Materials Chemistry and Physics 112 (2008) 167–172

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Materials Chemistry and Physics

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Comparative study of the photocatalytic performance of boron–iron Co-doped

and boron-doped TiO2 nanoparticles
Romana Khan a , Sun Woo Kim a , Tae-Jeong Kim a,∗ , Chang-Mo Nam b
a
Department of Applied Chemistry, Kyungpook National University, Taegu 702-701, Republic of Korea
b
Division of Health and Science, Yeongnam College of Science & Technology, Hyunchoong-Ro, Nam-Ku, Taegu 705-703, Republic of Korea

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

Article history: A series of nanosized boron-doped and boron–iron co-doped anatase TiO2 represented as Bx ,Fey -TiO2
Received 8 April 2008 (x = 1, 3, 5, y = 0, 0.5, 1, 3, 5 in wt%) were synthesized by a modified sol–gel method, and characterized
Received in revised form 2 May 2008 by various spectroscopic and analytical techniques. The presence of boron and/or iron causes a red shift
Accepted 16 May 2008
in the absorption band of TiO2 . The Bx ,Fey -TiO2 systems are very effective catalysts for the degradation
of toluene under UV or visible light. All reactions follow pseudo-first-order kinetics with the rate being
Keywords:
a function of either the dopants or the light source (UV or visible light). The relative quantity and most
Boron-doped TiO2
importantly the position occupied by dopant were found to be the crucial factors in co-doping with respect
Boron–iron co-doped TiO2
Visible light
to the properties and activity of the final product. In general, boron-doping enhances the reactivity while
Photocatalyst iron-doping works in an opposite manner, thus to show the following order of reactivity regardless of the
Toluene degradation light source: Bx -TiO2 > TiO2 > Bx ,Fey -TiO2 . Under the visible light, however, a reversal in this trend is made
depending on the relative amount of iron. Thus, for instance, when y ≤ 5, the trend becomes as follows:
Bx -TiO2 > Bx ,Fey -TiO2 > TiO2 .
© 2008 Elsevier B.V. All rights reserved.

1. Introduction Boron, however, has not been investigated as extensively as other

Heterogeneous photocatalytic oxidation using semiconductors
is an effective technique for air and water decontamination. Tita-
nium oxide (TiO2 ) is one of the most efficient semiconductor
photocatalysts for extensive environmental applications because
of its strong oxidizing power, non-toxicity, high photo-chemical
corrosive resistance, cost effectiveness, and ability to mineralize
refractory organic pollutants under ambient pressure and temper-
ature [1–3]. Yet, due to its large band gap (3.2 eV), TiO2 can only
be activated under UV light ( < 387 nm) irradiation. Only 4% of sun
light falls in this range and thus the use of solar energy is limited
for the practical applications of TiO2 as photocatalyst. Furthermore,
the electron–hole (e− –h+ ) recombination which severely limits the
achievable quantum yields, is another serious problem with its use
[4].
In order to accomplish solar-driven photocatalysis and at the
same time retard possible electron–hole recombination, doping
of TiO2 with main group elements as well as transition metals is
one of the most successful strategies. In this regard, it is worth
noting that non-metal dopants such as nitrogen, fluorine, iodine,
sulfur, and boron have recently drawn special attention [5–11].
∗ Corresponding author. Tel.: +82 53 950 5587; fax: +82 53 950 6594.
E-mail address: tjkim@knu.ac.kr (T.-J. Kim).
main group dopants, and thus the exact role of boron as a dopant
remains controversial. Some argue that boron-doping into TiO2
results in a red shift for the UV absorption band to the visible
region. The rationalization is that the impurity states newly intro-
duced by boron-doping overlap sufficiently with the 2p electronic
states of oxygen [11,12]. Yet, others hold the opposite to be true
by reporting that boron incorporation into TiO2 results in a blue
shift (rather than a red shift) due to a decrease in the crystal size
(quantization effect) [13–15]. Thus the exact role of boron on opti-
cal absorbance and photocatalytic activity of TiO2 awaits further
investigations.
In contrast to this controversy concerning the role of boron,
unanimous agreement is that transition metals narrow the band-
gap and at the same time reduce the recombination rate of
photogenerated electrons and holes. Among others, the Fe(III) ion
has been known for some time to be an effective dopant due to its
half-filled electronic configuration [16]. It has also been reported
that the photocatalytic activity of TiO2 doped with main group
elements such as sulfur or nitrogen can be further increased by
the presence of Fe(III) as a co-dopant [17]. Although the Fe(III)
cation is believed to act as a shallow trap in the titania lattice, the
exact mechanism for the recombination rate has yet to be clari-
fied [16,18,19]. In addition, the optimum concentration of Fe(III) as
well as the appropriate doping method, also remains in the realm
of debate [18,20,21].

0254-0584/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.matchemphys.2008.05.030
168 R. Khan et al. / Materials Chemistry and Physics 112 (2008) 167–172

Extensive research endeavors have so far been made in an
attempt to design and synthesize binary titanium oxides M-
TiO2 (M = metals or non-metals) or ternary systems M,M -TiO2
(M,M = metals and non-metals) for use as photocatalyst. Yet, few
studies are available on the synthesis of such systems as B,TM-TiO2
(TM = transition metals) not to mention their photocatalytic appli-
cations [11,15]. To the best of our knowledge and according to the
literature search, the influence of boron and iron co-doping on the
photocatalytic activity of TiO2 under UV and visible-light irradia-
tion in comparison with boron-doped TiO2 has been investigated
for the first time in this study. Intrigued by the controversy centered
around the roles of boron and Fe(III) in photocatalysis, we have pre-
and a, b and c are lattice parameters (in anatase form, a = b = / c). The morphology
and surface topography of the samples was examined by means of scanning elec-
tron microscopy (SEM, Hitachi, S-4300). Specific surface area measurements were
performed using a BET Surface Area Analyzer (Micrometrics, Pore sizer 9320). The
texture properties of the samples were characterized through nitrogen adsorption
at 77 K. The specific surface area was determined by the multipoint BET method
using the adsorption data in the relative pressure (P/P0 ) range of 0–1. The desorption
isotherm was used to determine the pore size distribution using the Barrett, Joyner,
and Halenda (BJH) method. The UV–vis diffuse reflectance spectra were measured by
using a SHIMADZU UV-2450 spectrophotometer. X-ray photoelectron spectra (XPS)
were recorded on a VG Microtech, MT 500/1 photoelectron spectrometer. All the
binding energies were referenced to the adventitious C 1s peak at 285 eV.
2.5. Measurement of photocatalytic activity

pared two types of TiO2 -based oxides: (1) Bx -TiO2 (x = 1, 3, 5 wt%);
(2) Bx ,Fey -TiO2 (x = 3; y = 0, 0.5, 1, 3, 5 wt%). This paper describes
their synthesis, spectroscopic characterization, physicochemical
properties, and the photocatalytic activities. Also described are the
studies of photocatalytic activity for the degradation of toluene as
a function of either light source (UV or visible light) or the relative
contents of boron and iron.
2. Experimental
2.1. General remarks
All commercial reagents such as tetrabutyl titanate, boric acid, iron
acetylacetonate, absolute ethanol, hydrochloric acid (37%) and ammonium hydrox-
ide (28%) were purchased from Aldrich and used as received. All syntheses were
carried out using deionized water and under nitrogen at room temperature. TiO2
was prepared according to the literature method described by us [22].
2.2. Synthesis of boron-doped TiO2
Boron-doped titanium oxides, Bx -TiO2 with various B-contents (x = 1, 3, and
5 wt%) were prepared initially by taking advantage of a modified sol–gel method
[22]. In a typical experiment for the synthesis of B1 -TiO2 , to a stirred solution of
Ti(OBu)4 (21.3 mL) in EtOH (120 mL) charged in a two-neck round bottom flask, were
added drop wise a solution of HCl (6.6 mL) in aqueous ethanol (22:120 v/v). Simul-
taneously was added drop wise a solution of H3 BO3 (0.29 g) in ethanol (30 mL). After
addition, the resulting sol was stirred for an additional 24 h and subsequently the
pH of the solution was raised to 9.0 by drop wise addition of NH4 OH (1.0 M) solution.
The gel thus formed was aged for 2 h, filtered and washed thoroughly with distilled
water for the complete removal of chlorides as confirmed by silver nitrate test. The
gel was then dried at 110 ◦ C for 12 h and was ground to powder mechanically. The
resulting dry powders were calcined to 500 ◦ C at the rate of 1 ◦ C min−1 and kept at
500 ◦ C for 5 h to obtain nanostructured TiO2 powders. Those with other B-contents
such as B3 -TiO2 , and B5 -TiO2 , were prepared in the same manner.
2.3. Synthesis of boron–iron co-doped TiO2
Boron–iron co-doped titanium oxides, Bx ,Fey -TiO2 with varying contents of
boron and iron (x = 3; y = 0.5, 1, 3, and 5 wt%) were prepared by the same method as
described above by replacing H3 BO3 with a mixture of H3 BO3 and Fe(acac)3 . Fe1 -TiO2
was also prepared for comparative purposes in the absence of boron sources.
The photocatalytic experiments were carried out for the decomposition of
gaseous toluene under UV and visible light irradiation in a batch reactor. The reactor
was equipped with a UV lamp (Philips TUV 10W/G10 T8; max = 254 nm) and a visi-
ble lamp (oslam halogen lamp 150 W with a 400 nm cutoff filter) as the light source.
The photon flux emitted from these lamps was determined actinometrically using
the potassium ferrioxalate method and was found to be 1.47 × 10−6 Einstein s−1 for
UV light and 3.9 × 10−6 Einstein s−1 for visible light. A set of three Pyrex glass plates
(each 270 mm × 50 mm × 5 mm) coated with catalyst were placed in the reactor. The
plates were coated with the photocatalyst using a method as described elsewhere
[23]. The reactor was connected to a glass mixing chamber where the temperature
was fixed at 70 ◦ C to ensure the evaporation of toluene. Reactor was connected on-
line through a gas sampling system to a Gas Chromatograph (GC-17A, Shimadzu)
equipped with a HP-5 capillary column (30 m × 0.32 mm; Agilent Technologies) to
monitor the toluene concentration at regular intervals. The injection port and the
column temperatures were 120 ◦ C and 200 ◦ C, respectively. The flame ionization
detector was maintained at 250 ◦ C. The reaction was started by injecting the reac-
tant toluene (7 ␮L) via micro-syringe into the mixing chamber to be circulated by a
peristaltic pump after evaporation and reach the gas–solid adsorption equilibrium.
After the concentration of toluene was stabilized as monitored by GC, the UV or
visible lamp was turned on and the degradation of the toluene was recorded at a 0.5
or 1 h time intervals. The rate of degradation was estimated to obey pseudo-first-
order kinetics and hence the rate constant for degradation, k, was obtained from the
first-order plot according to Eq. (4), where C0 is the initial concentration, C is the
concentration after a time (t) of the toluene degradation, and k is the first-order rate
constant:
 
C0
ln = kt (4)
C
3. Results and discussion
3.1. XRD analysis
Figs. 1 and 2 show the XRD patterns of Bx -TiO2 and Bx ,Fey -TiO2 .
All diffraction peaks can be assigned as pure anatase TiO2 after cal-
cination. These observations indicate that there has been virtually

2.4. Characterization

The crystallite structures of the calcined (at 500 ◦ C) materials were investigated
by analyzing the X-ray diffraction (XRD) patterns obtained with a Multi-Purpose X-
ray Diffractometer (X’pert PRO MRD/X’pert PRO MPD) operated at room temperature
with graphite-monochromated Cu K␣ radiation. The Scherrer’s formula

k
crystallite size = (1)
W cos 
(with a shape factor k = 0.89) was employed to determine the crystallite sizes of
samples with fwhms (W) and peak centers obtained by fitting the (1 0 1) peak to
the Lorentzian function and here  is the wavelength of X-ray radiation (1.54 Å). The
lattice parameters of the catalysts were measured using (1 0 1) and (2 0 0) in anatase
crystal planes by using equations


Bragg’s equation : d(h k l) = (2)
2 sin 
−2
formula for tetragonal system : d(h k l)
= h2 a−2 + k2 b−2 + l2 c −2 (3)

where d(h k l) is the distance between crystal planes of (h k l),  is the X-ray wave- Fig. 1. X-ray diffraction patterns of B-TiO2 : (a) TiO2 ; (b) B1 -TiO2 ; (c) B3 -TiO2 ; (d)
length,  is the diffraction angle of crystal plane (h k l), h k l is the crystal index, B5 -TiO2 .
 R. Khan et al. / Materials Chemistry and Physics 112 (2008) 167–172 169

in surface energies, which in turn hampers eventually the grain

growth [14].

3.2. UV–vis absorption spectra

The UV–vis spectra of TiO2 , Bx -TiO2 , and Bx ,Fey -TiO2 show a

Fig. 2. X-ray diffraction patterns of B-Fe-TiO2 : (a) TiO2 ; (b) B3 ,Fe0.5 -TiO2 ; (c) B3 ,Fe1 -
TiO2 ; (d) B3 ,Fe3 -TiO2 ; (e) B3 ,Fe5 -TiO2 .
no phase change in TiO2 in the process of doping or co-doping,
regardless of the amounts of dopants. Table 1 reveals the estimated
lattice parameters and crystallite size. The lattice parameters of all
samples remain almost unchanged along a- and b-axes, whereas
the c-axis parameter undergoes an increase with doping. In the case
of B-TiO2 , for instance, such an increase can be explained in terms of
the boron ions occupied in the interstitial sites of anatase TiO2 crys-
tal structure, thus causing the increase in the cell volume. It seems
unfeasible for B(III) to replace the Ti(IV) site because the radius of
B(III) (0.23 Å) is much smaller than that of Ti(IV) (0.68 Å). In the
case of B,Fe-TiO2 , however, is observed a noticeable increase of the
tetragonal c parameter. Such a lattice expansion is the result of the
compensating effects between substitution of Ti(IV) by Fe(III) [24]
and oxygen vacancy formation for maintenance of charge neutrality
[14,25].
The crystallite size, on the other hand, reduces with both dop-
ing as well as co-doping as indicated by the peak broadening in the
XRD patterns of B-TiO2 and Bx ,Fey -TiO2 as a function of B- or Fe-
contents (Table 1). Lattice deformation (i.e., increase in the c-axis)
and associated generation of oxygen vacancies produce a lattice
microstrain which has to be balanced by reduction in crystallite
size [26]. It is worth noting that the reduction in the crystallite
size is more pronounced with B-doping than with Fe-doping, as
we compare B1 -TiO2 (15 nm) with Fe1 -TiO2 (17 nm). These obser-
vations may be rationalized in terms of the interstitial B(III) ions
that balance the residual charge of TiO2 and thus lead to reduction
significant increase in the absorption at a wavelength lower than
380 nm (ca. 3.18 eV) can be assigned to the intrinsic band gap
absorption of anatase TiO2 (Fig. S1). The absorption edge of Bx -TiO2
moves into a longer wavelength, indicating the band gap reduction
in TiO2 as expected [27]. Although such a red shift is independent
of the boron content, it provides further supporting evidences for
the interstitial rather than substitutional state of B(III) ions in the
TiO2 lattice [11]. As stated earlier, a huge difference in the ionic
radii of B(III) and Ti(IV) rules out the possibility of substitution.
Neither does B(III) substitute oxygen as evidenced by the fact that
there exists no linear relationship between the red shift and the
boron content (Fig. S1 and Table 1). The red shift observed with
Bx -TiO2 may be explained in terms of the electronic midgap band
(a band located between valence and conduction bands) generated
by interstitial B(III) ions [28].
The absorption edge of the Bx ,Fey -TiO2 series is a function of the
iron contents and covers the range of 400–600 nm (Fig. S1). When
the absorption edge of B3 ,Fe1 -TiO2 was compared with that of Fe1 -
TiO2 , it was observed that both occupy the same position (Fig. S1).
This indicates that the role of iron (compare to boron) in co-doped
series (Bx ,Fey -TiO2 ) is more prominent as far as the red shift is con-
cerned. Such a red shift can be rationalized by the fact that the Fe(III)
ions (0.64 Å) can readily substitute the Ti(IV) ions (0.68 Å) from the
lattice to form an solid solution [25]. For instance, when the iron
concentration is low enough (0.5–1.0 wt%), the excitation of the 3d
electrons in Fe(III) to the conduction band of TiO2 becomes possible
to exhibit the edge at 415 nm [29]. If, however, the iron concentra-
tion is high enough (3.0–5.0 wt%), either the d–d transition in Fe(III)
(2 T1g , 2 T2g ← 2 A2g ) or the charge transfer transition between inter-
acting iron ions (Fe3+ + Fe3+ → Fe4+ + Fe2+ ) becomes more probable
to give the edge at ca. 500 nm [25,30]. It can thus be concluded
from these observations that the Bx ,Fey -TiO2 series may serve as
practical visible-light photocatalysts.
3.3. BET surface areas and pore size distributions
Table 1 summarizes the BET surface areas and pore volumes of
TiO2 , Bx -TiO2 , and Bx ,Fey -TiO2 . The most characteristic feature of
the table is that the B-doping, unlike the Fe-doping, increases both
surface area and pore volume of TiO2 . The average pore diameter
falls within the range of 3.8–6.8 nm typical of aggregated particles.
Finally, the isotherms with characteristic hysteresis loop (Type IV

Table 1
Some selected properties of TiO2 powders

Type of oxide Crystallite size (nm)a SBET (m2 g−1 )b V (cm3 g−1 )c Cell parameters a = b, c (Å)d k (min−1 )e (UV-light) k (min−1 )e (vis-light)
1
B -TiO2 15 72 0.16 3.7801, 9.4409 0.031 0.047
B3 -TiO2 15 71 0.15 3.7796, 9.4191 0.033 0.011
B5 -TiO2 13 86 0.19 3.7797, 9.3867 0.028 0.011
B3 Fe0.5 -TiO2 16 68 0.18 3.7736, 9.2969 0.007 0.0036
B3 Fe1 -TiO2 12 60 0.12 3.7848, 9.5591 0.003 0.0048
B3 Fe3 -TiO2 11 75 0.17 3.7751, 9.7362 0.004 0.001
B3 Fe5 -TiO2 10 72 0.15 3.7848, 9.5589 0.003 0.0003
Fe1 -TiO2 17 64 0.12 3.7875, 9.6111 0.002 0.002
TiO2 18 63 0.12 3.7872, 9.3561 0.025 0.0003
a
Measured by the Scherrer’s equation.
b
Measured by BET method.
c
Taken from the volume N2 adsorbed at P/P0 = 0.995.
d
Estimated according to Eqs. (2) and (3).
e
Calculated from the linear fitting of ln(C0 /C) vs. the reaction time.
170 R. Khan et al. / Materials Chemistry and Physics 112 (2008) 167–172
Fig. 3. SEM images of (a) TiO2 ; (b) B3 -TiO2 ; (c) B3 ,Fe1 -TiO2 ; (d) B3 ,Fe5 -TiO2 .
according to IUPAC classification of physisorption isotherms) indi-
cate the mesoporous nature of the series.
3.4. Morphology
Fig. 3 shows a typical SEM micrographs of TiO2 , B3 -TiO2 and
B3 ,Fe5 -TiO2 . A detailed SEM examination of the particle surfaces
reveals that the primary particles are quite uniform in size and
roughly spherical in shape, and that the agglomerates are fused
together to form comparatively larger irregular grains (not shown)
giving rise to highly porous materials. Moreover, all samples display
a narrow size distribution for the primary particles. Their particle
sizes may be arranged in the decreasing order as follows: TiO2 > Bx -
TiO2 > Bx ,Fey -TiO2 . All SEM results are in good agreement with the
XRD data.
3.5. XPS studies
The XPS spectrum for TiO2 exhibits two peaks in the Ti 2p region
(Fig. S2a). The one at 459.8 eV is assignable to Ti(IV) 2p3/2 , and the
other at 465.5 eV to Ti(IV) 2p1/2 [31]. The fact that a red shift is
observed with the Ti(IV) 2p3/2 peak on B-doping (Fig. S2b) and the
peak intensity linearly depends on the B-content suggests the for-
mation of Ti(III) on the surface of TiO2 . The Ti(III) center is known to
be the most reactive site for photocatalytic process and have a dual
function. Firstly, it provides a unique site for the formation of oxy-
gen species such as O− or O2 •− . Secondly, it can trap photoelectrons
thus inhibiting the e− –h+ recombination [32–34]. Furthermore, the
presence of Ti(III) sites makes the catalyst labile even to the visible
light since the valence state of localized oxygen vacancies is a lit-
tle lower than the conduction band of parent TiO2 by 0.75–1.18 eV
[5,35,36].
Unlike B-doping, iron-doping has no play on the red shift of the
Ti(IV) 2p3/2 peak, thus exhibiting little or no change in the position
of the same peak from the Bx ,Fey -TiO2 series. For example, as seen
in Fig. S2c, the peak position is virtually the same (459.8 eV) as that
of parent TiO2 at the high concentration of Fe-doping (y = 5). In this
case again, the presence of Ti(III) is ruled out.
Fig. S2d and e shows the O 1s photoelectron peaks of TiO2 and
B5 -TiO2 , respectively. The peak of TiO2 can be resolved into two
components: the one 530.9 eV assignable to Ti–O, and the other
(shoulder) at 533.04 eV to adsorbed O2 /OH groups on the surface.
The corresponding peaks of B5 -TiO2 are lower in binding energies
by approximately 1.8 eV than those of parent TiO2 probably due to
the boron–oxygen interaction in the lattice.
The O 1s patterns of B3 ,Fey -TiO2 series are virtually the same as
that of parent TiO2 except for the absence of shoulder in the case
of B3 ,Fe5 -TiO2 (Fig. S2f).
The presence of iron and boron, however, is not readily detected
by XPS. This may be due to the fact that the dopants exist either in a
high dissolution state in the TiO2 lattice (rather than isolated oxide
species on the surface of the TiO2 ) or disperse homogenously on the
surface of TiO2 so that their concentration is low than the detection
limit of XPS analysis. We have thus confirmed their presence by
 R. Khan et al. / Materials Chemistry and Physics 112 (2008) 167–172 171

Fig. 4. Degradation of toluene under UV: TiO2 (); B1 -TiO2 (䊉); B3 -TiO2 (♦); B5 -TiO2 Fig. 5. Degradation of toluene under UV: TiO2 (); B3 ,Fe0.5 -TiO2 (); B3 ,Fe1 -TiO2
(*). C0 = the initial concentration; C = the concentration at time t. (䊉); B3 ,Fe3 -TiO2 ( ); B3 ,Fe5 -TiO2 (); Fe1 -TiO2 ().

ICPAES and found that their concentrations are only slightly lower position is more influential than B3+ occupying interstitial posi-
than the ideal values. tion. In co-doped boron–iron TiO2 both dopants were found to work
independently, one being dominant over the other.
3.6. Photocatalytic activity Fig. 6 shows the visible-light activity of Bx -TiO2 , and B3 ,Fey -TiO2
for the same reaction. They all exhibit the catalytic activity in a
The photocatalytic degradation of toluene was performed in varying degree depending on the nature of doping. In particular, the
order to benchmark the catalytic activity of TiO2 , Bx -TiO2 , and Bx -TiO2 series demonstrate excellent reactivity achieving complete
Bx ,Fey -TiO2 . They all are versatile catalysts for the degradation of conversion within a short period of time (3–4 h). Here, the reac-
toluene under UV or visible light. All reactions follow pseudo- tivity depends almost linearly on the B-content. The high activity
first-order kinetics, and the relevant data are summarized in caused by boron-doping in Bx -TiO2 has already been explained in
Table 1. The table shows that the order of reactivity is a func- terms of midgap band (vide supra) as well as the formation of local-
tion of either the dopants or the light source (UV or visible ized oxygen vacancies. Visible light illumination produces ‘holes’
light). In general, boron-doping enhances the reactivity while in the midgap level, whereas UV illumination produces holes in
iron-doping works in an opposite manner, thus to show the the O 2p valance band (Fig. S3) [37,38]. Finally, in connection with
following order of reactivity regardless of the light source: Bx - Fig. 6, it is to be noted again that in co-doped series the iron-
TiO2 > TiO2 > Bx ,Fey -TiO2 . Under the visible light, however, a reversal doping retards greatly the reaction rate compare to boron-doped
in this trend can be made depending on the relative amount of TiO2 series as in the case of the same reaction under UV and that
iron. Thus, for instance, when y ≤ 5, the trend becomes as follows: the general trend in the decomposition rate depends inversely on
Bx -TiO2 > Bx ,Fey -TiO2 > TiO2 . the Fe-content. When compared in the boron–iron co-doped series
Fig. 4 shows that, under UV-light irradiation, there is no signifi- the optimum concentration of iron (1 wt%) is more efficient than
cant difference in photocatalytic activity between the B-doped and the other catalysts in the same series. All-in-all, the decomposition
the parent TiO2 . It was also observed that the decomposition rate rate under the visible light can be arranged in the fol-
does not considerably depend on the B-content within the Bx -TiO2
series.
Fig. 5 shows the degradation of toluene catalyzed by B3 ,Fey -
TiO2 as a function of the Fe-content. Most characteristically,
the decomposition rate decreases as the Fe-content increases
in the following order: TiO2 > B3 ,Fe0.5 -TiO2 > B3 ,Fe1 -TiO2 ∼ B3 ,Fe3 -
TiO2 ∼ B3 ,Fe5 -TiO2 . It appears that Fe(III) ions in the Ti(IV) matrix
can act as a shallow trap or recombination center, allowing the
e− –h+ pairs to recombine instead of taking part in the surface reac-
tion as illustrated in Fig. S3. Furthermore, the reactive Ti(III) center
generated as a result of boron-doping gradually disappears with
iron co-doping. Catalytic deactivation of iron can be seen even
more dramatically by comparing the decomposition rate by Fe1 -
TiO2 (2 × 10−3 min−1 ) with that by parent TiO2 (2.5 × 10−2 min−1 ).
It can be concluded that in co-doping the relative quantity and
most importantly the position occupied by dopant is the conclusive
factor in determining the overall properties and the catalytic perfor-
mance of the final product. While comparing the relative positions,
it can be concluded that the lattice (Ti(IV) substitution) is more
influential. For instance the crystallite size and lattice parameters,
Fig. 6. Degradation of toluene under visible-light by TiO2 (); B1 -TiO2 (䊉); B3 -TiO2
the absorption edge (Table 1, Fig. S1), the surface area (Table 1), ( ); B5 -TiO2 (*); B3 ,Fe0.5 -TiO2 (䊉); B3 ,Fe1 -TiO2 (); B3 ,Fe3 -TiO2 (); B3 ,Fe5 -TiO2 ();
the binding energies (Fig. S2) show that Fe3+ occupying the lattice Fe1 -TiO2 ( ).
172 R. Khan et al. / Materials Chemistry and Physics 112 (2008) 167–172
lowing order: B5 -TiO2 > B3 -TiO2 ∼ B1 -TiO2 > B3 ,Fe1 -TiO2 > B3 ,Fe0.5 -
TiO2 > Fe1 -TiO2 > B3 ,Fe3 -TiO2 > TiO2 > B3 ,Fe5 -TiO2 .
4. Conclusions
A series of nanosized, anatase Bx -TiO2 and Bx ,Fey -TiO2 (x = 1, 3,
5, y = 0, 0.5, 1, 3, 5 in wt%) were synthesized by a modified sol–gel
method. The presence of boron and/or iron causes a red shift in
the absorption band of TiO2 . These systems are very versatile cat-
alysts for the degradation of toluene under UV or visible light. All
reactions follow pseudo-first-order kinetics with the order of reac-
tivity being a function of either the dopants or the light source
(UV or visible light). In general, boron-doping enhances the reactiv-
ity while iron-doping works in an opposite manner, thus to show
the following order of reactivity regardless of the light source:
Bx -TiO2 > TiO2 > Bx ,Fey -TiO2 . It under the visible light, however, a
reversal in this trend can be made depending on the relative amount
of iron. Thus, for instance, when y ≤ 5, the trend becomes as fol-
lows: Bx -TiO2 > Bx ,Fey -TiO2 > TiO2 . It was found that in co-doping
the crucial factor for determining the properties and activity of the
final product lies in the relative quantity and most importantly
the position occupied by dopant. Higher activity observed with
boron-doping was explained in terms of such factors as small crys-
tal size, high surface area, mesoporous structure, and the formation
of Ti(III). The visible light activity of B-doped titania was explained
in terms of ‘holes’ generated in the midgap level. Retardation in the
reaction rate by Fe-doping was rationalized in terms of the forma-
tion of Fe(III) ions that can act as a shallow trap or recombination
center, allowing the e− –h+ pairs to recombine instead of taking part
in the surface reaction.
Acknowledgements
Financial supports by Korea Institute of Construction &
Transportation Technology Evaluation and Planning (Grant No.
C10A1000018-06A0200-01220). R. Khan acknowledges the finan-
cial support from KRF (KRF-2006-211-C00038). Dr. Jin-Ook Baeg
(Korea Research Institute of Chemical Technology) is also gratefully
acknowledged for DRS measurements. Spectroscopic and analytical
measurements were performed by KBSI and the Center for Scientific
Instruments, KNU.
Appendix A. Supplementary data
Supplementary data associated with this article can be found,
in the online version, at 10.1016/j.matchemphys.2008.05.030.
References
[1] M.A. Fox, M.T. Dulay, Chem. Rev. 93 (1993) 341–357.
[2] M.R. Hoffmann, S.T. Martin, W. Choi, D.W. Bahnemann, Chem. Rev. 95 (1995)
69–96.
[3] A. Fujishima, T.N. Rao, D.A. Tryk, J. Photochem. Photobiol. C 1 (2000) 1–21.
[4] D. Chatterjee, S. Dasgupta, J. Photochem. Photobiol. C 6 (2005) 186–205.
[5] R. Asahi, T. Morikawa, T. Ohwaki, K. Aoki, Y. Taga, Science 293 (2001)
269–271.
[6] M. Mrowetz, W. Balcerski, A.J. Colussi, M.R. Hoffmann, J. Phys. Chem. B 108
(2004) 17269–17273.
[7] J.C. Yu, J.G. Yu, W.K. Ho, Z.T. Jiang, L.Z. Zhang, Chem. Mater. 14 (2002)
3808–3816.
[8] X.T. Hong, Z.P. Wang, W.M. Cai, F. Lu, J. Zhang, Y.Z. Yang, N. Ma, Y.J. Liu, Chem.
Mater. 17 (2005) 1548–1552.
[9] T. Umebayashi, T. Yamaki, S. Tanaka, K. Asai, Chem. Lett. 32 (2003) 330–331.
[10] T. Ohno, M. Akiyoshi, T. Umebayashi, K. Asai, T. Mitsui, M. Matsumura, Appl.
Catal. A: Gen. 265 (2004) 115–121.
[11] W. Zhao, W. Ma, C. Chen, J. Zhao, Z. Shuai, J. Am. Chem. Soc. 126 (2004)
4782–4783.
[12] S.C. Moon, H. Mametsuka, E. Suzuki, Y. Nakahara, Catal. Today 45 (1998)
79–84.
[13] D. Chen, D. Yang, Q. Wang, Z. Jiang, Ind. Eng. Chem. Res. 45 (2006) 4110–4116.
[14] K.Y. Jung, S.B. Park, S.-K. Ihm, Appl. Catal. B: Environ. 51 (2004) 239–245.
[15] T.-H. Xu, C.-L. Song, Y. Liu, G.-R. Han, J. Zhejiang Univ. Sci. B 7 (2006) 299–303.
[16] W. Choi, A. Termin, M.R. Hoffmann, J. Phys. Chem. 98 (1994) 13669–13679.
[17] T. Ohno, Z. Miyamoto, K. Nishijima, H. Kanemitsu, F. Xueyuan, Appl. Catal. A:
Gen. 302 (2006) 62–68.
[18] M. Litter, J. Navı́o, J. Photochem. Photobiol. A: Chem. 98 (1996) 171–181.
[19] E. Piera, M.I. Tejedor-Tejedor, M.E. Zorn, M.A. Anderson, Appl. Catal. B: Environ.
46 (2003) 671–685.
[20] K. Ranjit, B. Viswanathan, J. Photochem. Photobiol. A 108 (1997) 79–84.
[21] S. Ikeda, N. Sugiyama, S. Murakami, H. Kominami, Y. Kera, H. Noguchi, K. Uosaki,
T. Torimoto, B. Ohtani, Phys. Chem. Chem. Phys. 5 (2003) 778–783.
[22] R. Khan, S.W. Kim, T.-J. Kim, H.S. Lee, Bull. Korean Chem. Soc. 28 (2007)
1951–1957.
[23] M.K. Nazeeruddin, A. Kay, I. Rodicio, R. Humpbry-Baker, E. Miiller, P. Liska, N.
Vlachopoulos, M. Gratzel, J. Am. Chem. Soc. 115 (1993) 6382–6390.
[24] C.Y. Wang, C. Bottcher, D.W. Bahnemann, J.K. Dohrmann, J. Mater. Chem. 13
(2003) 2322–2329.
[25] C. Adan, A. Bahamonde, M. Fernandez-Garcia, A. Martinez-Arias, Appl. Catal. B:
Environ. 72 (2007) 11–17.
[26] M. Fernandez-Garcia, A. Martinez-Arias, J.C. Hanson, J.A. Rodriguez, Chem. Rev.
104 (2004) 4063–4104.
[27] M. Anpo, Catal. Surv. Jpn. 1 (1997) 169–179.
[28] U. Diebold, Surf. Sci. Rep. 48 (2003) 53–229.
[29] T. Umebayashi, T. Yamaki, H. Itoh, K. Asai, J. Phys. Chem. Solids 63 (2002)
1909–1920.
[30] J. Zhu, W. Zheng, B. He, J. Zhang, M. Anpo, J. Mol. Catal. A: Chem. 216 (2004)
35–43.
[31] M. Murata, K. Wakino, S. Ikeda, J. Electron Spectrosc. Relat. Phenom. 6 (1975)
459–464.
[32] K. Suriye, P. Praserthdam, B. Jongsomjit, Appl. Surf. Sci. 253 (2007) 3849–3855.
[33] S.X. Liu, Z.P. Qu, X.W. Han, C.L. Sun, Catal. Today 93 (2004) 877–884.
[34] D.-R. Park, J. Zhang, K. Ikeue, H. Yamashita, M. Anpo, J. Catal. 185 (1999) 114–119.
[35] J. Yang, H. Bai, Q. Jiang, J. Lian, Thin Solid Films 516 (2008) 1736–1742.
[36] Y. Li, D.-S. Hwang, N.H. Lee, S.-J. Kim, Chem. Phys. Lett. 404 (2005) 25–29.
[37] R. Nakamura, T. Tanaka, Y. Nakato, J. Phys. Chem. B 108 (2004) 10617–10620.
[38] M. Sathish, B. Viswanathan, R.P. Viswanath, C.S. Gopinath, Chem. Mater. 17
(2005) 6349–6353.