Catalysis Today 240 (2015) 242247

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Catalysis Today
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Synergism and photocatalytic water splitting to hydrogen over

M/TiO2 catalysts: Effect of initial particle size of TiO2
S. Bashir, A.K. Wahab, H. Idriss
SABIC-Corporate Research and Innovation (CRI), KAUST, Thuwal 23955, Saudi Arabia

a r t i c l e

i n f o

Article history:
Received 26 January 2014
Received in revised form 5 May 2014
Accepted 10 May 2014
Available online 4 July 2014
Keywords:
TiO2 (anatase, rutile)
Synergism
TiO2 XPS valence band
TiO2 XPS Ti2p
hydrogen production
TiO2 particle size

a b s t r a c t
In order to study the effect of anatase/rutile phases of TiO2 on the photo-catalytic production of hydrogen (often invoked as synergism) two series of Pt/TiO2 materials were prepared. The initial phase of TiO2
in both series is anatase but their particle size is different. In one case the mean particle size of TiO2
is ca. 1520 nm (nano) and in the other it is ca. 100 nm (micro). Before the deposition of Pt, the two
semiconductors (nano and micro) were heated to elevated temperatures to obtain partial (and total)
transformation of the anatase phase to the rutile phase (UVvis, XRD, XPS-valence band). On this differently prepared mixed phases Pt was deposited (ca. 1 at.%; corrected XPS Pt4f/Ti2p = ca. 0.05) and each
series was tested for the photocatalytic production of hydrogen from water in presence of ethanol (5 vol.%)
as a sacricial agent (under identical conditions). Based on rates per unit mass no synergism for hydrogen
production was seen in both cases; this is in part due to the decrease in the BET surface area during the
phase transformation. However, strong synergism was observed for hydrogen production rates per unit
area when the initial starting semiconductor was anatase nano (while no synergism seen in the case of
the micro crystals). Maximum rate observed was in the 1030% rutile range. Possible reasons for these
differences are discussed.
2014 Elsevier B.V. All rights reserved.

1. Introduction
Hydrogen production from water can be obtained via many
methods including solar thermal water splitting [1], combined photovoltaic and electrolysis [2], photo electrochemical processes [3]
and photo catalysis [4]. Photocatalytic hydrogen production reactions carried out on semiconductor materials relies on many factors
including band gap energies, band edges (conduction and valence
band energy positions), electrons and holes diffusion, electronhole
recombination rates [4], bulk structure [5], surface structure [6,7]
and defects [810].
TiO2 , among the most active photocatalytic semiconductor
material, consists of several polymorphs the most common of them
are anatase with a band gap of 3.2 eV and rutile with a band gap
of 3.0 eV at room temperature. The lifetime of electrons in anatase
and rutile phases using time resolved microwave conductivity measurements (TRMC) was studied on powder [11] and single crystals
[12] and in both cases charge carriers in anatase were found to have
longer life time than those in rutile. For hydrogen production from
water and organic compounds the anatase phase is more active

Corresponding author. Tel.: +966 (12) 2755060.

E-mail addresses: idrissh@sabic.com, h.idriss@ucl.ac.uk (H. Idriss).
http://dx.doi.org/10.1016/j.cattod.2014.05.034
0920-5861/ 2014 Elsevier B.V. All rights reserved.

than the rutile one [13,14]. To increase the electron life time metal
deposition on the semiconductor surfaces such as Ag, Rh, Au, Pt and
Pd, are routinely used while to increase the hole life-time organic
compounds such as alcohols and glycols are added into the aqueous
media.
Mixed phase TiO2 anatase and rutile have however shown, in
many reports, superior activity than the expected arithmetic sum
of that of anatase and rutile separately. This observation that falls
under synergism has been the subject of considerable studies [15].
For example the rate of hydrogen production from ethanol over
1.5 wt.% Au/P25 (85% anatase and 15% rutile) is about two times
higher than that seen over 2 wt.% Au/anatase alone and the latter
is about 100 times more active than that of 2 wt.% Au/rutile; no
matter is the expression of the rate (per unit area, unit mass or
normalized to the XPS Au4f/Ti2p signal) [16]. Similar observations
were reported over Pt/TiO2 anatase, rutile and their mixtures [17].
Others [18] studied the photocatalytic activity of anatase and rutile
phase in the visible region. The activity of the mix phase under
visible light was explained as due to the lower band gap (3.0 eV)
rutile polymorph where the photoexcitation mainly occurred in
rutile phase with electrons being transferred to anatase phase. Nair
et al. [19] proposed the interfacial model for the synergistic effect
between anatase and rutile under UV and visible light. The transfer
of electrons from rutile to anatase in the presence of visible light and

S. Bashir et al. / Catalysis Today 240 (2015) 242247

2. Experimental
Two different series of 1 wt.% Pt/TiO2 were prepared by wet
impregnation. TiO2 powder sample containing pure anatase phase
obtained from Sigma Aldrich of about 20 nm size labeled as TiO2
(nano) and the one obtained from Fisher Scientic of about 0.1 m
labeled as TiO2 (micro) were used as the starting materials. TiO2
(nano) powder was annealed isochronally (for 1 h) at different temperatures in the 700800 C range while TiO2 (micro) powder was
annealed isothermally at 1000 C for different intervals of time.
These conditions were found to be the optimum ones to obtain the
mixed phase from each sample. Metal precursor solution was prepared by dissolving calculated amount of metal salt (PtCl2 obtained
from Sigma Aldrich) in 1 N HCl. The calculated amount of precursor
solution was then impregnated to each of the annealed samples
prepared. The impregnated mixture was subjected to stirring and
was left at 7080 C overnight. The resulting slurry was then dried
at 100 C for 24 h, followed by calcination at 350 C for 5 h in air. Following the above mentioned procedure, two series of 1 wt.% Pt/TiO2
(nano and micro) were obtained.
The powder XRD patterns of the samples were recorded on
a Philips Xpert-MPD X-ray powder diffractometer. A 2 interval
between 10 and 90 was used with a step size of 0.010 and a
step time of 0.5 s. The X-ray, Ni-ltered Cu K radiation source
operated at 45 mA and 40 kV. The percentages of
(K = 1.5418 A),
rutile in the mixed phase were calculated by the expression below
[28] and are presented in Table 1.
%Rutile =

 100

(A/R) 0.884 + 1

X-ray photoelectron spectroscopy was conducted using a

Thermo scientic ESCALAB 250 Xi, The base pressure of the chamber was typically in the low 1010 to high 1011 mbar range. Charge
neutralization was used for all samples. Spectra were calibrated
with respect to C1s at 285.0 eV. Pt4f, O1s, Ti2p, C1s and valence
band energy regions were scanned for all materials. Typical acquisition conditions were as follows: pass energy = 30 eV and scan
rate = 0.1 eV per 200 ms. Ar ion bombardment was performed with
an EX06 ion gun at 1 kV beam energy and 10 mA emission current;
sample current was typically 0.91.0 nA. Self-supported oxide disks
of approximately 0.5 cm diameter were loaded into the chamber
for analysis. UVvis absorbance spectra of the powdered catalysts

(a) 800
Counts/s (arbitrary unit)

700

(d) 37 % Rutile

600
500

(c) 29 % Rutile

400
300
(b) 10 % Rutile
200
100
0
24.5

(a) 3 % Rutile
25

25.5

26

26.5

27

27.5

28

28.5

2 theta (degrees)

(b)
Counts/s (arbitrary unit)

migration of electrons from anatase to rutile in case of UV light was

reported; the formation of potential charge barrier at the interface
contributed in the proposed mechanism.
In this study, the effect of anatase to rutile ratios on the photocatalytic activity coupled with crystallite (particle) size on the phase
transformation of anatase to rutile were investigated. Two different grades of TiO2 one with large crystallite size (micro) and the
other with small crystallite size (nano) were used. TiO2 samples
were annealed at different temperatures to get the varying percentages of anatase and rutile. Transformation of anatase to rutile
depends on many factors including impurity content [20,21], temperature [22,23], pressure [24] and particle size [25,26]. The effect
of initial particle size and the annealing temperature were studied here. The annealed TiO2 samples containing different ratio of
anatase and rutile were then impregnated with Pt and evaluated
for the photocatalytic H2 production from water using ethanol as a
sacricial agent. We have opted to use Pt because it is well studied
on TiO2 , well dispersed, easily reduced and has among the lowest
over-potential [27]. We nd no synergism when the initial phase
was micro size anatase particles but considerable synergism (on
the rate once normalized to unit area) when the initial TiO2 anatase
particles where of nano-size.

243

1200

(f) 78% Rutile

1000

(e) 68% Rutile

800

(d) 25% Rutile

(c) 7.6% Rutile

600
400

(b) 1.2% Rutile

200

(a) 0.5% Rutile

0
24.5

25

25.5

26

26.5

27

27.5

28

28.5

2 theta (degrees)
Fig. 1. (a) XRD pattern of TiO2 (nanoinitially anatase) annealed for 1 h in the
700800 C range. (b) XRD pattern of TiO2 (microinitially anatase) annealed at
1000 C for different periods of times (in hours) to obtain the indicated rutile %.

were collected over the wavelength range of 250900 nm on a

Thermo Fisher Scientic UVvis spectrophotometer equipped with
praying mantis diffuse reectance accessory. Absorbance (A) and
reectance (%R) of the samples were measured. The reectance
(%R) data was used to calculate the band gap of the samples using
the Tauc plot (KubelkaMunk function). BET surface areas of catalysts were measured using Quantachrome Autosorb analyzer by N2
adsorption. Catalysts were evaluated for hydrogen production in a
100 mL volume Pyrex glass reactor. 25 mg of catalyst sample was
introduced into the reactor. The catalyst sample was then reduced
under hydrogen ow at 350 C for 1 h followed by purging with
nitrogen gas for 30 min. Milli-Q deionized water (20 mL) and the
sacricial agent (1 mL i.e. 5% by volume) of ethanol were added into
the reactor. The nal mixture was subjected to constant stirring initially under dark condition for some time to get better dispersion
of catalyst powder and the sacricial agent in the water mixture.
The reactor was then exposed to the UV light; a 100 Watt ultraviolet
lamp (H-144GC-100, Sylvania par 38) with a ux of ca. 2 mW/cm2 at
a distance of 10 cm with the cut off lter (360 nm and above). Product analysis was performed by gas chromatograph (GC) equipped
with thermal conductivity detector (TCD) connected to Porapak Q
packed column (2 m) at 45 C and N2 was used as a carrier gas.
3. Results and discussion
XRD was carried out to study the phase transformation of
anatase to rutile of TiO2 (nano and micro) powders. Fig. 1a and b
shows the gradual transformation of the anatase phase into rutile

244

S. Bashir et al. / Catalysis Today 240 (2015) 242247

Table 1
Rutile content, BET surface area, and particles size of TiO2 (initially of nano (ca. 20 nm) and micro (ca. 100 nm) sizes).
Sample

Temperature ( C)

% Rutile

BET(m2 /g)

d (Anatase) (nm)

d (Rutile) (nm)

TiO2 nano

720
740
760
780
800

TiO2 micro

1000

0
3
10
29
37
56
0.5
1.2
7.6
25
68
78

55
30
20
16
13.5
11
9.8
5.4
5.2
6
4.5
4.5

22
32
38
40
45
48
93
97
103
95
100
110

0
8
38
76
87
97

108
114
101
118
122

The KubelkaMunk function, F(R) = (1R)2 /(2R), was used to calculate the band gap of the materials. The Tauc plot of the quantity
(F(R) E)1/2 against the radiation energy was used for measurement. Fig. 2a and b shows the band gaps of 1 wt.% Pt/TiO2 (nano)
photo catalysts, the pure anatase has the band gap of 3.2 eV and
with the increase in rutile content band gap decreases up to 3.0 eV
with the maximum rutile content of 37%. Fig. 4 shows the band gap
of 1 wt.% Pt/TiO2 (micro) series. The same trend was observed in
this case as well. With the increase in rutile content the band gap
started to decrease and at higher rutile content (up to 78%), slightly
lower than 3 eV.
Fig. 3a presents the XPS spectra of Pt4f of 1 wt.% Pt loaded on
isothermally annealed TiO2 (micro) powder samples. The chemical compositions of Pt on the surface, the ratio of Pt4f/Ti2p and
O1s/Ti2p were calculated using the corrected area under the XPS
curves of Pt4f7/2 and Pt4f5/2 and are presented in Table 2. Platinum was mostly present in the oxidized form in all samples (Pt2+ ).
The peak position at 72.672.8 eV corresponds to Pt4f7/2 of Pt2+
while that at 75.976.1 eV were assigned to Pt4f5/2 of Pt2+ . The peak

(a) 3.0E-09

0% Rutile
3 % Rutile
10 % Rutile
29% Rutile
37 % Rutile

Tauc units

2.5E-09
2.0E-09
1.5E-09
1.0E-09
5.0E-10
0.0E+00
2.5

(b)

2.0E-09

1.5E-09

Tauc units

when anatase powder was subjected to annealing isochronally at

different temperatures between 720 C and 780 C (annealing time:
1 h) in case of TiO2 (nano) and isothermally for different time (1 to
7 h at 1000 C) in case of TiO2 (micro). As indicated in the experimental section these conditions were found to be the optimum
(with these samples) for making the mixed phases, with large variations in the ratio anatase to rutile.
The anatase to rutile ratio was calculated by taking the intensity
of anatase phase (1 0 1) peak at 2 = 25.30 and rutile phase (1 1 0)
peak at 2 = 27.40 . The peak positions of anatase (1 0 1) and rutile
(1 1 0) were well in agreement with others [29] except for the peak
shifts of anatase (1 0 1) and rutile (1 1 0) in TiO2 (nano) with increasing annealing temperature. Peak shifts of 0.3 were observed in 2
values of anatase (1 0 1) and rutile (1 1 0) from 720 C to 780 C. Li
et al. [25] reported similar observations with initial anatase particle
sizes of 12 nm and 23 nm in the temperature range of 700800 C.
Compression in the lattice strain along the c direction of the
tetragonal anatase caused larger angular peak shifts due to the surface stress build up at higher temperature. Reduction of 0.06 A and
0.15 A in the lattice constant c for 23 nm and 12 nm anatase particles at 800 C, with negligible changes in the lattice constant along a
direction was reported. In the present study, the reduction in both
and c (0.131 A)
were observed with
lattice constants a (0.047 A)
increase in annealing temperature from 720 C (crystallite size:
32 nm) to 780 C (crystallite size: 45 nm) for TiO2 (nano) powder.
TiO2 (micro) samples have not shown major peak position shifts
except with the rutile content of 7.6% and 25%, in which the peaks
are shifting at lower 2 angles.
It has been reported that the small particle size TiO2 anatase
transforms into rutile at relatively low temperature compared to
the large particle size [30]. The increase in transformation at lower
temperature was reported due to the increase in nucleation sites
in the small crystalline size of anatase [26] and consequently to
larger surface areas [25]. In our case the initial BET surface area of
the TiO2 (nano; 55 m2 /gCatal .) is much higher than the TiO2 (micro;
10 m2 /gCatal .). Zhang et al. found the phase transformation kinetics
of anatase to rutile to be size dependent [31]. The transformation
proceeds through particle contacts and there was a slight variation
in activation energy with an initial particle size (around 218 kJ/mol
at 8.2 nm and 198 kJ/mol at 21.4 nm) and the pre-exponential factor was inversely proportional to the fourth power of the particle
size in the temperature range of 520600 C. In this study, with
the initial particle of TiO2 nano of about 25 nm and annealing temperature of 720 to 780 C for 1 h, the activation energy (calculated
from the changes in the rutile to anatase ratios up to ca. 30% conversion) was found to be 490 kJ/mol. Transformation of anatase to
rutile also depends on preparation method so the activation energy
also varies with the synthesis conditions. Activation energies of
299, 236, and 180 kJ/mol for initial anatase particle size of 23, 17
and 12 nm prepared by metal organic chemical vapor deposition at
annealing temperatures of 700 to 800 C have been reported [25].

2.6

2.7

2.8

2.9

3.0

3.1

3.2

3.3

3.4

3.5

3.1

3.2

3.3

3.4

3.5

eV
0.5% Rutile
1.2% Rutile
7.6% Rutile
25% Rutile
68% Rutile
78% Rutile

1.0E-09

5.0E-10

0.0E+00
2.5

2.6

2.7

2.8

2.9

3.0

eV
Fig. 2. (a) Plots of Tauc units versus (eV) for 1 wt.% Pt/TiO2 (nano) photocatalysts
with different % or rutile. (b) Plots of Tauc units versus (eV) for 1 wt.% Pt/TiO2 (micro)
photocatalysts.

S. Bashir et al. / Catalysis Today 240 (2015) 242247

(a)

Table 2
XPS Pt 4f, Ti2p and O1s for the Pt/TiO2 anatase (micro) series with different rutile %.
% Rutile

0.5

1.2

7.6

25

68

78

(b)

Fig. 3. (a) XPS spectra of Pt4f of 1 wt.% Pt/TiO2 (micro) at different rutile %. (b) XPS
spectra of Pt4f of 1 wt.% Pt/TiO2 (nano90% anatase) fresh and 5 min Ar+ sputtered.

position at 71.5 is related to Pt4f7/2 of metallic Pt peak while peak

at 74.8 is attributed to Pt4f5/2 of Pt0 . The peak positions and their
difference in the binding energy (E = 3.3) are well within the
expected values [32]. The metallic % of Pt (in general) was more
pronounced in the sample containing mainly anatase.
Fig. 3b displays the XP spectra of Pt4f of 1 wt.% Pt loaded on
TiO2 (nano) annealed at 740 C for 1 h (90% anatase). XPS analysis
was carried out for the as-prepared and the Ar ions sputtered samples. The oxidation states of Pt in the freshly prepared samples were
mainly Pt2+ and Pt4+ . The peak positions at 72.7 and 76.0 eV correspond to Pt4f7/2 and Pt4f5/2 of Pt2+ while those at 75.0 and 78.2
correspond to Pt4f7/2 and Pt4f5/2 of Pt4+ . After Ar ion sputtering
for 5 min, the sample was reduced and the oxidation states of Pt
change to metallic platinum; peaks positions shifted to the lower

245

Pt4f
Ti2p
O1s
C1s
Pt4f
Ti2p
O1s
C1s
Pt4f
Ti2p
O1s
C1s
Pt4f
Ti2p
O1s
C1s
Pt4f
Ti2p
O1s
C1s
Pt4f
Ti2p
O1s
C1s

Atomic (%)

Pt4f/Ti2p

O1s/Ti2p

1.1
24.2
53.3
21.3
1.6
23.5
52.4
22.3
1.1
23.4
52.8
22.5
1.2
22.8
52.4
23.5
0.9
24.1
56.1
18.9
1.0
23.7
55.1
20.2

0.05

2.2

0.07

2.2

0.05

2.3

0.05

2.3

0.04

2.3

0.04

2.3

binding energy at 71.7 and 75.0 for Pt4f7/2 and Pt4f5/2 of Pt0 with
the difference in the splitting binding energies of 3.3 eV.
Figs. 4a and b and Fig. 5 show the production of hydrogen
over the two series, 1 wt.% Pt/TiO2 (nano) and 1 wt.% Pt/TiO2
(micro) series. Hydrogen production rates were normalized with
respect to BET surface area of each catalyst. In both cases, the
least amount of hydrogen was observed with pure rutile phase of
1 wt.% Pt/TiO2 (nano) and 1 wt.% Pt/TiO2 (micro) with the corresponding hydrogen production rate of 2.6 108 mol/m2 min and
5.3 108 mol/m2 min, respectively. The rate of reaction for hydrogen with 1 wt.% Pt/TiO2 (anatase, nano) as well as 1 wt.% Pt/TiO2
(anatase, micro) was two orders of magnitudes higher than that
on the rutile phase (12 106 mol/m2 min). Similar observation
was seen on Au/TiO2 anatase and rutile series (14). In the case
of the nano series however, the rate (per unit area) increased
with increasing the content of rutile up to 1030%, afterward it
decreased; with further increase in rutile %. In the case of the micro
series the rate had a monotonic decrease (albeit with an osculation
at 25%) with increasing the rutile phase %. So it can be concluded
that synergism on this micro series is not noticeable at least when
compared to the initial starting materials (pure anatase phase).
It is unclear why in the case of catalysts prepared from one series
of Pt/TiO2 (nano), synergistic effect is seen whereas with catalysts
prepared from TiO2 (micro), no synergism is seen. One possible reason might be the effect of crystallite size and crystallinity of the
materials. Many reasons can be invoked for this observation but
most must be related to geometric and electronic effects of the
particle size. The valence band region of TiO2 anatase and rutile
has been studied by many authors in some details. While many
valence band analysis were conducted on the rutile TiO2 (1 1 0)
single crystal [33], far less was done on its counterpart anatase
TiO2 (1 0 1) because of lack of available single crystals [34,35]. However it is clear because of the different oxygen and titanium orbitals
hybridizations the valence band (and conduction band) has different shapes. XPS valence band reveals the presence of two main O2p
peaks with binding energy centered at about 4.5 and 7.5 eV. In the
case of anatase the high binding energy peak is larger than the low
binding energy peak while in the case of rutile they are of about the
same contribution (or the other way around). A recent work [36]
has addressed the projected density of states using the screened
hybrid functional (HSE06); this approach produces more accurate

246

S. Bashir et al. / Catalysis Today 240 (2015) 242247

(a)

Fig. 6. XPS of Ti2p3/2 of 1 wt.% Pt/TiO2 rutile, 1 wt.% Pt/TiO2 anatase and 1 wt.%
Pt/TiO2 (anatase/rutile).

(b)

Fig. 4. (a) H2 production from 1 wt.% PtTiO2 (nanoinitially anatase) with increasing rutile content. (b) H2 production for 1 wt.% Pt/TiO2 (microinitially anatase) with
increasing rutile content.

structural and band gap information than standard density functional approaches (such as LDA and GGA). The authors indicate a
shift in the VBM of the anatase compared to rutile based on their
computation and experimental (XPS) analyses. Based on this observation we have analyzed our core and valence band levels of some
of the materials studied in this work. The objective here is not to
give a full account of the electronic structure of the materials but
to see if indeed there are noticeable movements in the core and
valence lines of the composed material.
Fig. 6 presents the XPS Ti2p of pure rutile, pure anatase and the
hybrid material. The spectra were aligned to the C1s at 285.0 eV. The
Ti2p of rutile is found to be about 0.2 eV lower in binding energy
compared to that of anatase. Their narrow FWHM gives condence
that no contribution of reduced states is present. Interestingly the
FWHM of the Ti2p3/2 of the material composed of anatase and rutile
is larger than that of the rutile alone or anatase alone. The position
shift is in line with what is reported in Fig. 3 of reference [36].
Figs. 7 and 8 present the VB region of pure rutile TiO2 , pure anatase
TiO2 and anatase/rutile TiO2 . The spectra are aligned to the O2s
binding energy and the base line is shifted so all spectra have the
same initial offset for better comparison. We have opted to align the
spectra to the O2s to prevent the effect of any possible non-linearity
in the spectrometer because the C1s region is relatively far (260 eV
above the O2p region). We have also compared the fresh material to
that of the sputtered one to see into any effect due to the presence of
Ti3d states associated with oxygen defects. Fig. 7 presents the rutile
VB with its nger print of the O2p shape evident. Ar ions sputtering, as expected, results in the appearance of lines extending from
about 1 eV below the Fermi level (shaded area). TiO2 composed of

3.0E-06
2.5E-06
mol/min.m2cat

TiO2 nano
2.0E-06
1.5E-06
1.0E-06
5.0E-07
0.0E+00

TiO2 micro
0

20

40

60

80

100

%Rule
Fig. 5. Rates of H2 production over 1 wt.% Pt/TiO2 (nano and micro size) series.

Fig. 7. X-ray valence band of 1 wt.% Pt/TiO2 rutile before and after Ar ions sputtering
and 1 wt.% Pt/TiO2 (anatase/rutile).

S. Bashir et al. / Catalysis Today 240 (2015) 242247

247

size). The normalized rate of hydrogen production per unit area

was seen to increase when both phases (rutile and anatase up to
a ratio of about 1/3) were present in the case of TiO2 nano but did
not in the case of TiO2 micro. In other words synergism was seen
between the two phases for small particle sizes of TiO2 but not for
large particle sizes. Two effects were discussed as a cause of this
behavior: electronic and structural. XPS-valence band structure of
the Pt/TiO2 (anatase and rutile) appears to simply track those of
the pure phases and may not shed light on the electronic changes
associated with the valence band maxima of the materials. On the
other had some changes occur in the anatase crystallite strain in
the case of TiO2 nano in the range where synergism occurs.
References

Fig. 8. X-ray valence band of 1 wt.% Pt/TiO2 anatase and 1 wt.% Pt/TiO2
(anatase/rutile) before and after Ar ions sputtering.

anatase/rutile is also displayed with the O2p shape dominated by

that of anatase. Fig. 8 presents similar spectra but starting from
pure anatase. Inspection of both gures indicate that the VBM of
anatase is at a lower energy than that of rutile and that the composite materials is somewhere in between. Based on these gures
one can simply indicate that the VBM of the composite material
(anatase/rutile) falls somewhere in between that of anatase and
that of rutile.
There is however another plausible explanation related to synergism not based (at least directly) on its electronic structure. This
is related to the degree of crystallinity or perfection of the material. Because the more crystalline is the material the less likely
electronhole recombination will occur. It has been reported that
the larger crystallite size usually have smaller defects leading to
better photocatalytic activity while in case of smaller crystalline
particles the defects are more prominent. The defects near the
center and the boundaries in the materials promote electron hole
re-combinations which is the key limitation in case of photocatalytic reactions [37]. Fig. 5 indicate that pure anatase TiO2 of about
100 nm size is performing per unit area better than pure anatase
TiO2 of about 20 nm size. This means that charge carrier diffusion
from the bulk to the surface is not a major factor in photoreaction for TiO2 particles in this size range. It may also mean that the
100 nm size anatase TiO2 has fewer defects, per unit volume, than
the 20 nm size TiO2 . Upon heating the small anatase particles to
transform part of the phase to rutile the rate increases per unit
area, but decreases overall because the increase in particle size. The
increase in particle size results in a better degree of crystallinity and
therefore less electronhole recombination centers. In this process
the rutile phase is formed but may little contribute into the reaction. In other words the increase in the rate may be also be due to
a better crystallinity of TiO2 anatase and not directly related to the
interface anatase/rutile.
4. Conclusions
The photocatalytic reaction of water in presence of 5 vol.% of
ethanol was conducted on two series of Pt/TiO2 (nano and micro

[1]
[2]
[3]
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