Research Article

Cite This: ACS Catal. 2019, 9, 2355−2367 pubs.acs.org/acscatalysis

The Mechanism of Steam-Ethanol Reforming on Co13/CeO2−x: A DFT

Study
Meng-Ru Li,† Yang-Yang Song,† and Gui-Chang Wang*,†,‡
†
Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education) and the Tianjin key Lab and Molecule-Based
Material Chemistry, College of Chemistry, Nankai University, Tianjin 300071, P. R. China
‡
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan, 030001, P. R. China
*
S Supporting Information
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ABSTRACT: In the present work, density functional theory calculations are

performed to study mechanisms of ethanol steam reforming reactions on the
Downloaded via UNIV OF OKLAHOMA on February 14, 2019 at 23:24:51 (UTC).

Co13/CeO2−x model. The related adsorption situations and reaction cycles

were clarified. Ethanol will convert into CH3CO species through
dehydrogenation steps on the Cox+ site, followed by coupling with hydroxyl
from water dissociation on CeO2−x, yielding acetic acid on the interface. The
acetic acid will spread to the Co0 site to cleave C−C and then convert to
CO2. H2 forms on the Cox+ site. The coke formation is mainly caused by CH
accumulation on the Co0 site and could be released by CH oxidation on the
Cox+ site. The oxidation state of Co on the surface affects the activity of ESR
reactions. A higher oxidized Co site, featured with a lower ensemble size of
Co, facilitates recombination reactions (e.g., H2, acetic acid formation, and
CH oxidation). On the contrary, a more reduced Co site favors dissociation
reactions (e.g., C−C scission). The Cox+ site is the most favorable site for the
dehydrogenation of ethanol into CH3CO. CeO2−x will promote H2O dissociation via oxygen vacancy and lattice oxygen. On the
hydroxylated CeO2−x surface, mobile O on CeO2−x has a higher tendency of oxidizing Co, while mobile OH is mainly
responsible for releasing carbon deposition. In the experiment, keeping a high Co0/Co2+ ratio can gain high proportions of Co0
and Cox+ site, contributing to high ESR activity. Metal−oxide interaction should be strengthened to promote the spread of
mobile OH. Enhancing metal−oxide interface formation is essential for CH3COOH formation. The redox property of CeO2
needs to be increased through doping with other elements, contributing to more oxygen vacancies. Adding O2 could help
release carbon deposition.
KEYWORDS: ethanol steam reform, reaction mechanism, coke formation, Co/CeO2−x, density functional theory calculations

1. INTRODUCTION reaction,16−23 owing to high oxygen storage capacity and

Both rising global energy demands and serious environmental
problems call for the replacement of petroleum-based fuels
with alternative fuels. Hydrogen, the promising environ-
mentally friendly energy source, has attracted much attention.
To date, ethanol steam reforming (ESR) stands out among
numerous hydrogen production technologies (e.g., steam
reforming of methane,1−7 steam reforming of methanol)8−10
because of their high selectivity for H2.11 The strongly
endothermic ESR calls for the efficient catalyst at low
temperature. The non-noble Co-based catalysts could obtain
the low propensity to catalyze carbon deposition and low
selectivity of byproducts.12 The supports (CeO2, ZnO, MgO,
Al2O3, zeolites-Y, TiO2, SiO2, La2O2CO3, CeO2−ZrO2) affect
catalytic activity, selectivity, and carbon deposition signifi-
cantly.13 Acid supports (e.g., Al2O3) strongly facilitate
carbonaceous deposition, caused by the dehydration of
ethanol. On the contrary, the support oxides of basic nature
lead to the condensation of ethanol to higher oxygenates.14,15
The reducible metal oxides of only weakly basic (e.g., CeO2)
turn out to be the most suitable supports for ESR
oxygen mobility.24 Especially, Pang et al.25 observed that Co/
CeO2 catalysts doped with CaO in ESR reaction possess high
H2 yield (90%) under optimized conditions. The high
performance of CeO2 can be rationalized from highly mobile
lattice oxygen, assisting the removal of carbon and water
dissociation.26 Additionally, the oxidation state of cobalt is
affected by the reversibly changing Ce4+/Ce3+, via storing/
releasing oxygen.27 Turczyniak et al.28 have reported the
presence of Co(II) and metallic Co under higher pressure (4−
20 mbar) of ethanol/water on Co/CeO2, gaining higher
selectivity toward CO2 and H2. Notably, Del Rió et al.29
suggested that CoOx phase was required to obtain sufficient
CO2 selectivity. The metallic Co site is proposed to be active
for C−C scission, while the existence of Co2+ site promotes the
selectivity toward CO2.30 Under the ESR condition, the
Received: September 19, 2018
Revised: January 23, 2019
Published: January 28, 2019

© XXXX American Chemical Society 2355 DOI: 10.1021/acscatal.8b03765

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Figure 1. Structures of Co13 (a), CeO2 (b), Co13/CeO2(111) model (side view in c and top view in e), and Co13/CeO2−x(111) with oxygen
vacancy (side view in d and top view in f). Note: the atoms in yellow in (d) refer to the oxygen neighboring to the oxygen vacancy; the atoms in
yellow in (e) refer to the lattice oxygen which will be occupied by oxygen vacancy in (f).

Figure 2. AIMD simulation trajectory for Co13/CeO2−x(111) (a), the calculated reaction Gibbs free energy with different number of oxygen
vacancy under different pressure ratio of pH2O/pH2 (b), the charge of Co cluster in Co13/CeO2−x model (c), and the charge distribution of Co13/
CeO2−x (d). Note: the charge in panels c and d is calculated by Bader charge analysis.59,60

composition of the cobalt phase stays in the dynamic
equilibrium between metallic and oxidized Co phase.18
Theoretically, extensive calculations have focused on ethanol
decomposition/oxidation on metals31,32 and metallic ox-
ides.33−36 The ESR mechanisms on metallic Co site comprise
consecutive dehydrogenation of ethanol, C−C scission, water
dissociation, and water−gas shift sections.37 Accounting for the
activity of Co2+ and Co0 site toward ESR, our previous study
attempted to explore the role of the metallic and oxidized Co
sites, and proposed that controlling cobalt oxidation state is
essential for gaining high selectivity of CO2 and H2.38 In
experiment, supports dominantly determine Co oxidation
2356
state, changing reaction mechanisms.39−41 Mobile oxygen on
a reducible support is supposed to act as oxidant, affecting
redox properties of Co.28 However, DFT calculation of ESR
reactions on Co catalyst supported on a reducible support
(e.g., CeO2) remains lacking. Herein, we develop Co/CeO2
catalyst to explore the ESR mechanism based on the work of
Turczyniak et al.28
2. CALCULATION METHODS AND MODELS
Methods. The Vienna ab initio simulation package
(VASP)42−44 was applied to investigate ethanol steam
reforming reaction on Co catalyst supported on cerium
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Figure 3. Optimized configurations for the main species involved in ESR reactions on Co13/CeO2−x(111) model (units: eV and Å). Note: the
values in parentheses are the adsorption energies of species.
oxide, by the self-consistent periodical DFT calculations with
the projected augmented wave (PAW)45 pseudopotentials. All
the electronic structures were optimized using the Perdew−
Burke−Ernzerhof (PBE)46 form of the generalized gradient
approximation (GGA) expended in a plane wave basis, with
kinetic cutoff energy of 400 eV. The climbing image general
nudged elastic band (CI-NEB)47 method was employed to
locate the transition states (TSs). Spin polarization was
included in the calculations.
Models. The CeO2(111) surface, as the most stable surface
termination,48−50 was represented by the slab model, featured
with p(3 × 3) unit cell of three layers, which has been reported
to be efficient for calculation.51 The slab model was separated
by a 20 Å vacuum with the 1 × 1 × 1 Monkhorst−Pack k-point
mesh. The uppermost two layers were allowed to relax to
optimize the structure. The density functional theory (DFT
+U) method was used to treat the highly localized Ce 4f state.
The GGA+U52,53 method was applied to CeO2 surface with
the set U−J = 5.0 eV.19 The optimized Co13 cluster (See
Figure 1a) was placed onto the CeO2(111) surface (see Figure
1b), obtaining the Co13/CeO2(111) model. Subsequently,
Co13/CeO2(111) was simulated using extensive ab initio
molecular dynamics (AIMD) simulation54 (see Figure 2a).
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The Co13 cluster and the uppermost two layers of CeO2 were
relaxed in the canonical (NVT) ensemble, employing Nose−
Hoover thermostats55 at 675 K for 2000 fs with 1 fs time step,
to meet the experimental condition.28 There is a significant
change of Co13 configuration from its three-dimensional
structure in vacuum (Figure 1a) to a nearly two-dimensional
structure (Figure 2c). Afterward, the resulted Co13/CeO2−x
was optimized by the DFT method to obtain the stable Co13/
CeO2−x configuration.
For oxygen vacancy on CeO2(111) could be formed through
the reduction process: Co13/CeO2 + xH2 → Co13/CeO2−x +
xH2O, the existence of oxygen vacancy should be taken into
consideration. On Co13/CeO2, most lattice oxygen atoms on
the support will interact with the Co13 cluster, with the
remaining four lattice oxygen atoms available for oxygen
vacancy formation. In order to get the thermodynamic stability
of the Co13/CeO2(111) surface with different surface coverage
of oxygen vacancy, the atomistic thermodynamic approach56
was used to calculate the reaction Gibbs free energy of the
reduction process, with the number of oxygen vacancy x
ranging from 1 to 4. The zero reference states of μH2O(T, pΘ)
and μH2(T, pΘ) are set to be the total energies of H2O and H2
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Figure 4. Reaction network for ESR reactions on Co13/CeO2−x(111) model (eV). Note: the values in black are the activation barriers of the
elementary steps, and the values in blue refer to the reaction energies of the elementary steps.

(μH2O(0, pΘ) = EH
total
2O
and μH2(0, pΘ) = Etotal
H2 ), the reaction Gibbs
free energy can be expressed in eq 1:
ΔG = E(Co13/CeO2 − x ) − E(Co13/CeO2 ) − x
*[μ(H 2O) − μ(H 2)]
where E(Co13/CeO2−x) and E(Co13/CeO2) refer to the total
energies of Co13/CeO2−x and Co13/CeO2 slabs separately. The
chemical potentials of H2O and H2 under certain condition
were calculated in eq 2:
μ(T , p) = μ(T , pΘ ) + EZPE + RT ln(p /pΘ )
= EZPE + H(T , pΘ ) − T *S(T , pΘ )
+ RT ln(p /pΘ )
EZPE(H2O) and EZPE(H2) stand for the total energies of H2O
and H2 with ZPE correction. The enthalpy and entropy at the
temperature of T could be obtained from thermodynamic data
table, and the temperature of 675 K was adopted to agree with
the experimental condition.28 The pH2O/pH2 ratio varying from
(1)
0.01 to 1 was tested, aiming to get ΔG value with reaction
going on (see Figure 2b).
As shown in Figure 2b, oxygen vacancy will inhibit oxygen
release under reduction condition, increasing reaction Gibbs
free energy of oxygen release. Oxygen vacancy formation turns
to be more difficult, with more oxygen releasing from support.
Two oxygen vacancies were available with negative value of
reaction Gibbs free energy, with pH2O/pH2 ratio varying from
0.01 to 1. Subsequently, the Co13/CeO2−x(111) with two
(2) oxygen vacancies was optimized, keeping the Co13 cluster and
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Figure 5. Favorable pathway for ESR reaction on Co13/CeO2−x(111) (a) and the spread of oxygen vacancy on support of Co13/CeO2−x model (b)
(unit: eV). Note: the different color regions in panel refer to the different reaction sites (Co0 site, Cox+ site, Co13−CeO2−x interface and CeO2−x
surface) on Co13/CeO2−x(111) model. The values in back and blue refer to the activation barriers and the reaction energies of the corresponding
steps, respectively. The Osub-lattice, Ov‑top, Osub-latticeH, H2Osub-lattice, Ov‑sub in panel b refer to lattice oxygen on subsurface of CeO2−x, oxygen vacancy
on top surface of CeO2−x, hydroxyl formed by H binding to Osub-lattice, H2O formed on subsurface of CeO2−x, and oxygen vacancy on subsurface of
CeO2−x.

the uppermost two layers of CeO2 surface relaxed. The charge
distribution shows that the Co atoms, closer to support, are
oxidized partially, with the charge between 0 and +2 (see
Figure 2c,d), denoted as Cox+ site. The Cox+ site agrees with
the equilibrium state between CoO and metallic Co in situ
ESR conditions reported by Lin et al.,57,58 and is originated
from electron transfer with the support. Hence, the Co13/
CeO2−x(111) can be divided into four parts: Co0 site (top site
of Co13 cluster), Cox+ site (bottom site of Co13 cluster), the
interface between Co13 cluster and support, and support
CeO2−x.We will discuss ESR mechanisms on different sites of
Co13/CeO2−x. The adsorption energy (Eads), activation energy
(Ea), and reaction energy (ΔE) were calculated by the
following three formulas: Eads = EA/M − EA − EM, Ea = ETS
− EIS,, and ΔE = EFS − EIS, respectively. Here, EA, EM, EA/M,
ETS, EIS, and EFS mean the calculated energies of the adsorbate,
substrate, adsorption system, transition state, initial state (IS),
and final state (FS), respectively.
3. RESULTS
3.1. Adsorption of Pertinent Species. For Co13 cluster
and support CeO2−x are main active sites for ESR reactions, we
mainly discuss the adsorption of species on Co0, Cox+ site, and
support CeO2−x. It is observed that the adsorption energies of
most species on Co0 site are higher, in comparison with the
Cox+ site (See Figure 3). This is caused by the high electron
density of metallic Co site, and the observation agrees well
with our previous calculation results.38 Previous experimental
study61 reported that CeO2 surface fails to cleave C−C bond
and is mainly responsible for H2O dissociation. Hence we
mainly discuss the absorption of H2O, OH, and H on support.
For the adsorption of H2O, CeO2−x(111) is the most favorable
site for H2O adsorption, releasing 1.07 eV, and H2O will get
adsorbed over oxygen vacancy. Therefore, oxygen vacancy
plays an essential role in promoting H2O adsorption in the
Co13/CeO2−x(111) model.
3.2. ESR Mechanisms on Co13/CeO2−x(111) Model.
DFT calculations are applied on ESR reactions on different
sites of Co13/CeO2−x(111) model, that is, Co0 site, Cox+ site
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on Co13 cluster, CeO2−x(111) surface and Co13−CeO2−x(111)
interface. The overall ESR reactions are divided into three
sections: water dissociation, ESR reaction, and water−gas shift
reactions. For the metal−oxide interface reported to be active
for recombination reactions,16,39 we emphasize the essential
recombination reactions on the interface. The configurations of
transition states for ESR reactions on Co0 site, Cox+ site, and
support are displayed in Figures S1−S3 in Supporting
Information (SI). In the last section, we will further describe
the surface distribution of CeO2−x.
3.2.1. Water Dissociation Mechanisms. Figure 4 estab-
lished the most favorable route for water dissociation on the
Co13 cluster and support: H2O → OH + H, 2OH → H2O + O.
The rate-limiting step is primary water dissociation.
Apparently, either OH or O is inclined to form on CeO2−x
in the Co13/CeO2−x(111) model, which agrees well with
experimental report that support CeO2 could activate water
dissociation significantly.61 The enhancement of water
dissociation on the support is resulted from the basicity of
lattice oxygen, and the presence of the oxygen vacancy.
Especially, the oxygen vacancy can act as an active site for
water dissociation, in which the resulted OH and O species will
fill the oxygen vacancy to regenerate the catalyst. In this way,
the CeO2−x surface in the Co13/CeO2−x(111) model promotes
water adsorption and dissociation.
3.2.2. ESR Reactions Mechanisms. As illustrated in Figure
4, the barriers of the dehydrogenation steps on Cox+ site in
Co13/CeO2−x(111) model are lower than on Co0 site, in good
agreement with the observation in experiment,62 that is, the
oxygenated Co promoted the dehydrogenation of ethoxide. In
this case, top-sited ethanol on Co13 cluster will undergo
consecutive dehydrogenation steps, yielding CH3CO on Cox+
site in Co13/CeO2−x(111) model. The CH3CHO on Cox+ site
could hardly desorb as side product, owing to its high
desorption energy (0.96 eV). On the other hand, OH, resulted
from water dissociation on support in Co13/CeO2−x(111)
model, will spread to interface, overcoming a barrier of 0.38 eV
(see Figure 5a). Subsequently, the CH3CO couples with the
OH on interface yielding CH3COOH, taking 0.58 eV, which is
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Figure 6. Reaction energy profiles for coke formation on the Co13/CeO2−x(111) model.
lower than that for C−C scission in CH3CO (1.12 eV). The
resulted CH3COOH on the interface will spread to Co0 site,
cleaving C−C, producing trans-COOH, requiring 0.52 eV. The
spread of acetic acid is feasible because of its similar adsorption
energies on Co0 and Cox+ sites in Co13/CeO2−x(111) model.
The trans-COOH can generate CO2 via dehydrogenation step,
taking a barrier of 1.18 eV. The detached H will couple with
each other on Cox+ site, owing to a lower barrier (1.22 eV), in
comparison to that on Co0 site in Co13/CeO2−x(111) model.
3.2.3. Water−Gas Shift Mechanisms. As established in
Figure 4, the barrier for cleaving C−C in CH3CO on the Co0
site in Co13/CeO2−x(111) model is relatively high. Alter-
natively, the CH3CO on Co0 site could spread to Cox+ site,
followed by coupling with OH producing CH3COOH on Cox+
site. Nevertheless, less CO can be generated from C−C
scission on Co0 site, and could hardly get oxidized by OH or
O. Therefore, water-gas shift reactions could hardly take place,
and small amount of CO could also be obtained on Co0 site in
Co13/CeO2−x(111) model, in good agreement with less CO
observed in experiment.28
3.2.4. Surface Distribution on CeO2−x. Water could get
adsorbed over oxygen vacancy on the surface Ov‑top or
subsurface Ov‑sub, followed by primary O−H scission,
producing hydroxyl HOtop‑lattice or HOsub-lattice, and filling the
oxygen vacancy (see Figure 5b). Afterward, the resulted
neighboring OH can undergo disproportion reactions,
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producing water on the surface (H2Otop‑lattice) or subsurface
(H2Osub-lattice). However, the resulted H2O could hardly desorb
from surface or subsurface because of high desorption energy.
The accumulation of H2O will hinder disproportion reactions
producing H2O. In this way, the surface and subsurface get
hydroxylated easily. The hydroxylated CeO2−x surface is also
reported by Xu et al.,63 in which Ce(IV) facilitates OH
formation, resulting in high ESR efficiency. The hydroxyl
HOtop‑lattice or HOsub-lattice on CeO2−x can spread to the Co site,
taking part in acetic acid formation, as well as the release of
carbon deposition. Subsequently, oxygen vacancy will be
produced again through the consumption of hydroxyl.
In conclusion, acetate pathway dominates CO2 formation in
Co13/CeO2−x(111) model: CH3CH2OH → CH3CH2O →
CH3CHO → CH3CO (Cox+ site), the resulted CH3CO will
couple with OH f rom water dissociation on CeO2‑x, yielding
acetic acid: CH3CO → CH3COOH (interface). The resulted
acetic acid will spread to Co0 site, cleaving C−C: CH3COOH
→ CH3+trans-COOH →CH3+H+CO2 (Co0 site). The acetate
pathway was proposed to be prevailing with the existence of
oxidized Co site, producing CO2.64 A strong synergetic effect
was found in the Co13/CeO2−x(111) model: the metallic Co
site is responsible for C−C scission, and the Cox+ site favors
the dehydrogenation of ethanol into CH 3 CO and H 2
formation; The support is the most favorable site for water
dissociation. Meanwhile the interface promotes acetic acid
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Table 1. Activation Barriers for Key ESR Steps on Various Active Sites (Unit: eV)a
reaction steps Co0 Cox+ Co2+ interface CeO2−x
H2O→H+OH 1.16 0.91 0.79 0.27
CH3CO→CH3+CO 1.00 1.12 1.70
CH3CO+OH→ CH3COOH 0.85 0.66 0.08 0.58
CH3COOH→CH3+trans-COOH 0.52 1.06 1.38
2H→H2 1.40 1.22
CH+O→CHO 1.31 0.59 1.15
a
Note: the Co0, Cox+, interface and CeO2−x refer to the reaction sites on Co13/CeO2−x(111) model, and the Co2+ site refer to CoO(100) surface
with the data derived from our previous report38 and the related reaction information is shown in Figure S5 in SI.

Figure 7. Relationship between the barriers for the dissociation reactions and recombination reactions and the charge of Co site (a), the spread of
electron in recombination reactions and dissociation reactions (b), and the barriers for important reactions on different sites of Co13/CeO2−x(111)
model (c). Note: the Co2+ site refer to CoO(100) surface with the data derived from our previous report38 and the related reaction information is
shown in Figure S5 in SI.

formation, which was reported to be essential for ESR reaction
producing CO2.64 We find that the interaction between Co and
CeO2−x is stronger, indicated by higher binding energy of
−8.31 eV, compared with that on Co10/CoO(100) model
(−5.49 eV38). The stronger metal−oxide interaction in Co13/
CeO2−x(111) model leads to the lower barrier of acetic acid
formation (0.58 eV), in comparison to that on Co10/
CoO(100) (0.72 eV38).
3.3. Coke Formation Mechanism on Co13/CeO2−x(111)
Model. It is generally well-known that ethylene, acetone, and
hydrocarbon are the precursors for coke formation.65 For the
hydrocarbon, the most favorable path for C2 species on
metallic Co site is CH3CH2OH → CH3CH2O → CH3CHO
→ CH3CO, and the resulting CH3CO could hardly undergo
the subsequent dehydrogenation step, producing CH2CO, with
a high barrier of 1.46 eV. Instead, CH3CO species will bind to
OH, yielding acetic acid, followed by cleaving C−C to form
CHx species. Hence DFT calculations are applied on the form
of ethylene, acetone and CHx species on Co13/CeO2−x(111)
2361
model. As shown in Figures 4 and 6, the barrier of Cβ-H
scission in CH3CH2OH on Cox+ site is slightly higher than O−
H scission. Furthermore, the O−H scission is exothermic,
whereas the Cβ-H scission turns to be endothermic. As a
result, CH3CH2OH on Cox+ site prefers to cleave O−H rather
than Cβ-H, disfavoring CH2CH2 formation. Apparently, CH
accumulation on Co0 site is the main factor for deactivating
catalyst in Co 13 /CeO 2−x(111) model (see Figure 6).
Accordingly, Wang et al.66 also proposed that CHx on metallic
Co site, from C−C scission of acetic acid, is the precursor of
carbon deposition. We can speculate that CH accumulation
will deactivate metallic Co site, at the absence of the oxidized
Co site. However, in this case, the oxidized Co will release CH
accumulation via the route: CH+O → CHO → CO+H,
requiring mobile O. On the hydroxylated CoO2−x surface,
mobile O is covered with the detached H, producing mobile
OH. The mobile OH will spread to Cox+ site, taking 0.69 eV,
followed by dissociation reaction into O, aiming to oxidize CH.
Therefore, mobile OH, from CeO2−x in Co13/CeO2−x(111)
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Figure 8. Barriers for dehydrogenation steps on Co0 and Cox+ site (a), the barriers of dehydrogenation steps on different Co sites (b), and the
adsorption energies of carbon species on different Co sites (c). Note: We collected the barriers of the dehydrogenation steps on different Co sites
in panel a, and the corresponding information is listed in Table S1 in SI; the Co2+ site refers to CoO(100) surface with the data derived from our
previous report,38 and the related reaction information is shown in Figure S5 in SI.

model, will release carbon deposition on Cox+ site via oxidation
reaction.67
In summary, based on the calculation results above, we
compare the barriers for important reactions on different
oxidized Co sites, support, and metal−oxide interface (see
Table 1). It is observed that the H2O dissociation activity trend
is CeO2−x > Co2+ > Cox+ > Co0. The activity for C−C scission
on different sites follows: Co0 > Cox+ > Co2+. More oxidized
Co site will contribute to lower barriers of recombination
reactions (e.g., acetic acid, H2 formation, and CH oxidation).
H2 formation and CH oxidation take place on either Co0 site
or Cox+ site, following the activity sequence: Cox+ > Co0.
Acetic acid formation contributes to the activity trend: Co2+ >
Cox+ > Co0. Nevertheless, the metal−oxide interface is the
most active site for acetic acid formation in Co13/CeO2−x
model with the absence of Co2+ site. Accordingly, metal−oxide
has been proved to be essential for ESR reaction in
experiment.68
4. DISCUSSION
4.1. Ensemble Size Effect. The ensemble size refers to the
number of metal atoms in ensembles, reflected by the density
of the metal site. Obviously, metallic cobalt site provides larger
ensemble size, compared with the oxidized Co site. As reported
in our previous study,38 dissociation reactions (e.g., C−C
scission) are incline to occur on Co0 site. By comparison,
recombination reactions (e.g., CH3COOH, H2 formation, and
2362
CH oxidation), will proceed on the Co2+ site, with lower
density of Co sites. Herein we will extend the analysis into the
relationship between the selectivity toward dissociation/
recombination reactions and oxidation state of Co. As
established in Figure 7a, the higher the oxidation state of Co
site is, the lower the barrier for dissociation reactions will be,
and contrarily, the higher the barriers for recombination
reactions turn out to be. Experimentally, a previous report also
proposed that more reduced Co site favors C−C scission,
while more oxidized Co site promotes acetic acid formation
and oxidation reactions.30,62,69
Dissociation reactions, relating to bond breaking, favor the
electron spread, from the distribution in the breaking bond, to
the interaction between reactant and surface (see Figure 7b).
Hence strengthening the interaction between reactant and
surface (i.e., adsorption energy of reactant) promotes
dissociation reactions. Less oxidized Co site, featured with
larger ensemble size of Co, favors enhancing the adsorption of
reactant, which will promote bond breaking in dissociation
reactions. In the case of the Co13/CeO2−x model, the metallic
Co site, with higher adsorption energies of adsorbates, owns
lower barriers for dissociation reactions (see Figure 7c).
Recombination reactions, relevant to bond formation, need
more electrons to spread to the distribution in the forming
bond, from the interaction between reactant and surface. More
oxidized Co site, providing less ensemble size of Co, facilitates
the weakening of the interaction between reactant and surface,
and thus favors recombination reactions. In this case, the
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Figure 9. Decomposition of barrier for the oxidation of CH by O (a and b), the charge distribution of transition state for the oxidation of CH on
Cox+ site (c) and interface (d) on Co13/CeO2−x(111) model. Note: ΔECH−O int , ECH−O CH−O
int(TS), Eint(IS) are the changing interaction energy between CH and
O along the reaction from IS to TS, the interaction energies between CH and O in TS and IS, respectively. ΔECadsH, ΔECads(TS) H
, ΔECads(IS)
H
are the
difference of CH adsorption energy in TS and IS, adsorption energies of CH in TS and IS separately; ΔEads, ΔEads(TS), ΔEads(IS) refer to the
O O O

difference of O adsorption energy in TS and IS, the adsorption energies of O in TS and IS; ΔEcatalyst‑O catalyst‑O catalyst‑O
int,ads , Eint,ads(TS), Eint,ads(IS) are the interaction
energy change between deformed catalyst and O from IS to TS, the interaction energies between deformed catalyst and O in TS and IS; ΔΔEdeform catalyst,
catalyst(TS), ΔEcatalyst(IS) are the deforming energy change of catalyst from IS to TS, the deforming energies of catalyst in TS and IS; ΔΔEO
ΔEdeform deform deform
,
ΔEO(TS) , ΔEO(IS) are the deforming energy change of O from IS to TS, the deforming energies of O in TS and IS. The charge in panels c and d is
deform deform

calculated by Bader charge analysis.59,60

interface is featured with less ensemble size, in comparison to
Co site, and is the most active site for acetic acid formation.
In conclusion, the higher the oxidation state of the Co site is,
the less ensemble size the Co site will have, accompanied by
the lower adsorption energy of reactant. Thus, higher activity
of recombination reactions will be gained, and contrarily,
dissociation reactions will have lower activity.
4.2. Dehydrogenation Activity. As illustrated in Figure
8a, compared with the Co0 site, the Cox+ site in Co13/
CeO2−x(111) model has lower barriers of dehydrogenation
steps, and the dehydrogenation reaction is a redox reaction,
associated with the oxidizing ability of surface. Obviously, the
oxidized Cox+ site has a higher ability to accept an electron,
compared with the Co0 site (see Figure 3). Hence, the Cox+
site in the Co13/CeO2−x(111) model is featured with lower
barriers of dehydrogenation steps.
We compared the dehydrogenation steps on Co0, Cox+, and
Co2+ site, and we found that the barriers for the consecutive
dehydrogenation steps to produce acetaldehyde decrease,
along with the oxidation of Co (Figure 8b). Previous study
also reported that the more oxidized cobalt is active to convert
ethoxide groups to acetaldehyde.39−41 However, the subse-
2363
quent dehydrogenation in CH3CHO on Co2+ site carries a
much higher barrier than Co0 and Cox+ site, rationalized from
much lower adsorption energy of CH3CO on the Co2+ site
(Figure 8c). The activity of dehydrogenation step relates to not
only the oxidizing ability of surface but also the adsorption
strength of intermediates. In this case, one can infer that the
dehydrogenation of ethanol into CH3CO is more favored on
partially oxidized Co site, in comparison with the Co0 and
Co2+ site.38−40
4.3. Role of Mobile O. As established in Figure 7b, despite
of the lower ensemble size of Co site on interface, the
oxidation of CH by mobile O occurs on Cox+ site rather than
the interface in Co13/CeO2−x(111) model. Now, we are in a
position to discuss the insight of the activity for CH oxidation
on interface and Cox+ site. We use the energetic method,
developed by Hammer,70 to decompose the barrier of CH
oxidation step. For the recombination reaction A + B → AB,
we divide the barrier into three terms in eq 3:
A B A−B
Ea = ΔEads + ΔEads + ΔEint (3)
where ΔE A(B)
ads stands for the adsorption energy change of A
(B) from IS to TS, ΔE A−Bint refers to the change of the
DOI: 10.1021/acscatal.8b03765
ACS Catal. 2019, 9, 2355−2367
ACS Catalysis
Figure 10. Predicted favorable ESR mechanism on Co catalyst supported on CeO2−x with the proportions of Co0, Cox+, and Co2+ sites. Note: the
different color regions refer to the different reaction sites (Co0 site, Cox+ site, Co2+ site, the interface between Cox+ and Co2+ site and CeO2−x
surface) on Co13/CeO2−x(111) model.
interaction energy between A and B from IS to TS. As
illustrated in Figure 9a, the adsorption energy change of O
from IS to TS on interface (i.e., ΔE Oads) is more positive,
responsible for the higher barrier on interface. Furthermore, we
decompose the adsorption energy change of O from IS to TS
into the deforming energy items and the interaction energy
item between the deformed species shown in eq 4:
O deform catalyst − O
ΔEads = ΔΔEcatalyst + ΔΔEOdeform + ΔEint ,ads (4)
where ΔΔE deform
catalyst and ΔΔE O
deform
stand for the deforming
energy change of catalyst and O, upon the adsorption of O
from IS to TS. ΔE catalyst‑O
int,ads is the change of the interaction
energy between the deformed catalyst and O, upon the
adsorption of O from IS to TS. Therefore, the whole barrier for
the CH oxidation could be divided into five items in eq 5 (see
Figure 9b):
CH
Ea = ΔEads deform
+ ΔΔEcatalyst catalyst − O
+ ΔΔEOdeform + ΔEint
,ads
CH − O
+ ΔEint (5)
where ΔECH ads , ΔΔEcatalyst, ΔΔEO
deform deform
, ΔEcatalyst‑O
int,ads , and ΔEint,ads
CH−O
are the adsorption energy change of CH from IS to TS, the
deforming energy change of catalyst upon O adsorption from
IS to TS, the deforming energy change of O upon O
adsorption from IS to TS, the change of the interaction energy
between the deformed catalyst and O upon O adsorption from
IS to TS, and the change of the interaction energy between CH
and O from IS to TS.
As shown in Figure 9b, for the CH oxidation by mobile O
on interface, the deforming energy change of catalyst upon O
adsorption (i.e., ΔΔEdeform
catalyst) is more positive, leading to the
higher barrier for CH oxidation on interface. The deforming
energy of catalyst for CH oxidation on interface increases more
significantly from IS to TS, in comparison to that on Cox+ site,
indicative of stronger distortion of catalyst for CH oxidation on
interface. The stronger distortion of catalyst for CH oxidation
on interface is supposed to be related to more coordinated O
atoms surrounding Co. As CH oxidation on the interface
proceed from IS to TS, mobile O on interface will bind to Co
site, changing coordination number of Co, altering the
geometry of Co catalyst strongly, reflected by higher ΔΔE
deform
catalyst. Meanwhile, mobile O on interface will get involved into
oxidizing Co site, indicated by the higher charge of Co sites for
transition state of CH oxidation on interface (Figure 9d). It
could be predicted that mobile O on interface in Co13/
2364
Research Article
CeO2−x(111) model is more favorable to oxidize Co site
instead of CH.
4.4. ESR Mechanism on Co Catalyst with Co0, Cox+,
and Co2+. The oxidation of Co site may lead to the
complicated proportions of catalyst, comprising Co0, Cox+,
Co2+ sites, metal−oxide interface, and support. Herein we
extend the analysis of ESR mechanism on the Co catalyst with
the presence of Co0, Cox+, Co2+ site supported on CeO2−x
(Figure 10). The Cox+ site is the favorable site for CH3CO
formation, and CH3CO could hardly spread to Co2+ site,
owing to much lower adsorption energy of CH3CO on Co2+
site. H2O dissociation prefers to take place on the CeO2−x
support, followed by the spread toward the Co2+ site. The Co2+
site will assist H2O dissociation to some degree via oxidative
dehydrogenation step. Hence OH will accumulate on Co2+
site, which agrees well with OH-covered CoO surface reported
by Luo et al.71 The OH on Co2+ site will couples with CH3CO
on interface between Cox+ and Co2+, yielding acetic acid.
Subsequently, acetic acid will spread to Co0 site, cleaving C−C.
H2 will be formed on the Cox+ site.
The calculation of ESR reaction mechanism can help modify
experimental condition, including catalyst, reaction condition,
gaining high selectivity and activity of ESR reaction. ESR
catalyst should contain metallic Co site and oxidized Co site,
favoring acetic acid pathway. Especially, enhancing partly
oxidized and metallic Co proportions will contribute to higher
activity of acetate pathway through high ratio of Co0/
Co2+.69,72−74 Second, reducible support (i.e. CeO2−x) is
supposed to be the proper support for ESR. Third, O2 is
efficient for the release of carbon deposition. Besides,
enhancing metal−oxide interaction helps promote the spread
of O and OH.
5. CONCLUSIONS
The mechanisms of ESR reactions on Co13/CeO2−x model
have been explored by DFT in detail. The conclusions are
summarized:
(1) On the Co13/CeO2−x model, main product CO2 is
produced through acetate pathway: CH3CH2OH→
CH3CH2O → CH3CHO → CH3CO (Cox+ site). OH,
produced from water dissociation on CeO2‑x, spread to
metal-oxide interface, coupling with CH3CO: CH3CO →
CH3COOH (interface), CH3COOH spreads to Co0 site,
cleaving C−C: CH3COOH → CH3+trans-COOH →
CH3+CO2+H (Co0 site). H2 forms on Cox+ site.
DOI: 10.1021/acscatal.8b03765
ACS Catal. 2019, 9, 2355−2367
ACS Catalysis
(2) The acetate pathway requires the involvement of Co0
site, Cox+ site, and reducible support. The Co0 site is
responsible for C−C scission, owing to large ensemble
size of Co site. Cox+ site, with less ensemble size, has
higher activity for recombination reactions (e.g., H2
formation, CH oxidation). Furthermore, Cox+ site
owns higher oxidizing ability, favoring ethanol dehydro-
genation into CH3CO. The CoO2−x support promotes
water dissociation via oxygen vacancy and lattice oxygen.
The interface between Co site and support, with less
ensemble size, enhances acetic acid formation.
(3) The coke formation is mainly caused by CH
accumulation on Co0 site, and could be released by
oxidation reaction on Cox+ site. On the hydroxylated
support surface, mobile OH is mainly responsible for the
release of carbon deposition. Adding O2 can depress
carbon deposition efficiently.
(4) The oxygen vacancy can form on surface or subsurface.
However, the surface could get hydroxylated easily due
to high desorption energy of H2O. On the hydroxylated
surface, mobile OH is mainly responsible for the release
of coke formation. The mobile O on the support has a
higher tendency of oxidizing the Co site.
(5) The oxidation state of Co determines the activity for
ESR reaction. The Co oxidation state, relating to
ensemble size of Co site, affects the activity toward
dissociation/recombination reactions. The activity of
acetic acid formation follows the trend: metal-oxide >
Co2+ > Cox+ > Co0. H2 forms on the Co site, and the
activity is supposed to be Cox+ > Co0. CH prefers to
form on Co0 or Cox+ site and could be released by the
oxidation reaction. The activity sequence for CH
oxidation is supposed to be Cox+ > metal−oxide
interface > Co0. Contrarily, the activity trend for C−C
scission is Co0 > Cox+ > Co2+. The oxidizing ability of
the surface, indicated by electron-accepting ability,
determines the activity of dehydrogenation together
with adsorption strength. The activity for the dehydro-
genation into CH3CO is supposed to be Cox+ > Co0 >
Co2+, while that for water dissociation is CeO2−x > Co2+
> Cox+ > Co0.
(6) During an experiment, measures should be taken to
ensure the acetate pathway through: enhancing Co0/
Co2+ ratio to ensure high proportions of Co0 and Cox+
site, using CeO2−x support with higher oxygen mobility
(redox property), strengthening metal−support inter-
action, and promoting metal−oxide interface formation.
Adding O2 can assist depress carbon deposition.
■
ASSOCIATED CONTENT
*
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acscatal.8b03765.
Calculated TS structures for ESR reactions on Co0,
Cox+, metal-oxide interface and support in Co13/CeO2−x
model; calculated TS structures for coke formation on
Co13/CeO2−x model; calculated TS structures for ESR
reactions on CoO(100) surface; and activation barriers
of dehydrogenation steps on Co0 and Cox+ sites in Co13/
CeO2−x(111) model (PDF)
2365
Research Article
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: wangguichang@nankai.edu.cn. Tel.: +86-22-
23503824 (O). Fax: +86-22-23502458.
ORCID
Gui-Chang Wang: 0000-0001-8137-6007
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the National Natural Science
Foundation of China (Grant Nos. 21773123, 21421001,
91545106), the 111 project (B12015), the foundation of
State Key Laboratory of Coal Conversion (Grant No. J17-18-
908), and the Special Program for Applied Research on Super
Computation of the NSFC-Guangdong Joint Fund (the
second phase) under Grant No. U1501501.
■
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2367 DOI: 10.1021/acscatal.8b03765

ACS Catal. 2019, 9, 2355−2367