Journal of Photochemistry & Photobiology A: Chemistry 382 (2019) 111951

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Journal of Photochemistry & Photobiology A: Chemistry

journal homepage: www.elsevier.com/locate/jphotochem

Eco-friendly synthesized α-Fe2O3/TiO2 heterojunction with enhanced T

visible light photocatalytic activity
⁎
Hanan H. Mohameda,b, , Nuhad A. Alomaira,b, Sultan Akhtarc, Tamer E. Youssefa,b
a
Department of Chemistry, College of Science, Imam Abdulrahman Bin Faisal University, P. O. Box 1982, Dammam 31441, Saudi Arabia
b
Basic and Applied Research Center, Imam Abdulrahman Bin Faisal University, P.O. Box 1982, Dammam 31441, Saudi Arabia
c
Department of Physics Research, Institute for Research and Medical Consultations, Imam Abdulrahman Bin Faisal University, P.O. Box 1982, Dammam 31441, Saudi
Arabia

A R T I C LE I N FO A B S T R A C T

Keywords: The current study reports the eco-friendly synthesis of titanium oxide and iron oxide (TiO2/α-Fe2O3) hetero-
Flax seed extract junction using aqueous flax seed extract (FSE) as an alternative to hazardous chemicals, templates/surfactants
Ultrasonic waves and organic solvents, and utilizing the ultrasonic waves instead of high energy techniques. The use of anti-
TiO2α-Fe2O3 nanospheres oxidants presents in the flax seed crop was explored to synthesize Fe2O3, TiO2 and Fe2O3/TiO2 with controlled
TiO2/α-Fe2O3
morphology. The as-prepared materials were characterized by various techniques. Our results show the suc-
Photocatalysis
cessful synthesis of TiO2 nanoparticles (11 nm), α-Fe2O3 nanospheres (100–300 nm) and Fe2O3/TiO2 nano-
composites in the presence of FSE. The as-prepared materials exhibited the highly crystalline structure and
narrow size distribution with surface area up to 289 m2/g when compared to those produced in the absence of
FSE. Thus, demonstrating the role of FSE as an effective templating and stabilizing agent to synthesize nano-
materials with controlled size and shape. The produced green nanomaterials showed enhanced photocatalytic
performance in the visible region for the degradation of organic dye and excellent cycling properties as com-
pared to their corresponding nanomaterials prepared with chemical method. The TiO2/α-Fe2O3 nanocomposites
showed the best photocatalytic efficiency as compared to pure TiO2 or pure Fe2O3 nanomaterials, the activity
was increased with increasing the amount of α-Fe2O3. This enhanced efficiency of the nanocomposite was at-
tributed to increased energy harvesting ability, higher surface area and generation of electron-hole separation
due to spatial electron transfer from α-Fe2O3 to TiO2 which prolonging the photogenerated charge carrier.

1. Introduction Among the semiconducting photocatalysis materials, titanium oxide

Recently, intensive research has focused on preventing environment
and promoting the optimal use of our natural resources. Water re-
mediation has turned into a worldwide issue nowadays as serious
health problems or even death everyday resulted from water pollution
[1–3]. Different kinds of materials can cause water pollution, such as
herbicides, pesticides, toxic metal ions and pathogens. Several methods
have been explored to treat wastewater including electrochemical
oxidation using metal plate [4,5]. The removal of organics/inorganic
pollutants from the water have been studied using adsorption method
[6].
In view of rapid and efficient destruction of pollutants, the tre-
mendous efforts are going on to use photocatalytic process using
semiconductor nanomaterials, such as TiO2 [7], ZnO [8], ZnS [9], CdO
[10] and Bi2O3 [11] to treat wastewater alongside other methods.
(TiO2) has been extensively studied due to its low cost, high stability,
high photosensitivity and nontoxicity. However, rapid electron-hole
pair recombination constricts its photocatalytic performance. In addi-
tion, the wide band gap energy, 3.2 eV for anatase TiO2 limits its ac-
tivity in the visible light region [12,13].
Lot of efforts have been devoted to enhancing the photocatalytic
activity of TiO2 in visible light region by doping/depositing of metal
[14–18], sensitizing with organometallic dyes [19,20] and coupling
with narrower band gap semiconductor materials such, as WO3, Fe2O3
and Bi2O3 [21–23]. Hybridization of semiconductor nanomaterials de-
velop a new energy-level that can promote the charge carrier separation
and enhance the photocatalytic performance in the visible region.
Hematite (α-Fe2O3) with bandgap ˜ 2.1 eV is the most thermo-
dynamically stable phase of iron oxide as well as environmentally
friendly, commonly available and low cost, and highly resistance to

⁎
Corresponding author at: Department of Chemistry, College of Science, Imam Abdulrahman Bin Faisal University, P. O. Box 1982, Dammam 31441, Saudi Arabia.
E-mail address: hhbesisa@iau.edu.sa (H.H. Mohamed).

https://doi.org/10.1016/j.jphotochem.2019.111951
Received 1 March 2019; Received in revised form 9 June 2019; Accepted 27 June 2019
Available online 28 June 2019
1010-6030/ © 2019 Published by Elsevier B.V.
H.H. Mohamed, et al.
corrosion [24]. Such unique properties of α-Fe2O3 makes it a suitable
candidate for coupling with TiO2. The nanocomposite of TiO2 and
Fe2O3 was prepared using various established chemical and physical
methods including sol–gel, hydrothermal, solvothermal, sonochemical
and mechanochemical synthesis [25–27]. These techniques involving
the use of chemicals, toxic organic solvents and templating agents, such
as pluranic 123 [28] and sodium dodecyl sulfate (SDS) under harsh
conditions. Accordingly, these methods generate unsafe and hazardous
by-products, and often involve high energy consumption. To date, only
fewer studies performed to synthesize this wonderful nanomaterial
upon applying eco-friendly/green methods.
The eco-friendly methods utilized the low energy approaches, such
as the of sonicator [8,29] or microwave [30] at room temperatures as
well as used green materials and resources. The green resources include
plants, bacteria and fungi and use of water as solvent [31,32]. Using
plant extract in the synthesis has received more attention compared to
the other green resources, owing to its safe use, simplicity and cost
effective. Therefore, plants extracts can be used as an economic and
valuable alternative for the large-scale production of nanomaterials.
Extracts from plants may act as both inducing and templating agents in
the production of nanomaterials.
Our previous studies shown that the antioxidants and polyphenolic
compounds in the plant/plant waste extract act as stabilizing/tem-
plating and reducing agents for the synthesis of nanoparticles with
controlled morphology and structure [33]. In view of these successes,
current study reports the green synthesis of α-Fe2O3/TiO2 heterojunc-
tion using aqueous plant extract as alternative to hazardous chemicals
and solvents with the aid of ultrasonic waves. We explore the use of
common antioxidants presents in the flax seed fiber to synthesize Fe2O3,
TiO2 and Fe2O3/TiO2 nanomaterials. The synthesized products were
characterized by various analysis techniques such as, XRD, SEM, TEM,
FTIR, BET and UV–vis spectroscopy. The produced α-Fe2O3 nano-
spheres and TiO2/α-Fe2O3 nanocomposites (prepared with various α-
Fe2O3 ratios) displayed the excellent photocatalytic performance in the
visible region for water remediation and enhanced cycling properties.
2. Experimental
The nanocomposite of titanium oxide (TiO2) and iron oxide (Fe2O3)
was prepared in the presence of flax seed extract (FSE). For comparison,
a nanocomposite of TiO2 and Fe2O3 was also prepared by chemical
method using ammonium hydroxide (NH4OH) as templating agent in-
stead of FSE. Different microscopy and spectroscopy techniques were
used to investigate the effect of FSE on the structure and morphology of
both the prepared composites.
The preparation of nanocomposite was completed in the following
four steps: preparation of FSE, 2) synthesis of pure TiO2 nanoparticles,
3) synthesis of α-Fe2O3 nanospheres and 4) synthesis of TiO2/Fe2O3
nanocomposite. The detail of these synthesis steps is given below.
2.1. Preparation of flax seed extract (FSE)
The Flax Seeds (FS) was provided from western region farms, Egypt.
They were washed with distilled water and then dried in the air. The
dried seeds were finally ground to obtain a fine powder of FS. A 50 g of
the fine powder was dispersed in 750 ml distilled water and boiled for
1 h under reflux condition. The resulted gelatinous Flax Seed Extract
(FSE) was filtered to remove the solid particles and stored in the fridge
at −4 °C. To obtain the powder of FSE, the stored FSE was evaporated
using rotary evaporator at 25 °C and 20 mbar. The resulted FSE shows
shiny yellowish crystals. The schematic of FSE preparation and the
chemical compounds of FSE (in chemical symbols) is depicted in Fig. 1.
The as-prepared FSE powder was analyzed by Fourier-transform in-
frared spectroscopy (FTIR), X-ray diffraction (XRD), ultraviolet-visible
(UV–vis) spectroscopy and gas chromatography-mass spectrometry
(GC–MS). For GC–MS analysis, the solid extract was dissolved in
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Journal of Photochemistry & Photobiology A: Chemistry 382 (2019) 111951
methanol and measured the spectrum.
2.2. Synthesis of TiO2 nanoparticles
Pure TiO2 Nanoparticles were prepared using FSE. In a typical
synthesis, 5 mL of titanium IV tetraisopropoxide was added dropwise to
50 mL FSE suspension under ultrasonic vibration at room temperature.
The produced white suspension was continuously stirred for 2 h. The
solid product of TiO2 was collected by centrifugation, washed by dis-
tilled water and dried at 70 °C. Finally, the product was calcined at
500 °C for 1 h.
2.3. Synthesis of α-Fe2O3 nanospheres
Pure Fe2O3 nanoparticles were synthesized via sonochemical
method using iron III nitrate (Fe(NO3)3.9H2O, 99.99%) as α-Fe2O3
precursor and FSE as templating agent. In a typical synthesis, 5.0 g Fe
(NO3)3 was dissolved in 20 mL distilled water and the resulted solution
was transferred onto the ultrasonic bath (USC200 T, VWR International;
45 kHz, 60 W). A 20 mL of FSE suspension was added dropwise to the
Fe-III nitrate solution under ultrasonic vibration at 50 °C for 2 h. After
ultrasonic treatment, the solid product was separated from the sus-
pension by centrifugation, washed and then dried at 70 °C for 1 h, fol-
lowed by calcination at 500 °C for 1 h. The synthesis procedure is de-
picted in Fig. 2a. The α-Fe2O3 product was also prepared by chemical
method for comparison using (2 M) NH4OH as templating agent instead
of FSE under hydrothermal treatment.
2.4. Synthesis of TiO2/Fe2O3 nanocomposite
TiO2/Fe2O3 nanocomposite was synthesized by hydrolysis of tita-
nium IV tetraisopropoxide (Ti[OCH(CH3)2]4, 99.999%) (TTIP) in an
aqueous suspension of previously prepared α-Fe2O3 nanoparticles. The
TiO2/Fe2O3 nanocomposite with various ratios (10, 20, 50 and 100) of
Fe2O3 was prepared. To start, a desired amount of as-prepared α-Fe2O3
was dispersed in 50 mL distilled water. Then, 2 mL of TTIP was drop-
wise added to the α-Fe2O3 suspension under ultrasonic vibration at
room temperature. The resultant product was appeared in milky-red
color was continuously stirred for 2 h. The solid product of TiO2/α-
Fe2O3 composites was collected by rotary evaporator and calcined at
500 °C for 1 h. Depending on the ratio of Fe2O3, the prepared compo-
sites of TiO2/Fe2O3 are denoted as TF1:0.1, TF1:0.2, TF1:0.5 and TF1:1
for the ratio TiO2:Fe2O3. The schematic of α-Fe2O3 nanospheres pre-
paration and TiO2/α-Fe2O3 composite preparation using FSE is depicted
in Fig. 2a; and the formation mechanism of α-Fe2O3 nanospheres and
TiO2/α-Fe2O3 nanocomposite using FSE is depicted in Fig. 2b. This can
be described by the following equation:
Ultrasonic, Δ
Fe3 + + OH − [FES ] → 2Fe (OH )3 → α ‒Fe2 O3 + 3H2 O (1)
For comparison, TiO2/α-Fe2O3 nanocomposite was also prepared by
a chemical method. In a typical process, a 0.5 g of the prepared α-Fe2O3
was dispersed in 50 mL 1:1 water/isopropanol solution followed by
drop-wise addition of 1 ml TTIP. The suspension was continuously
stirred for 2 h, followed by evaporating the solvent using rotary eva-
porator. The produced solid was calcined at 500 °C for 1 h and denoted
as TFC.
2.5. Characterization
XRD measurements were performed using a Cu-K x-ray with tube
conditions of 40 kV. FTIR measurements were recorded on IR AFFIN-
ITY-1 Shimadzu. SEM images were taken by using FEI, Inspect S50 at
accelerating voltage of 20 kV. TEM analysis was performed on FEI,
Morgagni 268, operated at 80 kV. Selected area electron diffraction
(SAED) in the TEM were taken to highlight the presence of TiO2 and
H.H. Mohamed, et al. Journal of Photochemistry & Photobiology A: Chemistry 382 (2019) 111951

Fig. 1. Schematic representation of preparation of Flax Seed Extract (FSE).

Fe2O3 in the prepared composite as well to verify the XRD data. Raman measurements were performed on Shimadzu UV4100 spectrometer and
spectroscopy was studied using DXR Raman Microscope, DXR 532 nm UV–Vis absorption measurements were recorded on UV–vis
Laser. The thermal gravimetric (TGA) analysis was performed using Spectrophotometer-UVD-3200, LABOMED. The PL spectra were re-
DTA-TGA thermal analyzer Shimadzu. The UV–vis diffuse reflectance corded on Shimadzu RF-5301 Spectrofluorophotometer.

Fig. 2. (a) Schematic representation of preparation of α-Fe2O3 nanospheres and TiO2/ α-Fe2O3 nanocomposite, (b) formation mechanism of α-Fe2O3 spheres and
TiO2/ α-Fe2O3 composite using FSE.

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H.H. Mohamed, et al. Journal of Photochemistry & Photobiology A: Chemistry 382 (2019) 111951

Fig. 3. (a) XRD pattern, (b) FTIR, (c) diffuse reflectance spectrum and (d) chromatogram of the flex seed extract (FSE).

Table 1 2.6. Photocatalytic activity

Chemical compounds in the FSE as obtained from GC–MS measurements.
Compound Name/
Retention Time (min)
Dihydroxyacetone/ 10.563
Ethanol, 2,2'-oxybis/11.015
Glycerin/11.771
2-Hydroxy-gamma-
butyrolactone/12.167
Maltol/12.665
Detailed Information Function
The photocatalytic performance of the green α-Fe2O3, TiO2 and the
various TiO2/α-Fe2O3 nanocomposites were evaluated for the de-
gradation of the organic dye methylene blue (MB) as a model water
pollutant. The photocatalytic experiments were carried out using solar
simulating lamp (1 sun, 100 mW/cm2). 1 g/l of the photocatalyst was
dispersed in 100 ml followed by dissolving 20 ppm of MB dye. To obtain
good equilibrium, the suspension was kept on stir in the dark for
OH source for Fe2O3 30 min. Afterwards, the suspension was irradiated; liquid samples were
formation and taken before and during the irradiation then centrifuged to separate the
Templating Agent solid catalyst. The concentration of MB was determined by the UV–Vis
absorption spectroscopy.

3. Results and discussion

3-Deoxy-d-mannoic lactone/
21.16,21.68
3.1. Analysis of flax seed extract (FSE)

The as-prepared FSE solid powder was evaluated by XRD, FTIR and
Cyclohexasiloxane, UV–vis diffuse reflectance spectroscopy. Fig. 3a shows the XRD pattern
dodecamethyl-/14.84,
of the as obtained FSE crystals. A sharp band at 20.8° is observed which
22.76
might be appeared due to presence of some bioorganic compounds in
Cyclohexylmethyl hexadecyl the FSE. Fig. 3b shows the FTIR spectrum of the as obtained FSE. The
ester/18.3 strong peaks at 1504 and 1721 cm−1 assigned to ester OeCH3
stretching vibration and ester carbonyl C]O stretching vibration, re-
spectively. The peak at 1148 cm−1 represents the coupled CeC and
CeO vibrations, indicated the presence of carbohydrate. The broad
Sucrose/19.06 Templating Agent absorption peaks between 3600 and 3200 cm−1 are assigned to eOH
group and the peak at 2900 cm−1 assigned to CeH stretching vibration
[34]. The presence of eOH group could corroborate the presence of
Cyclononasiloxane, polyphenolic and phenolic glycosides which act as inducing and tem-
octadecamethyl-/ plating agents for the synthesis of the nanomaterials [35,36]. The op-
25.5,26.76,28.22
tical properties of FSE are analyzed by UV–vis spectroscopy (Fig. 3c),
Cyclooctasiloxane, showing broad absorption in the visible region which may be due to the
hexadecamethyl-/19.35,
antioxidants in the FSE. The GC–MS measurements confirm that FSE is
24.2
mainly consisting of polyphenolic compounds, esters, carbohydrate,
and cyclononasiloxane compounds (Fig. 3d). Owing these compounds,
the water-soluble extract of FSE exhibit strong antioxidant activity.
These antioxidants are responsible for the formation and stabilization of
the nanomaterials. According to the GC–MS measurements, the main

4
H.H. Mohamed, et al.
Fig. 4. XRD patterns of the as synthesized nanomaterials.
compounds in FSE are summarized in Table 1.
3.2. XRD analysis
The XRD patterns of α-Fe2O3, TiO2 and TiO2/α-Fe2O3 nanocompo-
site are shown in Fig. 4. The XRD pattern of α-Fe2O3 shows diffraction
peaks at 24.13°, 33.15°, 35.612°, 40.85°, 49.48°, 54.09°, 57.59°, 62.41°
and 63.99° which are indexed to the (012), (104), (110), (113), (024),
(116), (018), (214) and (300) for rhombohedral α-Fe2O3. The XRD
results revealed the formation of pure and well crystalline α-Fe2O3,
which agrees with the reported values (JCPDS Card No. 24-0072) [37].
XRD of TiO2 shows the diffractions peaks at 25.28°, 37.93°, 48.37°,
53.89°, 55.29°, 62.73°, 69.00° and 75.37° which are indexed to (101),
(100), (200), (105), (211), (213), (116) and (107) reflections of anatase
phase (JCPDS no. 21-1272) [38]. The XRD pattern of all TiO2/α-Fe2O3
nanocomposite samples shows the diffraction peaks of both TiO2 and α-
Fe2O3, evidencing the successful synthesis of the nanocomposite of TiO2
and α-Fe2O3. Moreover, the diffraction peak intensities that are corre-
sponding to α-Fe2O3 were increased with increasing the amount of α-
Fe2O3 in the nanocomposite samples.
3.3. SEM and TEM analysis
The morphological features of the prepared products (TiO2, Fe2O3
and TiO2/Fe2O3 composite) were investigated by SEM and TEM. The
specimens of TiO2 powders, prepared with and without FSE (Fig. 5a &
b) show the small-sized spherical nanoparticles. Though particle-ag-
glomerations were found, yet the individual particles could be identi-
fied in both cases, the average size of the particles was found less than
the scale bars given in the legends. Notably, the diameter of the TiO2
particles was noticed smaller in Fig. 5b than Fig. 5a. On the other hand,
the Fe2O3 particles were submerged and formed different shaped
compound particles (Fig. 5c & d). Interestingly, SEM image (Fig. 5c)
shows the homogeneous spherical shaped particles (referred as nano-
spheres) of α-Fe2O3 for the sample of α-Fe2O3 with FSE. The diameter
range of these spheres was between 100–300 nm. The morphology of
the TiO2/Fe2O3 composites is shown by Fig. 5e & f. SEM image (Fig. 5f)
shows the homogeneous spherical shaped α-Fe2O3 nanoballs covered
with fine TiO2 particles for the sample of TiO2/α-Fe2O3 (TF1:1) com-
posite. However, for the sample of composite without FSE (Fig. 5e),
these spheres were not completely produced and showed irregular
morphology.
TEM was performed further on the same products to obtain the
structure of the prepared product with more detail. TEM images of
TiO2, Fe2O3 and TiO2/α-Fe2O3 nanocomposites that were prepared in
the presence or absence of FSE are shown in Fig. 6. TiO2 with small
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Journal of Photochemistry & Photobiology A: Chemistry 382 (2019) 111951
particles (˜10 nm), higher particle distribution and increasing porosity
was observed when using FSE (Fig. 6b) compared to the TiO2 nano-
particles (16–26 nm) prepared in the absence of FSE (Fig. 6a). The TEM
images of the chemically prepared α-Fe2O3 that were prepared in the
absence or presence of FSE are shown in Fig. 6c & d. Nanospheres or
nanoballs of α-Fe2O3 with size ranging from 100 to 300 nm are ob-
served for the sample prepared in the presence of FSE, whilst irregular
large-sized compound particles were obtained for the sample prepared
in the absence of FSE. The individual particles were obvious within
these irregular shaped compound particles with average size less than
100 nm. By deep looking, it was revealed that the spheres
(100–300 nm) observed for the sample prepared in the presence of FSE,
they were also composed of nano-sized individual particles. But like-
lihood they more compact as compared to former sample and obscured
their identity. The TEM images of TiO2/α-Fe2O3 nanocomposites
(TF1:1) prepared in the absence and in the presence of FSE (Fig. 6f) are
displayed by Fig. 6e & f, respectively. The nanoballs prepared in the
presence of FSE were showing the uniform α-Fe2O3 spheres decorated
with uniformly distributed TiO2 nanoparticles on their surfaces, while
this ball-like morphology was irregular for the sample prepared in the
absence of FSE. Our results show that FSE is an effective template that
acts as stabilizing agent to synthesize products of Fe with controlled
morphology and size.
In addition to XRD, selected area electron diffraction (SAED) was
carried out on the three prepared products (in the presence of FSE):
TiO2, Fe2O3 and TiO2/Fe2O3 composite (TF1:1) to verify the presence of
TiO2 in the Fe2O3 by comparing their diffraction patterns. The results of
SAED patterns of these specimens are shown in Fig. 7. The electron
patterns of TiO2/Fe2O3 composite showed the combination of spots/
dotted rings as observed for pure TiO2 (continuous spotty rings) and
Fe2O3 (intense random spots) specimens, confirming the existence of
titanium oxide particles on iron oxide nanoballs surface. The char-
acteristics reflections of both TiO2 and α-Fe2O3 are labelled in the
patterns. The SAED results are also in consistent with XRD findings as
described by Fig. 4.
3.4. FTIR analysis
The FTIR spectra were taken for TiO2, Fe2O3 and TiO2/Fe2O3 spe-
cimens and shown by Fig. 8. The FTIR spectrum of pure TiO2 shows
peaks at 3400 and 1580 cm−1 which corresponds to water and hydroxyl
groups [39], and the broad band 400–900 cm−1 can be assigned to
TieOeTi bond (Fig. 8a) [40]. The FTIR spectrum of α-Fe2O3 spheres
shows peaks at 550 and 470 cm−1 which are attributed to the Fe-O
bond vibration [41]. The peak at 1625 and 3470 cm−1 can be attrib-
uted to the asymmetrical and symmetrical stretching vibration of –OH
H.H. Mohamed, et al.
Fig. 5. SEM micrographs of the as synthesized products (prepared in the absence or presence of FSE): (a, b) TiO2 nanoparticles; (c, d) α-Fe2O3 particles/spheres and
(e, f) TiO2/α-Fe2O3 nanocomposite (TF1:1 specimen).
group (Fig. 8b) [37]. The characteristic peaks observed at 475, 550,
1620 and 3450 cm−1 for TiO2/α-Fe2O3 nanocomposite sample confirm
the presence of both TiO2 and α-Fe2O3 in the nanocomposite (Fig. 8c).
3.5. UV–vis spectroscopy analysis
The optical properties of the prepared nanomaterials were studied
by UV–vis spectroscopy (Fig. 9). The UV–vis diffuse reflectance mea-
surements in the range between 300–650 nm (Fig. 9a) show that pure
TiO2 absorbed UV light and reflects visible light with a wavelength
ranging from 400 to 800 nm due to its wide band gap. On the other
hand, Fe2O3 specimen exhibits high absorption in the visible region
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Journal of Photochemistry & Photobiology A: Chemistry 382 (2019) 111951
with absorption edge of about 580 nm. The TiO2/α-Fe2O3 nano-
composites are absorbing more visible light than pure TiO2, which can
be primarily ascribed to electron transfer promotion from the valence
band of Fe2O3 to the conduction band of TiO2. Moreover, the absorp-
tion in the visible region increases with increasing the amount of Fe2O3
in the composites. For band gap calculations, the reflectance spectra of
all the samples were analyzed using the Kubelka-Munk relation to
convert the reflectance into a Kubelka-Munk function. The band gab
energy of the nanomaterials was estimated from the intercept of the
tangent of Kubelka-Munk plots (see Fig. 9b-g) and the results are shown
by Table 2. The obtained band gap energy of the TiO2 nanoparticles
(3.20 eV) and Fe2O3 (2.13) are found to be in good agreement with the
H.H. Mohamed, et al. Journal of Photochemistry & Photobiology A: Chemistry 382 (2019) 111951

Fig. 6. TEM images of the as synthesized products (prepared in the absence or presence of FSE): (a, b) TiO2 nanoparticles; (c, d) α-Fe2O3 particles/spheres and (e, f)
TiO2/α-Fe2O3 nanocomposite (TF1:1 specimen).

reported values. The band gab energy of the nanocomposites was de-
creased with the increase of Fe2O3 amount in the TiO2/α-Fe2O3.
3.6. TGA analysis
The N2 adsorption-desorption measurements were performed to
determine the porosity of the samples (Fig. 10). The adsorption/deso-
rption isotherms of the prepared samples displayed the typical H3
hysteresis loops. The pore size calculations revealed a wide range of
pore size distribution of the materials, evidencing the uniform and non-
accumulated particles. The specimens showed a large surface area,
about 124.23, 168.42, 189.00, 199.32 and 289.90 m2/g, respectively

Fig. 7. Selected area electron diffraction (SAED) patterns of the as prepared products: (a) TiO2 nanoparticles, (b) α-Fe2O3 balls and (c) TiO2/ α-Fe2O3 nanocomposite.

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Fig. 8. FTIR spectra of the as synthesized nanomaterials.

for pure TiO2, TF1:0.1, TF1:0.2, TF1:0.5 and TF1:1. It can be seen that
the nanocomposites provided higher surface area compared to pure
TiO2 specimen due to the surface modification derived from α-Fe2O3
nanospheres (see Table 3).
3.7. Photocatalytic activity
Photocatalytic performance of the eco-friendly prepared nanoma-
terials (TiO2, α-Fe2O3 and TiO2/α-Fe2O3 nanocomposites) were ex-
amined for the degradation MB dye under visible light irradiation. The
concentration of the dye was monitored by spectrophotometric

8
H.H. Mohamed, et al.
Fig. 9. UV–vis Diffuse Reflectance spectra of the as synthesized nanomaterials (a) and the corresponding Kubelka-Munk plots (b–g).
measurement. The absorption peak at 668 nm, assigned to MB de-
creases gradually with the increase of illumination time (Fig. 11a).
Fig. 11b shows the photocatalytic degradation efficiency of MB using
various nanomaterials. MB dye alone did not exhibit any noticeable
degradation under visible light. However, a slow degradation was ob-
served when pure TiO2 nanomaterial was used as a catalyst. An efficient
degradation was achieved in the presence of α-Fe2O3, degradation was
reached to about 45% in 60 min. Excitingly, the degradation of MB dye
was further increased when TiO2/α-Fe2O3 nanocomposites were used
as catalyst. In about 60 min, the degradation was reached to about 68,
75, 91.2 and 98% for TF1:0.1, TF1:0.2, TF 1:0.5 and TF1:1,
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Journal of Photochemistry & Photobiology A: Chemistry 382 (2019) 111951
respectively. These results indicate that that the photocatalytic activity
of the nanocomposite was increased with increasing the amount of
Fe2O3 in the TiO2/Fe2O3. It can be concluded that TiO2/α-Fe2O3 is the
best photocatalytic nanomaterial as compared to pure TiO2 or pure
Fe2O3 nanomaterials.
Based on the above findings, the enhancement of the visible light
photocatalytic activity of TiO2/α-Fe2O3 nanocomposites can be attrib-
uted to the following factors: 1) more energy harvesting by Fe2O3 na-
nospheres due to their small band gap, 2) large surface area of the
composite compared to pure materials, resulted in higher amount of
adsorbed dye for degradation. As the surface area increases by
H.H. Mohamed, et al. Journal of Photochemistry & Photobiology A: Chemistry 382 (2019) 111951

Table 2 Table 4
The Band Gap Energy of all samples obtained from the Kinetic parameters obtained from first order fitting the experimental points of
Kubelka-Munk plots (Fig. 8 (b–g)). Figure (10).
Sample Band Gap Energy Nanomaterial kobs (min−1) R2
eV
Pure TiO2 0.0036 0.98
Pure TiO2 3.20 Pure α- Fe2O3 0.011 0.98
Pure α- Fe2O3 2.13 TF 10 0.022 0.95
TF 10 3.10 TF 20 0.025 0.95
TF 20 2.90 TF 50 0.041 0.98
TF 50 2.40 TF 100 0.063 0.98
TF 100 2.20 TF 100 C 0.015 0.99

increasing the amount of Fe2O3 in the composite (see Table 3), the
degradation efficiency is increased due to higher surface area. 3) Pre-
vention of electron-hole re-combination due to spatial electron transfer
from Fe2O3 to TiO2, resulting in prolonging the photogenerated charge
carrier.
Further to photocatalytic investigations, the MB degradation ki-
netics were also investigated by plotting –ln (C/C0) with irradiation
time (Fig. 11b). A linear correlation was obtained for all the samples
which is fitting well with a pseudo first-order model (Fig. 11c). The
kinetic data is shown in the Table 4. The recyclability of the TiO2/α-
Fe2O3 nanocomposite (TF1:1) was studied up to 5-cycles of photo-
catalytic degradation of MB (20 mg L−1) (Fig. 11c). It was found that
about 92% degradation of MB was achieved even after the 5th cycle,
Fig. 10. N2 adsorption–desorption isotherms of the as synthesized nanomater- indicating that the TiO2/Fe2O3 nanocomposite can be used as stable
ials.
and recyclable catalyst under visible light irradiation.

Table 3
The Surface area and the porous parameters of the as prepared nanomaterials. 3.8. Mechanism of the photocatalytic activity
2
Nanomaterial BET (m /g) Pore Volume (cc/g) Pore size (nm)
Based on the above results, the mechanism of the photocatalytic
Pure TiO2 124.23 1.79 × 10−2
1.76 activity of TiO2/α-Fe2O3 nanocomposite can be described as following:
TF 10 168.42 3.82 × 10−2 2.63 under visible light irradiation the electron-hole pair will be generated in
TF 20 189.00 4.24 × 10−2 2.83 Fe2O3. The photogenerated electrons on CB of Fe2O3 can be transferred
TF 50 199.32 4.33 × 10−2 3.23 to the CB of TiO2 through the developed TiO2/α-Fe2O3 heterojunction,
TF 100 289.90 7.87 × 10−2 4.04
therefore, the rate of e−-h+ pair recombination will be reduced, in-
creasing the rate of charge carrier transfer and enhancing the

Fig. 11. (a)UV–vis absorption spectra of an

aqueous solution of MB during illumination in
the presence of α-Fe2O3, (b) efficiency of the
photocatalytic degradation of MB as the varia-
tion of C/C0 with irradiation time in the pre-
sence of various nanomaterials, (c) linear plots
of – ln C/C0 vs time for the experimental data in
Fig. 10(b) and (d) recyclability of the TiO2/α-
Fe2O3 nanocomposite in the photocatalytic
degradation of MB.

10
H.H. Mohamed, et al.
Fig. 12. (a) Schematic illustration of proposed mechanism of the photocatalytic degradation of MB dye on TiO2/α-Fe2O3 nanocomposite under visible light irra-
diation. (b) Photoluminescence spectra of pure Fe2O3 and TiO2/Fe2O3 nanocomposite (TF1:1).
photocatalytic activity. The possible mechanism of the photocatalytic
activity of TiO2/α-Fe2O3 nanocomposite was given by Fig. 12 (a) and
described by the following equations:
Fe2 O3 + hv → Fe2 O3 (e− + h+)
Fe2 O3 (e−) → TiO2 (e−)
TiO2 (e−) + O2 → O∙−
O∙− + MB dye → →CO2 + H2 O
Fe2 O3 (h+) + HO− → HO∙
HO∙ + MB dye → →CO2 + H2 O
The improved separation of charge carriers in TiO2/ Fe2O3 nano-
composite has been confirmed by photoluminescence spectroscopy
(Fig. 12(b)). Emission spectrum with maximum at 773 nm was observed
for pure Fe2O3. TiO2/Fe2O3 nanocomposite exhibits much lower emis-
sion intensity than pure Fe2O3, indicating the recombination of pho-
togenerated charge carrier is greatly inhibited in the TiO2/Fe2O3 het-
erojunction.
4. Conclusions
Eco-friendly, TiO2, α-Fe2O3 nanospheres and TiO2/α-Fe2O3 nano-
composite with various percentage ratios were successfully synthesized
using aqueous flax seed extract (FSE) under ultrasonic waves. The
crystal structure, morphology, optical properties and surface area of the
prepared nanomaterials was determined using various techniques. SEM
and TEM analysis revealed that the materials prepared in the presence
of FSE showed controlled shape and narrow particle distribution as
compared to those prepared without FSE, suggesting an important role
of FSE as bio-templating and stabilizing agent. The nanocomposites of
TiO2 and α-Fe2O3 displayed the enhanced photocatalytic performance
(in the visible region) for the degradation of organic dye MB as com-
pared to individual TiO2 and α-Fe2O3. The efficiency was increased
with the increase of α-Fe2O3 amount in the composite. The TF1:1 na-
nocomposite shows the best photocatalytic efficiency among the other
prepared nanocomposites: TF1:0.1, TF1:0.2 and TF1:0.5. This enhanced
efficiency can be attributed to higher surface area, enhanced energy
harvesting properties and electron-hole pair separation due to spatial
electron transfer from TiO2 to α-Fe2O3. The suggested method is simple,
low-cost and environmentally friendly for the production of nano-
particles as efficient photocatalyst for water remediation.
Declaration of Competing Interest
The authors declare that they have no competing interests.
Acknowledgments
The authors acknowledged College of Science and Basic and Applied
Research Center at Imam Abdulrahman Bin Faisal University. National
Journal of Photochemistry & Photobiology A: Chemistry 382 (2019) 111951
Research Center (NRC), Giza, Egypt, is gratefully acknowledged.
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