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org/acscatalysis Research Article

Hydrogenation of CO2 to Methane over a Ru/RuTiO2 Surface: A DFT

Investigation into the Significant Role of the RuO2 Overlayer
Jie Yu, Yabing Zeng, Qirou Jin, Wei Lin,* and Xin Lu*
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ABSTRACT: Understanding metal−support interactions is crit-

ical to the rational design of a catalyst for CO2 methanation. In this
regard, the density functional theory is employed to shed light on
the factors that determine the difference between RuTiO2- and
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TiO2-supported Ru nanoparticles. Structural observations and the

calculated ratio of cohesive energy and adsorption energy (Ecoh/
Eads) suggest that supported Ru6 could form as an epitaxial layer
along with RuTiO2 as well as display strong metal−support
interactions with TiO2 and thereby is used as a surface model to
simulate the nanoparticles employed in the experiment. Fur-
thermore, electronic analysis reveals that due to the existence of a
RuO2 overlayer, more electrons are transferred from the support to
the Ru cluster. Benefiting from this, CO2 is lower in adsorption
energy since electrons from Ru6/RuTiO2 are less likely to fill in the antibonding orbital of Ru−O interaction. Analysis of the
minimum-energy pathway indicates that the methanation of CO2 is led by C−O direct bond cleavage rather than the formate
pathway in the first place for both surfaces, which is consistent with the FTIR spectroscopy results. Besides, we noticed that different
reaction mechanisms control methane synthesis from the onset of CHO* formation. On the one hand, CHO* prefers an associative
mechanism on Ru6/RuTiO2 due to the lower d-band center of the support and facile formation of CH2O* species. On the other
hand, closer proximity of the d-band center to the Fermi level (EFermi) and preferable CH* formation promote CHO* on Ru6/TiO2
to undergo a dissociative pathway. Our comparative studies suggest that the RuO2 overlayer plays a key role in determining the
reaction mechanism of CO2 methanation for Ru/r-TiO2.
KEYWORDS: density functional theory, d-band center, RuO2 overlayer, methane formation, associative/dissociative mechanism

1. INTRODUCTION kJ/mol), multiple inactive elementary steps with high energy

Anthropogenic carbon dioxide (CO2) emission is one of the
major culprits for the greenhouse effect, so much effort has
been devoted to searching for alternative low-carbon-
containing fossil fuels.1,2 In addition to keeping the source of
pollution within limits, postdisposal of already produced CO2
as the raw material has already emerged as a hot topic globally
for the CO2-reduction research area. This is because CO2 is a
renewable and environment-friendly carbon feedstock that can
be applied to the synthesis of chemicals such as methanol,
methane, and so forth.3−8 CO2 methanation (CO2 + 4H2 =
CH4 + 2H2O), the so-called Sabatier reaction, has attracted
extensive attention for two primary reasons.9,10 On the one
hand, it takes advantage of the excessive electric energy
originating from biomass which could serve to produce H2 gas
and thereby realizes the recyclable usage of CO2.11−13 On the
other hand, higher selectivity is achieved from much lower
pressure compared with methanolization which is another
common CO2 hydrogenation product.14,15
Even though methane synthesis via CO2 hydrogenation is
feasible from the thermodynamic aspect (ΔG298.15K = −130.8
barriers limit its application. Thus, a higher temperature is
commonly required to ensure a high conversion rate. However,
this brings in another problem, where the reverse water−gas
shift reaction would occur at this temperature range and
reduce CH4 selectivity.16 To meet the need for both methane
selectivity and conversion rate, a suitable catalyst should be
designed. Among various choices, Ru-based catalysts have been
regarded by far as the optimal ones for CO2 methanation at
low temperatures because they are much more stable and
active over time than Ni-based catalysts which experience
severe deactivation resulting from coking and sintering and are
sensitive to oxidizing environments.17 For instance, Ru(0001)
has been verified computationally to exhibit higher activity for
Received: September 14, 2022
Revised: November 3, 2022
Published: November 16, 2022

© 2022 American Chemical Society https://doi.org/10.1021/acscatal.2c04539

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Figure 1. (a) Schematic representation of constructing RuTiO2 and TiO2. (b) Variation of the ratio of Ecoh/Eads as a function of the number of Ru
atoms in Run (n = 2−8) for both Run/RuTiO2 and Ru/TiO2. (c,d) AIMD plots of Ru6/RuTiO2 and Ru6/TiO2. (e) Most stable Ru6/RuTiO2 and
Ru6/TiO2, where Ru atoms are labeled accordingly, and the charge density difference of Ru6/TiO2 and Ru6/RuTiO2, where the isosurface value is
set to 0.0035 e/Å3. Yellow and blue isosurfaces denote the charge accumulation and depletion regions, respectively.

CO2 methanation than Ni(111).18 Moioli and Züttel found
that 0.5% Ru/Al2O3 exhibited much higher catalyst perform-
ance for CO2 methanation compared with Al2O3-supported Ni
of the same loading.19 By using the same catalysts, González-
Velasco et al. verified that CH4 formation of Ru/Al2O3 is about
10 times than that of Ni/Al2O3.20
For supported transition-metal catalysts, metal oxide
supports exert significant influence on the intermediate
adsorption, morphology of the active phase, and catalytic
performance. For Ru-based catalysts, TiO2 is arguable to be the
most suitable support.21−28 It is proposed that the high CH4
selectivity of Ru/TiO2 derives from strong metal−support
interactions (SMSIs), which is determined by the difference in
the crystalline phase. For instance, higher CH4 selectivity of
Ru/r-TiO2 (rutile) compared with Ru/a-TiO2 (anatase) is
attributed to better interfacial lattice compatibility between
RuO2 and r-TiO2.24,25,27,28 Regardless of high CH4 selectivity,
improvement of the conversion rate for Ru/TiO2 is still
challenging. CO is considered to be an important intermediate
involved in CO2 methanation.29−31 Zhang et al. employed a
coreduction method which allows for the generation of TiO2−x
overlayers at Ru/r-TiO2 interfaces. Based on their experimental
results, the SMSI is responsible for readily breaking the C−O
bonds of both CO2 and CO, thereby promoting methane
selectivity.32,33 Behm et al. also observed the same promotion
effect by encapsulation Ru in r-TiO2−x (defective r-TiO2).34
Even though high selectivity is achievable from their studies,
the conversion rate remains very low. It is therefore suspected
that interaction between Ru and TiO2 is not sufficient for the
optimal conversion rate.
Our attention has been drawn to a recent study by Wang et
al. For Ru/r-TiO2 annealed through both air and H2 gas in
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sequence, an equally high CH4 selectivity is achievable as the
traditional TiO2-supported Ru catalyst.29 In addition, air
annealing features Ru/r-TiO2 with a much higher conversion
rate. It is argued that in these samples, Ru/r-TiO2 is only
partially reduced and thereby preserves an overlayer of
ruthenium oxide (RuOx). The RuOx overlayer grants the Ru
cluster better dispersion, which has been verified by character-
ization techniques. Even though the SMSI is put forward as a
plausible explanation, more information is needed correspond-
ing to how the modified surface changes the chemical
properties (i.e., charge density redistribution and adsorption
of intermediate) of the catalyst. Besides, experimental results
offer little insight into the detailed mechanisms for each
elementary step of methane synthesis, which serves as the
foundation for a deeper understanding of the significant role of
the RuO2 overlayer. Herein, we employed the density
functional theory (DFT) to comparatively study the CO2
methanation on Ru/r-TiO2. Based on our calculation results,
key issues are dealt with including (1) the electronic properties
of catalysts with or without RuO2, (2) various modes of CO2
chemisorption on both surface models, (3) most preferred
pathways involved in CO2 methanation on both surface
models, and (4) how RuOx affects the catalyst performance of
Ru/r-TiO2.
2. COMPUTATIONAL METHODS
All the spin-polarized DFT calculations with a periodic
boundary were carried out using the Vienna ab initio
simulation package.35,36 The valence electrons and core
interactions were described through the Perdew−Burke−
Ernzerhof exchange−correlation functional37 and the projector
augmented wave.38 The electron configuration of Ru is
https://doi.org/10.1021/acscatal.2c04539
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[Kr]4d75s1, where (4p6, 4d7, 5s1) are explicitly treated as
valence electrons. The electron configuration of Ti is
[Ar]3d24s2, where (3s2, 3p6, 3d2, 4s2) are explicitly treated as
valence electrons. An energy cutoff of 400 eV and a Gaussian
smearing width of 0.05 eV were applied to models containing
all surfaces and intermediates. The dispersion-corrected vdW-
D3 functional was considered to evaluate the van der Waals
effect.39 It is argued that an appropriate description of Ti 3d
and Ru 4d orbitals, DFT + U, should be considered.40
However, our trial calculation indicates that the Hubbert U
corrections have little effect on energetics and do not affect our
analysis of the density of states (DOS). Therefore, we have not
considered Hubbert U in our studies. A (2 × 2 × 1) k-point
grid using the Monkhorst−Pack scheme was found to give
converged results.41 All the surfaces with or without
intermediates were optimized, and the unconstrained atoms
stopped optimization when the forces on them were below
0.05 eV/Å. The transition state (TS) was located using the
climbing image nudged elastic band method.42 To check
whether the predicted TS connects the initial state (IS) and
final state (FS), the vibrational frequency analysis was also
employed to find out if there is only one imaginary frequency
and whether it corresponds to the first-order saddle point in
the minimum-energy path. A supercell was constructed from
the optimized primitive unit cell of rutile TiO2 (r-TiO2) with
lattice parameters of a = 4.64 Å, b = 4.64 Å, and c = 2.96 Å.
The (110) facet was selected because it is the most stable one
among all the exposed planes of r-TiO2 and has been
confirmed by experiments as the exposed phase.28,43 Then,
the r-TiO2 surface (simply denoted as TiO2 unless mentioned
otherwise) with a nine-layer slab was modeled by a (4 × 2)
supercell (a = 12.15 Å and b = 12.94 Å). As presented in
Figure 1a, RuOx/TiO2 (denoted as RuTiO2) was built from a
heterojunction between a six-layer slab of the TiO2(110) facet
of the same size and a three-layer slab of the RuO2(110)
facet.44 During the structure optimization, the bottom three
layers were kept fixed, while the others including the surface
and intermediates were allowed to relax. A 20 Å vacuum slab
was applied to avoid interaction between each adjacent slab.
The basic units for the Ru cluster supported on both TiO2
and RuTiO2 were determined by employing several important
parameters. Among them, the adsorption energy (Eads) was
used to describe the interaction between the Ru cluster and
support of the individual Ru atom, which is defined as45
Eads = (E Run + Esupport E Ru n /support)/n
where n is the total number of adsorbed Ru. ERun, Esupport, and
d
ERun/support are the total energy of n number of Ru clusters
d
retaining the shape from the support, bare support (RuTiO2 or
TiO2) surface, and supported Run. The cohesive energy (Ecoh)
reflects the clustering ability of the Ru cluster on the bare
support, which is defined as45
Ecoh = [nE Ru1 + Esupport E Ru n /support ]/n
where ERu1 is the total energy of a single Ru atom in the gas
d
phase. Besides, the Ru−Ru interaction energy (ERu−Ru) defines
the metal−metal interaction of individual Ru atoms inside the
cluster, which is defined as45,46
E Ru Ru = Ecoh Eads
Research Article
The activation barrier (Ea) and reaction energy (Er) of each
elementary reaction step for the CO2 methanation over Run/
RuTiO2 and Run/TiO2 are defined as
Ea = E TS E IS (4)
Er = E FS E IS (5)
where EIS, ETS, and EFS represent the total energies of the IS,
TS, and FS, respectively.
The free energies of all ISs, FSs, and TSs at 500 K were
estimated by harmonic approximation. In addition, the free
energies of the gaseous species were calculated as
Gg(T ) = Eelec + E ZPE + Cp dT TS
where Cp is the heat capacity of the gaseous species as a
function of T, which is obtained from the NIST website.47
3. RESULTS AND DISCUSSION
3.1. Determination of Run/RuTiO2 and Run /TiO2
Sharing Similar Properties (Electronic and Structural)
as Nanoparticles Employed in the Experiment. In
general, it is hardly approachable to precisely simulate the
supported nanoparticles employed in the experiment due to
the existence of various isomers and little understanding
concerned with their bonding environments. Therefore, an
efficient approach in a theoretical study is to determine the
supported nanoclusters which display similar properties (both
electronic and structural) or serve as the reactive sites for
catalysis.48 On the one hand, it is reported that small-sized Ru
nanoparticles form as an epitaxial layer along with
RuTiO2((0001)Ru//(110)RuTiO2).29 On the other hand, it is
d
proposed that well-dispersed Ru nanoparticles supporting on
TiO2 exhibit SMSIs and optimal catalysis performance even
though the epitaxial layer is not observed.26−29 To simulate the
nanoparticles employed in the experiment, we devoted our
efforts to find if the Ru nanoclusters form as an epitaxial layer
on RuTiO2 or exhibit strong interaction with TiO2. In this
context, numerous isomers of the Run (n ≤ 8) cluster
supported on both RuTiO2 and TiO2 have been constructed,
optimized, and compared with each other depending on their
relative adsorption energy (Eads), from which the most stable
ones are determined [corresponding optimized structures on
the perfect Run/RuTiO2 and Run/TiO2 (n = 1−8), as shown in
Figures S1 and S2, and the defective Run/RuTiO2 and Run/
(1) TiO2 (n = 1−8) are shown in Figures S3 and S4].
As displayed in Figure 1a, there are two types of oxygen
atoms uncovered in the RuO2 and TiO2 overlayers, wherein
O2c composes the outmost layer and displays a bridged
configuration and O3c remains in the same plane with either Ru
or Ti atoms. For the most stable RuTiO2- and TiO2-supported
Ru monomer, Ru binds to two O2c, and their respective Eads
are −4.85 and −5.20 eV. When n becomes 2 and 3, Ru prefers
bonding with O3c, and their Eads increases apparently, which is
similar to that of Run/a-TiO2.45 For the most preferred
(2) configuration of the Ru4 isomer, the cluster adopts a
tetrahedron-like configuration on both supports and the
increasing amplitude of Eads gradually reduces. As a matter of
fact, the supported Ru4 cluster generally prefers a 3D
configuration and is regarded as the turning point, in which
metal−metal interaction rather than metal−support interaction
gradually becomes the dominant driving force. As expected,
(3) ERu−Ru is smaller than Eads for Ru3/TiO2 but becomes larger
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Table 1. Atomic Bader Charges (|e|) for Ru/RuTiO2, Ru/TiO2 Surfaces, and CO2 Adsorption on Both Surfacesa
C Oa
Ru/RuTiO2 plain surface
RT_CO2_MS* +1.05
RT_CO2_LS* +1.02
RT_CO2_SS* +1.35
Ru/TiO2 plain surface
T_CO2_MS* +1.13
T_CO2_LS* +1.06
T_CO2_SS* +1.15
Ru(0001) plain surface
Ru_CO2_MS* +1.19
a
Refer to Table S1 for a detailed analysis of the atomic Bader charges (|e|) of individual Ru atoms from the supported Ru clusters.
than ERu−Ru for Ru4/TiO2. Even though ERu−Ru in Ru4/RuTiO2
is still less than Eads, the difference is much smaller than the
former three (Figure S5). When n is greater than 5 (n = 6−8),
nanoclusters lie planar and parallel to both RuTiO2 and TiO2
surfaces.
Similar to the SMSI, epitaxial layer formation of the metal
cluster is affected not only by the metal−support interaction29
but also by the metal−metal interaction.48,49 To quantitatively
describe their relative dominance, the ratio of cohesive energy
and adsorption energy is used as a descriptor, in which a
smaller Ecoh/Eads indicates that the cluster shape is primarily
determined by the Ru−support interaction.50 As shown in
Figure 1b, compared with Run/TiO2, a much lower ratio of
Ecoh/Eads is observed for all investigated Run/RuTiO2. Besides,
the ratio does not experience much variation when n ≥ 6.
Taken together, we reasoned that both of these factors
contribute to the epitaxial layer formation of Run (n = 6−8) on
RuTiO2((0001)Ru//(110)RuTiO2), as shown in Figure S1.
d
Limited by the lattice parameters of the unit cell in our
study, an extended supercell (6 × 2) is further employed to
investigate if the trend continues for Run/RuTiO2 (n ≥ 8). As
shown in Figures S6 and S7, the ratio of Ecoh/Eads and
structural observation (Figure S7) further prove that the
epitaxial layer could exist even in larger-sized clusters, which is
consistent with the experimental results.29 Thus, Run/RuTiO2
(n = 6−8) are all qualified to simulate supported Ru
nanoparticles in the experiment. Given that similar CO2
configurations are slightly more stabilized on Ru6/RuTiO2
(see Figure S9a), it is determined as our surface model (simply
denoted as Ru/RuTiO2 in the following discussions unless
mentioned otherwise).
Furthermore, the ratio of Ecoh/Eads is applied to study the
growth pattern of Ru clusters on TiO2. As displayed in Figure
1b, the ratio of Ecoh/Eads is almost the same for Ru6/TiO2 and
Ru7/TiO2 but starts to increase when the cluster size becomes
8. By modeling with a (6 × 2) supercell, we noticed that the
increase of Ecoh/Eads is not only from Ru7/TiO2 to Ru8/TiO2
but also from Ru10/TiO2 to Ru11/TiO2. Hence, it is expected
that the cluster shape of TiO2-supported Run will become
controlled by Ru−Ru interaction and prefer 3D configurations
as long as the modeling clusters are large enough, which
complies well with the experiment results.29 It is also noticed
that the Ecoh/Eads values for these supported Ru clusters are
much lower than that of Run/a-TiO245 whereas higher than
that of Run/RuTiO2. Based on these findings, it is concluded
that Run exhibit SMSIs with r-TiO226−28 but disfavor the
formation of an epitaxial layer on it.29 As shown in Figure S8,
the most stable configurations of Run (n ≥ 6) remain 2D.
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Ob CO2 (total) Ru (total)
+2.54
−0.94 −1.02 −0.91 +3.42
−0.84 −1.04 −0.86 +3.44
−0.91 −1.03 −0.59 +3.03
+1.70
−1.01 −0.97 −0.85 +2.79
−0.99 −0.98 −0.91 +2.75
−0.88 −1.06 −0.79 +2.41
0
−1.02 −1.00 −0.83 +0.39
Similar to Run/RuTiO2, these 2D clusters are more reactive
than Run/TiO2 (n < 6) owing to more interfacial area provided
to activate the carbon dioxide.29,51 Compared with others
[Run/TiO2 (n ≥ 8)], a stronger MSI is observed for Ru6/TiO2
and Ru7/TiO2 owing to their relatively lower ratio of Ecoh/Eads.
For comparison, Ru6/TiO2 is selected as our surface model
(simply denoted as Ru/TiO2 in the following discussions
unless mentioned otherwise).
To evaluate the dynamic stability of both Ru/RiTiO2 and
Ru/TiO2, NVT ensemble simulations of the ab initio molecular
dynamics (AIMD) are applied under 500 K with the time step
set as 1 fs. As shown in Figure 1c,d, both surface models
remain stable without obvious distortion in configuration over
a time period of 5 ps.
We further characterized the structural properties of both
Ru/RuTiO2 and Ru/TiO2. As displayed in Figure 1e, the
optimized structures of both supported Ru clusters are similar
in shape. However, epitaxial formation makes the cluster shape
of Ru6 supporting on RuTiO2 resemble the (0001) facet of the
ruthenium surface. The average bond distance of Ru−O3c is
2.34 Å with little variations, which indicates that the cluster
exhibits intimate contact with the RuO2 overlayer. On the
contrary, individual Ru−O3c varies greatly in distance for Ru/
TiO2, wherein Rua and Ruf are much closer to the support than
the other four. Since the epitaxial layer is unable to form, the
cluster surface is more protruding than that of Ru6/RuTiO2
and thereby exhibits less intimacy with the support. This is also
in agreement with the above results drawn from the Ecoh/Eads
ratio. To explore the electronic interaction that accounts for
the configurational variations, the Bader charge of the Ru
cluster was calculated to characterize the charge transfer at the
interface. As listed in Table 1, the Ru clusters lose a total
amount of 2.54 and 1.70 |e| when supported on RuTiO2 and
TiO2, respectively. In light of these findings, it is concluded
that Ru/RuTiO2 exhibits a stronger interaction between the
cluster and support, which coincides with the experiment’s
results.29
Similar to CeO2, TiO2 has great potential to generate oxygen
vacancies (Ov), which might influence the shape of the
supported Ru clusters. Hence, Ru clusters mounting on both
defective RuTiO2 and TiO2 were also examined with one of
the O2c being removed. For the most stable configuration of
Run/RuTiO2−x (n = 1−8) shown in Figure S3, the preference
for 2D configuration is still fit for the cluster with a size as large
as 7. This also verifies the positive interaction between the
cluster and support. As the cluster keeps increasing, the 3D
configuration becomes dominant, suggesting that the cluster
tends to agglomerate. Accordingly, a similar trend has been
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Figure 2. (a) Optimized structures of the most stable chemisorbed CO2 and their respective adsorption energy on the Ru/RuTiO2, Ru/TiO2, and
Ru(0001) surfaces. The white, red, green, and gray spheres represent titanium, oxygen, ruthenium, and carbon atoms, respectively. The yellow,
orange, and pink spheres represent oxygen from CO2 adsorbed on Ru/RuTiO2, Ru/TiO2, and Ru(0001), respectively. (b,c) −COHP curves of all
adsorbed bonds belonging to the most stable CO2 adsorption configuration on Ru/RuTiO2 (RT_CO2_MS*) and Ru/TiO2 (T_CO2_MS*),
where the Fermi level (EFermi) is set to zero.

observable for the TiO2−x supported Run (see Figure S4). It is participate in CO2 stabilization. The carbon atom is activated
therefore expected that Ru clusters prefer forming a planar by Rue and thereby stretches the bond length of C−Oa (1.38
layer (2D) on the perfect support, whereas a defective support Å) and C−Ob (1.28 Å) relative to inert CO2 (1.18 Å). The
promotes the 3D configuration of the Ru cluster in order to corresponding Eabs is −0.73 eV. The less stable one favors a
avoid surface tension. This is quite different from Aun/TiO2 bidentate structure, denoted as RT_CO2_LS*, in which C
where a 2D configuration is more preferred on the defective rather than Ob builds connectivity with Rub and thereby loses
surface according to the calculation results by Grunwaldt et one Ru−O bond. Despite being less competitive in adsorption
al.52 Both findings further prove the significant role of the energy, the C−Oa bond distance is prolonged apparently,
support in determining the shape of the metal cluster. indicating that it is more activated than the C−Ob bond. The
3.2. CO2 Adsorption on Ru/RuTiO2 and Ru/TiO2. To configuration being the second less stable is RT_CO2_SS*,
understand how the difference in the support affects the where only one Ru−O bond is formed between CO2 and the
catalysis performance, we started by comparatively examining Ru cluster. Owing to the lowest binding strength, bond lengths
various chemisorption modes of CO2 on Ru/RuTiO2 and Ru/ of both C−O from adsorbed CO2 decrease.
TiO2, the optimized configurations of which are displayed in Besides, we also examined the CO2 chemisorption modes on
Figures 2a and S9b,c. The structural parameters related to the Ru/TiO2. As expected, tridentate T_CO2_MS* is the most
C−Oa, C−Ob, and Oa−C−Ob angles are summarized in Table stable configuration adsorbed on Ru/TiO2 owing to the lowest
2. In addition, the CO2 adsorption modes on Ru(0001) are adsorption energy (−0.46 eV). Three atoms from the cluster,
also studied for crosswise comparison. including Rua, Rub, and Ruf, are involved in building
3.2.1. Structural Analysis. For Ru/RuTiO2, the most stable connections with the oxygen atoms from adsorbed CO2.
adsorption mode is denoted as RT_CO2_MS*, wherein three With respect to the less stable one T_CO2_LS*, also being in
Ru−O bonds including Ru a−Oa, Ruf−Oa, and Rub−Ob a tridentate pattern, three Ru−O bonds (including Rub−Ob,
Ruc−Oa, and Rud−Oa) are found. Despite having a similar
Table 2. Parameters Related to C−Oa and C−Ob Bond configuration to T_CO2_MS*, it is slightly higher in
Distances (Å) and the Oa−C−Ob Angle (deg) of Different adsorption energy due to the extra deformation energy
CO2 Chemisorption Modes on Ru/RuTiO2, Ru/TiO2, and required to release the lattice strain from the smaller grid
Ru(0001) Surfaces composed of Rub, Ruc, Rud, and Rue. Compared with the other
two adsorption modes, T_CO2_SS* has lower binding
adsorption mode C−Oa C−Ob ∠Oa−C−Ob strength. As for Ru(0001), tridentate Ru_CO2_MS* is found
Ru/RuTiO2 RT_CO2_MS* 1.38 1.28 121.0 as the most stable configuration, which is much higher in Eabs
RT_CO2_LS* 1.50 1.22 118.9 than its counterparts adsorbed on the other two surface models
RT_CO2_SS* 1.30 1.23 131.6 (Figure 2a).
Ru/TiO2 T_CO2_MS* 1.34 1.30 121.9 3.2.2. Electronic Structure Analysis. In addition to
T_CO2_LS* 1.39 1.29 120.0 structural analysis, the Bader charge analysis is employed to
T_CO2_SS* 1.46 1.21 120.0 elucidate the electronic factors that determine the mutual
Ru(0001) Ru_CO2_MS* 1.30 1.30 123.0 effects between the chemisorbed CO2 and three surface
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Figure 3. Potential energy diagram of the most favorable pathway for CO2 methanation on Ru/RuTiO2. Refer to Table S2 for detailed information
about Ea and Er of the specific elementary step and Figure S11 for the optimized structures of IS, TS, and FS involved in this pathway.

Figure 4. Potential energy diagram of the most favorable pathway for CO2 methanation on Ru/TiO2. Refer to Table S3 for detailed information
about Ea and Er of the specific elementary step, and Figure S14 for the optimized structures of IS, TS, and FS involved in this pathway.

models. As summarized in Table 1, the overall Bader charge of
all adsorbed carbon dioxide is negative, indicating that the
direction of charge transfer is from the Ru cluster to CO2. For
Ru/RuTiO2 and Ru/TiO2, electron donations are more
localized around Ru atoms which are bound to CO2 (refer
to Table S1 for more information). For example, both
tridentate RT_CO2_MS* and T_CO2_MS* coordinate to
Rua, Rub, and Ruf, all of which contribute primarily to the
overall electron loss. Therefore, it is speculated that the relative
stability of the chemisorbed CO2 is affected by CO2-
coordinated Ru atoms, rather than the whole cluster. On the
contrary, electron donation from Ru(0001) is much more
delocalized throughout the entire surface plane, which is
reflected by incompatible electron gain and loss between CO2-
coordinated Ru atoms and CO2 (Table 1). This is also the
cause of Ru_CO2*_MS* being the least stable among the
three.
Furthermore, it is noticed that a similar configuration of
CO2 adsorbed on Ru/RuTiO2 has relatively lower adsorption
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energy compared with that of Ru/TiO2. To elucidate the
reason behind this, electronic configurations of RT_CO2_MS*
and T_CO2_MS* are further investigated via the crystal
orbital Hamilton population (COHP), which describes the
electronic contributions of the bonds taking place in the CO2−
Ru interaction (i.e., Oa−Rua, Oa−Ruf, Ob−Rub, and C−Rue).
The relative bond strength is quantized through integrated
COHP (ICOHP). As shown in Figure 2b,c, for both
configurations, all Ru−C and Ru−O bonds contribute greatly
to stabilizing carbon dioxide. Compared with T_CO2_MS*,
the values of ICOHP for RT_CO2_MS* are more negative,
indicating stronger interaction between adsorbed CO2 and Ru/
RuTiO2. In addition, small portions of contribution from
antibonding orbitals are observed right below the Fermi level
for all Ru−O interactions, which negatively affects the O−Ru
binding strength. For a more stable CO2 chemisorption
configuration, the Ru cluster should be more positively charged
to prevent electrons from filling in the antibonding orbitals of
the Ru−O bond. Comparatively, a more stabilized config-
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uration RT_CO2_MS* is attributed to the higher Ru+/Ru
ratio of Ru/RuTiO2.
3.3. Reaction Mechanisms of CO2 Methanation on
Ru/RuTiO2 and Ru/TiO2. We continued to investigate the
influence of the RuO2 overlayer on the reaction mechanism of
CO2 methanation. For an integrated CO2 methanation route
containing various elementary steps, each one is generally
classified as follows: associative mechanism in which
adsorbates accept a hydrogen atom and dissociative mecha-
nism where the C−O bonds of the intermediates are broken.
Before the investigation, it is worth noting that the Eads of the
two atomic hydrogens are −1.63 eV for Ru/RuTiO2 and −1.72
eV for Ru/TiO2. Owing to the facile H2 dissociation, the
isolated H atom is treated as the hydrogen source for all
associative pathways. The logic of this section is presented as
follows: as a start, we screened out the most preferred reaction
mechanism from various ones on a stepwise basis, which is
determined by their respective activation energy barrier (Ea)
and reaction energy (Er) (summarized in Tables S2 and S3).
Thereafter, the integrated route leading to methane synthesis is
put forward for both Ru/RuTiO2 and Ru/TiO2 (the potential
energy diagrams of the most favorable pathway for both surface
models are displayed in Figures 3 and 4, while the other
pathways are displayed in Figures S10 and S13).
3.3.1. Reaction Mechanisms for CO2 Methanation on Ru/
RuTiO2. 3.3.1.1. First Elementary Step. Normally, the reaction
mechanisms for the first elementary step of CO2 activation
include dissociation [CO2* = CO* + O* (S1)] and association
[CO2* + H* = HCOO* (S1′) and CO2* + H* = COOH*
(S1″)]. The dissociative mechanism starts from the chem-
isorbed RT_CO2_MS*, which breaks into CO* and O*. It is
the most competitive pathway owing to the lowest barrier
(0.21 eV) and the largest energy gap between the reactant and
product (−1.06 eV). The associative pathway toward HCOO*
occurs via donating the hydrogen atom from Rue to the carbon
of RT_CO2_MS*, where the barrier of TS1′ is 0.44 eV (see
Figure S12). The resulting bi-HCOO* stabilizes the system by
only 0.16 eV and therefore shows less thermodynamic
competitiveness. From the onset of formate species, it is
found that the reverse reaction of HCOO* + H = H2COO*
(S2′) is much lower in Ea than the forward one. Consequently,
HCOO* behaves as the “inspector”, which does not contribute
to methane formation. This finding complies well with the
experimental results.29 Concerned with the other associative
mechanism, the coupling of CO2* with H comes along with
exceedingly stretched Ob−Rub (2.32 Å), and our calculation
reveals that this leads to the unfavorable formation of trans-
COOH due to the highest barrier among three (0.72 eV). The
kinetic instability can be rationalized by substantial deforma-
tion energy produced to break the Ru−Ob bond. CO2 is more
conducive to undergo the dissociative pathway in the first
elementary step which is the same as Ru(mono-layered)/γ-
Al2O3 and Ru-doped CeO2 and Ru/zeolite.53,54
3.3.1.2. CHO* Formation. Followed by CO2* dissociation,
either O* or CO* could be hydrogenated (S2 or S2″). A
comparison between both reveals that hydroxyl formation is
more favorable than the other one due to the benefit of lower
activation and reaction energies. Furthermore, other pathways
including CO* dissociation (S2‴) and CO* protonation
(S2‴′) are also reviewed, despite that neither one is kinetically
accessible. Therefore, it is concluded that coke formation is
prevented on Ru/RuTiO2. To move on, we comparatively
studied the associative pathways involving either CO* (S3) or
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OH* (S3′). Comparing both elementary steps suggests that
the hydrogen atom bonding with CO* is the preferable one
because of its much more favorable barrier (0.57 eV) than that
of OH* (1.34 eV). The other associative pathway with respect
to COH* (S3″) generation is also invalidated owing to the
reaction barrier of TS3″ being as high as 1.46 eV. As a result,
CHO* is the only possible associative product.
3.3.1.3. CH2O* Formation via the Associative Mechanism.
Upon CHO* formation, further hydrogenation through either
carbon (S4, CH2O* formation) or oxygen atoms (S4″,
CHOH* formation) is plausible in theory. For the one
involving CH2O* generation via O−H coordination, the C−H
distance is slightly reduced in TS4, which is proportional to a
low activation barrier (0.22 eV). In the FS, the carbon atom
abandons the bridged configuration between Rud and Rue;
instead, a Ruc−C linkage is established and it stabilizes the
system only by −0.04 eV. On the contrary, Ob rather than C
couples with H* to produce CHOH*. However, with the
reaction barrier and reaction energy substantially increasing to
1.25 and 0.89 eV, respectively, this pathway is neither
kinetically nor thermodynamically feasible. In addition to the
associative pathways, formyl could also undergo a dissociative
mechanism. CHO* first isomerizes to iso-CHO* (S4′-1) which
is stabilized by 0.50 eV. Thereafter, C−O bond cleavage (S4′-
2) is triggered with an intrinsic barrier of 0.75 eV.
Comparatively, the formation of CH2O* via the associative
pathway is more preferred. However, the pathway involving
the C−O bond cleavage of iso-CHO* should also be
considered regardless of the higher barrier. Detailed discussion
about their reaction mechanisms will be given in Section
3.3.1.5.
3.3.1.4. Remaining Elementary Steps Leading to Methane
Formation. For the following elementary step, hydrogen
donated by Rue causes the driving force to generate CH2OH*
(S5). In the TS, hydrogenation features TS5 with reduced Ob−
H distance (1.34 Å) and increased reaction barrier (0.84 eV).
For the oxygen-guided hydrogenation activity from either CO*2
or CHO*, a relatively high barrier together with the
endothermic nature of the reaction energy is required. We
attributed this scenario to the passivation of the Ru−O bonds.
Furthermore, CH2OH* experiences bond cleavage between
C−O coordination and generates coexistent species [CH2 +
OH]* (S6). Despite the slightly destabilized final product, a
lower activation energy compared with the former one makes
this step kinetically favorable. The energy barrier of subsequent
OH* hydrogenation (S7) is 0.67 eV, which is followed by the
desorption of H2O* (S8). The desorption process is very
exothermic by 0.78 eV, which could be rationalized by CH*2
being transformed into a much more stable form of quadruple
coordination when inert H2O is produced (refer to Table S4
for its Eads). Thereafter, quadruple coordination is readopted
for CH*2 to accommodate another hydrogen atom which
elevates the system by 0.67 eV. The subsequent association is
with respect to CH2* (S9) and CH3* (S10) both being lower in
activation energy (0.42 eV for CH*2 and 0.23 eV for CH*3 ). For
the last elementary step, the second molecule of H2O* is
produced (S11) and desorbed (S12) with a 0.59 eV reaction
barrier and a 0.12 eV desorption energy after methane
generation.
3.3.1.5. Methane Formation Led by the Dissociative
Mechanism. As shown in Figure S12, the dissociative
mechanism on Ru/RuTiO 2 starts with the H-assisted
association of CH* to generate CH*2 (S5′) with the reaction
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barrier and energy being 0.29 and −0.84 eV, respectively. The
increasing steric effect makes the subsequent H2O* generation
(S6′) and desorption (S7′) very easy. For the next step, CH*2
further accepts a hydrogen atom (S8′) and renders CH*3
binding to Rub. It is found that the reverse reaction of S8′ is
barrierless even though the reaction energy for the forward one
is only endothermic by 0.37 eV. Methane formation is realized
through CH3* hydrogenation (S9′) with a reaction barrier of
1.19 eV and a reaction energy of 0.55 eV. Owing to the higher
barrier and endothermic nature of S9′, it is concluded that the
dissociative mechanism is less favorable.
3.3.2. Reaction Mechanisms for CO2 Methanation on Ru/
TiO2. Next, we directed our attention to Ru/TiO2, from which
all possible mechanisms involved in each elementary step for
CO2 methanation are reviewed carefully and the most
preferred route is proposed.
3.3.2.1. First Elementary Step. The first elementary step for
CO2 activation on Ru/TiO2 could lead to the generation of
[CO + O]*, HCOO*, and COOH*, which are classified as the
aforementioned mechanisms accordingly. To consider the
dissociative mechanism (T1), we referred to the T_CO2_MS*
which is the most stable among all investigated CO 2
chemisorption modes (Figure S9c). A nearly negligible barrier
and large energy gap between the initial and final step suggest
that this pathway is very competitive. A comparative study of
the isolated species between two surface models shows that the
adsorption energy of individual O* is higher on Ru/TiO2 than
the other owing to the weaker Ru−O interaction. This causes a
slight increase in adsorption energy related to the FS (see
Table S4 for details). On the other hand, HCOO* is produced
as a result of the associative mechanism (T1′) with the
activation and reaction energy being 1.37 and 0.05 eV,
respectively. As for the other associative product (T1″),
COOH* is formed with the highest activation energy among
the three. Taken together, both dissociative mechanisms are
prohibited kinetically. We also noticed that, compared with
Ru/RuTiO2, Ru/TiO2 has a higher association barrier but a
lower dissociation barrier. A detailed explanation of this
interesting finding will be provided in Section 3.4. Never-
theless, a dissociative mechanism is more preferred to the
associative one, which is the same as that for Ru/RuTiO2.
3.3.2.2. CHO* Formation. When it comes to the next
elementary step, either O* (T2) or CO* (T2′) could accept
hydrogen. On the one hand, O−H coupling requires slight
shrinkage of their mutual distance in the TS2, which
corresponds to the reaction barrier of 0.67 eV. At the same
time, with the FS being lower in adsorption energy by 0.62 eV,
this pathway turns out to be much more exothermic than that
of Ru/RuTiO2 (S2). However, the higher adsorption energy of
isolated OH* seems to fail to explain this (Table S4). Instead,
we attributed it to the less electronic repulsion between CO*
and OH* owing to their remote distance. On the other hand,
the activation energy for CO* hydrogenation is slightly lower.
However, the thermoneutral nature of the reaction energy
makes it less favorable at low temperatures. Therefore, the
hydrogenation of OH* is more favorable, which is the same as
that for Ru/RuTiO2. In addition, direct CO* bond cleavage
(T2″) is energetically inaccessible, which contradicts the
proposed mechanism on the TiO2−x-encapsulated Ru cluster.33
This finding suggests that the difference in the metal−support
interaction (MSI) has a significant influence on determining
the reaction mechanism for CO2 methanation.
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As a result of facile OH* formation, the hydrogenation
product is reconsidered between CHO* (T3) and H2O*
(T3′). From one aspect, the pathway involving CO*
hydrogenation has a reaction barrier of 0.90 eV. However,
the reaction energy is endothermic by 0.36 eV which promotes
its reverse reaction. On the other hand, the TS for OH*
hydrogenation is calculated to be slightly higher (0.92 eV).
H2O* generation is followed by its desorption (T4″) with a
0.44 eV increase in reaction energy, so it is also feasible under
500 K. Followed by T4″, CO* will continue to associate with
hydrogen like step T3. However, it turns out to be very
unlikely from the aspect of both thermodynamics and kinetics.
Based on the above reasoning, the only possible pathway is T3.
3.3.2.3. Formation of [CH + O]* via the Dissociative
Mechanism. As a turning point, both associative and
dissociative mechanisms are examined to find out which one
is applicable to CHO* on Ru/TiO2. As for the former one
(T4′), the reaction energy is endothermic by 1.14 eV, so
CH2O* formation is prohibited. For this elementary step, TS4′
cannot be located owing to the barrierless reverse reaction. We
also examined the dissociative pathway (T4), in which
preactivation involving isomerization into iso-CHO* is
required, thereby reducing the adsorption energy by 0.48 eV.
Thereafter, dissociation into two separate fragment species
(i.e., CH* and O*) occurs with only a 0.29 eV reaction barrier,
together with a −0.34 eV reaction energy. It is proposed that
unstable CHO* is very active toward direct bond cleavage on
the flat Ru surface.55−58 Thus, dissociation is considered to be
the dominant reaction mechanism for formyl on Ru/TiO2,
which is much different from the other (Ru/RuTiO2).
3.3.2.4. Remaining Elementary Steps Leading to Methane
Formation. For the next elementary step, dissociative products
CH* and O* are compared with each other with respect to H-
coupling. On the one hand, the CH* association (T5) leads to
CH*2 with 0.55 eV corresponding to the reaction barrier of
TS5. On the other hand, the hydrogenation of adsorbed O* is
found to be unlikely because of the steric effect. Upon CH*2
formation, the cluster becomes more crowded, and therefore,
H-coupling is only conducive to OH* (T6). Our results
suggest that it is a thermoneutral process which comes along
with a reaction barrier of 1.09 eV. The subsequent H2O
desorption (T7) is endothermic by 0.40 eV. Further
hydrogenation is related to both CH*2 (T8) and CH*3 (T9),
which are both much lower in barrier (0.31 eV for CH*2 and
0.34 eV for CH3*). For the last two elementary steps, H-
coupling is kinetically much more favorable for OH* (T11, Ea
= 0.91 eV) than O* (T10, Ea = 1.49 eV). The desorption of
the second H2O (T12) is endothermic by 0.19 eV.
3.3.2.5. Methane Formation Led by the Associative
Mechanism. Despite unfavorable CH2O* formation, the H-
assisted associative pathway originating from CHO* is also
considered. As shown in Figure S15, CH2OH* is formed
through the H-assisted association of CH2O* (T5′), and the
calculated reaction barrier is 1.47 eV, which is considerably
higher than S5 for Ru/RuTiO2. Thereafter, C−O bond
cleavage occurs and produces two fragments CH*2 and OH*
(T6′) with TS6′ being only 0.44 eV. The examination of the
FS reveals that triple coordination is very unstable and thereby
drives CH*2 to adopt a bridged configuration between Ruc and
Rud, and this accounts for the substantial decrease in reaction
energy. To move on, first, H2O* is generated from OH*
hydrogenation (T7′) with the reaction barrier TS7′ being 0.73
eV and the reaction energy being 0.33 eV. H2O desorption
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Figure 5. (a,b) Schematic representation of the most preferred pathway of CO2 methanation for Ru/RuTiO2 and Ru/TiO2. (c) Chart of energy
barriers for the RDS of Ru/RuTiO2 (associative and dissociative mechanisms) and Ru/TiO2 (associative and dissociative mechanisms).

Figure 6. (a) Comparisons of the reaction barrier (Ea) and reaction energy (Er) for Ru/RuTiO2 and Ru/TiO2 with respect to the dissociative
mechanism. (b) Charge density differences of CH3* on Ru/RuTiO2 and Ru/TiO2, where the isosurface value is set to 0.0009 e/Å3. The green and
brown isosurfaces denote the charge accumulation and depletion regions, respectively. (c) Comparisons of the reaction barrier (Ea) and reaction
energy (Er) for Ru/RuTiO2 and Ru/TiO2 with respect to the associative mechanism.

(T8′) comes along with a 0.80 eV energy released as a result of
the steric effect. Methane is formed via the subsequent
donation of a hydrogen atom to CH*2 (T9′) and CH*3 (T10′).
The reaction barriers calculated for respective hydrogenation
are 0.13 and 0.70 eV.
3.3.3. Comparison of the Reaction Mechanism between
Ru/RuTiO2 and Ru/TiO2. On the basis of the above analysis,
the reaction mechanism of CO2 methanation for two surface
models is schematically elucidated in Figure 5a,b. For Ru/
RuTiO2, direct C−O cleavage is the dominant pathway in the
first place, which is followed by consecutive hydrogenation of
both O* and CO*. After CHO* formation, H-assisted
association to generate CH2O* is the most preferred pathway,
which is followed by the formation of CH2OH*, CH*2 , CH*3 ,
and methane. CH2O* hydrogenation is determined to be the
rate-determining step (RDS) with an activation barrier of 0.84
eV. Comparatively, the dissociative mechanism is less favorable
with the RDS calculated to be 1.19 eV for S9 [CH3* + H* =
CH4(g)]. For Ru/TiO2, different reaction mechanisms control
the most favorable pathway of CO2 methanation. To be
specific, the dissociative mechanism is also dominant in the
first elementary step, which is followed by the generation and
isomerization of CHO*. From the onset of iso-CHO*, the
dissociative mechanism is more favorable than the associative
one, which generates [CH + O]*. Thereafter, CH* accepts
three hydrogen atoms to produce CH2, CH3*, and methane,
respectively. On the contrary, the associative mechanism is less
favorable because of two consecutive steps being kinetic
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prohibited (T4′ and T5′), even though the energy barriers of
RDS for both reaction mechanisms are very close.
3.3.3.1. Comparison of the Dissociative Mechanism
between Ru/RuTiO2 and Ru/TiO2. Furthermore, the dis-
sociative mechanism starting from CHO* is comparatively
investigated on a stepwise basis between two surfaces, and the
corresponding energy barrier and reaction energy are
presented in Figure 6a. In summary, two factors limit the
dissociative mechanism of Ru/RuTiO2. On the one hand,
compared with Ru/TiO2, CHO* dissociation on Ru/RuTiO2
(S4′-2) is much less preferred. Isolated species analysis shown
in Figure S16 indicates that CH* is too unstable to maintain
the bridged configuration between Rub and Rue as the one
found in the FS of S4′-2 and thereby easily relaxes into a
different configuration. This leads to a considerable increase in
the adsorption energy of the FS [CH + O + OH]*. The kinetic
explanation of the unfavorable TS will be further given in
Section 3.4. On the other hand, the hydrogenation of CH*3 to
generate methane on Ru/RuTiO2 is kinetically and thermo-
dynamically less favorable. For both surfaces, the stabilization
of CH*3 mainly involves interaction between C and Rub.
However, it is noted that one of the hydrogen atoms also
interacts with Rua and contributes to the coordination of CH3*
with Ru/RuTiO2 (see Figure 6b). This could be further
verified by Eads of the isolated CH*3 being more negative
(Table S4). The H−Rua interaction greatly increases the
stability of isolated CH3*, which makes it very retarded toward
further hydrogenation. On the contrary, this phenomenon is
not detected when it comes to Ru/TiO2 because of the uneven
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Table 3. The d-Band Center (ε) of Ru Atoms on Ru/RuTiO2 and Ru/TiO2a
εa εb
Ru/RuTiO2 without OH* −1.76 −1.72
with OH* −1.78
Ru/TiO2 without OH* −1.48 −1.63
with OH* −1.68
a
εa to εf represent the d-band centers of Rua to Ruf, respectively.
cluster surface (Rua−O3c is much shorter than Rub−O3c). As a
result, both the reaction barrier and reaction energy of S9′ are
much higher than T9. Furthermore, we observed a similar
CH3* configuration on Run/RuTiO2 (n = 7 and 8), suggesting
that the unfavorability of the dissociative mechanism is
universal (Figure S16).
Even though the dissociative mechanism has been
determined to be the dominant pathway for Ru/TiO2,
methane formation is greatly limited as a result of T10. Unlike
S10′ for Ru/RuTiO2, the hydrogen atom is forced to move
away from O* and take a bridged configuration between Rub
and Rue in order to avoid the steric effect. Despite a substantial
decrease in energy, the subsequent hydroxyl formation (T10)
initiated from such IS is both kinetically and thermodynami-
cally prohibited. A similar configuration is also observed for
Ru8/TiO2. Hence, it is speculated to be one of the reasons
leading to a lower conversion rate of the Ru/r-TiO2 catalyst.29
3.3.3.2. Comparison of the Associative Mechanism
between Ru/RuTiO2 and Ru/TiO2. The associative mechanism
from the onset of CHO* is also studied for both surfaces. As
shown in Figure 6c, two unfavorable elementary steps are
proposed to account for the inhibition of this pathway on Ru/
TiO2. For the first one, both the barrier and reaction energy of
the H-assisted association of CHO* (T4′) are equally high,
which promotes the reverse reaction. Thermodynamically, we
attributed this to the unstable isolated CH2O* (Table S4). For
the second one, the calculated barrier for CH2O* hydro-
genation (T5′) is as high as 1.47 eV, which further prevents the
associative mechanism from proceeding. A detailed explanation
of the kinetic reason for these two steps will be offered in the
next section.
3.4. Electronic Analysis of the Difference in the
Reaction Mechanisms for CO2 Methanation on Ru/
RuTiO2 and Ru/TiO2. As mentioned already, the reaction
mechanism for CO2 methanation varies greatly from Ru/
RuTiO2 to Ru/TiO2. So far, explanations have been solely
given from the perspective of the intermediates (IS and FS)
and thereby lack insightful understanding concerned with the
TS. In light of this, further proof is required.
It is generally accepted that for an intermediate adsorbed on
a metal support, the d-orbital of the metal support with a
narrow bandwidth is very sensitive during adsorbate−metal
interaction via either accepting or donating electrons, which
results in the splitting of adsorbate resonance into two parts
(i.e., bonding orbital below the Fermi level and antibonding
orbital above the Fermi level). Furthermore, strong interaction
also provides a driving force for the environmentally sensitive
metal d-band to either downshift or upshift as a result of orbital
hybridization. As a parameter to characterize the ability to eject
electrons from the d-orbital of the metal to the antibonding
orbital of the adsorbate, the d-band center proposed by
Nørskov has been utilized to study the relative stability of
adsorbed molecules or atoms.59,60 In addition, they demon-
strated that such a descriptor could be extensively applied to
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εc εd εe εf εavg
−1.51 −1.72 −1.73 −1.48 −1.65
−1.57 −1.98 −1.86 −1.79
−1.35 −1.43 −1.52 −1.50 −1.48
−1.47 −1.41 −1.36 −1.48
study the dissociation or association reactivity of the
intermediate. For instance, closer proximity of the d-band
center (ε) relative to the Fermi level (EFermi) forecasts a better
electron-donating nature of the substrate and thereby weakens
the bonds that are to be activated.61,62 The decomposition
energy barrier therefore decreases. On the contrary, ε, which is
far from the Fermi level is an indicator of inferior ability to
donate electrons and thereby favors bond formation such as
C−H and O−H interactions.63−65 By far, this theory has been
successfully employed to study CO2 dissociation on Al2O3-
supported Ru clusters.66 Conceptually, the d-band center is
expressed as
+
d (E )E dE
= +
d (E) dE
where ρd represents the DOSs projected onto the d-orbital of
individual Ru atoms (Rua to Ruf) from the supported cluster
and E represents energy relative to EFermi. For the transition-
metal Ru consisting of both α and β spins, the overall d-band
center is the average of the d-band center for α and β spins,
respectively.
The calculated d-band centers for Rua to Ruf from both Ru/
RuTiO2 and Ru/TiO2 are summarized in Table 3, along with
the corresponding projected DOS (pDOS) presented in
Figures S17andS18. The average d-band center for the
integrated Ru cluster is defined as εavg = (εa + εb + εc + εd +
εe + εf)/6, wherein εa to εf refers to the d-band center of Rua to
Ruf, respectively. As for Ru/RuTiO2, the d-band centers of Rua,
Rub, Rud, and Rue are akin to each other, indicating that they
are equivalent in the valence state. As for the other two, εc
(−1.51) and εf (−1.48) are relatively closer to the Fermi level,
which is attributed to the low coordination of Ruc and Ruf. As
a result, they slightly upshift the overall d-band center of the
cluster (εavg) to −1.65. On the other hand, the d-band centers
of the TiO2-supported cluster are quite different among Ru
atoms with the lowest and highest one assigned for Rub and
Ruc, respectively. Consequently, the calculated εavg for the Ru
cluster is −1.48, which is much closer to EFermi than that of Ru/
RuTiO2. Considering that the Ru cluster is more positively
charged on Ru/RuTiO2, it is expected to be the main reason
for the downshifted d-band center.
Next, we paid attention to evaluate the influence introduced
by the difference in the d-band center upon CO2 methanation
between two surface models. It is worth noting that the
intermediate is very sensitive toward the reaction site, so
consideration should be given to the average d-band center of
these areas rather than that of the integrated cluster.66 For the
initial elementary step of CO2 activation, it has been
mentioned that the dissociation barrier is higher on Ru/
RuTiO2, whereas the association barrier is higher on Ru/TiO2.
For both surface models, Rua, Rub, Rue, and Ruf are the
reactive sites, and the average d-band centers are −1.68 and
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−1.44 for Ru/RuTiO2 and Ru/TiO2, respectively. As a result,
more kinetic preference to carbonate and formate formation
on Ru/RuTiO2 than to the other is ascribed to the downshift
of the d-band center, which facilitates C−H and O−H bond
formation. Nevertheless, we should keep in mind that
dissociation is still the dominant mechanism for Ru/RuTiO2
because of the reasons already mentioned above.
For both surface models, the fourth elementary step is
considered as the turning point, for which either the associative
(CHO* + H* = CH2O*) or the dissociative pathway (CHO*
= CH* + O*) determines the fate of formyl. Previous results
have already elucidated that the relative stability of the final
product accounts for the difference in the reaction energy and
thereby determines the reaction mechanism. Otherwise, an
electronic explanation should also be given with respect to the
reaction barrier. As listed in Table 3 (see Figures S19 and S20
in the Supporting Information for pDOS), coadsorbed OH*
on Ru/RuTiO2 introduces little change toward εb and εc.
However, an apparent downshift of both εd and εe is detected
which pushes εavg (−1.79) to move away from EFermi. On the
other hand, Ru/TiO2 with the coadsorption of OH* has little
effect on εb and εd, whereas εc and εe either shift to a lower or
higher region, respectively. The average d-band center for
these four atomic Ru (−1.48) remains almost the same as εavg
calculated from the integrated Ru cluster. As a result, the
downshifted d-band center could be put forward to explain the
low barrier of the associative mechanism on Ru/RuTiO2,
whereas the upshifted d-band center could be used to explain
the low barrier of the dissociative mechanism on Ru/TiO2.
Based on these results, it is obvious that the alternation of the
reaction mechanism from the onset of CHO* is not only
influenced by the structural preference of the product but also
driven by electronic factors.
To continue, since OH* adsorption on Ru/RuTiO2 causes a
downshift of the d-band center related to the reactive sites
(Rub, Ruc, Rud, and Rue), its influence on the reaction barrier
of CHO* hydrogenation is also studied. As shown in Figure
S21a, the presence of OH* substantially decreases both the
activation energy and reaction energy of CHO* hydrogenation
compared with those without OH*. On the one hand, OH*
stabilizes CH2O* by releasing the surface tension of the cluster
and thereby decreasing the reaction energy. On the other hand,
the downshifted d-band center resulting from OH* adsorption
activates the formyl species and facilitates C−H bond
formation. In comparison, the reaction mechanism in terms
of direct bond cleavage of CHO* on Ru/TiO2 with or without
OH* is also reviewed. As shown in Figure S21b, the reaction
barriers for the two pathways are close to each other,
suggesting that OH* adsorption has little effect on the
dissociative mechanism kinetically. This is further verified by
the little fluctuation of the d-band center on Ru/TiO2 when
OH* is introduced. Furthermore, the d-band center could also
be exploited to explain the way how CH*3 interacts with H* on
Ru/RuTiO2 (displayed in Figure S22). As with Ruc (εc =
−1.57), CH3* binding to Rud (εd = −1.98) has a much lower
reaction barrier of hydrogenation, which results in facilitated
C−H bond formation.
4. CONCLUSIONS
In order to uncover the influence of the RuO2 overlayer on
Ru/TiO2 with respect to CO2 methanation, the DFT is
employed to comparatively investigate the difference between
Ru/RuTiO2 and Ru/TiO2. According to our results, Ru6 forms
14664
Research Article
as an epitaxial layer along with RuTiO2 and exhibits SMSIs
with TiO2 and therefore could be employed to simulate the
nanoparticles in the experiment. Compared with Ru/TiO2,
more electrons are transferred from RuTiO2 to the Ru cluster,
which complies well with the surface characterization. This
makes individual Ru atoms in the cluster more positively
charged and thereby facilitates CO 2 adsorption. The
minimum-energy pathway analysis reveals that for both surface
models, CO2 undergoes direct C−O bond cleavage rather than
the formate path in the first place, which is consistent with the
FTIR spectroscopy results. Furthermore, we also noticed the
difference in the reaction mechanism from the onset of CHO*
generation, where Ru/RuTiO2 favors further hydrogenation
toward CH2O* (an associative mechanism), whereas Ru/TiO2
favors direct C−O bond cleavage after isomerization (a
dissociative mechanism). The preference of CHO* hydro-
genation for Ru/RuTiO2 is attributed to much more stabilized
CH2O* species, along with the downshift of the d-band center.
On the contrary, CHO* dissociation is favored for Ru/TiO2
which is due to both the thermodynamic advantage of
generating [CH + O]* as well as the uplifted d-band center.
Overall, our calculation results prove that RuO2 plays a very
important role in determining the reaction mechanism of CO2
methanation for the Ru/r-TiO2 catalyst.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acscatal.2c04539.
Computational details of most stable structures of
perfect and defective Run/RuTiO2 and Run/TiO2,
other less unfavorable reaction mechanisms for each
elementary step, and the figures of pDOS (PDF)
■ AUTHOR INFORMATION
Corresponding Authors
Wei Lin − College of Chemistry, Fuzhou University, Fuzhou
350108, China; Fujian Provincial Key Laboratory of
Theoretical and Computational Chemistry, Xiamen
University, Xiamen 361005, China; orcid.org/0000-
0002-5046-4765; Email: wlin@fzu.edu.cn
Xin Lu − State Key Laboratory of Physical Chemistry of Solid
Surfaces, College of Chemistry and Chemical Engineering and
Fujian Provincial Key Laboratory of Theoretical and
Computational Chemistry, Xiamen University, Xiamen
361005, China; orcid.org/0000-0003-4968-9462;
Email: xinlu@xmu.edu.cn
Authors
Jie Yu − State Key Laboratory of Physical Chemistry of Solid
Surfaces, College of Chemistry and Chemical Engineering,
Xiamen University, Xiamen 361005, China
Yabing Zeng − College of Chemistry, Fuzhou University,
Fuzhou 350108, China
Qirou Jin − State Key Laboratory of Physical Chemistry of
Solid Surfaces, College of Chemistry and Chemical
Engineering, Xiamen University, Xiamen 361005, China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acscatal.2c04539
Notes
The authors declare no competing financial interest.
https://doi.org/10.1021/acscatal.2c04539
ACS Catal. 2022, 12, 14654−14666
ACS Catalysis pubs.acs.org/acscatalysis
■ ACKNOWLEDGMENTS
This work was financially supported by the National Natural
Science Foundation of China (92161117 and 21973014).
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