Journal of CO₂ Utilization 33 (2019) 242–252

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Journal of CO2 Utilization

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

Boosting CO2 methanation activity on Ru/TiO2 catalysts by exposing (001) T

facets of anatase TiO2
⁎
Shanshan Chaia, Yong Mena, , Jinguo Wanga, Shuang Liua, Qiaoling Songa, Wei Ana,
⁎⁎
Gunther Kolbb,c,
a
College of Chemistry and Chemical Engineering, Shanghai University of Engineering Science, Shanghai, 201620, PR China
b
Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, P.O Box 513, 5600 MB, Eindhoven, the Netherlands
c
Energy and Chemical Technology Division, Fraunhofer IMM, Carl.Zeiss-Str.18-20, D-55129, Mainz, Germany

A R T I C LE I N FO A B S T R A C T

Keywords: Catalytic reduction of CO2 to methane has been recognized as one of the most important strategic reactions to
Ru nanoparticles produce highly valuable chemicals and for storage of renewable energy (power-to-gas). This study demonstrates
TiO2 nanocrystal a crystal facet-dependent catalytic reduction of CO2 to CH4 on ruthenium nanoparticles deposited over TiO2
Exposed (001) facets nanocrystal with exposed (001) and (101) facets. Compared with TiO2 (101) nanocrystal with the same Ru
CO2 methanation
loading, Ru nanoparticles supported by TiO2 (001) exhibited a highly enhanced CO2 conversion rate and sig-
synergistic effect
nificantly improved methanation reactivity, along with a considerable durability. The physicochemical prop-
erties of the samples were characterized by HR-TEM, XRD, BET, FT-IR, UV–vis, Raman, ICP, and temperature-
programmed reaction with CO2, and CO2 + H2. In view of the difference in catalytic activity and the physi-
cochemical properties of the supported Ru/TiO2 catalysts, the results uncovered that the nature of the catalyst
support of Ru/TiO2 strongly affected the dispersion of Ru species and the synergistic effect between Ru and
underlying TiO2 supporting materials due to the strong metal-support interaction, and thus affected their cap-
ability to activate CO2 and determined the catalytic activity for CO2 methanation. Our work demonstrated the
important role of the exposed crystal facets of the underlying support and the resulting Ru particle which had a
large effect on CO2 methanation.

1. Introduction
As the major contributors for the greenhouse effect [1–3] and in-
exhaustible source of cheap carbon and oxygen resources [4,5], the
utilization of carbon dioxide has become one of the major strategic
research topics worldwide [2,6]. The hydrogenation of CO2 can not
only mitigate the global greenhouse phenomenon but also address the
growing energy demand. The photolysis and electrolysis of water using
renewable energy could provide the hydrogen required for CO2 con-
version [7,8]. Therefore, to reduce the reliance on fossil fuels and keep
carbon balance in nature, the use of carbon dioxide as a carbon source
for valuable products such as methane, methanol, ethanol, dimethyl
ether, formic acid and higher hydrocarbons by hydrogenation of CO2
has been extensively studied in the past decades [6,9–12].
Methane has been considered to become a major source of energy
and feed-stock for chemicals production after the petroleum age owing
to its worldwide reserves and its economic and environmental ad-
vantages over coal [13]. The methanation of CO2 is regarded as a
simple and highly efficient route towards methane. CO2 conversion
with H2 is highly exothermic. Sabatier and Senderens first discovered
transition metals catalysts for methanation reaction in the early 20th
century. Ni is the most widely applied and investigated catalysts be-
cause of its high reactivity and relatively low cost [14–19]. However,
Ni-based catalysts are also vulnerable to deactivation by coke formation
through either CH4 decomposition or via CO disproportionation (Bou-
douard reaction) and through sulphur poisoning. Noble metals in-
cluding Ru [20–25], Pd [26,27], Pt [28–30], and Rh [31,32], are also
active for CO2 methanation. Among these noble metals, Ru is the most
active catalyst in a wide range of operation temperatures.
The activity and selectivity of supported Ru-based catalysts are
strongly affected by the preparation method, the amount of metal
loading, the size of the dispersed metal particles, the interactions

⁎
Corresponding author.
⁎⁎
Corresponding author at: Department of Chemical Engineering and Chemistry, Eindhoven University of Technology, P.O Box 513, 5600 MB, Eindhoven, the
Netherlands.
E-mail addresses: men@sues.edu.cn (Y. Men), Gunther.kolb@imm.fraunhofer.de (G. Kolb).

https://doi.org/10.1016/j.jcou.2019.05.031
Received 25 March 2019; Received in revised form 25 May 2019; Accepted 26 May 2019
Available online 03 June 2019
2212-9820/ © 2019 Elsevier Ltd. All rights reserved.
S. Chai, et al.
between the support and the active metallic species, and the nature of
the support material. Abe et al. have developed a dry technique named
polygonal barrel-sputtering for modifying the surfaces of powder ma-
terials to deposit Ru nanoparticles onto TiO2 with narrow particle size
distribution without the need of any heating which can cause nano-
particle sintering [33]. They reported that the turnover number de-
termined for the CO2 methanation reaction decreased with increasing
size of Ru nanoparticles up to 6 nm and concluded that a low Ru par-
ticle size is essential for a high CO2 methanation reactivity for the TiO2-
supported Ru nanoparticle catalyst. Sassoye et al. have developed
highly stable and well defined monodispersed aqueous colloidal sus-
pensions of small ruthenium nanoparticles by adding a certain amount
of hydrogen peroxide. Highly dispersed ruthenium nanoparticles have
been proposed to be highly effective for the production of methane
from CO2 [34]. However, Kwak et al. reported that the activity of Ru/
Al2O3 catalysts for CO2 reduction is determined by the size of the metal
particles, and concluded that large metal clusters are favorable for CH4
formation [22,27]. Several excellent reviews describe that the catalysts
performance and stability are closely related to their particle size
[31,35–38]. It has been recognized also that the chemical nature of the
support or the metal-support interactions can have a marked impact on
the catalytic activity and selectivity [39]. Reducible metal oxides in-
cluding TiO2, ZrO2 and CeO2 have been widely used as support mate-
rials [20,21,40,41]. Among all the investigated Ru/oxide catalysts for
CO2 methanation, TiO2 was regarded as the most efficient support for
CO2 methanation [10]. The crystal phase of the TiO2 support plays an
important role that affects the structure and catalytic properties of the
Ru nanoparticles, dictates the morphology of Ru species. Kim et al.
demonstrated that the catalytic activity of CO2 methanation was
markedly affected by the crystallinity of the TiO2 support, and stated
that the RuO2 decorated on the mixing of anatase and rutile particles
(P25) shows a better performance for CO2 methanation, followed by
single phase anatase and rutile-supported catalysts [42].
Tailoring the crystal facets of catalyst support is important for
modulating the activity of high-performance catalysts with well-defined
surface structures [43–46]. Extensive experimental and theoretical
studies have both demonstrated that TiO2 with exposed (001) facets are
preferred than those with the (101) facets for being used as catalysts
and supports in many applications of catalysis, photocatalysis and
electroctalysis [44,47]. For instance, Wang et al. reported that the ex-
posed (001) facets possesses high surface energy and abundant oxygen
vacancies, thus favored the photocatalytic oxidation of aromatic alco-
hols [48]. A DFT study on formic acid adsorption by Gong et al. showed
anatase (001) possess O2c atoms with higher energies compared to
(101) containing the bulk O3c, demonstrating that the high reactivity of
anatase (001) is associated with low-coordinated O2c atoms [49]. A
combined experimental and DFT study of the CO2 capture by TiO2
anatase surfaces carried out by Mino et al. [50] revealed that the for-
mation of carbonate and bicarbonate species occurs preferentially on
the anatase (001) surface, and the higher reactivity of this surface is
related to a stronger (Lewis and Brønsted) basicity of the surface oxygen
sites. Cao et al. reported that the enhanced photoactivity for CO2 me-
thanation is ascribed to the increasing ratio of exposed TiO2 nano-
crystals facets from 5% to 51% (001) and the creation of surface het-
erojunction between (001) and (101) crystal facets [51]. Moreover, Jin
et al. reported that the higher photocatalytic CO2 reduction activity of
Pt nanoparticles over TiO2-001 was ascribed to the enhanced photo-
induced carrier separation efficiency than that on TiO2-010, which can
be further correlated with the different CO2 adsorption capability on
anatase TiO2-001 and TiO2-010 facets due to their different surface
electronic and atomic structures [52].
The crystal phases and crystal facets of oxide support are two im-
portant factors in determining the reactivity of metal-supported cata-
lysts. Despite the considerable progress achieved about the support
effect, in particular, the impact of crystal phases on CO2 methanation
over Ru/TiO2 catalysts so far [33,53,54], the influence of crystal facets
243
Journal of CO₂ Utilization 33 (2019) 242–252
of TiO2 on the structure and catalytic properties of the Ru nanoparticles
for CO2 methanation have not yet been well established. In this work,
single phase anatase became our choice of catalyst support to unravel
the role of different crystal facets played in the CO2 methanation and
Ru/TiO2 catalysts by exposing (001) and (101) facets of TiO2 were
prepared and studied for CO2 methanation. By using these Ru/TiO2
catalysts with specifically exposed (001) and (101) crystal facets, we
are able to investigate and understand the role played by (001) and
(101) crystal-facet for CO2 methanation, and to uncover the influence of
crystal facets of TiO2 support on the structure and catalytic properties
of the Ru nanoparticles for CO2 methanation. In this study, Ru deco-
rated over the TiO2 (001) facets exhibited excellent activity and dur-
ability for CO2 methanation compared to the TiO2 with exposed (101)
facets. The highly enhanced catalytic activity of Ru species loaded on
TiO2 (001) facets was ascribed to the nature of (001) facets with high
surface energy and abundant oxygen vacancies and the synergistic ef-
fect between Ru and TiO2. The method of preparation of catalysts was
selected based on the research experience of crystal facet effect over
TiO2 in our group and the previous studies by other groups [40,55,56].
2. Experimental section
2.1. Catalyst preparation
TiO2 nanocrystal with exposed (001) and (101) facets were pre-
pared by solvothermal hydrolysis according to previously published
work by the authors of the current paper [55]. To prepare TiO2 nano-
crystals with exposed (001) facets, tetrabutyl titanate (2.6 M, 50 mL,
CP, with a concentration of 98 wt.%) and HF (3.2 M, 8 mL, AR, with a
concentration of 40 wt.%) mixed and stirred at room temperature, then
transferred into a 100 ml Teflon-lined autoclave and sealed. The auto-
clave was then placed in an electric oven and kept at 180 °C for 24 h.
Then the precipitates were collected by centrifugation, washed with
distilled water several times and dried overnight at 80 °C, and the ob-
tained sample was denoted as T001 (all reagents are from Aladdin).
To prepare TiO2 nanocrystal with exposed (101) facets, tetrabutyl
titanate (0.6 M, 15 mL, CP, with a concentration of 98 wt.%) mixed with
acetic acid (13.3 M, 60 mL, AR, with a concentration of 36 wt.%) at
room temperature and also transferred into a 100 ml Teflon-lined au-
toclave, sealed and placed in an electric oven at 200 °C for 24 h. The
precipitates were collected by centrifugation, washed with distilled
water several times and dried overnight at 80 °C, and the obtained
sample was denoted as T101 (all reagents are from Aladdin).
The Ru/TiO2 catalysts were prepared as previously described
[40,56], and 2.5 wt.% Ru was added as nominal loading. In brief, they
were obtained by a drop wise addition of 15%v/v H2O2 (AR, 30 wt.% in
H2O, from Aladdin) diluted in H2O into 0.011 M RuCl3·xH2O (x = 3–5,
GR, from Sinopharm Chemical Reagent) dissolved in H2O so that the
final concentration of Ru ≈ 0.007 M. The solution was heated at 95 °C
for 2 h. Once cooled to room temperature, an appropriate amount of
TiO2 powder was added to the colloidal suspension of RuO2 nano-
particles to yield 2.5 wt.% of Ru in the final catalyst. The mixture was
put in an oven at 120 °C overnight then calcined at 400 °C for 4 h in
static air and washed several times with water to remove the chloride,
finally dried at 120 °C for 10 h. They were denoted as RT001 and
RT101, respectively.
2.2. Catalysts characterization
The samples were characterized by using high-resonance transmis-
sion electron microscopy (HRTEM, JEOL JEM-2100). Prior to TEM
measurements, a small amount of powder sample was ultrasonically
dispersed in an aqueous solution, and then the solution was dropped
onto the copper network. The crystalline phases of the samples were
identified by X-ray powder diffraction (XRD) using a diffractometer (D/
Max-r B) applying Cu-Kα radiation (λ =1.54056 Å) over the scan range
S. Chai, et al.
of 2θ between 20°-80°. The mean crystallite size (D) of the samples was
calculated via the Scherrer equation:
Kλ
D=
β1 cosθ (1)
2
The BET surface area (SBET), pore volume (VP) and pore diameter
(DP) were measured on a Micromeritics ASAP 2460 instrument at 77 K.
Prior to measurement, the samples were degassed at 100 °C with 1 h in
flowing N2 (99.999%). An inductive coupled plasma emission spectro-
meter (ICP, Varian, VISTAMPXICP) was used to test the actual loading
of Ru nanoparticles. Fourier-transform infrared (FT-IR) spectra of the
samples were collected by using a Nicolet 380 spectrometer. Prior to
the measurement, the samples were pressed into a thin self-supported
wafer and placed in the IR cell. FT-IR spectra of the catalysts were re-
corded in air within the range of 450–4000 cm−1. UV–vis diffuse re-
flectance spectra (UV–vis DRS) were recorded in the absorbance mode
at room temperature within the range of 200–800 nm. During the
measurement, BaSO4 (from Aladdin) was used as background material
in a UV-2450 spectrophotometer (Shimadzu, Japan). And Raman
spectra were collected on NEXUS-470, MC-2530 and Dilor Super
LabRam II respectively.
Hydrogen temperature-programmed reduction (H2-TPR) was car-
ried out on a Micromeritics Autochem II 2920 instrument equipped
with a thermal conductivity detector (TCD) to quantify the consumed
H2. The catalysts (50 mg) was pretreated in Ar (99.999%) atmosphere
at 200 °C for 1.0 h to remove adsorbed water, and then cooled to 50 °C
in Ar, followed by heating to 400 °C at a heating rate of 10 °C/min in a
flow of 10% H2/Ar.
The Ru dispersion was determined through H2-TPD on a
Micromeritics Autochem II2920 instrument. Prior to the TPD tests,
50 mg of the catalyst was reduced for an hour in a flow of 10% H2/Ar at
500 °C, and purged with Ar at 500 °C for 30 min, then cooled to 50 °C in
Ar. Finally the adsorption of H2 took place and then Ar was introduced
to perform the TCD measurement with a temperature ramp of 10 °C/
min to 900 °C. The dispersion of Ru was calculated based on the volume
of chemisorbed H2 using the following simplified equation:
2 × Vad × Mmetal × SF
D% =
p × Vm × dr (2)
where P denotes the weight fraction of Ru in the sample as determined
by ICP; Vm is the molar volume of H2 at standard temperature and
pressure(STP); dr is the reduction degree of Ru; Vad (mL·g−1) is the
volume of chemisorbed H2 at STP in the TPD procedure；M is the
molecular weight of Ru (101.07 g·mol−1); and SF is the stoichiometric
factor (Ru:H molar ratio in the chemisorption) which was assumed to
be 1.
Temperature programmed desorption of carbon dioxide was per-
formed on an Micromeritics Autochem II 2920 instrument coupled with
a Hiden HPR20 mass spectrometer. Before the tests 50 mg of the cata-
lysts were reduced in flowing 10% H2/Ar at 500 °C for 1.0 h. After
cooling down to 50 °C in an Ar stream, then 5% CO2/He was periodi-
cally injected into the sample until saturation. The sample was then
purged with He (99.999%) at room temperature for 60 min, and heated
with a temperature rate of 10 °C/min to 900 °C in He while the effluent
gases were monitored by a mass spectrometer with special attention to
the mass spectrometer m/e values of 15 (CH4), 44(CO2), 28 (CO) and 18
(H2O), respectively.
Temperature-programmed surface reaction (TPSR) measurements of
samples were performed in the same manner as the temperature pro-
grammed desorption of carbon dioxide described above, except that the
sample was heated under 10% H2/Ar to 900 °C instead of He. All the
gases used in the experimental were purchased from Shanghai Shenkai
Gas Technology Co. Ltd.
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Journal of CO₂ Utilization 33 (2019) 242–252
2.3. Catalysts activity measurements
The activity of the catalyst was measured in a continuous flow fixed
bed reactor and the reaction temperature was measured in the middle
of the catalyst bed with a K-type thermocouple placed within a quartz
capillary well (see Fig. S1). 200 mg catalyst was placed into a quartz
tube reactor with an internal diameter of 6 mm. Prior to the test, the
catalysts were pretreated at 500 °C in H2 (99.999%, 30 ml/min) for
1.0 h. The reaction was conducted from 150 °C to 400 °C at atmospheric
pressure and heated with a temperature rate of 10 °C/min, feed gases
were consisted of 10% CO2 (99.999%), 40% H2 and 50% N2 (99.999%)
at a flow rate of 20 ml/min and were analyzed via gas chromatography.
The product analysis in this work was performed on Shimazu GC-2014C
online-GC equipped with one TCD and one FID detector. In this work,
packed PQ column/C13X molecular sieve column and TCD detector are
used to separate and detect simple gases. The Rt-Q-BOND PLOT column
and FID are used to separate and detect hydrocarbons and oxygenates.
Product analysis was taken by averaging two measurements within a
TOS of 1.0 h at each temperature and a temperature step of 25 °C.
And to test the effect of H2O, the water (under condition of 5 vol.%
H2O) was injected continuously at a rate of 0.9 cm3·h−1 by syringe
pump into a vaporizer. For the test of CO methanation over the RT001
sample, the feed gases were consisted of 10% CO (99.999%), 40% H2
and 50% N2 at a flow rate of 20 ml/min. As for the effect of space
velocity test, the RT001 catalyst was tested on 250 °C with a total flow
rate of 20 ml/min (10 vol.% CO2, 40 vol.% H2 diluted in N2), and the
space velocity was varied by changing the amount of catalyst. All of the
separated gases were detected by a thermal conductivity detector
(TCD). All the gases used in the activity measurements were purchased
from Shanghai Shenkai Gas Technology Co. Ltd.
The relevant test results were calculated by the following equations:
CO2 (in) − CO2 (out)
CO2 Conversion (%) = × 100
CO2 (in) (3)
CH 4 (out)
CH 4 selectivity (%) = × 100
CH 4 (out) + CO(out) (4)
CO(out)
CO selectivity (%) = × 100
CH 4 (out) + CO(out) (5)
Y ield CH4 (%) = X CO2 ×SCH4 × 100 (6)
CO2 (in) × X CO2 ×SCH4
CH 4 formation rate(μmol·S−1·g−1 ) =
m (7)
Where CO2 (in) and CO2 (out) are the molar flows of the inlet and outlet
carbon dioxide, respectively, CH4(out) and CO(out) are the molar flows
of the outlet methane and carbon monoxide.
The turnover frequency (TOF) was calculated based on the formula:
CO2 (in) × X CO2
TOF=
m× M
P
×D%
metal (8)
Where X CO2 is CO2 conversion, m is the catalyst mass, P denotes the
weight of Ru in the sample as determined by ICP; Mmetal is the molar
weight of Ru; D% is the Ru dispersion, which was calculated by the H2-
TPD.
3. Results and discussion
3.1. Morphology and physical characteristics of the catalysts
Fig. 1 shows the XRD patterns of the TiO2 support before and after
loading of Ru. It can be seen that all the samples showed a typical
anatase phase with high crystallization degree, corresponding to 2θ of
25.8°, 37.7°, 47.8°, 54.0°,55.0° and 62.7° indicative of (101), (004),
(200), (105), (211) and (204) diffractions respectively (JCPDS file card
No. 12-1272) [48,55]. The phase of RuOx and Ru can hardly be
S. Chai, et al. Journal of CO₂ Utilization 33 (2019) 242–252

summarized in Table 1. After loading the Ru nanoparticles, the SBET of

RT001 and RT101 declined to 67.9 m2·g−1 and 69.5 m2·g−1, respec-
tively. Moreover, loading Ru over the T001 resulted in an increase of
the pore diameter but a decreasing pore diameter was found for the
T101 sample, while the pore size distribution of all the samples are
relatively narrow and below 25 nm.
Fig. S2 presents the FT-IR spectra of all the samples in the region of
450–4000 cm−1, which were similar to those reported in literature
[58]. The broad absorption band at 3438 cm−1 in the high energy re-
gion was ascribed to the stretching vibration of hydroxyl group of the
water molecule physically adsorbed on the sample surface [59]. The
bands at 1636 cm−1 can be assigned to the bending vibration of the
water molecules. The band located at 1460 cm−1 is an indicative of the
presence of the absorption peaks of COH, which were generated by
insertion of some organic moieties into TiO2 during the course of sol-
vothermal reaction. The bands at around 480 cm−1 in the spectra of all
the samples are unambiguously assigned to the characteristic adsorp-
tion band of Ti-O, while the bands tended to be weakened after loading
of Ru species, suggesting a perturbation of the TiO2 framework upon
Fig. 1. XRD patterns of all the samples. interaction with Ru. Fig. 4 depicts the UV–vis DRS spectra of all the
samples. The pure TiO2 samples T001 and T101 both show strong ab-
Table 1 sorption at around 385 nm (λ < 400 nm) in the UV region. The spectra
Structural parameters of the catalysts. around 200–300 nm show clearly that the absorption capability of T001
is stronger than that of T101. Upon introducing Ru nanoparticles over
Sample SBET/m2·g−1 Vp/cm3·g−1 Dp/nm Crystal sizea/ Exposed (001)
nm (%) the two supports, the band gaps were significantly altered. The Ru
loaded samples showed a stronger absorption capability in the range of
T001 110.1 0.35 10.9 12.9 80.0 350–800 nm but slightly weaker absorption in the range of 200–350 nm
T101 92.6 0.25 10.4 18.9 8.0
than their respective pure supports. It was also noted that the loading of
RT001 67.9 0.29 15.3 13.1 80.0
RT101 69.5 0.17 7.4 19.2 8.0 Ru nanoparticles didn’t change the sequence of the absorption cap-
ability on TiO2. The difference in the absorption could be related to the
a
As calculated by the Scherrer equation. strong metal-support interaction, while the specific surface area of
RT001 and RT101 are very similar.
detected by the XRD, probably owing to the high degree of dispersion of The crystalline phases and surface oxygen vacancies were further
the Ru species on the TiO2 surface. The octahedron TiO2 mainly ex- determined using Raman spectroscopy. Parker et al. have demonstrated
posed (101) facets, whereas (001) facets were the mainly exposed facets that the shifting and broadening of the Raman spectral peaks were
over decahedron TiO2, as the (001) facets were formed by the de- ascribed to the oxygen stoichiometry of the material by using a series of
formation growth of anatase TiO2 crystal from octahedron to decahe- heat treatment experiments [60]. They also measured the oxygen intake
dron. And the exposed (001) facets was grown when the up and down of the nanophase TiO2 samples by using the thermogravimetric analysis
crystal growth was retarded. (See Scheme S1 (a)). According to Scherrer (TGA). Their results revealed that the Raman spectra are relevant to the
equation, the increased half-height width of (004) is corresponding to oxygen stoichiometry of the samples, (Eg) vibrational mode and the
“h” in Scheme S1 (a), implying the increased percentage of exposed peak position and full width at half maximum of the anatase
(001) facets. As for the increased intensity of (101) peak is corre- “143 cm−1” present the O/Ti ratio of sample. The positive shift of
sponding to the “m” in Scheme S1 (a) [57], Scheme S1 (a) is a cutway Raman peak position toward a higher wavenumber is the experimental
view of Scheme S1 (b), the angle between (101) and (001) facets was evidence for the increased surface oxygen vacancies in TiO2 [61,62]. It
68.3°, thus the percentage of (001) facets could be calculated according can be seen from Fig. 5, that the signals of all the samples recorded 5
to the Scherrer equation (see details in supplementary information). distinctive peaks at 144(Eg) cm−1, 197(Eg) cm−1, 397(B1g) cm−1,
The mean crystallite size (D) and the percentage of exposed (001) facets 519(A1g) cm−1 and 640(Eg) cm−1 which are all corresponding to the
of the samples were calculated and summarized in Table 1. Only 8% of anatase phase of TiO2. This result is in good agreement with the XRD
TiO2(001) facets were exposed in the T101 and RT101, whereas the patterns. From 110 to 180 cm−1 in the magnified Raman spectra,
T001 and RT001 exposed 80% of (001) facets. compared to T101, the T001 sample showed a positive shift of the
Fig. 2 presents the HRTEM and FFT images of all the samples. Ob- principal peak by about 2.0 cm−1. This Raman positive shift indicates
viously, T001 and RT001 both show a highly truncated bipyramidal that the number of surface oxygen vacancies in the T001 sample is
morphology, and the flat square surfaces are identified as (001) facets higher than that of the T101 sample.
with an average length around 25 nm and thickness about 5.0 nm. For Besides, after introducing Ru species, the RT001 sample also has a
the T101 and RT101 samples, they showed an octahedron morphology positive shift when compared with the RT101 sample, indicating the
and the isosceles trapezoidal surfaces are (101) facets with an average RT001 also possesses an abundant surface oxygen vacancies on (001)
size of 20 nm. Besides, from the HRTEM and FFT images, one can see facets. Analogous results reported previously have been attributed to
that all the samples were presented as well-defined anatase TiO2 single the increased number of surface oxygen vacancies on (001) facets [62],
crystals. The average particle size of the ruthenium nanoparticles of the This is mainly because the Ti atom in (001) facets is 5-fold coordinated,
T001 sample was determined to be 1.35 nm which is more than double while it is coordinated with either 5 or 6 oxygen atoms in (101) facets.
the value of 0.56 nm which was found for the T101 sample. Comparing with the (101) facets, the (001) facets had much more
All the samples displayed a typical type IV of N2 adsorption-deso- abundant surface oxygen vacancies facets due to the lower coordination
rption isotherms with H3 hysteresis loop in the relative pressure (P/P0) with Ti atoms (See Fig. S3). In accordance with the XRD results, T001
range from 0.8 to 1.0 in Fig. 3. These samples possessed a typical me- and RT001 both exposed a higher extent of (001) facets than T101 and
soporous structure due to the agglomeration of nanoparticles and the RT101, and consequently the T001 and RT001 could provide more
SBET, VP and DP values were calculated by BET equation and oxygen vacancies on (001) facets which serve as active sites for CO2

245
S. Chai, et al. Journal of CO₂ Utilization 33 (2019) 242–252

Fig. 2. TEM images of all the samples; the insets are the corresponding HRTEM and Fast-Fourier transform (FFT) images, respectively.

activation. showed the similar up-shifting of hydrogen reduction peaks over RT001
The strong metal-support interaction (SMSI) effect was originally catalyst, indicating the enhanced interaction of Ru and TiO2 (001)
proposed by Tauster et al. to describe the drastic changes in the phy- support.
sical and chemical properties of group VIII noble metals particles dis-
persed on reducible oxides [63,64]. And the strong interaction between
3.2. Catalytic activities of all the samples
noble metal and support was generated due to the inhibited H2 che-
misorption over catalysts and the extent of chemisorption suppression
Fig. 7(a) compares the catalytic performance of all the samples.
usually taken as an indicator of the extent of metal-support interaction
During the experiments of CO2 methanation, CO and CH4 were the only
[65]. However, the strong metal-support interaction has also been often
major products. Apparently, without addition of Ru nanoparticles to the
used in the recent catalysis literatures to describe the synergistic effect
two supports, the bare catalyst supports of T001 and T101 both show
between metal and support that could enhance catalytic activity in a
very low catalytic activity for the CO2 methanation during the whole
concerted manner [10,66,67]. In the literatures, this synergistic effect
process, the conversion of CO2 on the T001 is slightly higher than the
can be experimentally evidenced by the enhanced activity and some
T101, and the selectivity of CH4 shows very similar result. The two
specific characterization techniques e.g. up-shifted hydrogen reduction
supports only showed about 2% selectivity for CH4, while nearly 98%
peaks in H2-TPR [53,66–68]. H2-TPR results of all the samples in Fig. 6
selectivity for CO. After loading Ru nanoparticles, the activity of

Fig. 3. N2 adsorption-desorption isotherms (a) and pore size distribution curves (b) of the samples.

246
S. Chai, et al.
Fig. 4. UV–Vis diffuse reflection spectra (DRS) of all the samples.
Fig. 5. Raman spectra of all the samples; the inset shows the magnified Raman
spectra from 110 to 180 cm−1.
Fig. 6. H2-TPR of all the samples.
catalysts was enhanced dramatically. A trace amount of CO was de-
tected on both Ru-loaded catalysts at a low temperature of 150 °C. The
formation of CH4 was observed above 175 °C. The yield of CH4
247
Journal of CO₂ Utilization 33 (2019) 242–252
increased with the reaction temperature and become substantial at
300 °C. By comparison, the RT001 catalyst exhibited a much higher
activity than the RT101 for CO2 methanation. The yield of CH4 over the
RT001 catalyst increased with the reaction temperature, and ap-
proached the equilibrium conversion at 350 °C. A study of the effect of
H2O showed that introducing water into the feed had an inhibiting
effect on the reaction. RT001 still exhibited a superior catalytic activity
for CO2 methanation in the presence of H2O.
The reaction rates for CH4 are presented in Fig. 7(d), the CH4 pro-
duction rates of the catalysts at 300 °C are shown in Table 2. The CH4
production rate over the RT001 catalysts was 5.12 μmol·s−1·g−1 , which
is much higher than the value of 3.39 μmol·s−1·g−1 over the RT101
catalyst, illustrating that the T001 is a superior support for Ru for the
hydrogenation of CO2 to CH4.
In order to deeply investigate the intrinsic difference between the
RT001 and RT101 catalysts, a kinetic study was performed under the
kinetically controlled regime which was proved by the Weisz-Prater
−r ′A(obs) ρc R2
criterion CWP = De CAs
< 1 (see more details in supplementary in-
formation). Fig. 8(a) displays the Arrhenius plots of the two catalysts,
providing the apparent activation energies for CO2 methanation and
showing reasonable linearity in the temperature range under in-
vestigation (150–190 °C). As listed in Table 2, the apparent activation
energy for the RT001 and RT101 samples is 69.8 KJ/mol and 74.6 KJ/
mol, respectively, indicating that the intrinsic activity of CO2 metha-
nation on the RT001 and RT101 catalysts are largely affected by the
exposed TiO2 crystal facets and their associated different Ru particle
sizes. The different methanation activities may be explained by the
different amounts of active sites originating from different dispersion of
Ru on the carrier materials and a different number of surface oxygen
vacancies.
The stability of RT001 catalyst was evaluated under atmospheric
pressure at a WHSV = 6 L·h−1·g−1 and a reaction temperature of
325 °C. As shown in Fig. 8(b), all the CO2 conversion was always above
80% without any apparent deactivation. The CH4 selectivity remained
100%, and no selectivity towards CO was detected for the duration of
the test. The RT001 catalyst demonstrated therefore a very stable per-
formance for 50 h. Fig. S4 showed that the exposed (001) crystal facets
were still present after 50 h of stability test. In addition, the TEM inset
in Fig. S4 demonstrated that after 50 h stability test the RT001 sample
remained the original truncated bipyramidal morphology, and the Ru
nanoparticles are well dispersed on T001 with the average size of Ru
nearly same as that on the fresh sample. H2-TPD measurements showed
that the Ru dispersion over the used RT001 is 31.1%, similar to the one
on the fresh sample (32.0%). Moreover, the stable crystalline structure
was also confirmed by the unchanged XRD patterns of fresh and used
RT001 samples. Therefore, the excellent stability of RT001 catalyst is
assumed to be closely associated with the strong anchoring of the Ru
nanoparticles on the (001) crystal facets of the TiO2 nanocrystals.
Fig. 9 displays the catalytic activity at 250 °C over the RT001 cat-
alysts at different space velocities. It was found that CH4 selectivity
increased with decreasing space velocity at the expense of CO. Un-
expected high CO selectivity was found on RT001 at a low CO2 con-
version, and the CO selectivity increased with increasing space velo-
cities. This finding strongly suggests that CO is a primary product that
undergoes secondary reactions through successive CO hydrogenation
over the Ru/TiO2 catalysts. In the literatures, the reaction mechanisms
proposed for CO2 methanation have been classified into two main ca-
tegories. The first one involves the conversion of CO2 to CO prior to
methanation, and the subsequent hydrogenation follows the same me-
chanism as CO mechanation [10,13]. The other reaction mechanism
involves the direct hydrogenation of CO2 to CH4 without forming CO as
intermediate during the reaction [10,13]. Based on the conversion-de-
pendent CO selectivity result of RT001 catalysts obtained at different
space velocities, CO was identified to be an important intermediate for
the CO2 methanation, which is further considered to occur in a CO-
S. Chai, et al. Journal of CO₂ Utilization 33 (2019) 242–252

Fig. 7. (a) CO2 conversion of all the samples.

(b) CH4 selectivity of all the samples. (c) CO
selectivity of all the samples. (d) CH4 formation
rate of all the samples. Reaction conditions:
pretreatment temperature 500 °C with 30 ml/
min H2 for 1 h, the feed flow rate amounted to
20 ml/min (10 vol.% CO2, 40 vol.% H2 diluted
in N2).

Table 2
Chemical parameters for the catalysts.
Sample Ru (wt%)a Ru dispersion (%)b CH4 formation rate (μmol·s−1·g−1)c TOF (10−2·s−1)d Ea (kJ·mol−1)e

RT001 2.39 32.0 5.12 7.24 69.8

RT101 2.41 51.1 3.39 2.98 74.6

a
Values determined by ICP.
b
Values calculated based on the H2-TPD results.
c
The reaction rate(r) was defined as the mole number of CH4 produced per gram of catalyst per second at 300 °C.
d
the TOF values was calculated at 300 °C.
e
Values calculated from the Arrhenius plots.

Fig. 8. Arrhenius plots of CO2 hydrogenation

over the RT001 and RT101 catalysts. Reaction
conditions: 200 mg catalyst were tested with a
feed flow rate of 20 ml/min (10 vol.% CO2,
40 vol.% H2 diluted in N2) between 150 and
190 °C. (b) Long term test of the RT001 sample
for CO2 conversion and CH4selectivity.
Reaction conditions: 200 mg catalysts were
tested with a feed flow rate of 20 ml/min
(10 vol.% CO2, 40 vol.% H2 diluted in N2) at a
reaction temperature of 325 °C.

mediated cascade CO2→CO→CH4 reaction mechanism. This result
seems to be reasonable since the CO molecule is prone to be activated
comparing to inert molecule CO2.
3.3. The role of CO in CO2 methanation
A considerable amount of CO had been detected at low reaction
temperatures in the range between 150 °C and 175 °C, but it became
undetectable at temperatures exceeding 200 °C. To further explore the
role of CO in this reaction, the effects of different feed composition and
space velocity on the CH4 production rate and product distribution
were studied for a wide range of weight hourly space velocity values at
250 °C over the RT001 catalyst. Additional investigations were per-
formed using CO as initial reactant. As shown in the Fig. 10, the CH4
formation rate varied in the following order: RT001 (CO+H2) > RT001
(CO2+H2) > RT101 (CO2+H2) > T001 (CO2+H2) ≅ T101 (CO2+H2).

248
S. Chai, et al.
Fig. 9. The effect of space velocity (L·h−1·g−1) on the conversion and product
selectivity of CO2 methanation at 250 °C.Reaction conditions: catalysts were
tested with a feed flow rate of 20 ml/min (10 vol.% CO2, 40 vol.% H2 diluted in
N2).
Fig. 10. Comparison of the reaction rate of CO2 methanation over the RT001
and RT101 samples and of the reaction rate of CO methanation over the RT001
sample. Reaction conditions: 200 mg catalysts were tested with a feed flow rate
of 20 ml/min (10 vol.% CO2, 40 vol.% H2 diluted in N2).
It is obvious that CO methanation is more readily to take place com-
pared with CO2 methanation, implying that the CO hydrogenation step
is not the rate-limiting step for cascade CO2 conversion.
3.4. The impact of underlying TiO2 support on CO2 methanation
All the relevant chemical parameters for the RT001 and RT101
catalysts are listed in Table 2. The actual Ru loading is determined to be
2.39% over the T001 and 2.41% over the T101 supports, respectively,
which are both very close to the nominal loading of added Ru pre-
cursors. Only a very small amount of ruthenium is lost during the cat-
alyst preparation. The value of Ru dispersion over the T101 support is
remarkably higher than over the T001 support, 51.11% versus 32.03%
respectively, indicating that the size of the Ru nanoparticles is much
smaller for the T101 sample than that of the T001 sample. The che-
misorption results were also consistent with the results obtained from
TEM measurements. Recently, Kwak et al. have reported that the ac-
tivity and selectivity of Ru/Al2O3 catalysts were very sensitive to the
cluster size of the Ru nanoparticles dispersed on the support, large Ru
clusters tended to favor the CH4 formation [22,27]. In the present
249
Journal of CO₂ Utilization 33 (2019) 242–252
study, the TOF of CH4 formation over RT001 was almost 2.5 times
higher than the value over RT101 (see Table 2). Our reactivity data also
indicated that a larger Ru cluster size is more favorable for CH4 for-
mation, agreeing well with literature reports on other Ru-based cata-
lysts for CO2 methanation [22,27]. Based on our activity data and
characterization results, we concluded that the nature of the TiO2 cat-
alyst support has a strong impact on the dispersion of the Ru species.
To shed further light on the origin of the superior activity of the
RT001 catalyst, the chemisorption behaviors of CO2 and H2 over all the
samples were investigated in more detail by CO2-TPD and CO2-TPSR,
respectively. Fig. 11 shows the CO2 desorption profiles obtained from
CO2-TPD over RT001 and RT101. The results of CO2-TPD showed the
significantly stronger CO2 adsorption over RT001 than those on RT101.
The strong peak of CO2 desorption could be observed at 84 °C and 93 °C
well below 150 °C over RT001 and RT101, respectively. By contrary, no
obvious desorption peaks of CO2 and CO were detected at the initial
temperature of the CO2-TPD profiles on the bare supports of T001 and
T101 (Fig. S4), while only water was desorbed from the surface of the
two supporting materials, in line with the activity data. The peak in-
tensity of adsorption CO2 over RT001 is much more intense than that on
the pure support, indicating that CO2 is effectively adsorbed over the
sites located at the interface between Ru and TiO2 in RT001 catalysts
[69], and the strong interaction of metal and support promotes CO2
adsorption. Previous studies [70,71] have demonstrated that the CO2
methanation requires the cooperation of metal site which is able to
dissociate H2, and the oxygen vacancy located in metal-support inter-
face which is able to activate CO2. It has been well documented in the
literatures that the high oxygen vacancy provides active sites to benefit
CO2 adsorption and activation and further improve the catalytic ac-
tivity for CO2 conversion [72–76]. For instance, a combined theoretical
and experimental result by Chen et al. show that CO2 binding is
strengthened by 0.32 eV compared to Pt when an oxygen vacancy is
generated at Pt–TiO2 interface, indicating that the activation of CO2
occurs at metal-support interface with oxygen vacancy generating by
the metal-support interaction and the enhanced activity of Pt/oxide for
CO2 reduction is originated from the sites at the Pt–oxide interface,
where the synergy between Pt and oxide plays an important role [76].
Fig. 12 displays the CO2-TPSR profiles of the RT001 and RT101
catalysts under the atmosphere of 10% H2/Ar after adsorption of CO2. It
shows again that the desorption peak of CO2 on the RT001 catalysts is
more intensive than on the RT101 catalysts, which is in accordance
with the results of CO2-TPD. Moreover, for the signals of CH4 were
shown in Fig. 12 (b), we can see that the peak intensity of CH4 on the
RT001 catalyst is obviously also stronger than over the RT101 catalyst
during the whole desorption process, demonstrating that RT001 cata-
lyst is able to more efficiently promote CH4 formation via effective CO2
activation. No desorption of CO was observed as it gets visible in
Fig. 12(c). H2O is another product of CO2 methanation also during the
TPD experiments (see Fig. 12(d)). The release of H2O takes place in the
same temperature range as for CO2 which further confirms the occur-
rence of CO2 methanation over the Ru/TiO2 samples. The CO2-TPSR
profile of T001 and T101 are displayed in Fig. S6. No obvious deso-
rption peaks of CO2, CH4 or CO could be observed during the TPD
process and only some desorbed from the surface over the two supports
similar to the result of CO2-TPD, illustrating the low reactivity of T001
and T101 for the CH4 formation despite the high capability of CO2
adsorption on the T001 surface. In this CO2-TPSR experiment, the Ru-
containing catalysts exhibited a remarkable ability for CH4 formation.
Oxygen vacancy has long been considered as the reactive site on the
surface of metal oxides [10]. In Ru/TiO2 catalysts, the oxygen vacancy
may act as an important site in adsorbing and activating carbon-oxygen
bond. Previous reports have revealed the close relationship between the
concentration of oxygen vacancy and the metal–support interaction,
illustrating the metal-support interaction at metal–support interface
plays a key role in the concentration of oxygen vacancy [20,77]. The
loading of Ru onto CeO2 has been found to greatly promote the
S. Chai, et al. Journal of CO₂ Utilization 33 (2019) 242–252

Fig. 11. Mass signals of (a) CO2 (m/e = 44), (b) CO (m/e = 28), (c) H2O (m/e = 18) and (d) CH4 (m/e = 15) during the CO2-TPD process over RT001 and RT101
after CO2 preadsorption.

Fig. 12. Mass signals of (a) CO2 (m/e = 44), (b) CH4 (m/e = 15), (c) CO (m/e = 28), and (d) H2O (m/e = 18) during the CO2-TPSR process over RT001 and RT101.
Determined under H2 atmosphere during the temperature ramp after CO2 preadsorption.

250
S. Chai, et al.
formation of oxygen vacancy. Wang et al. reported that the surface
oxygen vacancy rather than Ru metal in Ru/CeO2 catalyst is the active
site for the rate-controlling step of CO2 methanation and abundant
oxygen vacancies at the interface of Ru and CeO2-NCs could facilitate
the CO2 activation [20]. Our results of Raman, CO2-TPD, and CO2-TPSR
presented in this work suggest that the strong interaction of Ru and
TiO2 (001) lead to highly enhanced concentration of oxygen vacancies
located in the interface of Ru and support, and facilitate the adsorption
of CO2 as well as the activation of C]O inert bond, thus promoting the
overall reactivity owing to the facet-dependent and Ru-promoted for-
mation of oxygen vacancy.
In terms of reaction mechanism, our conversion-dependent CO se-
lectivity result indicates a CO-mediated cascade CO2→CO→CH4 reac-
tion mechanism over Ru supported TiO2 (001). According to the test of
CO methanation over RT001, the activation of CO2, rather than CO
hydrogenation step, seems to be a more kinetic-relevant step for cas-
cade CO2→CO→CH4 transformation. This is also consistent with the
results of the morphology/facet-dependent and Ru-promoted oxygen
vacancy obtained from CO2-TPD and Raman measurements.
Early studies found the loading of small Ru metal nanoparticles on
the reducible supports (e.g., TiO2, CeO2) can significantly enhance their
COx methanation performance owing to the metal–support interactions
[10,77]. The activity and selectivity of these catalysts have been shown
to be very sensitive to the cluster size and the interaction between the
active metals and oxide supports. In particular, for Ru/TiO2 catalysts,
TOFs of both CO and CO2 methanation increase by a factor of 40 and
25, respectively, with increasing mean particle size of Ru from 2.1 to
4.5 nm, accompanied by an increase of methane selectivity [78]. The
observed dependence of TOF on crystallite size indicates that hydro-
genation of CO/CO2 occurs preferably on flat Ru surfaces, the fraction
of which is higher for larger metal crystallites. A late study by Kwak
et al. dealing with size effect of Ru over Al2O3 reported the dramatic
decrease in CO and increase in CH4 selectivity with increasing Ru
particle size, confirming the size-dependent activity and selectivity
[22].
The results that CO2 methanation is favored over Ru loaded on TiO2
(001) facets in this study may be explained by the decreased fraction of
coordinately unsaturated Ru atoms at edges and corners relative to the
total amount of surface metal atoms with increasing Ru crystallite size,
which can facilitate the formation of CH4 by supplying large amounts of
atomic hydrogen to the hydrogenation step. Moreover, the Ru with
large particle size and low unsaturation in the sample of RT001 pro-
mote the formation of abundant surface oxygen vacancies, in compar-
ison with Ru loaded over TiO2 (101) facets. The observed highly en-
hanced methanation activity in the catalyst of Ru loaded on TiO2 (001)
is due, most probably, to the synergistic effect of concerted reaction
between the oxide-activated CO2 and the metal-activated hydrogen,
owing to the strong metal-support interaction. Based on previous re-
ports and the results in this work, it is concluded that oxygen vacancy
located in the Ru/TiO2 interface serves as the active site for activation
and conversion of CO2 to CO, while Ru provides site for CH4 production
via CO hydrogenation and regeneration of oxygen vacancy.
4. Conclusions
In this work, Ru nanoparticles supported by TiO2 (001) exhibited a
highly enhanced CO2 conversion compared with TiO2 (101), and the
superior reactivity data by using TiO2 (001) surface can be satisfactorily
explained by the measurements based on HR-TEM, Raman spectra, H2-
TPR, and chemisorption measurements. Our activity data and char-
acterization results in this work provide evidences that CO2 methana-
tion activity over Ru-based catalysts can be determined by the choice of
support material and exposed crystal facets, which can affect not only
the size of supported Ru nanoparticles, but also the number of available
surface oxygen vacancy effective for CO2 activation. As demonstrated
by activity and characterization results, modulating the exposed crystal
251
Journal of CO₂ Utilization 33 (2019) 242–252
facet of support in Ru/TiO2 catalysts were identified to be one of the
effective strategies to enhance the population of surface oxygen va-
cancies in facilitating CO2 adsorption and thereby boost CO2 metha-
nation efficiencies. The highly enhanced catalytic activity of Ru species
loaded on TiO2 (001) facets was originated from the nature of (001)
facets with high surface energy and abundant oxygen vacancies, which
could provide more active sites for CO2 activation and result in the
synergistic effect of ruthenium and TiO2 due to the strong metal-sup-
port interaction. Therefore, RT001 catalysts displayed an excellent ac-
tivity and durability, demonstrating its promising potential for appli-
cations in hydrogenation of carbon dioxide.
Acknowledgements
This research was supported by Science and Technology
Commission of Shanghai Municipality (18030501100), the Program for
Professor of Special Appointment (Eastern Scholar) at Shanghai
Institutions of Higher Learning, the Talent Program of Shanghai
University of Engineering Science, National Natural Science Foundation
of China (21503133), and Shanghai Talent Development Foundation
(2017076).
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.jcou.2019.05.031.
References
[1] J. Hansen, M. Sato, R. Ruedy, K. Lo, D.W. Lea, M. Medina-Elizade, Proc. Natl. Acad.
Sci. 103 (2006) 14288–14293.
[2] N. MacDowell, N. Florin, A. Buchard, J. Hallett, A. Galindo, G. Jackson,
C.S. Adjiman, C.K. Williams, N. Shah, P. Fennell, Energ. Environ. Sci. 3 (2010)
1645–1669.
[3] T.R. Knutson, R.E. Tuleya, J. Climate 17 (2004) 3477–3495.
[4] D. Jo, J.B. Lim, T. Ryu, I.S. Nam, M.A. Camblor, S.B. Hong, J. Mater. Chem. A 3
(2015) 19322–19329.
[5] R.N.E. Huaman, T.X. Jun, Renew. Sustain. Energ. Rev. 31 (2014) 368–385.
[6] K.M. Yu, I. Curcic, J. Gabriel, S.C. Tsang, ChemSusChem 1 (2008) 893–899.
[7] J. Rossmeisl, Z.W. Qu, H. Zhu, G.J. Kroes, J.K. Nørskov, J. Electroanal. Chem. 607
(2007) 83–89.
[8] B. Girginer, G. Galli, E. Chiellini, N. Bicak, Int. J. Hydrogen Energ. 34 (2009)
1176–1184.
[9] C.S. Budi, H.C. Wu, C.S. Chen, D. Saikia, H.M. Kao, ChemSusChem 9 (2016)
2326–2331.
[10] W. Wang, S.P. Wang, X.B. Ma, J.L. Gong, Chem. Soc. Rev. 40 (2011) 3703–3727.
[11] J. Ma, N.N. Sun, X.L. Zhang, N. Zhao, F.K. Xiao, W. Wei, Y.H. Sun, Catal. Today 148
(2009) 221–231.
[12] T. Le, A. Striolo, C.H. Turner, D.R. Cole, Sci. Rep. 7 (2017) 9021.
[13] M.A.A. Aziz, A.A. Jalil, S. Triwahyono, A. Ahmad, Green Chem. 17 (2015)
2647–2663.
[14] H.C. Wu, Y.C. Chang, J.H. Wu, J.H. Lin, I.K. Lin, C.S. Chen, Catal. Sci. Technol. 5
(2015) 4154–4163.
[15] Y. Yan, Y.H. Dai, H. He, Y.B. Yu, Y.H. Yang, Appl. Catal. B 196 (2016) 108–116.
[16] J.K. Kesavan, I. Luisetto, S. Tuti, C. Meneghini, G. Iucci, C. Battocchio, S. Mobilio,
S. Casciardi, R. Sisto, J. CO2. Util. 23 (2018) 200–211.
[17] Y. Yan, Y.H. Dai, Y.H. Yang, A.A. Lapkin, Appl. Catal. B 237 (2018) 504–512.
[18] D. Wierzbicki, R. Baran, R. Dębek, M. Motak, M.E. Gálvez, T. Grzybek, P. Da Costa,
P. Glatzel, Appl. Catal. B 232 (2018) 409–419.
[19] B. Mutz, H.W.P. Carvalho, S. Mangold, W. Kleist, J.D. Grunwaldt, J. Catal. 327
(2015) 48–53.
[20] F. Wang, S. He, H. Chen, B. Wang, L.R. Zheng, M. Wei, D.G. Evans, X. Duan, J.Am.
Chem. Soc. 138 (2016) 6298–6305.
[21] Y. Zhu, S.R. Zhang, Y.C. Ye, X.Q. Zhang, L. Wang, W. Zhu, F. Cheng, F. Tao, ACS
Catal. 2 (2012) 2403–2408.
[22] J.H. Kwak, L. Kovarik, J. Szanyi, ACS Catal. 3 (2013) 2449–2455.
[23] C.S. Kellner, A.T. Bell, J. Catal. 75 (1982) 251–261.
[24] G. Garbarino, D. Bellotti, E. Finocchio, L. Magistri, G. Busca, Catal. Today 277
(2016) 21–28.
[25] Y. Guo, S. Mei, K. Yuan, D.J. Wang, H.C. Liu, C.H. Yan, Y.W. Zhang, ACS Catal. 8
(2018) 6203–6215.
[26] J.N. Park, E.W. McFarland, J. Catal. 266 (2009) 92–97.
[27] J.H. Kwak, L. Kovarik, J. Szanyi, ACS Catal. 3 (2013) 2094–2100.
[28] S.K. Beaumont, S. Alayoglu, C. Specht, N. Kruse, G.A. Somorjai, Nano Lett. 14
(2014) 4792–4796.
[29] H.H. Shin, L. Lu, Z. Yang, C.J. Kiely, S. McIntosh, ACS Catal. 6 (2016) 2811–2818.
[30] K.P. Yu, W.Y. Yu, M.C. Kuo, Y.C. Liou, S.H. Chien, Appl. Catal. B 84 (2008)
S. Chai, et al.
112–118.
[31] A. Karelovic, P. Ruiz, Appl. Catal. B 113-114 (2012) 237–249.
[32] J.C. Matsubu, V.N. Yang, P. Christopher, J. Am. Chem. Soc. 137 (2015) 3076–3084.
[33] T. Abe, M. Tanizawa, K. Watanabe, A. Taguchi, Energy Environ. Sci. 2 (2009)
315–321.
[34] C. Sassoye, G. Muller, D.P. Debecker, A. Karelovic, S. Cassaignon, C. Pizarro,
P. Ruiz, C. Sanchez, Green Chem. 13 (2011) 3230–3237.
[35] G.L. Bezemer, J.H. Bitter, H.P.C.E. Kuipers, H. Oosterbeek, J.E. Holewijn, X.D. Xu,
F. Kapteijn, A.J. van Dillen, K.P. de Jong, J. Am. Chem. Soc. 128 (2006) 3956–3964.
[36] J.M. González-Carballo, F.J. Pérez-Alonso, M. Ojeda, F.J. García-García,
J.L.G. Fierro, S. Rojas, ChemCatChem 6 (2014) 2084–2094.
[37] A. Karelovic, P. Ruiz, J. Catal. 301 (2013) 141–153.
[38] M. Behrens, F. Studt, I. Kasatkin, S. Kuhl, M. Havecker, F. Abild-Pedersen,
S. Zander, F. Girgsdies, P. Kurr, B.L. Kniep, M. Tovar, R.W. Fischer, J.K. Nørskov,
R. Schlögl, Science. 336 (2012) 893–897.
[39] X. Liu, Y. Men, J.G. Wang, R. He, Y.Q. Wang, J. Power Sources 364 (2017) 341–350.
[40] A. Kim, D.P. Debecker, F. Devred, V. Dubois, C. Sanchez, C. Sassoye, Appl. Catal. B
220 (2018) 615–625.
[41] W.H. Li, X.W. Nie, X. Jiang, A.F. Zhang, F.S. Ding, M. Liu, Z.M. Liu, X.W. Guo,
C.S. Song, Appl. Catal. B 220 (2018) 397–408.
[42] A. Kim, C. Sanchez, G. Patriarche, O. Ersen, S. Moldovan, A. Wisnet, C. Sassoye,
D.P. Debecker, Catal. Sci. Technol. 6 (2016) 8117–8128.
[43] Y. Li, W.J. Shen, Chem. Soc. Rev. 43 (2014) 1543–1574.
[44] G. Liu, H.G. Yang, J. Pan, Y.Q. Yang, G.Q. Lu, H.M. Cheng, Chem. Rev. 114 (2014)
9559–9612.
[45] L. Cheng, Y. Men, J.G. Wang, H. Wang, W. An, Y.Q. Wang, Z.C. Duan, J. Liu, Appl.
Catal. B 204 (2017) 374–384.
[46] F. Ji, Y. Men, J.G. Wang, Y.L. Sun, Z.D. Wang, B. Zhao, X.T. Tao, G.J. Xu, Appl.
Catal. B 242 (2019) 227–237.
[47] A. Vittadini, A. Selloni, F.P. Rotzinger, M. Grätzel, Phys. Rev. Lett. 81 (1998)
2954–2957.
[48] J.G. Wang, Z.F. Bian, J. Zhu, H.X. Li, J. Mater. Chem. A 1 (2013) 1296–1302.
[49] X.Q. Gong, A. Selloni, A. Vittadini, J. Phys. Chem. B 110 (2006) 2804–2811.
[50] L. Mino, G. Spoto, A.M. Ferrari, J. Phys. Chem. C. 118 (2014) 25016–25026.
[51] Y.H. Cao, Q.Y. Li, C. Li, J.L. Li, J.J. Yang, Appl. Catal. B 198 (2016) 378–388.
[52] J. Mao, L.Q. Ye, K. Li, X.H. Zhang, J.Y. Liu, T.Y. Peng, L. Zan, Appl. Catal. B 144
(2014) 855–862.
[53] Q.Q. Lin, X.Y. Liu, Y. Jiang, Y. Wang, Y.Q. Huang, T. Zhang, Catal. Sci. Technol. 4
(2014) 2058–2063.
252
Journal of CO₂ Utilization 33 (2019) 242–252
[54] J.H. Xu, X. Su, H.M. Duan, B.L. Hou, Q.Q. Lin, X.Y. Liu, X.L. Pan, G.X. Pei,
H.R. Geng, Y.Q. Huang, T. Zhang, J. Catal. 333 (2016) 227–237.
[55] J.G. Wang, P.H. Rao, W. An, J.L. Xu, Y. Men, Appl. Catal. B 195 (2016) 141–148.
[56] D.P. Debecker, B. Farin, E.M. Gaigneaux, C. Sanchez, C. Sassoye, Appl. Catal. A Gen.
481 (2014) 11–18.
[57] J. Zhu, S.H. Wang, Z.F. Bian, S.H. Xie, C.L. Cai, J.G. Wang, H.G. Yang, H.X. Li,
CrystEngComm 12 (2010) 2219–2224.
[58] Z. Wang, C.Y. Yang, T.Q. Lin, H. Yin, P. Chen, D.Y. Wan, F.F. Xu, F.Q. Huang,
J.H. Lin, X.M. Xie, M.H. Jiang, Adv. Funct. Mater. 23 (2013) 5444–5450.
[59] X.X. Huang, Y. Men, J.G. Wang, W. An, Y. Wang, Catal. Sci. Technol. 7 (2017)
168–180.
[60] J.C. Parker, R.W. Siegel, J. Mater. Res. 5 (1990) 1246–1252.
[61] J.C. Parker, R.W. Siegel, Appl. Phys. Lett. 57 (1990) 943–945.
[62] J. Zhu, J. Ren, Y.N. Huo, Z.F. Bian, H.X. Li, J. Phys. Chem. C. 111 (2007)
18965–18969.
[63] S.J. Tauster, S.C. Fung, R.L. Garten, J. Am. Chem. Soc. 100 (1978) 170–175.
[64] S.J. Tauster, Acc. Chem. Res. 20 (1987) 389–394.
[65] G.L. Haller, D.E. Resasco, Adv. Catal. 36 (1989) 173–235.
[66] Z. Mohamed, V.D. Dasireddy, S. Singh, H.B. Friedrich, Int. J. Hydrogen Energ. 43
(2018) 22291–22302.
[67] D.I. Kondarides, P. Panagiotopoulou, X.E. Verykios, J. Phys. Chem. C 115 (2011)
1220–1230.
[68] S. Bernal, F.J. Botana, J.J. Calvino, C. López, J.A. Pérez-Omil, J.M. Rodríguez-
Izquierdo, J. Am. Chem. Soc. 92 (1996) 2799–2809.
[69] A. Beuls, C. Swalus, M. Jacquemin, G. Heyen, A. Karelovic, P. Ruiz, Appl. Catal. B
113–114 (2012) 2–10.
[70] J.A.H. Dreyer, P. Li, L. Zhang, G.K. Beh, R. Zhang, P.H.L. Sit, W.Y. Teoh, Appl.
Catal. B 219 (2017) 715–726.
[71] D. Li, N. Ichikuni, S. Shimazu, T. Uematsu, Appl. Catal. A Gen. 180 (1999) 227–235.
[72] J.Y. Ye, C.J. Liu, D.H. Mei, Q.F. Ge, ACS Catal. 3 (2013) 1296–1306.
[73] Y.X. Pan, C.J. Liu, D.H. Mei, Q.F. Ge, Langmuir 26 (2010) 5551–5558.
[74] S.C. Yang, W.N. Su, J. Rick, S.D. Lin, J.Y. Liu, C.J. Pan, J.F. Lee, B.J. Hwang,
ChemSusChem 6 (2013) 1326–1329.
[75] S. Kattel, P. Liu, J.G. Chen, J. Am. Chem. Soc. 139 (2017) 9739–9754.
[76] S. Kattel, B.H. Yan, J.G. Chen, P. Liu, J. Catal. 343 (2016) 115–126.
[77] F. Wang, C.M. Li, X.Y. Zhang, M. Wei, D.G. Evans, X. Duan, J. Catal. 329 (2015)
177–186.
[78] P. Panagiotopoulou, D.I. Kondarides, X.E. Verykios, Appl. Catal. B 88 (2009)
470–478.