Applied Catalysis A: General 429–430 (2012) 31–38

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Applied Catalysis A: General

journal homepage: www.elsevier.com/locate/apcata

Photocatalytic reduction of CO2 over noble metal-loaded and nitrogen-doped

mesoporous TiO2
Xiukai Li a,b,c,∗ , Zongjin Zhuang a,b,c , Wei Li a,b,c , Huiqi Pan a,b,c
a
China-Australia Joint Research Center for Functional Molecular Materials, Jiangsu University, Zhenjiang 212013, PR China
b
Scientific Research Academy, Jiangsu University, Zhenjiang 212013, PR China
c
School of Chemistry and Chemical Engineering, Jiangsu University, Zhenjiang 212013, PR China

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

Article history: Nitrogen-doped mesoporous TiO2 photocatalysts were developed for CO2 photoreduction by water in
Received 31 January 2012 gas phase. The effects of nitrogen doping and noble metal loading were investigated in detail. The
Received in revised form 1 April 2012 characteristics of samples were investigated by techniques, such as XRD, FT-IR, TEM, XPS, nitrogen
Accepted 2 April 2012
adsorption–desorption, and UV–vis diffuse reflectance spectroscopy. The loading of noble metals (i.e.,
Available online 9 April 2012
Pt, Au, and Ag) generally improved the photocatalytic activity, and the efficiency follows the order:
Pt > Au > Ag. It was found that the loading of Pt also promoted the transformation of catalyst associated
Keywords:
carbon residues to methane. With unique properties, such as the mesoporous structure, light absorption,
Mesoporous TiO2
CO2 photoreduction
and the electron transfer character, the nitrogen-doped mesoporous TiO2 samples showed good activity
Nitrogen doping for CO2 photoreduction to methane under visible light. The optimum loading amount of Pt was 0.2 wt.%,
Noble metal and the optimum doping amount of N was 0.84% on the basis of the lattice oxygen atoms. Aspects such as
Visible light the origination of visible light sensitivity in terms of nitrogen doping, the effect of noble metal loading,
and the reaction mechanism were also discussed.
© 2012 Elsevier B.V. All rights reserved.

1. Introduction
Global warming caused by the emission of green house gases,
primarily carbon dioxide (CO2 ), is attracting increasing attention
all over the world. For the considerations of environment protec-
tion and the sustainable development of human society, it is highly
desired to convert atmospheric CO2 into useful substances. Among
various approaches for the transformation of CO2 , the photocat-
alytic reduction of CO2 to reusable hydrocarbons using water as
the reductant and solar light as the photon source is of particular
interest [1–5]. Previous work demonstrated that CO2 could be pho-
tocatalytically reduced to hydrocarbons in both liquid phase and
gas phase [6–10].
Most of the research on CO2 photoreduction has been related
to TiO2 under UV light [11–15]. From the view point of practical
application, TiO2 is reasonably cheap, photo-stable, and non-toxic,
making it a perfect candidate for photocatalytic processes. How-
ever, TiO2 photocatalysts with the band gap values of about 3.0
and 3.2 eV for, respectively, rutile and anatase phases, can only
be activated by the UV light ( < 400 nm) that accounts for only
∗ Corresponding author at: Scientific Research Academy, Jiangsu University, No.
301 Xuefu Rd., Zhenjiang 212013, PR China. Tel.: +86 511 88797815;
fax: +86 511 88797815.
E-mail address: li.xiukai@gmail.com (X. Li).
4% in the solar spectrum. In order to better utilize the solar light,
researchers have devoted extensive work to modifying TiO2 for vis-
ible light photocatalysis [16–19]. The mostly adopted strategy to
narrow the band gap of TiO2 is to introduce doping elements, met-
als or nonmetals, into its crystal lattice [20–22]. As to nonmetal
doping, the dopants could be N [22,23], C [24], S [25], P [26] and so
forth, among which special attentions were paid to N because of its
particular doping property and the induced visible light sensitiv-
ity [22,23,27–29]. It is intriguing and important to investigate CO2
photoreduction over modified TiO2 under visible light, however,
there were few such reports up to date [30,31].
Noble metal or transition metal loading plays important roles
in TiO2 photocatalysis. The loaded cocatalysts could serve as
electron traps to suppress the recombination of the photo-
generated electron–hole pairs and hence the photocatalytic activity
is improved. The effect of metal loading is extremely remarkable in
CO2 photoreduction. There have been reports that TiO2 samples
with metal loading are efficient catalysts for CO2 photoreduction
[7,11,13]; in contrast, the unloaded TiO2 samples are almost inac-
tive under the same reaction conditions [32–35]. It seems that it
is very important to make clear the role of loaded metal in CO2
photoreduction. However, usually only one metal was used as
cocatalyst in one work, and there is a lack of the systematic study
on different kinds of cocatalysts.
Mesoporous materials possess unique pore character, larger
surface area value, and generally higher catalytic activity compared

0926-860X/$ – see front matter © 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.apcata.2012.04.001
32 X. Li et al. / Applied Catalysis A: General 429–430 (2012) 31–38
with the non-porous ones [36–38]. In this work, mesoporous TiO2
samples were doped with nitrogen for CO2 photoreduction under
visible light. The effects of nitrogen doping and noble metal (i.e., Pt,
Au, and Ag) loading on the photocatalytic activity were investigated
in detail.
2. Experimental
2.1. Catalyst preparation
Mesoporous TiO2 was synthesized by the well established soft-
template method [36]. The purities of chemicals used are analytical
grade. In a typical synthesis procedure, 20 ml of Ti(OBu)4 was
added dropwise to an aqueous CTAB solution (4 wt.%, 100 ml).
The obtained mixture was stirred at 40 ◦ C for 4 h, and then aged
at ambient temperature for 24 h. The slurry was transferred to a
Teflon-lined autoclave and thermally treated at 100 ◦ C for 48 h.
The white precipitate was separated by filtration, washed thor-
oughly with ethanol and distilled water, and then dried at 80 ◦ C
for 12 h. The powder was further calcined at 400 ◦ C for 8 h in
air to remove the organic template. For a comparison study, an
anatase sample was prepared by a synthesis procedure similar
to that for mesoporous TiO2 , except that the organic template
and the hydrothermal treatment were not adopted. For nitrogen
doping, the obtained mesoporous TiO2 was annealed at desired
temperature for 4 h in a tube furnace under flowing NH3 (flow rate:
100 ml min−1 ). The nitrogen-doped sample was purged with Argon
at 400 ◦ C for 1 h to remove the surface adsorbed ammonia species,
and then cooled down to room temperature in the Argon flow. The
photodeposition of noble metals (i.e., Pt, Au, and Ag) onto the TiO2
samples was performed in an aqueous methanol solution under
UV light irradiation. H2 PtCl6 ·6H2 O, HAuCl4 ·4H2 O, and AgNO3 were
used as Pt, Au, and Ag precursors, respectively.
2.2. Sample characterization
The phase compositions of samples were identified by X-Ray
Powder Diffraction (Cu K␣ radiation, Bruker AXS-D8) in the 2 range
of 1–90◦ . The UV–vis diffuse reflectance spectra were recorded at
room temperature on a Shimadzu UV-2450 UV–vis spectrometer
with barium sulfate as the reference sample. FT-IR spectra of the
samples were collected on a Nicolet Nexus 470 FT-IR spectropho-
tometer at room temperature by KBr method. Specific surface areas
of samples were deduced by the BET method (N2 adsorption) with
a NOVA-2000E instrument. Morphologies of samples were charac-
terized using a high resolution transmission electron microscope
(HR JEM-2100, JEOL). The XPS measurement was performed using
a PHI Quantera SXM Analyzer. The binding energies (BEs) were cali-
brated against the C 1s signal (284.6 eV) of contaminant carbon. The
real amount of noble metal loaded on sample surface was analyzed
by ICP (Varian ICP-OES).
2.3. Activity evaluation
The photocatalytic reduction of CO2 with gaseous H2 O as a
reductant was carried out in a quartz tubular reactor (length:
28.0 cm, Ø3.0 cm; volume: 159 ml) as previously described [2]. A flat
quartz plate was used to hold the catalyst (typically 0.1 g). A 350 W
Xe-lamp (Nanshen Company, Shanghai) equipped with 420 nm cut-
off filter was used as light source. The average irradiation intensity
inside the reactor was 34.8 and 38.2 mW cm−2 under UV and visible
light irradiation, respectively. Before the photocatalytic reaction,
high purity CO2 (99.995%) was bubbled through deionized water
and then flowed through the reactor for more than 1 h to ensure
that air was eliminated. The reactor was then sealed and the light
was turned on to start the reaction. The volume ratio of water vapor
A: anatase
A B: brookite
Intensity / a.u.
B A
A
A A
A e
d
c
b
a
20 30 40 50 60 70 80
2 /°
Fig. 1. XRD patterns of (a) non-doped mesoporous TiO2 , and the samples nitridized
at (b) 500 ◦ C, (c) 525 ◦ C, (d) 550 ◦ C, and (e) 575 ◦ C.
to CO2 in the feed gas was 0.06:1. The internal temperature of the
reactor was controlled at 60 ± 2 ◦ C. The products in the gas phase
were analyzed with a gas chromatograph system (GC-9790A), using
a flame ionization detector (FID) equipped with a FFAP capillary
column (30 m × 0.32 mm × 0.5 ␮m) for organic compounds deter-
mination, and a thermal conductor detector (TCD) equipped with
a 5A molecular sieve column (3 m × 3 mm) for inorganic gas deter-
mination. The error of measurement was less than 1%.
3. Results and discussion
3.1. Characterization
3.1.1. XRD
XRD was performed to analyze the structural phase and crystal
size of samples. Fig. 1 shows that the as prepared mesoporous TiO2
sample crystallized basically in anatase phase with trace amount
of brookite. For the nitrogen-doped samples, the intensities of the
diffraction peaks increase with the rise in nitridation tempera-
ture, indicating the enhanced crystallinities of TiO2 particles. There
was no obvious change in phase composition after nitrogen dop-
ing, signifying that the synthesized mesoporous TiO2 was rather
stable during the nitridation process. The crystallite sizes of sam-
ples were roughly estimated from the XRD patterns, and the data
are listed in Tables 1 and 2. The crystallite size does not change
notably with Pt loading but increases with increasing nitridation
temperature. There was no small-angle diffraction peak recorded
in XRD measurement, signifying the lack of long-range order for
the mesoporous structure of the samples.
3.1.2. Physical property
The N2 adsorption–desorption isotherms of samples and their
corresponding pore size distribution are illustrated in Fig. 2, with
the related data given in Table 2. All of the samples exhibited type
IV isotherms with a sudden increase in the volume of gas uptake
within the relative pressure (P/P0 ) range of approximately 0.7–1.0
(Fig. 2A), signifying typical mesoporous structures of uniform pore
size. The hysteresis loops are observed for the samples have been
nitridized at the temperatures above 500 ◦ C, indicating the meso-
porous structures were well retained after nitrogen doping. Fig. 2B
depicts the pore size distributions of samples. The pore size dis-
tribution is mono-modal for all the samples. The average pore
 X. Li et al. / Applied Catalysis A: General 429–430 (2012) 31–38 33

Table 1
The physical characteristics of the noble metal-loaded and unloaded mesoporous TiO2 samples.

Samples BET surface Mean pore Total pore volume Crystallite sizea Amount of Pt
area (m2 g−1 ) diameter (nm) (cm3 g−1 ) (nm) loadedb (wt.%)

Meso-TiO2 151.8 6.6 0.34 2.3 –

0.1 wt.%Pt/TiO2 135.0 6.6 0.31 2.2 0.09
0.2 wt.%Pt/TiO2 147.4 7.8 0.43 2.3 0.12
0.3 wt.%Pt/TiO2 137.0 7.7 0.29 2.3 0.24
a
Estimated according to the Scherrer’s formula: D = (K)/(ˇ cos ).  = 0.1542 nm, K = 1.0.
b
Deduced from ICP analysis.

Table 2
The physical characteristics of the N-doped and non-doped mesoporous TiO2 samples.

Samples BET surface Mean pore Total pore Crystallite Band gapa (eV) N (at.%)
area (m2 g−1 ) diameter (nm) volume (cm3 g−1 ) size (nm)

Meso-TiO2 151.8 6.6 0.34 2.3 3.18 –

TiO2 –N (500 ◦ C) 78.4 9.7 0.26 3.2 3.18 (2.75) 0.62
TiO2 –N (525 ◦ C) 69.5 12.6 0.28 6.0 3.18 (2.72) 0.84
TiO2 –N (550 ◦ C) 60.3 12.6 0.26 6.5 3.18 (2.64) 0.88
TiO2 –N (575 ◦ C) 42.3 12.6 0.16 6.9 3.18 (2.56) 0.88
a
The values in the parentheses indicate the band gap values related to N 2p state.

diameter is 3.9 nm for the as synthesized mesoporous TiO2 . It is 3.1.3. FT-IR

noted that the mean pore diameter increases with increasing nitri- Fig. 3 shows the FT-IR spectra of the N-doped and non-
dation temperature while the surface area value changes in the doped mesoporous TiO2 samples. All of the samples show similar
opposite trend, probably because of the sintering of TiO2 particles FT-IR spectra, indicating the structure of TiO2 did not change
at higher nitridation temperature. after nitrogen-doping. The absorption bands at about 3400 and
1625 cm−1 are assigned to the surface adsorbed water and hydroxyl
groups [39,40]. It is clear that the amount of surface adsorbed water
A and hydroxyl groups decreases at elevated nitridation tempera-
e ture. The absorption band corresponds to Ti O N was not observed
600 for the nitrogen-doped samples, probably because the amount of
doped N is very small.
Pore Volume (cm g )
-1

d
3

3.1.4. TEM
400
Transmission electron microscopy (TEM) was used to inves-
c
tigate the exact microstructure of samples. From Fig. 4A one
can see that the non-doped mesoporous TiO2 sample consists of
b aggregated nanoparticles with diameter of 8–10 nm. As the N2
200
adsorption–desorption measurements indicate that the current
TiO2 samples have mesoporous structure (Fig. 2), we deduced that
a these closely packed uniform nanoparticles create interparticle
0
0.2 0.4 0.6 0.8 1.0
Relative Pressure, P/P0

0.014 e
a B
0.012
d
Transmittance (a.u.)
dV / dD (cm g nm)

0.010
c
-1

0.008
3

b b
0.006
c
1625
0.004 d

0.002 e a
0.000

0 10 20 30 40 50 60 4000 3500 3000 2500 2000 1500 1000 500

-1
Pore Diameter / nm Wavenumber (cm )

Fig. 2. (A) N2 adsorption–desorption isotherms and (B) the corresponding BJH Fig. 3. FT-IR spectra of nitrogen-doped and non-doped mesoporous TiO2 samples.
pore size distribution curves of (a) non-doped mesoporous TiO2 , and the samples (a) Non-doped TiO2 , (b) TiO2 –N (500 ◦ C), (c) TiO2 –N (525 ◦ C), (d) TiO2 –N (550 ◦ C),
nitridized at (b) 500 ◦ C, (c) 525 ◦ C, (d) 550 ◦ C, and (e) 575 ◦ C. and (e) TiO2 –N (575 ◦ C).
34 X. Li et al. / Applied Catalysis A: General 429–430 (2012) 31–38
Fig. 4. Representative TEM images of samples. (A) Non-doped mesoporous TiO2 , (B) TiO2 –N (525 ◦ C), (C) and (D) 0.2 wt.% Pt/TiO2 .
mesoporosity. As such mesoporosity is interparticle porosity rather
than intraparticle porosity, the long-range ordered mesoporous
structure cannot be observed. The mesopores resulted from the
nanoparticle assembly can also be observed for the nitrogen-doped
TiO2 sample (Fig. 4B). Fig. 4C and D depict the images of 0.2 wt.%Pt
loaded TiO2 . Similar aggregation of TiO2 nanoparticles can be
observed. The particle size of TiO2 is about 8–10 nm, while the
particle size of loaded Pt is about 2–4 nm.
3.1.5. Optical property
Shown in Fig. 5A are the UV–vis diffuse reflectance spectra
of serial nitrogen-doped and non-doped mesoporous TiO2 sam-
ples. The non-doped mesoporous TiO2 is white in color and shows
absorption only in the UV region ( < 400 nm); its energy band
gap estimated from the sharp absorption edge is ca. 3.18 eV. The
nitrogen-doped mesoporous TiO2 samples are yellow colored and
their optical absorption were extended to the visible region of
400–500 nm. For the nitrogen-doped samples the visible light
absorption increases with increasing nitridation temperature. The
main absorption edges of the nitrogen-doped mesoporous TiO2
dose not change significantly compared to that of the non-doped
sample. It is likely that nitrogen doping creates a new N 2p state
slightly above the valence band top consists of O 2p state, and this
pushes up the valence band top and leads to visible light response
as a consequence [41,42]. The band gap values related to O 2p and
N 2p states are listed in Table 2. One can see that the band gap
value related to N 2p states decreases with increasing nitridation
temperature.
Fig. 5B shows the UV–vis diffuse reflectance spectra of meso-
porous TiO2 as well as the samples loaded with Pt, Au, and Ag
by means of photodeposition. The noble metal loaded samples are
gray and have obvious absorption in the visible region, despite the
fact that their main absorption edges lie at the same position as
that of unloaded TiO2 . The results of ICP analysis indicate that the
real amounts of noble metal loaded on sample surface are slightly
lower than the intended value (Table 1). The inset of Fig. 5B shows
the enlarged area of the spectra from 300 to 700 nm. The absorp-
tion edge of the unloaded TiO2 sample decreases quickly to zero at
the wavelength above 400 nm, in contrast the noble metal-loaded
samples have absorption in the visible light region of 400–700 nm.
The characteristic absorption peaks attributed to the surface plas-
mon resonance (SPR) of Au and Ag nanoparticles are observed at
around 550 and 430 nm [43,44], respectively. The SPR peak for the
Pt nanoparticles is typically below 450 nm with broad peak shape,
thus usually it can hardly be observed [45,46].
3.1.6. XPS
To explore the states of the doped nitrogen species, the
nitrogen-doped samples were subjected to X-ray photoelectron
spectroscopy (XPS) analysis. Fig. 6A shows the XPS survey spec-
trum of the representative TiO2 –N (525 ◦ C) sample. Obviously, Ti,
O, and C elements exist at the surface of the sample, whereas
the peak intensity is different. The nitrogen concentration is too
low to be detected by only one scan at the surface of the sam-
ple. Fig. 6B depicts the N 1 s XPS spectra of TiO2 –N (525 ◦ C) with
20 scans, showing the peaks at the binding energy positions of ca.
398∼403 eV. After background subtraction and curve fitting, the N
1 s peak could be decomposed to two component peaks centered at
ca. 400.1 and 401.9 eV. These two peaks are attributed to the signals
of the molecularly chemisorbed nitrogen species (N2 ) or nitroxide
species (e.g., NO and NO2 ) [22,28,47–49]. The peak related to the
signal of Ti N bonding (at ca. 396–397 eV) was not observed in the
present work. It follows that the molecularly chemisorbed nitro-
gen species and the nitroxide species contribute to the visible light
 X. Li et al. / Applied Catalysis A: General 429–430 (2012) 31–38 35

absorption of the current nitrogen-doped mesoporous TiO2 . There

were approximately 0.84% of lattice O atoms substituted by N atoms
for the TiO2 –N (525 ◦ C) sample. The data of doped N for the other
samples are listed in Table 2. One can see that he amount of doped
N increases with increasing nitridation temperature.

3.2. Activity evaluation

3.2.1. The effect of noble metal loading

Noble metal or transition metal loading usually improves
the photocatalytic activity of semiconductors. In this study, the
effects of Pt, Au, and Ag loading on CO2 photoreduction over
mesoporous TiO2 were investigated in detail. Methane is the only
one hydrocarbon product detected in the gas phase over all the
samples. From Fig. 7A one can see that the unloaded mesoporous
TiO2 sample showed poor activity and there was trace amount of
methane detected. The loading of noble metal generally promoted
the formation of methane. The efficiency of cocatalyst follows
the order: Pt > Au > Ag. The optimum loading amounts for Pt,
Au, and Ag are 0.2 wt.%, 0.2 wt.%, and 0.1 wt.%, respectively. The
0.2 wt.% Pt-loaded sample is the most active, over which the
amount of evolved CH4 reached 5.7 ␮mol g−1 cat. after 120 min of
UV irradiation; the data is twelve times that achieved over the
unloaded TiO2 sample. It is supposed that the loaded noble metal

A
a: non-doped
b: 500°C
Absorbance / a. u.

c: 525°C
d: 550°C
Absorbance / a. u.

e: 575°C

350 400 450 500

Fig. 6. XPS spectra of TiO2 –N (525 ◦ C). (A) Survey spectrum and (B) peak fitting of
Wavelength / nm
N 1s spectrum. The spectrum was obtained after the surface of the powder was
a-e sputtered with Ar+ to remove the adsorbed contaminants.

particles could serve as efficient electron traps, which suppressed

250 300 350 400 450 500 550 600 650 the recombination rate of photogenerated electron–hole pairs
Wavelength / nm and therefore enhanced the photocatalytic activity. It is clear that
there exists an optimum loading amount for noble metal. The
appropriate amount of metal particles loaded on sample surface
B
can trap the larger number of photoexcited electrons, resulting in
a: unloaded the enhanced photocatalytic activity. However, excess metal par-
Absorbance / a. u.

b: 0.2 % Pt
c: 0.2 % Au ticles would serve as the recombination centers that decrease the
Absorbance / a. u.

d: 0.2 % Ag photocatalytic activity. Moreover, the excess metal particles can

mask the TiO2 surface and reduce the light absorption capability of
a-d
the catalyst, and therefore reduce the photoexcitation to generate
the active electrons. The optimum loading amount of cocatalyst
usually varies with different materials and different reactions.
300 400 500 600 700
Fig. 7B shows methane evolution as a function of irradiation
Wavelength / nm time over 0.2 wt.% Pt loaded TiO2 . One can see that the amount
of detected methane increased linearly with irradiation time. Con-
trolled experiments show that in the presence of CO2 and water
a-d vapor there was trace amount of product detected under the
dark condition or under UV irradiation without any photocata-
lyst, indicating that the present reaction of CO2 reduction by water
200 300 400 500 600 700 800 proceeded photocatalytically. It has been reported that the car-
Wavelength / nm bon residues on sample surface could be involved in the formation
of products, thus the activity test in the presence of water vapor
Fig. 5. (A) The UV–vis diffuse reflectance spectra of (a) the non-doped mesoporous
but in the absence of CO2 is needed to exclude the contribution of
TiO2 , and the samples nitridized at (b) 500 ◦ C, (c) 525 ◦ C, (d) 550 ◦ C, and (e) 575 ◦ C.
(B) The UV–vis diffuse reflectance spectra of (a) the unloaded mesoporous TiO2 , and catalyst associated carbon residues [15]. We therefore performed
the samples loaded with (b) 0.2 wt.% Pt, (c) 0.2 wt.% Au, and (d) 0.2 wt.% Ag. the blank tests for the best performed 0.2 wt.%Pt/TiO2 catalyst in
36 X. Li et al. / Applied Catalysis A: General 429–430 (2012) 31–38

3.0 8
A
Methane formation / μmol h gcat .-1

Methane formation / μmol gcat -1

.
2.5
-1

6
Amount of metal loading: a
2.0 non-metal loading 5
0.05wt.%
0.1wt.% 4
1.5
0.2wt.%
0.3wt.% 3
1.0 b
2

0.5
1

0.0 0
Ag Au Pt
-20 0 20 40 60 80 100 120 140
10
B Irradiation Time / min
Methane formation / μmol gcat .-1

9
Fig. 8. Photocatalytic reduction of CO2 to methane over 0.2 wt.% Pt-loaded TiO2
8 a: catalyst+CO2+H2O, dark
samples under UV light. (a) Mesoporous TiO2 and (b) common anatase without
b: CO2+H2O, UV ligh mesoporous structure. Reaction conditions: catalyst, 0.1 g; reaction temperature,
7
60 ± 2 ◦ C; CO2 :H2 O = 0.06:1; irradiation intensity, 34.8 mW cm−2 .
6
c: catalyst+N2+H2O, UV light d
d: catalyst+CO2+H2O, UV light
5 of methane reached 5.7 ␮mol g−1 after 2 h irradiation, while over
the common anatase sample the yield of methane reached only
4
2.3 ␮mol g−1 after the same irradiation time. It is obvious that the
3 mesoporous structure of TiO2 is favorable for a higher photocat-
2
alytic activity.

1 c 3.2.3. The effect of nitrogen doping

0 a
0 20 40 60 80
Irradiation Time / min
Fig. 7. Photocatalytic reduction of CO2 to methane over the non-doped mesoporous
TiO2 under full Xe-arc. (A) The effects of different noble metal loading. (B) The
activity tests of CO2 photocatalytic reduction over 0.2 wt.%Pt/TiO2 under differ-
ent conditions. Reaction conditions: catalyst, 0.1 g; reaction temperature, 60 ± 2 ◦ C;
CO2 :H2 O = 0.06:1; irradiation intensity, 34.8 mW cm−2 .
nitrogen atmosphere. From Fig. 7B one can see that methane was
formed under UV irradiation in the absence of carbon dioxide but in
the presence of water vapor, nitrogen, and photocatalyst, indicat-
ing that methane could be produced from the catalyst associated
carbon residues. However, the amount of methane produced from
−1
carbon residues (0.3 ␮mol g−1
cat. h ) is insignificant compared with
b Fig. 9 shows the rate of methane formation from CO2 photore-
duction over serial nitrogen-doped and non-doped TiO2 samples
100 120
under visible light irradiation. For all the samples 0.2 wt.% Pt was
loaded as cocatalyst. Because pure TiO2 can hardly respond to visi-
ble light, the non-doped TiO2 sample showed very poor activity for
methane formation. The CH4 evolution rate increased with increas-
ing nitridation temperature up to 525 ◦ C, and then decreased when
the nitridation temperature exceeded 525 ◦ C. This result is under-
standable. More nitrogen atoms were doped into the lattice oxygen
positions of TiO2 at higher nitridation temperature, giving rise to
better visible light absorption as has been evidenced by the UV–vis
diffuse reflectance spectra (Fig. 5A). However, because the atomic
3.0
a: TiO2-N(525°C) a
Methane formation / μmol gcat -1
.

−1 2.5
that (2.9 ␮mol g−1cat. h ) produced from CO2 photoreduction, sug- b: TiO2-N(500°C)
gesting that in the present study methane was formed mainly from
c: TiO2-N(550°C)
CO2 photoreduction. As Fig. 7A has shown that there was smaller 2.0
amount of methane detected over unloaded TiO2 even in the CO2 d: TiO2-N(575°C)
atmosphere, it could be deduced that Pt loading could promote the e: TiO2
1.5
formation of CH4 from carbon residues in the presence of water
vapor.
1.0 b
3.2.2. The effect of the mesoporous structure c
The activity of the present mesoporous TiO2 was compared with 0.5
a common anatase sample without mesoporous structure, and the d
results are shown in Fig. 8. The common anatase phased TiO2 was
0.0 e
prepared by a synthesis procedure similar to that for mesoporous
TiO2 , except that the organic template and the hydrothermal 0 50 100 150 200 250 300 350
treatment were not adopted. The surface area value of the meso- Irradiation time / min
porous TiO2 is 151.8 m2 g−1 , and the surface area value of the
Fig. 9. Photocatalytic reduction of CO2 to methane over nitrogen-doped and non-
common anatase is 117.7 m2 g−1 . From Fig. 8 one can see that
doped TiO2 samples under visible light irradiation. 0.2 wt.% Pt was loaded as
the mesoporous TiO2 showed much higher activity than the com- cocatalyst for all the samples. Reaction conditions: catalyst, 0.1 g; reaction temper-
mon anatase sample. Over the mesoporous TiO2 sample the yield ature, 60 ± 2 ◦ C; CO2 :H2 O = 0.06:1;  > 420 nm; irradiation intensity, 38.2 mW cm−2 .

diameters and the number of valence electrons of N and O are differ-
ent, larger amount of N doping would result in more defect sites and
non-stoichiometry in the material, which reasonably decreases the
photocatalytic activity. Owing to the overall effects of visible light
absorption and defect sites, generally there is an optimum amount
of doped N to achieve the best photocatalytic activity [42,50,51]. As
aforementioned, approximately 0.84% of lattice O atoms were sub-
stituted by N atoms in the best performed TiO2 –N (525 ◦ C) sample.
3.2.4. Stability
The reaction of CO2 photoreduction over the 0.2 wt.% Pt loaded
TiO2 –N (525 ◦ C) sample was repeated for three times, and the
results are shown in Fig. 10. In each cycle the initial CH4 evo-
lution rate could be recovered, and there was no CH4 evolved
when the light was turned off. The above results indicate that the
nitrogen-doped TiO2 photocatalyst was stable under the present
experimental conditions and that the reaction proceeded photo-
catalytically.
3.2.5. Reaction mechanism
For CO2 photoreduction by gaseous water, it was proposed that
the photocatalyst was first excited by the irradiation light to gen-
erate electrons (e− ) at the conduction band and holes (h+ ) at the
valence band. The adsorbed H2 O molecules reacted with h+ to form
H+ , H+ then reacted with e− to form H• radicals. Subsequently,
CO2 was reduced by H• to hydrocarbons [52–54]. As to the cur-
rent nitrogen-doped mesoporous TiO2 photocatalyst, the doped
nitrogen created a new N 2p state slightly above the valence band
top consists of O 2p state (Fig. 11). Upon visible light irradiation,
electrons were excited from the highest occupied N 2p orbitals
to the conduction band. XPS analysis indicates that the state of
doped nitrogen in the current mesoporous TiO2 are molecularly
chemisorbed nitrogen species (N2 ) or nitroxide species (e.g., NO
and NO2 ). Nitrogen species related to Ti N bonding was detected by
neither XPS nor XRD. The origination of the visible light sensitiza-
tion of nitrogen-doped TiO2 has long been debated. Some previous
studies indicate that all of the doped nitrogen species contribute to
the visible light absorption, while only the Ti N bond is responsi-
ble for the visible light photocatalytic activity [22,29]. The present
nitrogen-doped mesoporous TiO2 samples show activities for CO2
photoreduction under visible light, supporting that the molecularly
1.5 Run 1 Run 2
Methane formation / µmol gcat -1
.
1.0
0.5
0.0
0 100 200 300 400
Irradiation time / min
Fig. 10. Repeated reactions of CO2 photocatalytic reduction over 0.2 wt.% Pt loaded
TiO2 –N (525 ◦ C) under visible light irradiation. Reaction conditions: catalyst, 0.1 g;
reaction temperature, 60 ± 2 ◦ C; CO2 :H2 O = 0.06:1;  > 420 nm; irradiation intensity,
38.2 mW cm−2 .
X. Li et al. / Applied Catalysis A: General 429–430 (2012) 31–38 37
CO2
+
H
-
e •
H
CB Pt CH4
hν
N 2p
VB O 2p
+
h
+ H2O
H
Fig. 11. The schematic drawing of CO2 photoreduction to methane over Pt-loaded
TiO2−x –Nx .
chemisorbed nitrogen species or nitroxide species may also induce
the visible light photocatalytic activity in certain reactions.
The separation and transportation of photogenerated carriers
(i.e., electrons and holes) is crucial for the photocatalytic activity.
The effect of noble metal loading on the photocatalytic activ-
ity is closely related to the working functions of semiconductors
and noble metals. When noble metal particles are attached onto
semiconductor surface, the electrons could transfer from the semi-
conductor with lower working function to the noble metal particles
with higher working function, leading to the longer lifetime of the
photoexcited electrons and the improved photocatalytic activity.
Pt has higher working function (5.65 eV) than Au (5.1 eV) and Ag
(4.26 eV) [55], thus the photogenerated electrons can transfer more
efficiently from TiO2 particles to the loaded Pt particles. However,
because the adsorption, transportation, and activation of different
reactants on metal surface are quite different, the effect of noble
metal loading on the photocatalytic activity may vary with differ-
ent reactions. The dispersion and valence state of the noble metal
as well as its interaction with the catalyst may also influence the
promotive effect on the activity. As a result, the optimum cocat-
alyst and the optimum loading amount are different in different
studies. For examples, Au showed the best promotive effect in the
photocatalytic oxidation of benzene to phenol [46], while Pt was
the best cocatalyst in the photocatalytic H2 generation from oxalic
acid solution [56].
In the present study, methane was the only one hydrocar-
bon product detected. The distribution of the products in CO2
Run 3 photoreduction is closely related to the band structure of the pho-
tocatalyst and the reduction–oxidation potentials of the products
[57,58]. The conduction band potential of TiO2 is −0.5 V [4]. The
reduction potentials of probable products are: CO2 /CH4 : −0.24 V;
CO2 /CH3 OH: −0.32 V; CO2 /COOH: −0.43 V [4]. Because the reduc-
tion potential for the formation of methane from CO2 is lower than
that required for methanol and formic acid, carbon dioxide might be
preferably reduced to methane over the TiO2 photocatalyst. How-
ever, it should be pointed out that the distributions of products also
depend significantly on the reaction system and the catalyst sur-
face properties. Actually, there were different products detected
over TiO2 in different work [10–15]. There was no molecular O2
detected in the current study of CO2 photoreduction. There have
been reports that the produced O2 can be photoadsorbed on the
500 600 700 800 surface of TiO2 , and that the oxygen molecules on TiO2 surface
could be physisorbed and chemisorbed [59,60]. We suppose that
similar phenomena may also occur in the current study. Molecular
hydrogen was not detected either. It is likely that the photogen-
erated H• radicals and H2 were quickly consumed by CO2 in the
photocatalytic reaction process.
38 X. Li et al. / Applied Catalysis A: General 429–430 (2012) 31–38
4. Conclusions
In this study, nitrogen-doped mesoporous TiO2 photocatalysts
were developed for CO2 photoreduction by water in gas phase. All of
the TiO2 samples were crystallized basically in anatase phase. The
TEM image revealed that the mesoporosity was originated from
the close packing of the TiO2 nanoparticles. The mesoporous struc-
tures could be well retained after nitrogen doping. With increasing
nitridation temperature, the mean pore diameter increases while
the surface area value decreases. The nitrogen-doped samples have
good visible light absorption. XPS analysis indicates that the doped
nitrogen was in the state of molecularly chemisorbed nitrogen
species (N2 ) or nitroxide species (e.g., NO and NO2 ).
Methane is the major hydrocarbon product in CO2 photore-
duction over the current mesoporous TiO2 samples. Noble metals
loading generally improved the photocatalytic activity, and the
efficiency follows the order: Pt > Au > Ag. The optimum loading
amount of Pt was 0.2 wt.%. The optimum nitridation tempera-
ture to achieve the best visible light activity was 525 ◦ C, and the
amount of doped N was 0.84% on the basis of the lattice oxygen
atoms. Pt loading also promoted the formation of CH4 from carbon
residues in the presence of water vapor. The nitrogen-doped TiO2
photocatalyst was stable after three cycles of CO2 photocatalytic
reduction.
In summary, by means of nitrogen doping and noble metal load-
ing, good visible light-responsive activity for CO2 photoreduction
was obtained over mesoporous TiO2 . The unique mesoporous struc-
ture, the optical property, and the synergism with noble metal
determine the overall catalyst performance.
Acknowledgments
This research was supported by the National Natural Science
Foundation of China (No. 21003064), the Research Foundation
of Jiangsu University (No. 09JDG042), and the Scientific Research
Foundation for the Returned Overseas Chinese Scholars, State Edu-
cation Ministry.
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