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Journal of Molecular Catalysis A: Chemical 276 (2007) 4146

Effect of tantalum addition on anatase phase stability and

photoactivity of aqueous solgel derived mesoporous titania
K.V. Baiju a , P. Shajesh a , W. Wunderlich b , P. Mukundan a ,
S. Rajesh Kumar c , K.G.K. Warrier a,
aMaterials and Minerals Division, National Institute for Interdisciplinary Science and Technology,
Formerly Known as Regional Research Laboratory (CSIR), Thiruvananthapuram 695019, India
b Tokai University, Faculty of Engineering, Department of Material Science, Kanagawa 259-1292, Japan
c Centre for Materials for Electronic Technology, Hyderabad 500051, India

Received 15 May 2007; accepted 18 June 2007

Abstract
The effect of the addition of tantalum to nanocrystalline titania matrix on the photocatalytic activity is presented. The tantalum addition increases
the anatase phase stability to above 1000 C by inhibiting the increase in crystallite size of titania. All the tantalum added titania compositions
have higher surface area than pure titania. Transmission electron micrograph images support the reduction in crystallite size of titanium oxide in
presence of tantalum. Addition of tantalum above 1 mole percentage increases photocatalytic activity considerably and the activity is much higher
than that of commercially available Hombikat UV 100 titania. All the compositions containing tantalum have higher photoactivity than pure titania.
The synergistic effect of high surface area and small crystallite size is found to be responsible for the observed photocatalytic activity rates. The
aqueous solgel method adopted for the preparation of tantalum added titania from cheaper salt precursors and the resultant highly photoactive
titania make this investigation promising for various technological applications.
2007 Elsevier B.V. All rights reserved.

Keywords: Solgel; Titanyl oxysulphate; Photocatalyst; Anatase; Rutile

1. Introduction various extent [917]. Current literature available on tantalum

doping is restricted to the change in electrical properties and a
Titania is a well known wide band gap semiconducting comprehensive documentation of the more important effects on
material with a wide range of applications. Scientific interest photoactivity is required [18,19]. Visinescu et al. [20] correlated
in titania has grown immensely followed by an explosive blue shift in band gap and crystallisation with photoactivity of
increase in research on this material over the last decade. The sputtered tantala doped titania film. Recently, Wang et al. [21]
technological exploitation of this material is mainly based on its reported the photoactivity of polymer templated titania/tantalum
property of photoactivation [14]. From solar cells to medium mixed oxide and they explain the high photoactivity of the sys-
for environmental cleanup, titania has provided the cutting edge tem by considering the change in optical property and surface
for a range of technologies [57]. Mainly two aspects of pho- area of the mixed oxide system. Here we have studied the effects
tocatalytic activity of titania are looked upon, one is to increase of tantalum addition on the photoactivity of titania and have
the photocatalytic activity itself while the other is to shift the tried to understand the influence of other parameters like surface
band gap to the visible region of the electromagnetic spectra area, crystallite size and phase assemblage on the activity.
[8]. Selective doping with metal ions and oxides like Cr3+ , Fe3+ ,
Sb5+ , Pt, Si4+ , Mo5+ , WO3 , La3+ , Eu3+ , Nd3+ , Pr3+ , Er3+ , Dy3+ , 2. Experimental
ZrO2 have been successful in increasing the photoactivity to
2.1. Material preparation

Corresponding author. Tel.: + 91 471 2490674; fax: +91 471 2491 712. Titanyl oxysulphate (TiOSO4 , Aldrich, 99.99% purity) was
E-mail address: wwarrierkgk@yahoo.co.in (K.G.K. Warrier). used as the precurssor for the synthesis of titania sol. In a

1381-1169/$ see front matter 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.molcata.2007.06.017

MOLCAA-6817; No. of Pages 6

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typical experiment, titanyl oxysulphate was dissolved in 500 ml the error due to the adsorption of methylene blue by titania from
of distilled water (0.2 M) and hydrolysed by slow addition of the measurements the initial concentration of methylene blue
ammonium hydroxide (10%, S.D. Fine Chemicals, India) solu- was measured only after equilibration. The suspension was then
tion under constant stirring at room temperature (32 C), until irradiated with UV using a Rayonet Photoreactor (Netherlands)
the pH of the reaction mixture was 8.0. The precipitate obtained with constant stirring. The UV source was fifteen 15 W tubes
was separated by filtration and was washed free of sulphate ions (Philips G15 T8) arranged in circular fashion emitting radiation
(confirmed by the BaCl2 test) with distilled water. The precip- in the region 200400 nm. The degradation of the dye was moni-
itate was further dispersed in 1000 ml of hot distilled water and tored using a UVvis spectrometer (Shimadzu, Japan, UV-2401
was peptised by the addition of 10% HNO3 (Merck, India) solu- PC). A blank dye solution was also irradiated, for about 1 h to
tion. A stable sol was obtained at a pH range 1.72.2. Tantalum confirm that the dye was not photobleached by the radiation in
oxalate (M/s CMET, Hyderabad, AR grade, 99% purity) solution the UV chamber.
corresponding to 1, 2, 5 and 10 mole percentage of tantalum was
added drop wise in separate batches of titania sol and kept under 3. Results and discussions
stirring for a period of 1 h. The sols were concentrated over steam
bath and subsequently dried in an electric hot air oven at 70 C to 3.1. XRD analysis
obtain the xerogel. These gels were further calcined at different
temperatures between 500 and 1100 C with a 10 C min1 An aqueous solgel method was used for the preparation
ramp and soaking for 1 h at respective temperatures. of tantalum added titania nano particles. The source of titania
and tantalum were titanyl sulphate and tantalum oxalate, which
2.2. Characterisation are much cheaper than their alkoxide counter part. The X-ray
diffraction pattern of anatase has a main peak at 2 = 25.2 corre-
The surface area measurements and pore analysis were car- sponding to the 1 0 1 planes (JCPDS 21-1272) and the main peak
ried out by nitrogen adsorption using Micromeritics Gemini of rutile phase is due to its 1 1 0 planes (JCPDS 21-1276) present
2375 surface area analyser after degassing each sample at 200 C at 2 = 27.4 . The X-ray diffraction patterns of titania, with and
for 2 h. XRD patterns of the calcined gels were taken in a Philips with out tantalum addition, calcined at different temperatures
X pert X-ray diffractometer in the diffraction angle 2 range are given in Figs. 13.
2060 using Cu K radiation. The amount of rutile in the Considerable stability of the anatase phase is observed for
sample was estimated using the Spurr equation [22] the tantalum added titania samples and stability increases with
1 increasing concentration of tantalum. Only 21% of titania is
FR = present as anatase in pure titania after calcination at 700 C,
[1 + {0.8 IA (1 0 1)/IR (1 1 0)}]
while it is 88% in presence of 5 mol% tantalum added titania.
where FR is the mass fraction of rutile in the sample and IA (1 0 1) Significant is the case for 10 mol% tantalum added titania where
and IR (1 1 0) are the integrated main peak intensities of anatase no phase transformation is observed. Pure titania completely
and rutile, respectively. The crystallite size was calculated using transforms to rutile at 800 C, while complete transformation
Scherrer equation [23] occurs only above 1000 C for the 10 mol% tantalum added tita-
K
D=
cos
where K is the shape factor taken as 0.9 for the calculations
presented, the wavelength of the X-ray, the full width at half
maxima, and is the diffracting angle.
The TEM observation of the calcined titania powder was
performed on a Hitachi HF 2200 TU file emission microscope
operating at an accelerating voltage of 200 kV.
The diffuse reflectance spectrum was measured using UVvis
spectrometer (Shimadzu, Japan, UV-2401 PC) keeping BaSO4
as standard.
The photocatalytic activity of the titania with and without tan-
talum addition after calcination at 500 and 600 C was studied
by measuring the amount of methylene blue degraded under UV
radiation. For the methylene blue degradation studies, aliquots
were prepared by dispersing 0.1 g of titania powder in 250 ml of
6.4 109 mol l1 methylene blue solution (AR grade, Quali-
gens Fine Chemicals, India). Absorption maximum between 640
Fig. 1. XRD patterns of different TiO2 samples calcined at 700 C for 1 h: (A)
and 680 nm in the UV spectrum of methylene blue was used for Anatase, (R) Rutile (T) Ta2 O5 . (a) Pure TiO2 , (b) 1 mol% Ta2 O5 added TiO2 ,
determining the concentration. The suspension was equilibrated (c) 2 mol% Ta2 O5 added TiO2 , (d) 5 mol% Ta2 O5 added TiO2 , and (e) 10 mol%
by stirring in the dark for 1 h prior to measurements. To eliminate Ta2 O5 added TiO2 .
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Fig. 4. Phase transformation from anatase to rutile of pure and Ta2 O5 added
Fig. 2. XRD patterns of different TiO2 samples calcined at 800 C for 1 h: (A) TiO2 calcined at different temperatures for 1 h. () Pure TiO2 , () 1 mol%
Anatase, (R) Rutile (T) Ta2 O5 . (a) Pure TiO2 , (b) 1 mol% Ta2 O5 added TiO2 , Ta2 O5 added TiO2 , () 2 mol% Ta2 O5 added TiO2 , () 5 mol% Ta2 O5 added
(c) 2 mol% Ta2 O5 added TiO2 , (d) 5 mol% Ta2 O5 added TiO2 , and (e) 10 mol% TiO2 , and () 10 mol% Ta2 O5 .
Ta2 O5 .

[24]. The mesoporous nature of the titania samples is evident.

nia, indicating the high order of thermal stability of the anatase The surface area obtained for tantalum added samples are much
phase. The fraction of rutile phase present at different tempera- higher than that obtained for pure titania at all calcined temper-
tures for the different samples is given in Fig. 4. X-ray diffraction atures. The surface area obtained for pure and tantalum added
patterns indicate the presence of small peaks corresponding to titania samples calcined at different temperatures are plotted in
orthorhombic Ta2 O5 (JCPDS 79-1375) in the compositions con- Fig. 5. The surface area of the samples follows the same trend
taining 5 and 10 mol% tantalum added titania. at all calcined temperatures. There is an increase in surface area
for up to 2% addition and beyond which a decline is observed.
3.2. BET surface area analysis But even for 10% tantalum addition the surface area is higher
than that of pure titania.
Textural characteristics of the samples calcined at 500, 600
and 800 C was derived from N2 -adsorption analysis. The 3.3. UV spectral analysis
adsorption isotherms (see Supplementary data) of all samples
show type IV behaviour with the characteristic hysterisis loop The electronic bands of different titania samples were stud-
ied using UVvis/diffuse reflectance spectroscopy. The obtained
spectra are provided in Fig. 6. All the samples show bands around
300350 nm characteristic of segregated crystallites of anatase

Fig. 3. XRD patterns of different TiO2 samples calcined at different temper-

atures: (A) Anatase, (R) Rutile (T) Ta2 O5 (a) 1 mol% Ta2 O5 added TiO2 , (b)
2 mol% Ta2 O5 added TiO2 , (c) 5 mol% Ta2 O5 added TiO2 , (d) 10 mol% Ta2 O5
added TiO2 calcined at 900 C, (e) 5 mol% Ta2 O5 added TiO2 , and (f) 10 mol% Fig. 5. Surface area vs. concentration of tantala of pure and tantala added titania
Ta2 O5 added TiO2 calcined at 1000 C. at (a) 500 C, (b) 600 C and (c) 800 C.
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Fig. 6. DRS spectrum of TiO2 samples calcined at 500 C for 1 h. (a) Pure TiO2 ,
(b) 1 mol% Ta2 O5 added TiO2 , (c) 2 mol% Ta2 O5 added TiO2 , (d) 5 mol% Ta2 O5 Fig. 7. Crystallite size of the anatase phase in pure and Ta2 O5 added TiO2
added TiO2 , and (e) 10 mol% Ta2 O5 added TiO2 . calcined at different temperatures for 1 h. () Pure TiO2 , () 1 mol% Ta2 O5
added TiO2 , () 2 mol% Ta2 O5 added TiO2 , () 5 mol% Ta2 O5 added TiO2 ,
and () 10 mol% Ta2 O5 added TiO2 .
[25]. It can be seen that increasing the concentration of tantalum
in the titania matrix results in absorption starting from a lower 10 mol% tantalum added titania has a crystallite size of 6 nm
wavelength region, i.e. UVvis absorption spectra shows a blue and confirms the quantum size effects reasoned above.
shift in the absorbance onset value in the case of tantalum added The crystallite sizes plotted as a function of temperature
titania. There is a significant shift in absorbance onset value for reveal that the progressive tantalum addition hinders the growth
the 10 mol% tantala added sample. The phenomenon of blue of anatase titania. Thermodynamic stability of anatase phase
shift of absorbance onset values is observed for semiconduct- compared to rutile in smaller crystallites is a well known phe-
ing systems when the domain size reaches nano regimes where nomenon and hence the increased stability of the anatase phase
quantum size effects start to get pronounced [26]. observed here is due to the restriction in crystallite growth
imposed by tantalum.
3.4. Crystallite size determination
3.5. Photoactivity studies
The crystallite size obtained for the different titania samples
are given in Fig. 7. The crystallite size can be seen to decrease The photocatalytic activity of the titania samples calcined at
with increasing tantalum concentration. The blue shift in the 500 C tested against methylene blue degradation is given in
band edge is hence due to the quantum size effects resulting Fig. 9. Photo degradation of methylene blue on titania surface
from the smaller size of anatase crystallites as a result of the follows a first order rate equation [27,28]. Hence, a linear fit
progressive tantalum addition. The TEM images of pure and to the plots of log(c0 /c) against time was done using origin 7
10 mol% tantalum added titania samples, presented in Fig. 8a software. The increase in tantalum content increases the activity
and b show that pure titania has a crystallite size of 23 nm and of titania as evident from the graph. There is a considerable shift

Fig. 8. TEM images of (a) TiO2 sample at 600 C and (b) 10 mol% Ta2 O5 added TiO2 at 600 C.
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Fig. 10. The rate constants for the samples calcined at () 500 C and ()
Fig. 9. Photocatalytic degradation profile of pure and tantalum added titania
600 C are plotted against the percentage of tantalum. Rate constant obtained
calcined at 500 C. ()Pure TiO2 , ()1 mol% Ta2 O5 added TiO2 , ()2 mol%
for Hombikat UV 100 is shown as the dashed line.
Ta2 O5 added TiO2 , ()5 mol% Ta2 O5 added TiO2 , and ()10 mol% Ta2 O5
added TiO2 . () Hombikat UV 100 TiO2 .

Precursor gel calcined at 500 C has only anatase phase for

in rate when concentration of tantalum is increased from 1 to all samples including pure titania. Hence, the ratio of anatase to
2 mol%. Further increase in photoactivity with tantalum content rutile phase can be ruled out as influencing the photocatalytic
is not that pronounced. In fact a slight decrease is observed for activity. The slope for the plots of log(c0 /c) versus time gives
the 10 mol% tantala added titania. For comparison of activity the rate constants for the first order reaction. The rate constants
a commercially available titania sample, Hombikat UV 100 is for the samples calcined at 500 and 600 C are plotted against
also tested. Addition of tantalum above 1 mol% gives titania with the percentage of tantalum in Fig. 10. The difference in surface
much better activity than commercially available Hombikat UV area alone will not be able to account for the observed trend.
100 titania. For the 500 C calcined sample, the 2% tantala added titania
The addition of tantalum into titania matrix increases the has a surface area of 92 m2 g1 and has activity three times than
anatase phase stability. Increasing addition of tantalum seems that of the 1 mol% tantalum added titania which has a surface
to result in the segregation of tantalum oxide as evidenced by area of 78.8 m2 g1 . At the same time the 10 mol% tantala added
the appearance of its peaks in the XRD [JCPDS 79-1375]. This in titania has a surface area of only 63 m2 g1 but has activity close
disagreement with the observation of Sacerdoti where they could to that of the 2 mol% tantala added titania. When calcined at
not find any peaks related to tantalum oxide in their XRD pat- 600 C for compositions below 2 mol% tantalum addition there
terns [29]. But there is a significant difference in the preparation is an increase in activity but for samples with 2 mol% tantala and
procedures adopted. While we have used salt precursors for both above there is significant decrease in activity. Even for the 1 and
tantalum and titania they had chosen all alkoxide precursors. 2 mol% tantala added titania the surface area decreases but the
The decrease in crystallite size is a common observation and activity can be seen to increase by about an order in magnitude.
considering the comparable ionic radii of tantalum (0.064 nm) Table 1 provides the samples tested in the decreasing order
and titanium ions (0.061 nm) we conclude that substitution of of their activity. Crystallite size, surface area and rutile fraction
titanium ions by tantalum ions takes place for all concentrations. in the sample are all provided for clarity of discussion. From
Increasing concentration leads to segregation of tantala. In either the table it can be seen that the samples with high activity has
case the stability of anatase phase is increased progressively. either crystallite size below 9 nm or has a mixture of phases.

Table 1
Sample Calcination temperature Crystallite size Surface area Percentage rutile Rate (mol l1 s1 )

5% Ta added TiO2 500 8.5 87.9 0 0.03157

2% Ta added TiO2 500 8.71 92.2 0 0.03085
10% Ta added TiO2 500 7.15 63.2 0 0.03022
10% Ta added TiO2 600 8.96 49 0 0.0242
2% Ta added TiO2 600 11.66 67.1 17 0.0178
5% Ta added TiO2 600 9.8 61.9 0 0.01782
1% Ta added TiO2 600 15.4 45.1 26 0.0134
Pure TiO2 600 19.08 19.1 28.35 0.01118
1% Ta added TiO2 500 11.35 78.8 0 0.00904
Pure TiO2 500 12.8 48.7 0 0.00553
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