Journal of Colloid and Interface Science 450 (2015) 213–223

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Journal of Colloid and Interface Science

www.elsevier.com/locate/jcis

Highly effective Fe-doped TiO2 nanoparticles photocatalysts for visible-

light driven photocatalytic degradation of toxic organic compounds
Swati Sood a, Ahmad Umar b,c,⇑, Surinder Kumar Mehta a, Sushil Kumar Kansal d,⇑
a
Department of Chemistry, Panjab University, Chandigarh 160014, India
b
Department of Chemistry, College of Science and Arts, Najran University, P.O. Box-1988, Najran 11001, Saudi Arabia
c
Promising Centre for Sensors and Electronic Devices (PCSED), Najran University, P.O. Box-1988, Najran 11001, Saudi Arabia
d
Dr. S.S.B University Institute of Chemical Engineering & Technology, Panjab University, Chandigarh 160014, India

g r a p h i c a l a b s t r a c t

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

Article history: This paper reports the synthesis of various molar concentrations of iron (Fe)-doped TiO2 nanoparticles
Received 11 February 2015 and their efficient use as potential photocatalysts for photocatalytic degradation of toxic and harmful
Accepted 9 March 2015 chemical, paranitrophenol. The nanoparticles were synthesized by a novel and facile ultrasonic assisted
Available online 16 March 2015
hydrothermal method and characterized in detail by various analytical techniques in terms of their mor-
phological, structural, compositional, thermal, optical, pore size distribution, etc properties. The
Keywords: photocatalytic activities of the as-prepared Fe-doped TiO2 nanoparticles were examined under visible
Fe doped TiO2 nanoparticles
light illumination using para-nitrophenol as target pollutant. By detailed experimental findings revealed
Ultrasonic–hydrothermal synthesis
Photocatalyst
that the Fe dopant content crucially determines the catalytic activity of TiO2 nanoparticles. The maximum
Para-nitrophenol degradation rate of para-nitrophenol observed was 92% in 5 h when the Fe3+ molar concentration was
0.05 mol%, without addition of any oxidizing reagents. The prepared nanoparticles demonstrated excel-
lent photocatalytic response because of their small size, excellent crystalline structure, increase in
threshold wavelength response and maximum separation of photogenerated charge carriers. Further,
the determination of reaction intermediates has also been carried out and plausible mechanism of
photocatalytic degradation of para-nitrophenol has been proposed.
Ó 2015 Elsevier Inc. All rights reserved.

⇑ Corresponding authors at: Department of Chemistry, College of Science and

Arts, Najran University, P.O. Box-1988, Najran 11001, Saudi Arabia (A. Umar).
Fax: +91 172 2534920, +966 534574597.
E-mail addresses: ahmadumar786@gmail.com (A. Umar), sushilkk1@yahoo.co.in,
sushilkk1@pu.ac.in (S.K. Kansal).

http://dx.doi.org/10.1016/j.jcis.2015.03.018
0021-9797/Ó 2015 Elsevier Inc. All rights reserved.
214 S. Sood et al. / Journal of Colloid and Interface Science 450 (2015) 213–223
1. Introduction
Nitrophenols are the one among the highly persistent organic
contaminants found in industrial effluents, agricultural and
urban wastewater, which are extensively used in production of
various drugs, chemicals, pesticides, dyes and pigments [1–5].
Nitrophenols impose dreadful health hazards to living organisms
like cancer and disorders in various vital organs, blood and the cen-
tral nervous system. Substituted phenols such as para-nitrophenol,
ortho-nitrophenol, and dinitrophenols have been enlisted as
‘‘Priority Pollutants’’ by the US E.P.A. [6–8]. Dyes constitute another
class of harmful and visibly recognized pollutants present in
wastewaters. Various industries such as textile, printing, pulp
and paper, food, leather tanning, hair coloring and photographic
industries are responsible for their massive usage and indiscrimi-
nate disposal into the water bodies [9–13]. It thus becomes a mat-
ter of prime concern to completely degrade these organic
pollutants before discharging them into the environment.
Nowadays, one of the most advanced and globally accepted
techniques is the photocatalysed oxidation processes using semi-
conducting metal oxide nanoparticles like TiO2 which has rela-
tively wide band gap of 3.2 eV. Thus, TiO2 is photoactive only
under ultraviolet (UV) light region of the solar spectrum. While,
the major portion of the freely available solar energy comprises
of visible light [13–16]. Because of the massive energy crisis, fab-
rication of new visible light responsive nanomaterials for the
photocatalytic decomposition of organic pollutants is attaining a
major concern. One of the strategies is to introduce a metal ion
dopant into the matrix of photocatalyst, which yields following
benefits: (a) Inhibits recombination of photogenerated e/h+ pairs
(b) increases the threshold wavelength response range into visible
region. Amongst various metals, Fe is considered to be a suitable
transition metal candidate as dopant because: (i) the ionic radius
of Fe3+ (0.69 Å) is nearly same as that of Ti4+ (0.745 Å) as a result,
Fe3+ can be conveniently integrated into TiO2 matrix; (ii) its stable
half filled d5 configuration and (iii) Furthermore, Fe3+ act as charge
carrier trap and inhibits the recombination of photogenerated elec-
tron–hole pair, and logically adds to enhanced photoactivity. But,
the role of Fe3+ ions in TiO2 photocatalysis is somewhat controver-
sial. In literature, many authors have reported enhancement in
photocatalytic activity upon introduction of Fe dopant [17–23].
And, there also have been few reports citing the detrimental
behavior of Fe ions in photocatalysis, as they behave as charge car-
rier traps and promote electron–hole recombination [23–25]. So, it
is interesting to study the effect of Fe3+ ions on the catalytic behav-
ior of TiO2.
Till now, TiO2-based photocatalysts have been synthesized
globally by a number of techniques, specially the solvothermal
processes because these chemical solution synthesis routes offer
certain advantages [26–28]. Uniform doping of metal ions into
the lattices of metal oxide can be achieved with high dispersion
ability. Additionally, by monitoring experimental conditions, one
can easily synthesize nano-architectured materials with variable
sizes and tunable properties. Since last decade, significant research
has been dedicated to the heterogeneous semiconductor photocat-
alytic technology for degrading 4-nitrophenol (4-NP) with
Fenton’s, UV with H2O2, UV with Photo-Fenton reagents and UV,
TiO2 and H2O2 [29–36]. But, these suffer through some shortcom-
ings like incomplete removal of the pollutant and addition of
chemicals further enhances the problem of environmental
pollution.
In the present work, Fe (III) doped TiO2 photocatalysts have
been synthesized by a hydrothermal method assisted by ultrasonic
radiations. The synthesized nanomaterials have been further
characterized using various techniques to study their crystalline
phase, morphology, surface area, composition, optical and
luminescent properties. The photocatalytic activity of the catalysts
and the effect of dopant concentration on photodegradation of
4-NP and methylene blue (MB) dye under visible light have been
investigated. The intermediates produced during the course of
degradation and the plausible mechanism has also been studied.
2. Experimental
2.1. Materials
All the materials used in this work are of analytical reagent
grade. Iron (III) nitrate nonahydrate (Ferric nitrate (Fe
(NO3)39H2O), sodium hydroxide (NaOH), nitric acid (HNO3) and
ethanol (C2H5OH) were purchased from Merck (India) and tetra-
butyl titanate (Ti(BuO)4) used for the preparation of the catalysts
from Sigma–Aldrich (Germany). The target pollutants, 4-nitrophe-
nol and methylene blue (C.I. 52015) were obtained from Merck,
India. The commercially available photocatalysts, TiO2 P25 from
Degussa (Germany) and ZnO from Merck (India) were used. All
the solutions were prepared in doubly distilled water.
2.2. Synthesis of as-prepared Fe-doped TiO2 nanoparticles
Tetrabutyl titanate (Ti(BuO)4), used as TiO2 precursor was
added drop-wise to 10 M NaOH solution. Further, 50 mL of Ferric
nitrate solution (the molar ratio of Fe:Ti = 0.025, 0.05, 0.075,
0.1 mol% Fe) was added to it drop-wise. The pH of solution was
maintained <7 by addition of 0.1 N HNO3. The reaction mixture
was then irradiated with high intensity ultrasonic radiations for
1 h, subsequently treated hydrothermally at 200 °C for 12 h. The
obtained precipitates were then centrifuged and washed several
times with distilled water and ethanol. After proper washing, the
obtained products were dried overnight in an electric oven at
80 °C. All the dried products were then ground to get fine powders,
which were subjected to calcination treatment at 450 ° for 2 h. The
samples thus, obtained with molar ratio of Fe:Ti = 0.025, 0.05,
0.075 and 0.1 mol% Fe were designated as 0.025 FeT, 0.05 FeT,
0.075 FeT and 0.1 FeT, respectively. Pristine TiO2 nanoparticles
were also obtained following the same method, without adding
Fe (III) salt.
2.3. Characterization of as-prepared Fe-doped TiO2 nanoparticles
The crystal structure of prepared samples was studied by pow-
der X-ray diffraction (XRD) with a PANalytical Model X’Pert PRO
diffractometer using Cu Ka radiation (k = 1.54056 Å) at 45 kV and
40 mA by scanning at a rate of 2° (2h) min1. In order to study mor-
phology and structures, Field emission scanning electron micro-
scope (FESEM) JEOL-JSM-7600F and Transmission electron
microscope (TEM) a Hitachi H-7500 electron microscope at
120 kV was used. FT-IR spectra were recorded between the wave
number of 400 and 4000 cm1 on thermoscientific (Nicolet iS50)
FT-IR spectrometer, equipped with a diamond ATR. A Perkin–
Elmer STA 6000 TGA/DSC analyzer was used to carry out the
thermogravimetric analysis of the sample. The analysis was per-
formed at a constant heating rate of 10 °C per minute up to
1000 °C. The PL spectrum was measured on Hitachi F-7000 fluores-
cence spectrophotometer (5J1-004 model) using quartz cuvette of
1 cm path length at the excitation wavelength of 300 nm. The
UV–vis absorption studies of the photocatalysts were conducted
on UV–vis diffuse reflectance spectrophotometer (Shimadzu
UV-2450), with BaSO4 as reference. X-ray photoelectron spec-
troscopy (XPS) was performed on AMICUS, Kratos Analytical
 S. Sood et al. / Journal of Colloid and Interface Science 450 (2015) 213–223 215

(Shimadzu group company), using monochromatic source Mg Ka

(1253.6 eV). BET surface area of the samples was analyzed by nitro-
gen adsorption–desorption in a N2 adsorption analyzer (NOVA
2000e) USA. All the samples were degassed at 423 K for 8 h. The
BET surface area was determined by using the multipoint BET
method. The pore-size distribution was found by the Barret–
Joyner–Halender (BJH) method using the adsorption branch of iso-
therm. The pH of solutions was adjusted using a Mettler Toledo
(FEP20) pH meter.

2.4. Photocatalytic experiments and identification of reaction

intermediates

The photocatalytic experiments were performed in a specially

designed double walled batch photo reactor. The experimental
procedure for the photodegradation was similar to our previous
reports [37]. The catalytic activity of all photocatalysts was studied
for degradation of 4-NP (10 mg/L aqueous solution, pH 4) and MB
(10 mg/L aqueous solution, pH 7) with catalyst loading of 0.5 g/L.
The pH of the solution was adjusted using 0.1 N HCl (or) 0.1 N
NaOH. In order to attain adsorption–desorption equilibrium, the
reaction mixture was magnetically stirred in dark for half hour. A
150 W Philips CFL bulb was used as a visible light source (the aver-
age light intensity was 1475 lux, wavelength range of 400 nm–
520 nm). At certain intervals, the aliquot was drawn and filtered
through a 0.45 lm Millipore filter. Obtained filtrates were then
analyzed by studying the maximum absorbance values at different
time intervals using a Systronics-2202 spectrophotometer.
Liquid chromatography–mass spectroscopy (LC–MS) was
employed to study the reaction intermediates produced during
4-NP degradation using the Q-TOF Microwaters LCMS system com-
posed of C18 column (Waters X-Terra, 100 mm  2.1 mm, 5 lm).
Fig. 1. XRD pattern of (a) synthesized TiO2 nanoparticles; (b) different Fe doped x%
The mobile phase composed of an isocratic gradient of 70% ace- TiO2 nanoparticles.
tonitrile (CH3CN) and 30% H2O + 5 mM ammonium acetate
(NH4CH3CO2) + 0.1% (v/v) acetic acid (CH3CO2H).

iron or iron compounds, which shows that there is dispersion of

3. Results and discussion
Visible light responsive photocatalysts i.e. Fe-doped TiO2 nano-
particles (x% FeT) were synthesized by an ultrasonic–hydrothermal
method and then characterized in details to determine their crys-
talline, morphological, compositional, optical, photoluminescent
properties. The photocatalytic activity of the prepared samples
was investigated for the degradation of 4-NP and MB.
3.1. Characterizations and properties of as-prepared Fe-doped TiO2
nanoparticles
The XRD patterns of prepared TiO2 and Fe doped TiO2 nano-
powders at different doping concentrations are shown in Fig. 1.
XRD studies show that the TiO2 and Fe (III) doped catalysts
annealed at a temperature of 450 °C have both anatase and rutile
structures with a dominance of anatase structure. In Fig. 1(a), the
2h peaks observed at 25.61°, 38.10°, 48.47°, 54.24°, 55.36°,
62.99°, 69.20°, 70.59°, 75.47° in the XRD pattern of TiO2 nanopow-
ders are consistent with anatase (1 0 1), (1 0 3), (0 0 4), (2 0 0), (1 0 5),
(2 1 1), (2 0 4), (1 1 6), (2 2 0) and (1 0 7) lattice planes (JCPDS No. 21-
1272). The diffraction peaks corresponding to rutile phase also
appeared at 2h = 27.5° and 41.54° corresponding to (1 2 1) and
(1 1 1) planes (JCPDS No. 21-1276). The peaks for pristine and
doped TiO2 appear similar, but in case of Fe doped TiO2 samples,
there was some noticeable reduction in peak intensity. This sug-
gests that some perturbation takes place in anatase structure after
the introduction of Fe (III) ions [Fig. 1(b)] [25,38–40]. The diffrac-
tograms of all the samples do not show any diffraction peaks of
metal ions on TiO2, which can be attributed to very low dopant
amount in these samples or replacement of Ti (IV) ions by Fe (III)
ions into TiO2 matrix. For the coordination number 6, the ionic
radius of Ti4+ is 0.745 Å and that of Fe3+ is 0.69 Å, it is easily
assumed that Ti4+ is substituted by Fe3+ [41–43]. Because of low
iron content no Fe2O3 phase was formed [25–27]. Scherrer formula
was used to find the crystallite size of the synthesized products
and was found to be 25 nm. These observations show that Fe3+
ions have been successfully introduced into TiO2.
The detailed morphological characterization of Fe doped TiO2
were examined by field emission scanning electron microscopy
(FESEM) and transmission electron microscopy (TEM). It can be
seen from FESEM images (Fig. 2) that the prepared nanoparticles
are of about 20 nm in size, possess spherical shapes and are grown
in high-density. Slight agglomeration was also seen. A detailed
TEM analysis was carried out to obtain more information about
the nature of Fe ions doped on TiO2 matrix and it was observed
as shown in Fig. 3 that the crystals included both TiO2 (bigger)
and Fe dopant (smaller) particle. The grey particles in TEM images
are TiO2 nanoparticles and the dark particles are Fe dopants on the
grey surface of TiO2 particles [28,42]. Nearly spherical shaped par-
ticles ranging from 10 to 20 nm are observed. The particle sizes
obtained from FESEM and TEM analysis are nearly in agreement
with each other
FTIR spectra were also recorded between the wave number of
400 and 4000 cm1 for all the samples. The FTIR spectrum of all
the FeT samples is shown in Fig. 4 for which nearly similar patterns
were observed. Various well-defined peaks were seen. The peak at
3330 cm1 is assigned to the absorption of surface OH bonds. The
216 S. Sood et al. / Journal of Colloid and Interface Science 450 (2015) 213–223

Fig. 2. Typical FESEM images of (a) and (b) 0.025 FeT; (c) and (d) 0.05 FeT; (e) and (f) 0.075 FeT; (g) and (h) 0.1 FeT samples at different magnifications.

peak at 1640 cm1 corresponds to H O–H bending vibration of
adsorbed water [11,43]. It was deduced that, the introduction of
Fe (III) ions into TiO2 matrix results in such changes that lead to
the absorption of more amounts of OH groups. This is further an
added advantage in the photocatalytic properties of the catalyst.
Ti–O stretching peaks are also observed around 400–500 cm1
[11].
Thermal analysis of the doped TiO2 catalyst was performed.
Fig. 5 shows the TGA and DSC curves for the 0.05 FeT catalyst. It
is seen that catalyst possesses excellent thermal stability and high
purity. The final weight loss (up to a temperature of 1000 °C) of the
sample is only about 3%. The weight loss of about 1% seen till 100C
is because of loss of adsorbed water on the surface of the catalyst.
Further, the region of weight loss from 200 to 600 °C can be
observed because of decomposition of organic solvents, also
reflected in the DSC curve’s exothermic peaks localized at mainly
360 °C. After 600 °C, no major weight loss is seen, which confirms
the stability and purity of prepared catalyst.
In order to study the optical absorption characteristics of the
prepared samples, UV–vis diffuse reflectance spectroscopy was
performed. Fig. 6 shows the UV–vis DRS spectra of TiO2 and FeT
samples. It was observed that absorption was significantly
enhanced with increasing content of Fe dopant. The introduction
of dopant (Fe3+ ions) into TiO2 matrix, leads to enhancement in
absorption of light, extending the spectral response of photocata-
lyst to 426 nm. By increasing the Fe content, the Ebg are hence,
decreased. The Ebg of 0.1 FeT catalyst is 2.9 eV, which is lower than
that of bare TiO2 catalyst prepared by this method (3.2 eV).
The changes in color of the samples observed, from white
(TiO2), cream (0.025 FeT, 0.05 FeT) to crème yellow (0.1 FeT) can
 S. Sood et al. / Journal of Colloid and Interface Science 450 (2015) 213–223
Fig. 3. Typical TEM images of as-prepared (a) and (b) 0.05 FeT and (c) and (d) 0.075 FeT nanoparticles.
Fig. 4. Typical FTIR spectra of as-prepared different Fe doped x% TiO2 nanoparticles.
Fig. 5. TGA/DSC curve of as-prepared 0.05 mol% Fe doped TiO2 nanoparticles.
217
be attributed to the increase in visible light absorption upon
increasing the Fe (III) dopant concentration. It has been suggested
that this visible light absorption can arise because of: (i) the forma-
tion of a Fe3+/Fe4+ dopant energy level within the band gap of TiO2.
(ii) d–d transition of Fe3+ (2T2g ? 2A2g, 2T1g) or the charge transfer
(CT) transition between the Fe ions [26,27]
To investigate the role played by Fe3+ ions on fate of charge car-
riers, room temperature PL was recorded for all the samples from
320 to 550 nm wavelength range at an excitation wavelength of
300 nm at a PMT operating voltage of 600 V. It has been reported
that, bare TiO2 nanoparticles exhibit the inter-band recombination
emission peak at around 360 nm [44–46]. As compared to sole
TiO2, Fe doped samples revealed a decrease in the PL intensity,
which indicates that they inhibit the recombination of photo elec-
tron and hole pairs (Fig. 7). It can also be seen that 0.075 and
0.050 mol% Fe samples show a maximum decrease in intensity
Fig. 6. Typical UV–vis spectra of as-prepared different Fe doped x% TiO2
nanoparticles.
218 S. Sood et al. / Journal of Colloid and Interface Science 450 (2015) 213–223
Fig. 7. Typical room-temperature photoluminescence spectra of as-prepared
different Fe doped x% TiO2 nanoparticles.
which is because of optimum dopant amount which acts as trap for
photo-electron and hole pairs, thereby improving the separation of
charge carriers [17–23]. But at higher concentration of 0.1% molar
Fe (III) ions, the emission spectrum is different. At higher concen-
trations Fe ions act as recombination centers instead [24,25].
Therefore, leading to an expected increase in intensity as compared
to other Fe doped TiO2 samples of lesser dopant concentration.
Since, the Fe doped TiO2 samples possess excellent optical and
photoluminescent behavior, further X-ray photoelectron spec-
troscopy (XPS) analysis was also performed in order to investigate
its electronic environment and oxidation state. Fig. 8(a) shows the
Fig. 8. (a) XPS spectrum of as-prepared 0.05 mol% Fe doped TiO2 nanoparticles; (b) core level spectra of characteristic Ti 2p; (c) Fe 2p; and (d) O 1s.
XPS survey spectrum of 0.05 FeT and Fig. 8(b)–(d) depicts core
level spectra of characteristic elements. From Fig. 8(a) it is clear
that 0.05 FeT sample contains Ti, O and Fe. The peak for C 1s at
binding energy of 284.8 eV was observed due to the adventitious
hydrocarbon from XPS instrument. Fig. 8(b) shows the Ti 2p bind-
ing energy region. The Ti 2p3/2 and Ti 2p1/2 spin–orbital splitting
photoelectrons for the sample is located at binding energies of
458.7 eV and 464.3 eV, respectively. These values are all in good
agreement with values of Ti4+ [28,47]. Fe 2p spectrum shown in
Fig. 8(c) depicts peak at 707.6 and 722 eV, which belong to the
binding energy of Fe 2p3/2 and Fe 2p1/2 respectively [23,28]. This
suggests that dopant of Fe in TiO2 lattice shows a chemical state
of Fe3+. In the O (1s) spectrum (Fig. 8(d)) peak seen at binding
energy 529.9 eV corresponds to the lattice oxygen of TiO2 [17].
N2 physical adsorption–desorption studies were conducted to
determine the surface area and the pore structure of the synthe-
sized catalyst. The BET isotherms and their relative Barret–
Joyner–Halender (BJH) pore size distributions obtained from the
adsorption branch of the isotherms of the catalysts are shown in
Fig. 9. It was observed that the prepared catalysts possess meso-
porous surface as the isotherms are of Type IV. The multipoint
BET specific surface area for bare TiO2, 0.025 FeT, 0.05 FeT, 0.075
FeT and 0.1 FeT samples was found to be 50.21 m2/g, 45.04 m2/g,
44.96 m2/g and 40.17 m2/g and 37.33 m2/g respectively (from the
adsorption data in relative pressure (P/P0) range 0.05–0.3). It was
observed that the surface area for undoped and doped catalyst
were found to be closer but showed a relative decrease. From the
(BJH) pore size distributions it was observed that the samples
showed a narrow pore size distribution. Table 1 summarizes the
surface area, pore volume and pore radius data obtained from vari-
ous methods for different photocatalysts.
 S. Sood et al. / Journal of Colloid and Interface Science 450 (2015) 213–223 219

Fig. 9. N2 adsorption–desorption BET isotherm for (a) 0.025 mol% Fe-doped TiO2 nanoparticles; (b) 0.05 mol% Fe-doped TiO2 nanoparticles; (c) 0.075 mol% Fe-doped TiO2
nanoparticles; and (d) 0.1 mol% Fe-doped TiO2 nanoparticles. The insets show the BJH pore size distributions (from the adsorption branch of the isotherms).

Table 1
Surface area, pore volume and pore radius obtained from different methods for Fe doped TiO2 nanoparticles.

Catalyst property 0.025 mol% Fe 0.05 mol% Fe 0.075 mol% Fe 0.1 mol% Fe
BJH DH DFT BJH DH DFT BJH DH DFT BJH DH DFT
Cumulative surface area adsorption (m2/g) 27.28 27.73 33.16 28.73 29.25 33.21 26.46 26.86 31.07 26.78 27.23 33.62
Cumulative surface area desorption (m2/g) 31.03 31.54 – 31.31 31.85 – 30.39 30.85 – 30.54 31.04 –
Cumulative Pore volume (adsorption) (cc/g) 0.150 0.146 0.094 0.143 0.140 0.091 0.184 0.179 0.097 0.146 0.142 0.094
Cumulative Pore volume (desorption) (cc/g) 0.1504 0.147 – 0.144 0.141 – 0.185 0.1805 – 0.147 0.144 –
Pore radius adsorption (nm) 1.605 1.605 – 1.598 1.598 1.448 2.028 2.027 – 1.604 1.604 –
Pore radius desorption (nm) 1.588 1.588 – 1.575 1.575 – 1.602 1.602 – 1.602 1.602 –

3.2. Photocatalytic degradation of 4-NP
As has been mentioned above, owing to its highly stable and
stubborn nature, the photocatalytic degradation of 4-NP is gener-
ally carried out by using oxidizing reagents such as Fenton’s,
H2O2, photo-Fenton reagents under UV light. But, in this work we
are trying to obtain better photocatalytic results without addition
of any oxidizing reagent and by monitoring the concentration of
Fe (III) ions doped in TiO2. Fig. 10(a) shows the absorption spectra
of 4-NP (pH 4) at different time intervals using 0.05 mol% FeT cata-
lyst under visible light irradiation. It is seen that absorbance at kmax
315 nm progressively decreases as the irradiation time increases.
This indicates that the pollutant is successfully degrading on the
surface of photocatalyst with time. However, without addition of
any photocatalyst no considerable degradation was observed
(Fig. 10(b)). The experiments were also conducted without
illumination, in order to check the physical adsorption of pollutant
over the catalyst. A very slight decrease in concentration of the pol-
lutant was observed, showing that the decrease in absorbance is
primarily due to photodegradation process, as illustrated in
Fig. 10(b).
It has always been interesting to study the effect of Fe3+ ions on
the catalytic activity of titania. So, in order to evaluate the
photocatalytic activity of FeT catalyst and determine the optimum
220 S. Sood et al. / Journal of Colloid and Interface Science 450 (2015) 213–223

Fig. 10. (a) UV–vis absorbance spectra of visible light induced degradation of 4-NP aqueous solution (10 mg/L), (0.05 mol% Fe-doped TiO2 nanoparticles, Catalyst dose:
0.05 gm/L, pH: 4); (b) Comparison of photocatalysis, adsorption and photolysis; (c) Effect of Fe doping on % degradation rate of 4-NP; (d) Comparison of % photodegradation of
synthesized catalysts with those of commercial catalysts.

content of Fe (III) ion dopants, a set of experiments were performed
for photocatalytic degradation of aqueous solutions of 4-NP under
visible light illumination. As shown in Fig. 10(c) it was found that,
as compared to the bare TiO2, the 4-NP photocatalytic degradation
rate of Fe doped samples is higher. The maximum degradation rate
of 92% in 5 h is observed when the Fe doping content is 0.050 mol%
because this causes maximum separation of photogenerated
charge carriers, hence resulting in excellent photocatalytic activity.
If Fe content is further increased, it leads to a decrease in the
photocatalytic behavior of the catalyst, also well supported by
the PL spectra.
In order to study the effect of very high Fe dopant concentra-
tion, photocatalytic experiments under similar conditions were
also performed by using 1 mol% Fe doped TiO2 sample. And it
was found that a very high Fe concentration in TiO2 can drastically
affect the photocatalytic activity. The photocatalytic degradation
rate was reduced merely to 28%. This is because at very high
amounts of Fe ions act as recombination centers for the photoelec-
trons and holes. And hence prove detrimental for the photocat-
alytic activity of TiO2.
As we are well aware that because of tremendous development
in the field of semiconductor photocatalysis, there are a wide num-
ber of commonly and commercially available photocatalysts. So it
has become essential to compete with the efficiency of such
photocatalysts which are available in market. So, we compared
the obtained degradation rates of prepared photocatalyst with that
of commercially available photocatalysts such as ZnO (Merck) and
TiO2 (P25) as illustrated in Fig. 10(d). And it was found that the
prepared 0.05 FeT sample shows maximum degradation rate, while
ZnO and P25 are not very effective in degrading 4-NP in visible
light. The excellent visible light photocatalytic activity of the pre-
pared Fe doped TiO2 nanoparticles can be attributed to their excel-
lent crystallinity, unique morphology, more number of surface
absorbed OH ions, better visible light response and inhibition of
recombination of photogenerated electrons and holes.
3.3. Identification of degradation intermediates and possible
degradation pathways
Since, 4-NP is a highly toxic and hazardous compound, it is
important to study the pathway and the intermediates produced
during the course of degradation reaction. We know that, OH is
an electrophilic radical which attacks the activated ring position.
Phenolic group (–OH) being an electron donating group (edg)
enhances the electron density at the ortho and para positions of
the ring. On the other hand NO2 is an electron withdrawing group
 S. Sood et al. / Journal of Colloid and Interface Science 450 (2015) 213–223
(ewg) which is strongly deactivating and a meta-director. In com-
pounds where both edg and ewg are present as in the case of nitro-
phenols, the electrophilic attack takes place at ortho and para
positions with respect to the –OH group [34]. As a result in 4-NP,
the electrophilic attack by the OH may result in formation of
para-nitrocatechol (PNC) (Reaction (1)). The primary intermediate
obtained during the photocatalytic degradation of 4-NP is PNC
which was determined by the LCMS analysis (m/z 156). Similar
results have been reported in literature [34,48]. Further, the pres-
ence of 1,2,4 trihydroxybenzene (THB) was also observed. The
attack of OH radical on ortho and para positions of PNC results
in the formation and hence detection of THB at m/z value of
126.9 in LCMS (Reaction (1)) [49]. Another pathway is the abstrac-
tion of NO2 from 4-NP, resulting in the formation of Hydroquinone
(HQ) shown in Reaction (2). Another identified intermediate was
benzoquinone (BQ) at m/z value of 108, produced because of highly
oxidizing reaction of reaction of HQ with oxygen radical O2
(Reaction (2)). LC–MS spectra obtained for the parent and inter-
mediate compounds have been provided in the Supplementary
information.
The fate of radicals such as H and NO2 generated in reactions 1
and 2 are shown in reactions 3 and 4, respectively. The H reacts
with water to produce hydrogen and OH, which may be utilized
for the oxidative processes or may react with photogenerated elec-
tron to produce OH (Reaction (3)). As shown in Reaction (4), NO2
may also react with photogenerated electron to generate NO 2 and
subsequently to NO 3 ions (m/z 62). From these studies it was
inferred that 4-NP breaks down subsequently into intermediates
such as PNC, BQ, THB and simpler molecules such as NO 3 . The
schematic reactions of 4-NP degradation have been illustrated in
Scheme 1.
3.4. Photocatalytic degradation of MB dye
To confirm the versatility in visible light driven catalytic behav-
ior of the prepared catalysts, a number of photocatalytic degrada-
tion experiments were carried out using all the prepared catalysts
Scheme 1. Proposed pathway for the photocatalytic degradation of 4-NP using Fe doped TiO2 as photocatalyst.
221
on a widely used textile dye, MB. Fig. 11(a) shows that the charac-
teristic absorbance for the dye, in UV region i.e. 244 nm and
291 nm as well as that in visible region at 664 nm are diminishing
with time. Different Fe doped TiO2 samples (0.025 FeT, 0.05 FeT,
0.075 FeT and 0.1 FeT) were employed and the optimum dopant
concentration was found to be 0.075 mol% Fe (degradation rate
of 93% in 180 min). This is because of its high visible light response
and maximum decrease in PL intensity which inhibits the
recombination of photo-electrons and hole pairs. The comparison
of photocatalytic degradation efficiency rates for different catalysts
has been shown in Fig. 11(b). As already been discussed, the PL and
UV–vis studies support the obtained observations. The excellent
photocatalytic degradation results thus support the high visible
light activity and efficient removal of these pollutants from aque-
ous solutions, without addition of any oxidizing agent.
3.5. Proposed mechanism of photocatalytic reaction
The schematic diagram of visible light driven photocatalytic
reaction taking place on the surface of Fe (III) doped TiO2 has been
illustrated in Fig. 12. When light falls on the surface of TiO2
photocatalyst doped with Fe (III) ions (FeT), photogenerated elec-
trons and holes are generated (1). Fe3+ ions present in TiO2 can
act as electron and hole trap (2,3), resulting in formation of Fe2+
and Fe4+ ions, which are less stable as compared to Fe3+ ions
(due to half filled stable d5 configuration). So, the trapped charges
can be easily released back to form stable Fe3+ ions. This leads to
generation of OH radical and O2 anion (4–6). However, if Fe con-
centration is high, they may act as recombination centers for the
charge carriers thereby, reducing the photocatalytic activity (7,8).
Through a series of redox reactions, a number of charged species
and radicals with high redox potentials are generated (9–12).
These highly oxidizing species further oxidize the organic mole-
cules (P) and lead to formation of intermediates (S) and finally
their complete mineralization (13). The reactions have been
schematically shown from (1–13):
þ
FeT þ hm ! e þ h ð1Þ
222 S. Sood et al. / Journal of Colloid and Interface Science 450 (2015) 213–223

Fig. 11. (a) UV–vis absorbance spectra of visible light induced degradation of Methylene Blue dye aqueous solution (10 mg/L), (0.075 mol% Fe-doped TiO2 nanoparticles,
Catalyst dose: 0.05 gm /L, pH: 7); (b) Effect of Fe doping on % degradation rate of MB.

Fig. 12. Schematic diagram of mechanism of photocatalytic reaction taking place on the surface of Fe doped TiO2 nanoparticles.

Fe3þ þ e ! Fe2þ ð2Þ O þ H2 O !  OH þ OH ð12Þ

þ
Fe3þ þ h ! Fe4þ ð3Þ P þ  OH ! Intermediates þ  OH=OH  =O2
! CO2 þ H2 O; other simpler molecules ð13Þ
Fe2þ þ O2 ! Fe3þ þ O2 ð4Þ

4þ 3þ
Fe2þ þ Ti ! Fe3þ þ Ti ð5Þ
4. Conclusions
4þ  3þ
Fe þ OH ! Fe þ  OH ð6Þ To conclude, TiO2 nanoparticles doped with different molar
concentrations of Fe (III) ions were successfully fabricated by an
Fe3þ þ e ! Fe2þ ð7Þ ultrasonic assisted hydrothermal method followed by calcination.
Fe (III) doped TiO2 nanoparticles possess small size, hence larger
þ
Fe2þ þ h ! Fe3þ ð8Þ surface areas, more adsorbed OH groups and high visible light
response. From PL studies it was confirmed that optimal doping
3þ 4þ
Ti þ O2 ! Ti þ O2 ð9Þ of Fe (III) ions into TiO2 matrix leads to the inhibition of
recombination of charge carriers thereby, enhancing photochemi-
þ
O2 þ h ! O ð10Þ cal quantum efficiency. All this contribute to their excellent
photocatalytic activity for the degradation of para nitrophenol
O þ h ! O
þ
ð11Þ and Methylene Blue dye under visible irradiation. Also, the effect
of Fe dopant on photocatalytic behavior of TiO2 nanoparticles
 S. Sood et al. / Journal of Colloid and Interface Science 450 (2015) 213–223
was critically examined. The maximum degradation rate of para-
nitrophenol was 92% in 5 h when the Fe molar concentration was
0.05 mol%, without addition of any oxidizing agents. So, this work
is presented as a promising and easy work in the field of environ-
mental remediation in treatment of highly stable and toxic mole-
cules such as nitrophenols and dyes.
Acknowledgments
The authors greatly acknowledge the financial support received
under the UGC (Major Project), Government of India through a pro-
ject grant F. No. 41-364/2012(SR) and TEQIP-II grant of Dr. S.S.
Bhatnagar UICET, Panjab University, Chandigarh. Ahmad Umar
would like to acknowledge the support of the Ministry of Higher
Education, Kingdom of Saudi Arabia through a grant (PCSED-001-
11) under the Promising Centre for Sensors and Electronic
Devices (PCSED) at Najran University, Kingdom of Saudi Arabia.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.jcis.2015.03.018.
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