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CO2 methanation property of Ru nanoparticle-loaded TiO2 prepared

by a polygonal barrel-sputtering method
Takayuki Abe,* Masaaki Tanizawa, Kuniaki Watanabe and Akira Taguchi
Received 8th October 2008, Accepted 5th December 2008
First published as an Advance Article on the web 14th January 2009
DOI: 10.1039/b817740f

Highly dispersed Ru nanoparticles loaded on a TiO2 support (Ru/TiO2(B)), which affects the
hydrogenation of CO2 to CH4 (methanation), were prepared by employing a ‘‘dry’’ modification
method using a barrel-sputtering instrument. The loaded Ru nanoparticles exhibited a narrow particle-
size distribution with a mean diameter of ca. 2.5 nm. Methanation of CO2 on the Ru/TiO2(B) catalyst
produced a 100% yield at ca. 160
C, which is more than 200
C below that required for Ru/TiO2
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prepared by a conventional ‘‘wet’’ impregnation method. In addition, the methanation reaction

over Ru/TiO2(B) proceeded at temperatures as low as room temperature with a reaction rate of
0.04 mmol min1 g1.

Introduction
Carbon dioxide (CO2) is a recognized as a major factor respon-
sible for the so-called greenhouse effect, the ever-increasing
amounts of CO2 in the atmosphere are causing climate changes
on a global scale.1 Therefore, a reduction in CO2 emission into
the atmosphere is an urgent necessity. However, the levels of CO2
are increasing with increasing in the world’s population and
improvement in living standards. As a result, the control of CO2
emission by means of regulations such as those represented by
the Kyoto Protocol, may no longer be feasible. Although various
physical and chemical techniques have been proposed for the
fixation of exhausted CO2, such as fixation in carbonates,
geological or ocean storage, or afforestation,1 their immediate
practical application has drawbacks in terms of economic
factors, safety, efficiency, and reliability.
Catalytic approaches for CO2 fixation can play an important
role, because CO2 can be artificially converted into reusable
chemicals.1 Among the catalytic reactions of CO2, hydrogena-
tion of CO2, the so-called methanation reaction, is a suitable
Hydrogen Isotope Research Center, University of Toyama, 3190 Gofuku,
Toyama, 930-8555, Japan. E-mail: tabe@ctg.u-toyama.ac.jp; Fax:
+81-76-445-6931; Tel: +81-76-445-6933
technique for the fixation of CO2; this technique can be used to
convert exhausted CO2 into methane (CH4), which can be
recycled for use as a fuel or a chemical.1e–g Temperatures in the
range of 300–400
C are generally applied to this reaction,2 and
additional CO2 is generated for producing the energy required
to maintain such temperatures. To overcome this drawback,
a catalyst capable of affecting the methanation reaction at lower
temperatures is required. Gr€ atzel et al. reported the formation
of CH4 over a Ru/TiO2 catalyst prepared by means of a wet
process. They stated that the reaction started from room
temperature at atmospheric pressure.3 However, Melsheimer
et al. stated that the catalyst was characterized by a critical
preparation technique.4 We also prepared samples under
the prepared conditions described by Gr€ atzel et al., and then
we examined the physical and methanation properties of the
samples. The results of our experiments are described later in
this paper. Mechanical milling of a mixture of a transition metal
and an oxide material under CO2 and H2 atmosphere at 80 kPa
leads to the formation of CH4 at temperatures below 100
C;5
however, the use of mechanical devices and the maintenance
of a high-pressure environment leads to the generation of
additional CO2.
Nanoparticles loaded on various supports exhibit high
catalytic activity for several reactions.6 A number of ‘‘wet’’

Broader context
CO2 is a recognized as a major cause of the so-called greenhouse effect. Catalytic approaches for CO2 fixation could play an
important role, because CO2 can be artificially converted into reusable chemicals. Among the catalytic reactions of CO2, hydro-
genation to form CH4 (methanation), which can recycle CO2 to a reusable fuel, is one candidate for such a fixation process.
A barrel-sputtering method (cf. J. Phys. Chem. C, 2007, 112, 1479) allowed us to fabricate highly dispersed Ru nanoparticles on
a TiO2 support by a ‘‘dry’’ impregnation method. The obtained Ru/TiO2 catalyst can efficiently carry out CO2 methanation with
100% yield at ca. 160
C, which is more than 200
C below that required for Ru/TiO2 prepared by a conventional ‘‘wet’’ impregnation
method. Moreover, the Ru/TiO2 catalyst proceeds the methanation at temperatures as low as room temperature with a reaction rate
of 0.04 mmol min1 g1. While there are some problems with the methanation reaction for practical use, such as hydrogen supply, the
remarkable low temperature reaction could be of interest in CO2 recycling process where cheap and large amounts of by-product
hydrogen can be utilized in a narrow as possible area (called ‘CO2 local recycling system’).

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techniques, including the sol-gel method, liquid precipitation,
and colloidal micelles, have been developed for the production of
uniformly sized nanoparticles of metals dispersed on powdery
supports.6b,c However, in these techniques, heating is required
for loading of the prepared nanoparticles onto the powdery
supports, and the heating induces growth of the nanoparticles.
We have recently developed a ‘‘dry’’ technique for modifying
the surfaces of powdery materials; this technique, which we have
named ‘‘barrel-sputtering’’, allows the fabrication of highly
dispersed naked metal nanoparticles on a powdery support
without any heating.7 In the present study, we attempted to load
Ru nanoparticles onto a TiO2 support by the barrel-sputtering
method, and studied the phyisical and catalytic properies of the
prepaerd samples.
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Experimental
Sample preparation
Titanium dioxide (TiO2 (anatase), ST-41, obtained from Ishihara
Sangyo Kaisha, Ltd., Osaka, Japan) was used as a support after
being dried overnight in an oven at 180
C. Metallic Ru plates
(purity; 99.9%, 50  100 mm2) were used as the sputtering target.
Sputter deposition of the metal nanoparticles on the support was
conducted by the barrel-sputtering equipment shown in Fig. 1.7a,b
A hexagonal barrel that could be swung using a motor drive was
placed in a vacuum chamber to hold a powdery support. The
support loaded into the barrel was lifted up to a certain level
along the wall of the barrel by swinging the barrel; the powdery
support subsequently fell down along the barrel wall by its own
weight and struck the wall. As a result, it was effectively stirred
during the sputter deposition. The angle of the target stage could
be freely varied to face the support, thereby allowing the sputter
deposition efficiency to be enhanced.
In this study, 3.0 g of TiO2 powder was loaded into the barrel.
The vacuum chamber was carefully evacuated up to 8.0  104
Pa, and then high-purity argon gas (purity: 99.995%) was grad-
ually introduced into the chamber until the pressure increased up
to 0.8 Pa. Radio-frequency (13.56 MHz) magnetron sputtering
was performed for 25 min with an input power of 100 W, leading
to a deposition of Ru on each particle surface in the powder. The
amount of Ru loaded onto a support was adjusted to be
approximately 0.8 wt% by controlling the sputtering duration.
During sputtering, a swinging motion of 75
at a speed of
Fig. 1 Schematic representation of the hexagonal barrel-sputtering
system.
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4.2 rpm was provided to the hexagonal barrel. After sputtering,
N2 gas (99.9998%) was gradually introduced to increase the
pressure up to 1 atmosphere, whereupon the prepared samples
could be extracted. The prepared TiO2 supported Ru, denoted
as Ru/TiO2(B), was used as the catalyst for the methanation
reaction without any pretreatment.
In order to allow the growth of Ru nanoparticles, samples
were prepared by thermal treatment of Ru/TiO2(B) at 500, 700 or
800
C under H2 flow (30 mL min1) for 3 h: these samples are
denoted as Ru/TiO2(B500), Ru/TiO2(B700), and Ru/TiO2(B800),
respectively.
For comparison purposes, TiO2 supported Ru catalysts were
prepared by a conventional wet method. The TiO2 supported Ru
catalyst, denoted as Ru/TiO2(W), was prepared by the incipient
wetness method. TiO2 (5.0 g) was added to a solution of
RuCl3$3H2O (Acros, 0.1293 g) in 5 ml of water. The resultant
slurry was dried at 80
C for 16 h and then calcined in air at
350
C for 8 h. The sample was reduced under flowing H2
(30.0 ml min1) at 400
C for 3 h in the reactor and subsequently
used in the catalytic reaction without contact with the air.
In addition, the TiO2 supported Ru catalyst was prepared by
following the Gr€ atzel method.3a The obtained sample is denoted
as Ru/TiO2(G). Prior to the catalysis, Ru/TiO2(G) was reduced
under flowing H2 (3.0 mL/min1) at 220
C for 1 h in the
reactor.
Characterization
Characterization of the prepared sample was carried out by
means of X-ray diffraction (XRD; Philips, PW1825/00), induc-
tive coupling plasma analysis (ICP; PerkinElmer, Optima
3300XL) and transmission electron microscopy (TEM; JEOL,
JEM-2100). Furthermore, X-ray photoelectron spectroscopy
(XPS) measurements were conducted (XPS; Shimadzu/Kratos,
AXIS-HSX).
Catalysis
The catalytic reaction was performed under atmospheric pres-
sure in a fixed-bed flow reactor made of quartz and with an inner
diameter of 6 mm. The reactor was heated in a furnace, and two
thermocouples (one located in the catalyst in the fixed bed and
the other located outside the quartz reactor) were used to control
the temperature. Catalyst powder (1.0 g) was placed in the
reactor; Ru/TiO2(G) was diluted by adding unloaded TiO2 in
order to control the amount of Ru of 0.80 wt%. The reaction gas
mixture consisting of CO2 and H2 in a molecular ratio of 1 : 4 was
mixed with Ar and passed at a given feed rate (F/W). The reac-
tion effluent was analyzed by using an online-gas chromatograph
equipped with a thermal conductivity detector and an active
carbon column. Subsequently, the feed gas was switched to pure
Ar, and the temperature of the catalyst was increased at a rate of
3.0
C min1. This sequence was repeated starting from room
temperature and then by increasing the temperature in steps of
10, 20 40 or 50
C. In the range of temperatures examined, the
products obtained were CH4 and H2O. The reaction effluent
was separately analyzed by quadrupole mass spectroscopy
(ANELVA, M-100QA): this proved that hydrocarbons other
than CH4 were not produced.
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The catalytic activity of Ru/TiO2 was also evaluated through Fig. 3(A), (B) and (C) show TEM images of Ru/TiO2(B),
a batch test by using the same reactor by stopping the flow of Ru/TiO2(W) and Ru/TiO2(G), respectively. In the case of
reactant gas for a given time and by maintaining a certain Ru/TiO2(B), it can be observed that small dots were highly
temperature. dispersed on the TiO2 supports. The XPS results suggest that
The methane yield and turnover number (TONCH4) are defined these dots consist of metallic nanoparticles of Ru. The
as particle-size distribution, which is calculated from more than
CH4 molecules formed 100 nanoparticles on Ru/TiO2(B), is overlaid in Fig. 3(A). The
Yield ð%Þ ¼  100 sizes of the nanoparticles were distributed in the range 0.7–
CO2 molecules fed
7.5 nm, and more than 80% of the nanoparticles were smaller
CH4 molecules formed than 3.0 nm. The mean particle size (D) was calculated to be
TONCH4 ¼ about 2.5 nm (Table 1). The TEM images of Ru/TiO2
NRu;atoms;cat:  s
prepared by the wet method (Ru/TiO2(W)) are considerably
Here, NRu,atoms,cat. denotes the total number of Ru atoms loaded different from those of Ru/TiO2(B). The sizes of metallic Ru
on the surface of 1.0 g of catalyst (see below). particles on Ru/TiO2(W) are distributed over a wider range
(1.4–29.0 nm, D ¼ 9.5 nm). For Ru/TiO2(G), the particle size
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distribution and the mean particle size are found to be in the

Results and discussion
range 0.9–30.6 nm and 5.2 nm, respectively. The mean particle
Characterization size of Ru/TiO2(G) is smaller than that of Ru/TiO2(W),
however, it is apparent that Ru nanoparticles in Ru/TiO2(G)
From the ICP measurments, the amount of Ru loaded on Ru/
are more agglomerated as compared to those in Ru/TiO2(W).
TiO2(B), Ru/TiO2(W) and Ru/TiO2(G) were determined to be
It can be observed that the barrel-sputtering method is
0.80, 0.75, and 3.60 wt%, respectively.
advantageous, particularly for loading highly dispersed nano-
The prepared Ru/TiO2 catalysts were subjected to physical
particles on a support. The absence of large particles of Ru for
characterization. XRD measurements on Ru/TiO2(W) (shown in
Ru/TiO2(B) explains the absence of Ru signals in the XRD
Fig. 2(C)) showed the presence of diffraction signals attributed to
measurements.7c
metallic Ru (JCPDS 06-0663) at 42.15 and 44.00
(CuKa), along
TEM images of the samples of Ru/TiO2(B500), Ru/TiO2(B700),
with diffraction signals for TiO2 with the anatase structure
and Ru/TiO2(B800) are shown in Fig. 3(D), (E) and (F), respec-
(JCPDS 83-2243, Fig. 2(A)). Although definitive diffraction
tively. The sizes of the Ru nanoparticles increased with the
signals assignable to metallic Ru were observed in the XRD
treatment temperature, and the mean nanoparticle sizes of the
pattern of Ru/TiO2(G) (Fig. 2(D)), the signals were slightly
samples were estimated to be 3.4, 5.0, and 6.4 nm, respectively
broader than those of Ru/TiO2(W). Signals corresponding to Ru
(Table 1).
oxide were not observed. In the case of Ru/TiO2(B), on the other
From the mean particle size of the Ru nanoparticles (D), the
hand, only signals corresponding to TiO2 were obtained
number of Ru atoms on the nanoparticle surface can be
(Fig. 2(B)). However, XPS studies on Ru/TiO2(B) showed
calculated. The weight (WRu,nanoparticle in g) and surface area
a signal with a binding energy of 279.5 eV; no signal attributed to
(S.A.Ru,nanoparticle in m2) of an Ru nanoparticle are expressed as
Ru oxides4,8 was observed, indicating that metallic Ru was
follows:
present on the TiO2.
1
WRu;nanoparticle ¼ rRu  pD3  1021
6

S.A.Ru,nanoparticle ¼ pD2  1018

Here, the symbol rRu denotes the density of Ru (12.41 g cm3).

The number of Ru nanoparticles in 1.0 g of the catalyst
(NRu,nanoparticles in number) can be expressed in terms of the
amount of Ru supported, Wcat., in wt%, as follows:
Wcat: 1
NRu;nanoparticles ¼ 
100 WRu;nanoparticle
Thus, the total surface area of Ru nanoparticles in 1.0 g of
catalyst (S.A.Ru,cat. in m2) is calculated as follows:

S.A.Ru,cat. ¼ NRu,nanoparticles  S.A.Ru,nanoparticle

The surface density of Ru atoms in a closed-packing model,

which corresponds to the number of Ru atoms in the (001) plane
Fig. 2 X-Ray diffraction patterns of (A) unsupported TiO2, (B) Ru/ of the unit cell of a Ru hexagonal structure, is 0.1739  1020 (in
TiO2(B), (C) Ru/TiO2(W) and (D) Ru/TiO2(G). number per m2, a0 ¼ 0.27058 nm). Hence, the total number of Ru

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Fig. 3 TEM images of TiO2 supported Ru nanoparticles. (A) Ru/TiO2(B), (B) Ru/TiO2(W), (C) Ru/TiO2(G), (D) Ru/TiO2(B500), (E) Ru/TiO2(B700),
(F) Ru/TiO2(B800) and (G) Ru/TiO2(B) after use in methanation reaction at 180
C for one week. The particle size distribution obtained for more than
100 nanoparticles of Ru is overlaid.

Table 1 Sample ID and the summary of the characterization and methanation activity

Metal Sample Mean particle Surface area of Ru Onset temperature TONCH4 at

content [wt%] treatment size (D)/nm (S.A.Ru.cat.)/m2 g-cat.1 of CH4 formation/
C 160
C/s1

Ru/TiO2(B) 0.80 as-prepared 2.5 1.55 60 1.5  102

80a 4.6  103a
Ru/TiO2(B500) 0.80 500
C, 3h (H2) 3.4 1.14 80 8.5  103
Ru/TiO2(B700) 0.80 700
C, 3h (H2) 5.0 0.77 100 4.8  103
Ru/TiO2(B800) 0.80 800
C, 3h (H2) 6.4 0.60 140 3.2  104
Ru/TiO2(W) 0.75 400
C, 3h (H2) 9.5 0.38 120 1.0  103
RuTiO2(G) 0.76 220
C, 1 h (H2) diluted 5.2 0.71 80 4.9  103
a
Value at F/W of 1.16 mL g1 s1.

atoms on the surface of 1.0 g of catalyst (NRu,atom,cat. in number)
can be expressed as follows:
NRu,atom,cat. ¼ S.A.cat.  0.1739  1020
The values of NRu,atom,cat. in Ru/TiO2 catalysts are listed in
Table 1.
Methanation activity
Fig. 4(A) shows the relationship between the reaction tempera-
ture and the yield of CH4 over Ru/TiO2 catalysts at a reaction-
gas feed rate (F/W) of 0.24 mL g1 s1. With Ru/TiO2(W) pre-
treated at 400
C for 3 h in H2, the formation of CH4 was
observed at temperatures above 120
C, where the yield of CH4
was 0.3% at 120
C. The yield of CH4 increased with the reaction
temperature and became quantitative at 380
C. On the other
hand, CH4 was formed over Ru/TiO2(B) at temperatures above
60
C, where the yield was 0.3% at 60
C even without any
pretreatment: remarkably, the onset temperature for CH4
formation was reduced by about 60
C as compared with the case
of Ru/TiO2(W). The yield of CH4 increased with the reaction
temperature, and it reached a 100% yield at 160
C, which was
about 220
C less than the corresponding temperature for
Ru/TiO2(W). Ru/TiO2(G) exhibited a lower onset temperature

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Fig. 4 (A) Temperature dependence of the methane yield at methana-
tion of CO2 over TiO2 supported Ru nanoparticles; (C) Ru/TiO2(B), (:)
Ru/TiO2(G), (-) Ru/TiO2(W) and (B) Ru/TiO2(B) diluted with
unsupported TiO2. (B) Change of the methane yield as a function of
reaction time in very early range at 180
C.
for methane formation (80
C) and a lower complete reaction
temperature (240
C) as compared to those exhibited by
Ru/TiO2(W). However, these values were still higher than those
of Ru/TiO2(B). The turnover numbers (TONCH4) at 160
C were
calculated to be 1.5  102, 1.0  103 and 4.9  103 s1 for
Ru/TiO2(B), Ru/TiO2(W), and Ru/TiO2(G), respectively, as
shown in Table 1. These data demonstrate that the catalytic
activity of Ru/TiO2(B) was significantly higher than those of
Ru/TiO2(W) and RuTiO2(G). It should be noted that in Fig 4(A),
the yield of CH4 was found to be higher than 100%. However, the
yield of methane gradually decreased and reached 100  3%
within 30 min, as shown in the time course of methanation by
Ru/TiO2(B) at 180
C shown in Fig. 4(B).
A study of the effect of F/W for Ru/TiO2(B) (Fig. 5) showed
that an increase in F/W caused a slight increase in the onset
temperature of the reaction and the temperature required for
100% yield. When the F/W was set at 1.16 mL g1 s1, the former
and latter temperatures were 80
C and 210
C, respectively;
these temperatures were still significantly lower than those for
Ru/TiO2(W).
A batch test was conducted to obtain a more accurate value of
the onset temperature for CH4 formation (Fig. 6). In the case of
Ru/TiO2(B) at 25
C (room temperature), the formation of CH4
was clearly observed 5 min after the feed gas was introduced into
the reactor. Since the amount of CH4 generated increased lineally
with the reaction time, the rate of generation divided by the
weight of the catalyst was calculated to be 0.04 mmol min1 g1.
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Fig. 5 The effect of F/W for Ru/TiO2(B) on methanation of CO2 as
a function of reaction temperature; (B) 0.17, (C) 0.24, (O) 0.48 and (:)
1.16 ml g1 s1, respectively. The reaction curve at F/W of 0.24 mL g1 s1
is the same with that in Fig. 4(A).
Fig. 6 Change of the amount of methane as a function of the reaction
time by a batch-type reaction; (C) Ru/TiO2(B) at 25
C (room temper-
ature), (B) Ru/TiO2(B) at 40
C, (:) Ru/TiO2(G) at 25
C and (O)
Ru/TiO2(G) at 40
C, respectively.
For Ru/TiO2(B) at 40
C, the rate of generation was 0.11 mmol
min1 g1, which was about three times that at room temperature.
As for Ru/TiO2(G), on the other hand, the formation of CH4 was
observed 60 min after the gas was introduced. The rate of CH4
generation was estimated to be 0.002 mmol min1 g1 at room
temperature, and 0.01 mmol min1 g1 at 40
C. In the case of Ru/
TiO2(W) at room temperature or 40
C, CH4 generation was not
observed even 1 h after the feed gas was introduced: at 80
C,
0.05 mmol min1 g1 of CH4 was observed.
On the basis of the physical properties discussed above, the
considerable difference in methanation activity between Ru/
TiO2(B), Ru/TiO2(W) and Ru/TiO2(G) is considered from the
viewpoint of the surface area of Ru nanoparticles (S.A.Ru.cat.). As
listed in Table 1, the S.A.Ru,cat. values for Ru/TiO2(B), and Ru/
TiO2(W) differ by a factor of 4.1. Therefore, we measured the
dependency of the CH4 yield on the reaction temperature when
the amount of Ru/TiO2(B) catalyst in the reactor was reduced to
one quarter of the previous amount, as shown in Fig. 4(A). It
should be noted that the total powder volume in the reactor was
adjusted by adding unloaded TiO2. The formation of CH4 was
observed at above 80
C, and a 100% yield was attained at
210
C. These temperatures were higher than those for
Ru/TiO2(B), but the amount of CH4 formed at 160
C remained
Energy Environ. Sci., 2009, 2, 315–321 | 319

about 20 times that formed on Ru/TiO2(W). Although the
S.A.Ru,cat. values for Ru/TiO2(B) and Ru/TiO2(G) differ by
a factor of about 2.2, the reaction curve of Ru/TiO2(B) catalyst
reduced to one quarter is still higher than that of Ru/TiO2(G).
These results indicated that the high catalytic activity of
Ru/TiO2(B) cannot be attributed solely to the S.A.Ru,cat., and
that another factor is involved. To clarify the effect of the size of
nanoparticles, the catalytic activities of Ru/TiO2(B500), Ru/
TiO2(B700), and Ru/TiO2(B800) were tested, as shown in
Fig. 7(A). The same reaction curves of Ru/TiO2(B), Ru/TiO2(W),
and Ru/TiO2(G) shown in Fig. 4(A) are included for comparison.
The onset temperature for CH4 formation increased from 60
C
for Ru/TiO2(B) up to 140
C for Ru/TiO2(B800). The temperature
of 100% yield increased from 160
C for Ru/TiO2(B) to 380
C
for Ru/TiO2(B800). In addition, the TONCH4 at 160
C decreased
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from 1.5  102 s1 for Ru/TiO2(B) to 3.2  104 for Ru/
TiO2(B800) (Table 1). The catalytic activity of Ru/TiO2(B800) was
almost the same as that of Ru/TiO2(W), and the activity of Ru/
TiO2(B700) was similar to that of Ru/TiO2(G). These results
strongly suggest that the methanation activity depends on the
particle size of the loaded Ru nanoparticles (Table 1). Fig. 7(B)
shows the dependencies of the onset temperature and TONCH4
on the mean particle diameters. The onset temperature decreased
linearly with the particle diameter in the range of 2.5–6.0 nm, but
remained almost constant at about 120
C for particle diameters
Fig. 7 (A) Change of the methane yield depends on the mean particle
diameter as a function of reaction temperature; (B) Ru/TiO2(B500) with
3.4 nm, (O) Ru/TiO2(B700) with 5.0 nm and (,)Ru/TiO2(B800) with 6.4
nm. The reaction curves for (C) Ru/TiO2(B) with 2.5 nm, (:) Ru/
TiO2(G) with 5.2 nm and (-) Ru/TiO2(W) with 9.5 nm, the same as
Fig. 4(A), are also included. (B) Relationships between (C) the onset
temperature of methane formation or (B) TONCH4 at 160
C and the
mean particle diameter of Ru on TiO2.
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Fig. 8 Time course of methane yield by hydrogenation of CO2 over
Ru/TiO2(B) at (C) 180
C, (:) 140
C and (-) 80
C.
greater than about 6 nm. The particle-size dependency of the
TONCH4 was a mirror image of that of the onset temperature.
These results indicate that the remarkable reduction in the onset
temperature and the higher activity of Ru/TiO2(B) can be
attributed to the presence of Ru nanoparticles smaller than about
6.0 nm. In the case of Ru/TiO2(G), the particle size is distributed
in a wide range of about 1–30 nm, showing a presence of nano-
particles smaller than about 6.0 nm (Fig. 3(C)). This unusual
phenomenon in Ru/TiO2(G) is attributed to the predominant
contribution of Ru nanoparticles smaller than 6 nm.
The activation energies of Ru/TiO2(W) and Ru/TiO2(G) for
the reaction were calculated to be 44.5 and 59.8 kJ mol1 from an
Arrhenius plot of the reaction curve shown in Fig. 4(A). In the
case of Ru/TiO2(B), however, two distinct activation energies
were identified at temperatures in the range of 60–100
C and
120–160
C, and their values were estimated to be 76.1 and
59.2 kJ mol1, respectively, suggesting that the reaction mecha-
nism for Ru/TiO2(B) in the lower temperature range is different
from that for Ru/TiO2(W) and Ru/TiO2(G). Furthermore, the
frequency factor for Ru/TiO2(B) is about two orders of magni-
tude greater than that for Ru/TiO2(W). The most likely expla-
nation for this is that the frequency factor is related to the
dispersibility of Ru nanoparticles on TiO2. That is, because
methanation is an exothermic reaction, the heat of the reaction
generated on a certain nanoparticle is probably transmitted to
neighboring particles and it accelerates subsequent reactions on
these particles. However, a more detailed study aimed at the
clarification of the mechanism is in progress.
It has been shown that Ru/TiO2(B) is a stable catalyst for the
reactions at 80 and 140
C for 24 h, and 180
C for one week
(Fig. 8). The catalytic activity remained constant at each
temperature. TEM studies conducted on the catalyst used at
180
C revealed no change in the size or size distribution of Ru
nanoparticles as compared with the state of the as-prepared
sample (Fig. 3(G) and (A)), indicating that Ru/TiO2(B) is suffi-
ciently stable for long-term use in reactions.
Conclusions
The CO2 methanation reaction on Ru/TiO2(B) prepared by the
barrel-sputtering method, by which highly dispersed Ru nano-
particles were deposited on the TiO2 support, produced a 100%
yield of CH4 at 160
C, which was significantly lower than that
This journal is ª The Royal Society of Chemistry 2009

required in the case of Ru/TiO2(W) and Ru/TiO2(G). In addi-
tion, the methanation reaction over Ru/TiO2(B) proceeded at
temperatures as low as room temperature with a reaction rate of
0.04 mmol min1 g1.
We notice that there are two major problems of practical
application of Ru/TiO2(B). The first problem is the fact that
methane is one of the gases which promotes the greenhouse
effect. However, the combination of the catalytic formation of
methane from CO2 exhausted and the reuse of the formed
methane can control the emission of CO2 into the atmosphere.
The second problem is the manner in which hydrogen is obtained
without CO2 being newly exhausted. The use of the by-product
hydrogen obtained in ironworks and petrochemical plants
appears to be a realistic solution to the problem. Thus, the
CO2 recycling process by the Ru/TiO2(B) catalyst should be
Published on 14 January 2009. Downloaded on 4/14/2024 3:26:21 AM.
performed in an area as narrow as possible; the recycling system
(called a ‘CO2 local recycling system’) should be situated at the
place where cheap and large amounts of by-product hydrogen
can be utilized. In addition, the use of Ru/TiO2(B) might be
useful in confined spaces that can not obtain sufficient energy, for
example, in spaceships and space stations.
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