following equation, 100 min resulted in a high porosity and in the precipitation of
Tauc plot [36,37] i.e., hematite and hercynite (FeAl2O4) with photocatalytic properties.
The largest rate constant (k) was 3.81  103 min1 for MB
(hna)1/n ¼ A(hn - Eg) (2) decomposition under visible light-exposure on heat-treated
40F10AS. The samples that did not contain alumina (Al2O3) were
where h is Planck’s constant, n is the frequency of the light applied, not advantageous for photocatalytic effect. While they contain a
a is the absorption coefficient, n is a number that characterizes the large amount of Fe2þ in the form of fayalite, this was not significant
type of the transition process (in this case n ¼ 0.5) and A is the in the enhancement of photo-reaction. As for the photo-Fenton
proportionality factor. Using the Tauc plot, we deduced the band degradation ability by adding H2O2, the best sample was 40F20AS
gap energy (Eg) of heat-treated 40FyAS samples with ‘y’ of 0, 10, 15, yielding the highest first-order rate constant of 8.61  102 min1.
20 to be 1.90, 1.97, 2.08 and 2.09 eV, respectively, as shown in Fig. 8. These results indicate that Fe3þ ions also show photo-Fenton cat-
These values are smaller than that of a-Fe2O3, indicating that the alytic abilities and that the precipitated amount of a-Fe2O3 and
band gap becomes narrow when Al2O3 is dispersed with hematite light-scattering ability caused by the introduction of Al2O3 is
(a-Fe2O3) [35]. These results strongly support that alumina content effective for the visible light photocatalytic activity. It has been
can enhance photocatalytic activity. However, it seems that it also proved that this newly developed iron-containing aluminosilicate
increases the band gap energy. Thus there is an optimum of the glass can be applied to wastewater treatment as an efficient photo-
alumina content, where the largest degradation rate can be Fenton catalyst with good recyclability.
reached.
Mo€ssbauer spectroscopy results showed that the Feþ3 (Td)
content increases with Al2O3 content. These photo-Fenton catalysts
for the degradation of MB are a heterogeneous catalyst. It has been
considered that Fe3þ shows photo-Fenton abilities in many cases
where the iron ions on the surface are reduced to Fe2þ by reacting
with H2O2 with an extra step [38,39]. Some researchers also
showed some cases where excited dye molecules assist the con-
version of Fe3þ to Fe2þ [40]. The above and previous results support
that novel mesoporous 40F20AS is a magnificent photo-Fenton
catalyst.
The stability and recyclability of photo-catalyst is crucial for
practical applications. Therefore, cycling experiments for the
photo-Fenton-conciliated degradation of MB with 40F20AS was
performed. After completion of each process of photocatalytic ex-
Fig. 9. Reusability of heat-treated 40F20AS for the degradation of Methylene Blue
periments, the solid catalyst was centrifuged and then pour out the
(MB). (For interpretation of the references to colour in this figure legend, the reader is
Methylene Blue solution followed by oven-dried at 60
C for 9 h. referred to the Web version of this article.)
 I. Khan et al. / Journal of Alloys and Compounds 816 (2020) 153227 7

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