Effect of Iron Doping on the Properties of TiO2 Nanoparticles

Synthesized by Sol Gel Method

Mukesh Kumar1,a, Amanpal Singh1, Vanish Kumar2, Sumit Sharma1, Sumita Rani1,
Dinesh Kumar1
1
Electronic Science Department, Kurukshetra University, Kurukshetra-136119, Haryana, India
2
Central Scientific Instruments Organization, Chandigarh, India
a
kumarmukesh@gmail.com

Keywords: Titanium dioxide, nanoparticle, Sol gel, XRD, UV Vis spectroscopy

Abstract. The iron doped titanium dioxide nanoparticles were synthesized using Sol Gel
method. The effect of Fe doping on the bandgap and particle size was studied using XRD and
UV-Vis spectrophotometer. It was observed that size of particles decreased with increasing the
doping concentration. The particle size was found to be decrease from 25.5 nm to 14.6 nm on
increasing the concentrtion of iron from 0.00 mol% to 0.1 mol%. . The band gap was also found
to decrease with Fe doping from 3.85 eV to 3.03 eV.

Introduction
Titanium dioxide, TiO2, has attracted the attention of researchers worldwide because of its
applications in various fields. It exists in three main crystal structures: anatase, rutile, and
brookite. Different structures lead to different physical properties, which, in turn, are the basis
of various applications of TiO2. For instance, anatase is commonly used for photocatalysis
because of its high photoreactivity [1] and rutile is largely used for pigments due to its effective
light scattering properties [2]. Therefore, understanding of the mechanism and the factors
affecting phase stability and phase transformation is important. This will help in designing and
controllably manipulating relative phase types and their concentrations for more efficient uses.
With the increase of temperature, the possible phase transformation sequences among three
TiO2 main structures can be described as anatase to rutile, anatase to brookite to rutile, brookite
to rutile, and brookite to anatase to rutile. The transformation behavior depends on several
parameters such as the initial particle size [3–5], impurity (doping) concentration [6,7] starting
phase [8, 9] and reaction atmosphere. Rutile is the stable phase in bulk at room temperature,
while phase stability of nanoparticles depends on the particle size.
nanoparticles prepared by Sol Gel method can be of high purity and the process is
relatively cheap. The latter advantage results from the availability of high-purity chemical
precursor materials in conjunction with the simplicity of sol–gel preparation at room
temperature. Metal doping can alter the phase transformation and, consequently, the
photocatalytic activity of TiO2. One dopant of interest for photocatalysis and other
electromagnetic applications is iron. In the present paper the effect of iron doping on the crystal
size and bandgap of Sol Gel synthesized nanoparticles of TiO2 are reported.

Experimental
Titanium Tetra Iso-propoxide was mixed with ethanol and acetic acid in 1:9:0.5 molar ratios.
This solution was put on the continuous stirring with the help of magnetic stirrer. The obtained
sol was clear, homogenous with yellowish appearance. Then Ferric Chloride and 25 ml Ethanol
solution was added drop wise to the above solution with continuous stirring. The amount of
Ferric Chloride added varies according to dopant concentration and was kept at 0.005, 0.01,
0.05, 0.08, 0.2mol%. The solution was kept under constant stirring at 75 °C temperature on hot
plate for 1 hour. Then the sample was placed into crucible and then into oven at 100°C for one
day. The final product was crushed into fine powder with the help of Mortar and Pestle. The
crushed powder was calcinated at different temperatures for one hour in electric furnace.

Results and Discussion

In Fig. 1, the X-ray diffraction pattern of doped sample indicates the typical peaks of TiO 2
without any dopant related peaks up to 0.04 mol% Iron doping. The dopant ions may have been
moved either into interstitial sites or substitutional sites of the TiO 2 nanocrystal structure.
At 0.08% Iron doping peak of Fe 2O3 (020) was observed, which suggests that saturation
of iron has been occurred at 0.04 mol%. Presence of Fe 2O3 (020), (111), (112) and Fe (111)
crystals were observed at 0.1% doping. Nanoparticles of iron doped TiO 2 was found to be
smaller in size than pure TiO 2. This may be due to smaller radius of iron and formation of more
dense gel. By XRD analysis the particle size was found to be 25.5 nm, 24.3 nm, 22.5 nm, 14.6
nm, 14.6 nm for 0.005 mol%, 0.01 mol%, 0.05 mol%, 0.08 mol%, and 0.1 mol% iron doped
TiO2 nanoparticles.

Fig. 1 XRD diffraction pattern of TiO2 calcined at 400 degree for one hour. a,
r and b represents anatase, rutile and brookite phase of TiO 2 respectively.

As doping amount of iron was increased, the sharing of rutile phase also increased. In
fact, the presence of iron at 0.05mol% clearly facilitates the transformation from anatase to
rutile. In XRD data it is clear that at 0.05mol% rutile phase present just at 400°C, while in
undoped it appeared at 600°C.
 Fig. 2 UV-VIS spectra of titanium dioxide nanoparticles

Fig. 2 shows the UV-VIS spectra for different Iron concentration in TiO 2. The clear band
edge absorption in ultraviolet range could be observed in related spectra. It was observed that as
the concentration of iron increased in TiO 2, the band gap decreased. The Band gap decreased
from 3.85 eV to 3.03 eV on increasing dopant concentration 0.00 mol% to 0.1 mol%
respectively. Further, red shift associated with the presence of ions can be attributed to a charge
transfer transition between iron ions electrons and TiO 2 conduction and valence band. This
decrease in band gap may be due to lower band gap of dopant (iron), as dopant concentration
increases more mid gap states will be formed and hence decrease in overall band gap of
nanoparticles occurs. The most common approach to sensitize titania to visible light is by
doping the photo catalyst with transition metal ions in order to create intra band-gap states close
to the conduction or valence band edges and therefore, the resultant composite oxide will have a
lower band-gap energy (< 3.2 eV) than the pure titania..
Fig. 3 and 4 shows FE-SEM images of pure TiO 2 samples calcined at 400°C and 0.05%Fe
doped respectively. It was revealed that the dimension of TiO 2 nanoparticles are in the range of
40 to 50 nm, and the doped nanoparticles are of smaller in size i.e. 20 to 30 nm. It could be
observed from XRD and SEM analysis that the particle size of TiO 2 nanoparticles was
decreased with increasing dopant concentration. The particle in the above Figures shows the
formation of agglomerates of nanoparticles.
 Fig. 3 SEM images of pure TiO2

Fig. 4 SEM images of 0.05mol%Fe doped TiO2.

Conclusion

This paper has addressed issues central to the synthesis and characterization of iron doped Titanium
Dioxide nanoparticles. From XRD analysis it was concluded that Anatase phase presents at 400°C,
while Rutile phase presents at 800°C calcinations temperature. Transition temperature for Anatase
to Rutile phase was found to be 600°C. 0.05 mol% iron doped TiO 2 showed no peaks of iron, while
a peak of Fe2O3 was observed at 0.08 mol% iron doped TiO2. It concludes that saturation of iron
doping occurs at 0.05 mol% in TiO 2. From XRD data, the particles size was found to be 35 nm to
55 nm for pure TiO 2 calcined at different temperatures and reduction in size was observed from
25.5 nm to 14.6 nm after iron doping in TiO 2. A significant drop in band-gap energy of TiO 2 was
found between 3.85 to 3.03 eV on increasing the concentrtion of iron from 0.00 mol% to 0.1 mol%.

References
[1]. A.Sclafani, L.P almisano and E.Da vi: J., Photochem. Photobiol. Vol. A 56 (1991), p. 113
[2]. J.H.Braun: J. Coating Technol. Vol. 69 (1997), p. 59
[3]. H.Z.Zhang and J.F .Banfield: J. Mater. Chem. Vol. 8 (1998), p. 2073
[4]. H.Z.Zhang and J.F .Banfield; J. Phys. Chem. Vol. B 104 (2000), p. 3481
[5]. M.R.Ranade, A.Na vrotsky, H.Z.Zhang, J.F Banfield, S.H.Elder, A.Zaban, P.H.Borse, S.K.K
ulkarni, G.S.Doran, and H.J.Whitfield: PNAS 99 (2002), p. 6476

[6]. X.S.Y e, J.Sha, Z.K.Jiao and L.D.Zhang: NanoStruct. Mater. Vol. 8 (1997), p. 919
[7]. J.A.Gamboa and D.M.P asquevich: J. Am. Ceram. Soc.Vol. 75 (1992), p. 2934
[8]. B.Le vy: J. Electroceram. Vol. 1 (1997), p. 239
[9]. F.E.Ghodsi, F.Z.T epehan and G.G.Tepehan: Thin Solid Films Vol. 295 (1997), p. 11