pubs.acs.

org/journal/ascecg Research Article

Effect of Rutile Content on the Catalytic Performance of Ru/TiO2

Catalyst for Low-Temperature CO2 Methanation
Zhiying Zhao, Qiaorong Jiang, Qiuxiang Wang, Mingzhi Wang, Jiachang Zuo, Hanming Chen,
Qin Kuang,* and Zhaoxiong Xie*
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ABSTRACT: Hydrogenation of carbon dioxide (CO2) to methane (CH4) bears the

potential not only to alleviate excessive emission of CO2 but to produce clean energy for
direct use. However, due to the high temperature required for the activation of CO2, it is
necessary to develop a catalyst with high activity and high CH4 selectivity at low reaction
temperature for CO2 methanation. In this study, we synthesized titanium dioxide (TiO2)
supports with different rutile contents by calcination and investigated the relationship
between the rutile content of TiO2 supports in Ru/TiO2 catalysts and their performance
for low-temperature CO2 methanation. The characterization results indicated that Ru
species grew preferentially on the rutile phase of the support TiO2, and the interaction
between Ru species and TiO2 became stronger with increasing rutile content. In addition,
the concentration of oxygen vacancies on the support, which would provide more
adsorption sites for CO2, increased with the decreasing rutile content. The best reactivity
was achieved with a rutile content between 15% and 30%. This work included a thorough
investigation on the effect of rutile content on the performance of low-temperature CO2 methanation and provided guidance for the
preparation of Ru/TiO2 catalyst with high activity.
KEYWORDS: Ru/TiO2, CO2 methanation, Rutile content, Interaction, Oxygen vacancy

■ INTRODUCTION
The catalytic hydrogenation of carbon dioxide (CO2) to
methane (CH4) was first discovered by Sabatier in 1902 and is
termed CO2 methanation or the Sabatier reaction.1 Since the
industrial revolution, the overuse of fossil fuels has exacerbated
environmental and energy-related problems. To reduce the
adverse impact of excessive CO2 emission, CO2 methanation
has received renewed attention in recent decades.2−4 Chemical
conversion of CO2 to CH4 could not only reduce CO2
emission but also generate clean energy that can be used
directly at the same time.5 Therefore, CO2 methanation was
considered to be one of the most promising energy storage
strategies. For an efficient activation of the C−O bond in CO2,
reaction temperatures above 350 °C are usually reported in
most of the literature for CO2 methanation.6,7 However, the
high reaction temperature requires an actual increase in energy
consumption and commonly causes serious aggregation of
active metal species on catalysts.8 Therefore, designing a
catalyst with high activity and high CH4 selectivity at low
reaction temperatures rationally is still one of the major goals
in CO2 methanation.7 Up to now, supported metal-based
catalysts (e.g., Ni, Ru, and Rh) have been reported as potential
catalysts for this reaction in a large number of studies.9,10
Among them, Ru-based catalysts are more promising for CO2
methanation applications since they are less conducive to
deactivation by carbon deposition than Ni and less expensive
than Rh.11−14
Previous studies suggested that the metal sites in supported
metal/oxide catalysts were able to dissociate hydrogen (H2),
while the oxide and the metal−oxide interface were responsible
for the adsorption and activation of CO2.15−17 Therefore, the
type of oxide support and the construction of the metal−oxide
interface were also important to promote the performance of
CO2 methanation.18 Titanium dioxide (TiO2) has been widely
used as the catalyst support in thermocatalysis due to its low
price, high stability, and abundant oxygen vacancies.19−21 Liu
and co-workers22 highlighted the importance of oxygen
vacancies for the adsorption of CO2, showing that CO2
bonds weakly on the surface of a silica-supported platinum
catalyst (Pt/SiO2) due to the nonreducibility of SiO2. In
contrast, Pt/TiO2 with more oxygen vacancies exhibited higher
activity for the conversion of CO2 to CO. In the recent 20
years, Ru/TiO2 has been reported as a typical catalyst for CO2
methanation, while the phase of TiO2 was identified as one of
Received: August 15, 2021
Revised: October 5, 2021
Published: October 13, 2021

© 2021 American Chemical Society https://doi.org/10.1021/acssuschemeng.1c05565

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the significant factors determining the catalytic performance in
CO2 hydrogenation.23−26 In earlier research, the existence of a
strong interaction between Ru species and the rutile phase of
TiO2 was discovered, which could prohibit the aggregation of
Ru species to a great extent.27,28 However, the existing reports
only focused on the advantages of rutile TiO2 but did not
conduct detailed studies on the effect of introducing the
anatase phase of TiO2 to the catalyst on CO2 methanation
performance at low reaction temperature. As we all know,
rutile TiO2 provides fewer oxygen vacancies due to its
comparatively lower reducibility and smaller specific surface
area compared to the anatase TiO2 phase.29,30 However, since
oxygen vacancies significantly contribute to CO2 hydro-
genation, the influence of the phase content on low-
temperature CO2 methanation requires further exploration.
In this work, we prepared a series of Ru/TiO2 catalysts with
different phase contents through a simple impregnation
method and high-temperature calcination. It was found that,
at a rutile content in the range of 15−30%, both the interaction
between Ru species and the TiO 2 support and the
concentration of oxygen vacancies were moderate and suitable
for CO2 methanation at low reaction temperature. This study
provides a new perspective on the influence of the TiO2 phase
on low-temperature CO2 methanation.
■
EXPERIMENTAL SECTION
Materials and Chemicals. Ethanol and hydrogen peroxide
(H2O2) aqueous solution (30% w/v) were purchased from
Sinopharm Chemical Reagent Co., Ltd.; ruthenium(III) chloride
(RuCl3) (99.9%) was purchased from J&K Scientific Ltd.; and
titanium isopropoxide [Ti(OC3H7)4] (99.9%) was purchased from
Energy Chemical Co., Ltd. All chemicals were used without further
purification.
Preparation of TiO2 Supports. The TiO2 support was
synthesized by the reported sol−gel method.31 The preparation
process comprised the following steps: (1) 3 mL of Ti(OC3H7)4 was
dispersed in 10 mL of ethanol, and then 50 mL of distilled water was
added. After stirring for 20 min, the produced white precipitate was
centrifuged (9500 r/min) and washed with water three times to
remove residual ethanol. (2) The white product was slowly added to
15 mL of aqueous H2O2 solution and stirred continuously until it
dissolved to form an orange solution, which then changed into a
transparent orange sol. Finally, the sol slowly thickened to form a gel.
(3) The gel was dried under an infrared lamp and then calcined at 500
°C (5 °C/min) for 3 h in air. The obtain TiO2 support was denoted
as TiO2-A. (4) The TiO2-A samples were calcined at 600, 700, or 800
°C for 3 h, and the obtained supports were denoted as TiO2-600,
TiO2-700, or TiO2-800, respectively.
Preparation of Ru/TiO2 Catalysts. Ru/TiO2 catalysts were
prepared by an impregnation method. In a typical synthetic process of
Ru/TiO2-A, 300 mg of TiO2-A was impregnated in 0.663 mL of
aqueous RuCl3 solution (Ru: 9.0469 mg/mL) and then stirred (250
r/min) at room temperature for 10 h. The sample was dried at 60 °C
for 12 h and then calcined at 500 °C (5 °C/min) for 2 h in air.
Similarly, Ru/TiO2-600, Ru/TiO2-700, and Ru/TiO2-800 catalysts
were prepared by replacing TiO2-A with TiO2-600, TiO2-700, and
TiO2-800, respectively. The theoretical loading of Ru was 2%.
Characterization of Samples. Powder X-ray diffraction (XRD)
was performed on a Rigaku Ultima IV X-ray diffractometer with Cu
Kα (λ = 0.154 06 nm) radiation. The rutile content of each catalyst
was obtained by Rietveld refinement. X-ray photoelectron spectros-
copy (XPS) was performed on a PHI Quantum-2000 instrument. The
binding energies of all elements were calibrated against the C 1s peak
at 284.8 eV. The specific surface area (SBET) of the sample was
measured by N2 adsorption−desorption isotherms at −196 °C using a
Micromeritics Tristar 3020.
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High-angle annular dark-field scanning transmission electron
microscopy (HAADF-STEM), high-resolution transmission electron
microscopy (HRTEM), and element mapping analyses were
performed with a Phillips FEI Tecnai 20 microscope operated at
200 kV; selected area electron diffraction (SAED) was performed on a
JEOL JEM-2100 microscope. The morphology and size of samples
were characterized by a Hitachi S-4800 scanning electron microscope
(SEM).
CO2 (and CO) temperature-programmed desorption (CO2-TPD
and CO-TPD) experiments were performed on self-built equipment
(Hiden Analytical QIC-20 quadrupole mass spectrometer). In a
typical experiment process of CO2-TPD, an amount of 60 mg of
catalyst was reduced at 400 °C for 1 h under an atmosphere of 5%
H2/Ar and then cooled to room temperature in He (99.999%)
atmosphere. Afterward, a stream of CO2 (99.99%) was introduced
into the reactor for 20 min. After the adsorption of CO2, the catalyst
was scrubbed with He (99.999%) for 30 min to remove physically
adsorbed CO2. Finally, the catalyst was heated in He (99.999%) to
500 °C. Online mass spectrometry was employed to track ion
fragments including CO2 (m/z = 44). In the experiment process of
CO-TPD, the adsorption gas was changed to 1% CO/He, while
keeping other conditions unchanged. Online mass spectrometry was
employed to track ion fragments including CO (m/z = 28).
In situ diffuse reflectance infrared Fourier transform spectroscopy
(DRIFTS) was conducted on a Thermo Nicolet 6700 spectrometer
equipped with ZnSe filters and a high-temperature reaction chamber.
Before the in situ CO2 methanation DRIFTS experiment, the catalyst
was reduced in a 5% H2/Ar flow at 400 °C for 1 h and then cooled to
300 °C in a reducing atmosphere. After that, a stream of 15% CO2/
45% H2/N2 was introduced into the chamber and reacted for 5 min.
Finally, the 15% CO2/45% H2/N2 flow was switched to 5% H2/Ar for
5 min. The spectra (64 scans) were collected with a resolution of 4
cm−1.
The dispersion of Ru species (D) was calculated by eq 132
6(v /a) 6Mns
D= =
d ρNAd (1)
where v denotes the volume occupied by a Ru atom (Å3), a denotes
the polycrystalline surface occupied by a Ru atom (Å2), d denotes the
mean particle size (Å), M denotes the atomic mass (g mol−1), ns
denotes the number of surface atoms per area unit (m−2), ρ denotes
the density (g cm−3), and NA denotes Avogadro’s number (6.022 ×
1023 mol−1). In the case of a hexagonal closed-packed (hcp) Ru(001)
surface, eq 1 was transformed to
12.9
D=
d (2)
Catalytic Tests. CO2 methanation reactions were performed in a
fixed-bed reactor at atmospheric pressure. An amount of 50 mg of
catalyst was loaded in a quartz tube. The reaction gas consisted of H2
(27 mL/min), CO2 (9 mL/min), and N2 (24 mL/min). Before the
reaction test, the catalyst was reduced at 400 °C for 1 h in 20% H2/N2
(60 mL/min). A specific reaction rate was determined under different
conditions, using 10 mg of catalyst and a reaction gas composed of H2
(45 mL/min), CO2 (15 mL/min), and N2 (40 mL/min) to control
the reaction at a low CO2 conversion. CO2 conversion was calculated
by the following equation:
COout + CH4 out
Conv CO2 = × 100%
COout + CH4 out + CO2 out (3)
CO selectivity and CH4 selectivity were calculated as the following
equations
COout
Sel CO = × 100%
COout + CH4 out (4)
CH4 out
Sel CH4 = × 100%
COout + CH4 out (5)
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where CO2 out, COout, and CH4 out represent the molar amounts of
CO2, CO, and CH4 in the effluent, respectively.
■
RESULTS AND DISCUSSION
Figure 1 shows the composition and morphology of TiO2-A
obtained via the sol−gel method and other TiO2 supports (i.e.,
Figure 1. (a−d) SEM images of samples, (e) XRD patterns of
samples, and (f) particle size and rutile content of samples.
TiO2-600, TiO2-700, and TiO2-800) obtained by subsequent
calcination treatment of TiO2-A at different temperatures.31
The size of TiO2 particles was about 20−30 nm in TiO2-A
(Figure 1a). With the increase of the second calcination
temperature, the size of TiO2 particles increased gradually to
30−50 nm for TiO2-600, 50−70 nm for TiO2-700, and 100−
150 nm for TiO2-800 (Figure 1b−d). According to the
measured N2 adsorption−desorption isotherms [Figure S1,
Supporting Information (SI)], specific surface areas of TiO2-A,
TiO2-600, TiO2-700, and TiO2-800 were 38, 15, 13, and 2 m2/
g, respectively (Table S1, SI). XRD patterns (Figure 1e)
Figure 2. CO2 methanation on Ru/TiO2 catalysts (2% Ru) at different temperatures; m = 50 mg, reduction temperature = 400 °C, feed: 15% CO2
+ 45% H2 in N2 (total flow rate = 60 mL/min). (a) CO2 conversion and (b) CH4 selectivity.
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indicated that only the anatase phase (ICDD PDF: 01-071-
1167) was detected in TiO2-A, while a small amount of rutile
phase (ICDD PDF: 01-076-0318) was detected in TiO2-600
and its content gradually increased with the second calcination
temperature. The contents of rutile phase in different samples,
determined by Rietveld refinement of XRD data, are listed in
Table S1 (SI). The content of rutile phase in TiO2-600 was
only 15−30%, while that in TiO2-800 exceeded 94%. It is
worth noting that the increasing trends of rutile content and
particle size with calcination temperature are basically the
same, as shown in Figure 1f. This indicates that those particles
with relatively larger sizes in the sample are rutile TiO2.
Ru species was deposited onto the mentioned four TiO2
supports through the impregnation method. The methanation
performance of the obtained Ru/TiO2 catalysts determined at
200, 250, and 300 °C are shown in Figure 2. The CO2
conversions over these catalysts increased with the reaction
temperature (Figure 2a). At all reaction temperatures, the CO2
conversion first increased and then decreased with the increase
in rutile content of the TiO2 support, and the highest
conversion was achieved on the catalyst Ru/TiO2-600 with a
rutile content of 15−30%. For the same catalyst, the CO2
conversion reached 21% at 300 °C and remained stable for 80
h (Figure S2, SI). Interestingly, no significant difference in the
CH4 selectivity was observed for the different catalysts (Figure
2b), which exceeded 99% at all investigated reaction
temperatures. The catalysts were further characterized to
reveal the influence of rutile content on CO2 conversion.
The dispersion status of Ru species on Ru/TiO2 catalysts
obtained by calcination at 500 °C in air were determined by
TEM. As illustrated in Figure 3, some nanoparticles with dark
contrast were observed on the Ru/TiO2 catalysts, which were
attributed to RuOx species. Notably, RuOx nanoparticles on
the Ru/TiO2-A, Ru/TiO2-600, and Ru/TiO2-700 catalysts are
of similar size, which are 2.5 ± 0.7, 2.5 ± 0.4 and 2.2 ± 0.4 nm,
respectively. By contrast, the RuOx particle size was slightly
larger on Ru/TiO2-800 (3.0 ± 0.8 nm). Due to their small
sizes and low loading, diffraction peaks related to Ru species
were not detected in the XRD patterns (Figure S3, SI). To
explore the reasons why CO2 conversion over Ru/TiO2-A, Ru/
TiO2-600, and Ru/TiO2-700 catalysts first increased and then
decreased, these three catalysts were selected for in-depth
study.
Figure 4 shows TEM characterization results of Ru/TiO2
catalysts after reduction at 400 °C. Ru species were still highly
dispersed on TiO2 particles in Ru/TiO2-A with a pure anatase
phase, but the sizes were significantly increased (Figure 4a).
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Figure 3. TEM images and corresponding particle size distributions of catalysts obtained by calcination at 500 °C in air: (a) Ru/TiO2-A, (b) Ru/
TiO2-600, (c) Ru/TiO2-700, and (d) Ru/TiO2-800.
Figure 4. TEM images of (a) Ru/TiO2-A, (b) Ru/TiO2-600, and (c) Ru/TiO2-700 catalysts after reduction at 400 °C in H2/N2. (d) HAADF-
STEM images of Ru/TiO2-600 and the corresponding elemental mapping images of Ru/TiO2-600 catalyst after reduction at 400 °C. Ru
nanoparticles are indicated by white arrows.
Interestingly, Ru species were found to grow preferentially on
the TiO2 particles of larger size (dark lines indicated by white
arrows in Figure 4b) in Ru/TiO2-600 after reduction in H2. A
similar phenomenon was observed on Ru/TiO2-700, which
was also composed of mixed phases of rutile and anatase
[Figures 4c and S4 (SI)]. This selective enrichment behavior
of Ru species was seen more clearly in the HAADF-STEM
image and corresponding elemental mapping images of Ru/
TiO2-600 (Figure 4d).
To explore the exact dispersion of Ru species on TiO2
particles of different phases, HRTEM and SAED character-
izations were carried out on Ru/TiO2-600 using Ru/TiO2-A as
a reference. As visible in the HRTEM image of Ru/TiO2-A
(Figure 5a), the Ru species were located on anatase particles
[TiO2-A(101), d = 0.35 nm]. In contrast, Ru species
preferentially grew on rutile particles [TiO2-R(110), d = 0.32
nm] in Ru/TiO2-600 (Figure 5b). Furthermore, Ru/TiO2-600
was analyzed by SAED and HAADF-STEM techniques. As
shown in Figure 5c,d, the value of 1/d for the diffraction spots
(indicated by the yellow arrow) in the SAED pattern recorded
from a large-sized TiO2 particle with deposited Ru species was
3.077 1/nm, which was consistent with the lattice fringe
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spacing (0.32 nm) of rutile (110). According to the dark-field
TEM image corresponding to these rutile (110) diffraction
spots (Figure 5e), Ru species (indicated by white arrows in
Figure 5c) indeed grew preferentially on the rutile particles.
The average sizes of Ru species (Figure S5, SI) on Ru/TiO2-A,
Ru/TiO2-600, and Ru/TiO2-700 after reduction at 400 °C in
H2 were 4.5, 3.4, and 3.0 nm, and the corresponding
dispersions of Ru species calculated by eq 2 were 28.7%,
37.9%, and 43%, respectively. The observed increase in the
dispersion of Ru species with increasing rutile content might
indicate that rutile TiO2 could stabilize Ru species to some
extent and then prevent them from aggregating. Also, it had
been documented that RuO2 sinters heavily on anatase but
spreads and forms epitaxial layers on rutile.25,28 According to
the literature and the above TEM characterization results, one
can infer that the Ru species on the Ru/TiO2 catalysts
prepared in this work grew preferentially on rutile particles.
This phenomenon was still observed on the catalysts after CO2
methanation reaction (Figure S6, SI). Meanwhile, the average
sizes of Ru species on Ru/TiO2-A, Ru/TiO2-600, and Ru/
TiO2-700 after CO2 methanation reaction were 4.3, 3.5, and
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Figure 5. HRTEM images of (a) Ru/TiO2-A and (b) Ru/TiO2-600 catalysts reduced at 400 °C. The insets are the magnified pictures of marked
lattice fringes. (c) TEM image of Ru/TiO2-600 catalyst after reduction at 400 °C, (d) SAED pattern, and (e) dark-field TEM image of the catalyst
corresponding to the selected diffraction spots indicated by the yellow arrow in part d. Ru particles are indicated by white arrows.

Figure 6. C 1s and Ru 3d XPS spectra of (a) Ru/TiO2-A, (b) Ru/TiO2-600, and (c) Ru/TiO2-700 reduced at 400 °C in H2.

3.4 nm, respectively. This meant that the size of the catalyst
did not change much after reaction.
XPS was employed to analyze the chemical states of Ru
species in Ru/TiO2 catalysts of different rutile content. The
binding energy of Ru 3d5/2 and the valence state of Ru species
are listed in Table S2 (SI). After calcination at 500 °C in air
(Figure S7, SI), only one peak at 280.2 eV (Ru 3d5/2)
corresponding to Ruδ+ (0 < δ < 4) was observed on Ru/TiO2-
A. By contrast, an additional peak (Ru 3d5/2) at higher binding
energy (281.8−282.0 eV) was present on Ru/TiO2-600 and
Ru/TiO2-700, which was attributed to Ru4+. The proportion of
Ru4+ species in the two catalysts were 16% and 18%,
respectively.33 After reduction at 400 °C in H2 (Figure 6a)
or the CO2 methanation reaction (Figure S8a, SI), Ru/TiO2-A
only exhibited one Ru 3d5/2 peak assigned to Ru0 species
(279.6 eV), which indicated that all Ru species in Ru/TiO2-A
changed to the metallic state.34 However, in Ru/TiO2-600 and
Ru/TiO2-700, a large number of Ru0 species (279.6−279.7
eV) was generated, but a considerable portion of oxidized Ru
species (281.0−282.0 eV) remained. After reduction at 400 °C
in H2, the proportion of Ruδ+ species in Ru/TiO2-600 and Ru/
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TiO2-700 were 25% (Figure 6b) and 30% (Figure 6c),
respectively. The results revealed that after high-temperature
reduction, the predominant state of Ru species loaded on pure
anatase was Ru0. When the rutile phase was present, the
catalyst could still retain some oxidized Ru species, and the
proportion of residual oxidized Ru species increased with the
rutile content. As a possible explanation, the preferential
growth of Ru species on rutile particles led to a stronger
interaction between the Ru and support and the observed
higher average oxidation states of Ru species. Lin et al.27 also
reported that the Ru species on pure anatase support could be
reduced to the metallic state at 400 °C, while the Ru species on
the pure rutile support could maintain their oxidation state due
to the strong interaction between RuO2 and rutile.
According to the TEM and Ru-XPS characterization results,
the increase of rutile content indeed led to a strong interaction
between TiO2 and Ru species, which partly prevented sintering
of the active sites and resulted in a higher reactivity of the
catalyst. However, while the rutile content of Ru/TiO2-700
was higher than that of Ru/TiO2-600, the reactivity of Ru/
TiO2-700 was lower than that of Ru/TiO2-600. To explore the
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Figure 7. (a) O 1s XPS spectra and (b) CO2-TPD curves of catalysts reduced at 400 °C.

Figure 8. In situ DRIFTS of the CO2 methanation reaction at 300 °C on Ru/TiO2-600 catalyst. (a) The catalyst was exposed to 15%CO2/45%H2/
N2 for 5 min and (c) the catalyst was scrubbed with 5%H2/Ar for 5 min after the treatment of part a. Parts b and d are the enlargements of the
partial region (1200−2200 cm−1) in parts a and c, respectively.

reason for this seeming contradiction, O-XPS and CO2-TPD
were performed. Two peaks were observed in the O-XPS
spectra (Figure 7a) of the three catalysts: one peak near 529.8
eV was assigned to lattice oxygen (Olat), while the other peak
located at 531.8 eV was attributed to oxygen atoms in the
vicinity of the oxygen vacancy (Ovac).35 The fractions of the
oxygen vacancies in Ru/TiO2-A, Ru/TiO2-600, and Ru/TiO2-
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700 were calculated as 16%, 12%, and 10%, respectively, using
the term Ovac/(Olat + Ovac).
According to the literature, oxygen vacancies on the surface
of catalysts could serve as active Lewis acidic sites and
contributed significantly to the adsorption−desorption process
of CO2.36,37 Therefore, CO2-TPD characterization was
conducted to obtain more information about the surface
characteristics. As shown in Figure 7b, the area of the
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desorption peak near 72 °C decreased dramatically with the
increase of the rutile content of the support. In general, this
desorption peak (low-temperature region) was attributed to
the desorption of CO2 weakly adsorbed on the catalyst (e.g.,
adsorbed on surface hydroxyl groups).38,39 High-temperature
calcination would not only lead to a sharp reduction in the
specific surface area of the TiO2 support (Table S1, SI) but
also lead to a dramatic drop in surface hydroxyl groups,
thereby resulting in a decrease in the adsorption amount of
CO2.40 Moreover, the temperature of the desorption peak
located in the high-temperature region also decreased from
316 °C for Ru/TiO2-A to 294 °C for Ru/TiO2-600, while no
obvious desorption peak was observed for Ru/TiO2-700. As
stated above, the oxygen vacancy concentration decreased
significantly with the increase of the rutile content, which
caused the drastic decrease in the number of CO2 adsorption
sites (strong CO2 adsorption sites) on the support.41 Zhang et
al.42 found that oxygen vacancies could promote the
adsorption of CO2, and the order of CO2 adsorption ability
on Au/CeO2 was in accordance with the concentration of
oxygen vacancies, which was similar to the results in this
investigation. It should be stated that, during the activation
process of CO2, the oxygen vacancies in the rutile phase and
anatase phase both are involved in the reaction due to the
highly disordered and mixed status between them. In
summary, the adsorption sites of CO2 on the catalyst
significantly decreased with the increase of rutile content,
which led to the decline in the amount of adsorbed CO2. As a
result, the reactivity of Ru/TiO2-700 was worse than that of
Ru/TiO2-600.
Furthermore, CO2 methanation was investigated by in situ
DRIFTS. The apparent activation energy (Ea) for Ru/TiO2-A,
Ru/TiO2-600, and Ru/TiO2-700 catalysts were 89, 86, and 86
kJ/mol, respectively (Figure S9, SI). The similar Ea values
suggested the presence of the same active species in these three
catalysts, meaning that the support phase did not affect the
reaction mechanism.28,43 Consequently, Ru/TiO2-600 was
chosen to study the CO2 methanation reaction mechanism,
and the characterization results are shown in Figure 8. Under
the reaction gas mixture, the signal intensities attributed to
gaseous CH4 species (3016 and 1304 cm−1) increased
gradually as the reaction progressed at 300 °C (Figure 8a).44
Simultaneously, the signal intensities ascribed to *HCOO
species (1508 and 1342 cm−1) exhibited a trend similar to that
of gaseous CH4 species (Figure 8b).45 When switching the gas
from 15%CO2/45%H2/N2 to 5%H2/Ar at 300 °C, the peak
intensities of CH4 and *HCOO species decreased monotoni-
cally with increasing contact time (Figure 8c,d). More
specifically, the intensity of the peak assigned to Ru-bonded
carbonyl species (1982 cm−1) was extremely low and did not
change during these two experiments, indicating that the
adsorption of CO on Ru species was very weak.46 Meanwhile,
CO-TPD curves also showed that CO had almost desorbed
completely from the catalyst in He (99.999%) at room
temperature and no obvious desorption peak related to CO
adsorbed on the catalyst was observed in the heating process
(Figure S10, SI), which also meant that the adsorption
strength of CO on the catalyst was very weak. Thus, one could
conclude that CH4 might not be produced through the reverse
water−gas shift reaction (RWGS) followed by CO hydro-
genation but that *HCOO might be the real intermediate
species. Wang et al.47 discovered that CO2 methanation
followed the formate route on Ru/CeO2, and CH4 was formed
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through sequential hydrogenation after the dissociation of
formate, which was similar to the above conclusion from the
experimental observations.
On the basis of all of the characterization results and
literature reports, one can conclude that the rutile content in
Ru/TiO2 constituted an important contribution to the catalyst
performance in low-temperature CO2 methanation in this
work. The concentration of oxygen vacancies would be fairly
high if the rutile content was small, which could facilitate the
formation of *CO2.48,49 However, when the rutile content was
high, Ru species could be better dispersed on TiO2 due to the
preferential growth, which was conducive to the stabilization of
the metal−oxide interface. Specifically, metallic Ru species
could dissociate H2, and *HCOO was formed through the
hydrogenation of CO2.50,51 Furthermore, the metal−oxide
interface could enhance the binding ability of *HCOO to
promote the dissociation of its C−O bond.50 After scission of
the C−O bonds, CHx species would be continuously
hydrogenated and finally form CH4. When the rutile content
was about 15−30%, both factors were balanced to achieve the
highest reactivity for CO2 methanation. Kim et al.28 found that,
for Ru on pure anatase and Ru on pure rutile, the amount of
available Ru species was lower on the surface of the catalysts
compared to Ru on the mixed-phase TiO2 support, thus
causing a decrease in reactivity. When it comes to P25 (80%
anatase + 20% rutile), there is a relatively suitable interaction
strength between Ru species and P25, which led to a higher
catalytic activity in CO2 methanation. The rutile contents of
P25 and Ru/TiO2-600 in this research are in the same range.
■ CONCLUSION
In this work, catalysts with Ru supported on TiO2 with
different rutile contents were specifically prepared to
investigate the effect of the support phase on the catalytic
performances of catalysts in low-temperature CO2 methana-
tion. It was found that Ru species grew preferentially on the
rutile phase of the catalysts, and the deposited Ru and its
metal−oxide interface displayed higher stability with increasing
rutile content. However, the characterization results of O-XPS
and CO2-TPD indicated that the concentration of oxygen
vacancies (i.e., the adsorption sites for CO2) on the support
decreased with the increase of rutile content. At a rutile
content of 15−30% in Ru/TiO2-600, these two opposing
factors were balanced, resulting in the highest reactivity of this
catalyst among the investigated Ru/TiO2 materials. The in situ
DRIFTS analysis suggested *HCOO as the main intermediate
species, leading to the conclusion that CO2 was first adsorbed
on oxygen vacancies and then *HCOO was formed by
hydrogenation. Eventually, CH4 was generated through
successive hydrogenation of CHx after the dissociation of the
C−O bonds in *HCOO. In summary, this research studied the
effect of rutile content on reaction performance in detail and
provided guidance to construct catalysts with high activity for
low-temperature CO2 methanation in the future.
■
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acssuschemeng.1c05565.
The particle size and rutile content of each TiO2
support, binding energy and valence state of Ru species,
the specific surface area (SBET) of samples, the stability
https://doi.org/10.1021/acssuschemeng.1c05565
ACS Sustainable Chem. Eng. 2021, 9, 14288−14296
ACS Sustainable Chemistry & Engineering
pubs.acs.org/journal/ascecg
test of Ru/TiO2-600 catalyst, XRD patterns under
different conditions, TEM images and particle size
distribution of catalysts after reduction and reaction,
XPS spectra of catalysts after calcination in air and
reaction, apparent active energy test, and CO-TPD
curves of catalysts (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
Qin Kuang − State Key Laboratory for Physical Chemistry of
Solid Surfaces, Collaborative Innovation Center of Chemistry
for Energy Materials, Department of Chemistry, College of
Chemistry and Chemical Engineering, Xiamen University,
Xiamen 361005, China; orcid.org/0000-0002-4111-
291X; Email: zxxie@xmu.edu.cn
Zhaoxiong Xie − State Key Laboratory for Physical Chemistry
of Solid Surfaces, Collaborative Innovation Center of
Chemistry for Energy Materials, Department of Chemistry,
College of Chemistry and Chemical Engineering, Xiamen
University, Xiamen 361005, China; Pen-Tung Sah Institute
of Micro-Nano Science and Technology, Xiamen University,
Xiamen 361005, China; orcid.org/0000-0002-4225-
6536; Email: qkuang@xmu.edu.cn
Authors
Zhiying Zhao − State Key Laboratory for Physical Chemistry
of Solid Surfaces, Collaborative Innovation Center of
Chemistry for Energy Materials, Department of Chemistry,
College of Chemistry and Chemical Engineering, Xiamen
University, Xiamen 361005, China
Qiaorong Jiang − State Key Laboratory for Physical
Chemistry of Solid Surfaces, Collaborative Innovation Center
of Chemistry for Energy Materials, Department of Chemistry,
College of Chemistry and Chemical Engineering, Xiamen
University, Xiamen 361005, China
Qiuxiang Wang − Instrumental Analysis Center, Huaqiao
University, Xiamen 361021, China
Mingzhi Wang − State Key Laboratory for Physical Chemistry
of Solid Surfaces, Collaborative Innovation Center of
Chemistry for Energy Materials, Department of Chemistry,
College of Chemistry and Chemical Engineering, Xiamen
University, Xiamen 361005, China
Jiachang Zuo − State Key Laboratory for Physical Chemistry
of Solid Surfaces, Collaborative Innovation Center of
Chemistry for Energy Materials, Department of Chemistry,
College of Chemistry and Chemical Engineering, Xiamen
University, Xiamen 361005, China
Hanming Chen − State Key Laboratory for Physical
Chemistry of Solid Surfaces, Collaborative Innovation Center
of Chemistry for Energy Materials, Department of Chemistry,
College of Chemistry and Chemical Engineering, Xiamen
University, Xiamen 361005, China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acssuschemeng.1c05565
Author Contributions
The manuscript was written through contributions of all
authors. All authors have given approval to the final version of
the manuscript.
Notes
The authors declare no competing financial interest.
14295
■
Research Article
ACKNOWLEDGMENTS
This work was supported by the National Key Research and
Development Program of China (2017YFA0206801) and the
National Natural Science Foundation of China (22071202,
21931009, 21721001, and 21773190).
■
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