Article

pubs.acs.org/JPCC

First-Principles Study of C2 Oxygenates Synthesis Directly from

Syngas over CoCu Bimetallic Catalysts
Xin-Chao Xu, Junjie Su, Pengfei Tian, Donglong Fu, Weiwei Dai, Wei Mao, Wei-Kang Yuan, Jing Xu,
and Yi-Fan Han*
State Key Laboratory of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, Peoples
Republic of China
*
S Supporting Information

ABSTRACT: Density functional theory (DFT) calculations

were used to study C2 oxygenate from syngas over bimetallic
Co/Cu catalysts. The thermodynamics and kinetics for all
possible elementary steps involved in the formation of C2
oxygenate from syngas have been investigated on both pure
and Cu-doped Co(0001) surfaces. By comparing the results on
two surfaces, the role of copper in improving the selectivity
toward C2 oxygenates has been identied as two aspects: (1)
controlling the Co ensemble size and blocking the active sites
for CO bond cleavage, which results in inhibition of CHx
coupling to hydrocarbons; (2) providing undissociated CO/
HCO as well as reducing the barriers for HCO insertion
toward the formation of oxygenate precursors. With the combination of the mechanistic study and the charge analysis on the
bimetallic surface, we conclude that the nature of the copper promotion is mainly a geometric eect rather than an electronic
eect.

1. INTRODUCTION costs, an appropriate way is to combine two or more types of

For the purpose of relieving the concerns about global climate
change and shortage of fossil fuel resources, there is an ever
increasing demand for seeking more environmentally friendly
and ecient ways to utilize the traditional fossil fuels.1,2 One
promising route is the conversion of fossil fuels, such as coal,
biomass or natural/shale gas, to syngas (a mixture of CO and
H2), which can then be catalyzed to value-added C2 oxygenates,
including ethanol, acetaldehyde, and acetic acid.3,4
The study on this process has been carried out ever since
Fischer and Tropsch discovered the coal-to-liquid process in
1910s.5 The catalysts for C2 oxygenate synthesis can be roughly
divided into four categories:69 (1) Rh-based catalysts.
Supported Rh shows high selectivity to C2 oxygenates under
mild conditions, but the low productivity or conversion of CO
(ca. 5.0%), along with the high price of Rh, prevents those
catalysts from further practical applications. (2) Modied
methanol synthesis catalysts (Cu-based). Cu-based catalysts
generally yield branched alcohols by the so-called isobutanol
synthesis, only with a poor selectivity. (3) Modied Fischer
Tropsch (F-T) type catalysts (essentially Fe- or Co-based).
Those catalysts have been reported to yield mainly straight
chain alcohols and hydrocarbons. (4) Mo-based catalysts.
Modied Mo-based catalysts give rise to a good selectivity and
productivity as well as an inherent sulfur resistance. Never-
theless, the harsh demands for reactors and reaction conditions
have limited the application of this process. Thus, to achieve a
better compromise between the catalytic performance and the
these catalysts and create new catalytic systems. Several
catalysts have been proposed according to this strategy,
including bimetallic CoCu,1014 RhCu,15,16 and FeCu7,17
catalysts. Among them, CoCu based catalysts have attracted
the most attention due to their high selectivity and low cost.
The CoCu catalysts for oxygenate synthesis were rst
developed and patented in Institut Francais du Petrole (IFP) in
the 1970s.18,19 It was reported that the selectivity toward
oxygenates, mainly saturated straight-chain terminal alcohols,
could reach as high as 9095% over promoted catalysts. Since
then, many researchers have devoted to elucidating the origin
of active sites and the mechanism of the oxygenate synthesis
process over CoCu catalysts.10,2030 Two viewpoints have
been used to explain the nature of the active sites in CoCu
catalysts for oxygenate synthesis: (1) The formation of
oxygenates may proceed via a dual-site mechanism. In this
mechanism, the carbonaceous chain would be formed on large
cobalt ensembles, and the terminal OH group is provided by a
CO species adsorbed on alloy-modied copper atoms; (2) the
production of oxygenates is attributed to a synergy between
metallic copper and partially reduced cobalt species, in which
the Cu mainly promotes the reduction of Co species and acts as
a diluter to control the surface Co ensemble size.
Received: June 30, 2014
Revised: December 2, 2014
Published: December 6, 2014

2014 American Chemical Society 216 dx.doi.org/10.1021/jp5065159 | J. Phys. Chem. C 2015, 119, 216227
The Journal of Physical Chemistry C
Figure 1. Top view (a) and side view (b) of Cu6Co3 surface and possible adsorption sites on Cu6Co3. According to the number of Co and geometric
conguration, the adsorption sites are denoted as (1) Co3hol, (2) Co2hol, (3) Co1hcp, (4) Co1fcc, (5) Co2brg, (6) Co1brg, and (7) Cotop.
Mo et al.29 revealed the interactions of the dierent
components from Co/CuZnO catalysts using steady state
isotopic transient kinetic analysis (SSITKA) for CO hydro-
genation. The activity for Co/CuZnO catalysts found to be
signicantly decreased compared to a Co/Al2O3 catalyst;
however, the selectivity to oxygenates was enhanced owing to
blocking a signicant portion of active sites for hydrocarbon
synthesis. Xiang et al.12 developed a highly selective CuCo
catalyst that possesses a Co-rich core structure and a Cu-
dominated mixed shell, and the selectivity to long chain
alcohols has been found superior to traditional CuCo
catalysts. This study indicates that the CoCu interaction,
especially in the near-surface region in which a Cu-rich surface
conguration is predominant, can play an important role in
promoting the production of alcohols. Moreover, combining
theoretical calculations and experimental study, Prieto et al.31
identied a CuCo alloy phase with Co-rich compositions as the
ideal catalyst surface for long-chain alcohols.
Density functional theory (DFT) calculations have demon-
strated to be a powerful tool for elucidating kinetic
behaviors32,33 and gaining insight into the reaction mechanism.
Actually, the DFT method has been applied to investigate the
F-T synthesis and oxygenate formation process over Co-based
catalysts.3438 It has been suggested that the oxygenate
synthesis process is initiated by CO dissociation through a H-
assisted mechanism, in which CO is rst hydrogenated to
produce CHxO species, followed by a CO bond cleavage,
resulting in the formation of CHx species. As for the chain
growth toward higher oxygenates, a CO insertion model is the
most preferred, but more recent studies also propose that a
HCO insertion model may be an alternative mechanism.
To the best of our knowledge, the theoretical study of the
detailed reaction mechanism for this reaction system has been
rarely reported. In order to elucidate the eect of Cu on Cu
Co catalysts, elementary steps involved in C2 oxygenate
formation from syngas on both pure and Cu-doped
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Co(0001) surfaces were investigated rst. Then, based on the
results on the two surfaces, the role of Cu for C2 oxygenate
synthesis is discussed. We expect this study will greatly improve
the understanding of this reaction and the subsequent design of
high-performance catalysts.
2. COMPUTATIONAL METHODS
2.1. Surface Model. To simulate the structures of
bimetallic catalysts, two kinds of models were widely adopted.
The rst one is the bulk alloy or solid solution model, in which
the two components are intimately mixed by forming a single
solid phase microstructure. It has been successfully applied to
the study of NOx decomposition over RhAg bimetallic
catalysts.39 The second one is the near surface alloy (NSA)
model, which has been widely used for investigating Pt-based
oxygen reduction electro-catalysts.40 In this model, the
formation of alloy structure is expected to occur only at the
near surface region, while the bulk region remains a pure phase.
In general, the choice of the model for bimetallic catalysts is
determined by how intimately the two components interact
with each other.
For CoCu catalysts, it is well established that the bulk
CuCo alloy does not exist due to the low solubility of one metal
into the other.41 However, a simple mechanical mixing of two
metals did not change the cobalts selectivity.42 Actually, it has
been reported that alloying phenomena may exist at the
nanoscale.43 Hence, the NSA model may serve as a feasible
choice. Furthermore, since Cu has a larger tendency to
segregate to the surface compared to Co,44 a Cu-rich surface
conguration45 is observed when exposing to syngas atmos-
pheres. Additionally, Co atoms may either homogeneously
distribute or aggregate to form local ensembles on a Cu-rich
CuCo surface. To further identify the surface structure of a
CuCo catalyst, we perform calculations with dierent Co
arrangements and reveal that Co atoms prefer to aggregate
rather than homogeneously distribute on the Cu6Co3 surface in
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thermodynamics (Supporting Information (SI), Figure S1). 3. RESULTS AND DISCUSSION

Thus, in our model, 2/3 of surface atoms in Co(0001) were 3.1. Reaction Intermediates. The preferred adsorption
substituted by Cu atoms, it results in a surface conguration of sites and BEs of reaction intermediates involved in various
a triangular Co ensemble surrounded by 6 Cu atoms, Cu6Co3 reaction routes on Co9 and Cu6Co3 (Table 1). The most
(Figure 1). The model can provide the representative
adsorption sites for reaction intermediates, including Co sites Table 1. Preferred Adsorption Sites, and Corresponding BEs
(Co3hol, Co2brg, and Co1top), bimetallic sites (Co2hol, Co1hcp, of Surface Intermediate Species on Cu6Co3 and Co9a
Co1fcc, and Co1brg) and Cu sites. The nomenclature is dened
based on the number of Co involved in and the detailed Co9 Cu6Co3
adsorption sites (Figure 1). Here, we only considered a close- species Eb/eV sites Eb/eV sites
packed surface without step-edge sites for the following C 6.91 C-hcp 6.89 CCo3hol
reasons: (1) As indicated by previous experimental work,68 O 5.90 O-hcp 5.73 OCo3hol
Co terraces are the kinetically relevant sites for particles larger H 2.84 H-fcc 2.65 HCo3hol
than 10 nm; (2) CO insertion, the most widely adopted chain H2 3.50 H-brg 3.36 HCo2brg
growth mechanism toward C2 oxygenates, seems to be CO 1.81 C-hcp 1.79 CCotop
structure insensitive.34 CH 6.43 C-hcp 6.23 CCo3hol
2.2. Calculation Method. Periodic plane-wave spin- CH2 4.04 C-hcp 3.81 CCo3hol
polarized DFT calculations were carried out by using the CH3 2.01 C-hcp 1.78 CCo3hol
Vienna Ab-initio Software Package (VASP)46,47 with a plane- HCO 2.26 C-brg, O-brg 2.13 CCotop, OCotop
wave energy cuto of 400 eV. The interactions between valence COH 4.39 C-hcp 4.19 CCo3hol
and core electrons were described by a projector augmented CH2O 0.79 C-brg, O-top 0.79 CCo2brg, OCotop
wave (PAW) method,48,49 and the generalized gradient CHOH 3.02 C-hcp 2.90 CCo3hol
approximation (GGA) with the PerdewBurkeErnzerhof CH3O 2.88 O-hcp 2.62 OCo3hol
(PBE) functional50 was used in the calculations. Co lattice CH2OH 1.62 C-brg, O-top 1.59 CCo2brg, OCotop
was treated as an hcp structure, and the calculated lattice CH3OH 0.28 O-top 0.31 OCotop
constant is 2.49 , agreeing well with the experimental value of CHCO 3.46 C-hcp, C-fcc 3.15 C-Co3hol, C-Co2hol
2.51 .51 CH2CO 1.14 C-hcp, C-top 1.10 C-Co3hol, C-Cotop
For the pure Co catalyst, a three-layer Co(0001)-(3 3) slab CH3CO 1.63 C-top 1.65 C-Cotop
(denoted as Co9) with a vacuum region of 10 between slabs CHCHO 4.39 C-brg, O-top 4.08 C-Co2hol, OCotop
was employed to simulate the surface. The top two layers and CH2CHO 2.01 C-top, O-top 1.99 C-Cotop, OCotop
the adsorbates were allowed to relax until the energy dierence CH3CHO 0.33 O-top 0.32 OCotop
between two consecutive steps was less than 1.0 104 eV, CH4 / / / /
while the bottom layer was constrained at the bulk positions. A C2H4 0.25 (C, C)-top 0.28 (C, C)-Cotop
4 4 1 MonkhorstPack k-point mesh52 was used to sample a
For adsorbates containing two carbon atoms, the C atom in CHx (x =
the Brillouin zone. For isolated molecules and atoms, 13) is represented as C, while C is used to represent the carbon
calculations were carried out in a 15 15 15 unit atom from CO/HCO.
cell with a k-point setting of -point only. The calculation
parameters for a Cu6Co3 surface are the same as that for Co9.
With these settings, binding energies (BEs) were found to be favorable adsorption structures of reaction intermediates are
converged within 0.05 eV with respect to slab thickness, given in the SI. From these results, most of the intermediates
interslab spacing, and k-point sampling. The BEs of adsorbates have similar adsorption congurations on both Co9 and
on both surfaces, Eb, were calculated as eq 1: Cu6Co3 surfaces. In the proceeding section, the adsorption
E b = Eadsorbate/substrate (Eadsorbate + Esubstrate) (1)
geometry and thermochemistry of all intermediates on Co9 will
be described in detail. For the sake of brevity, the adsorption
where Eadsorbate/substrate, Eadsorbate, and Esubstrate are the total details on Cu6Co3 will not be deliberately presented, but a
energies of the combined adsorbate/substrate system, adsor- comparison between the two surfaces will be made.
bate species in gas phase and the clean surfaces. Hence, a 3.1.1. Adsorption Geometry and Thermochemistry on Co9.
negative (positive) value indicates an exothermic (endother- 3.1.1.1. C, O, H, H2, CO, CHx (x = 13), CH4, C2H4. C, O, H,
mic) adsorption, respectively. Transition states were located by and H2 species prefer to bind at 3-fold hollow sites on Co9,
combining the nudged elastic band (NEB)53,54 and Dimer corresponding to BEs of 6.91, 5.90, 2.84, and 3.50 eV,
methods.55 A linear interpolation between reactant and product respectively. It should be noted that the H2 species can only
states was used to generate the initial path (at least ve images) molecularly bind at the hollow site, while it can easily dissociate
for all NEB calculations. The highest energy structure along the on other sites of the surface. CO also binds at the 3-fold hollow
converged NEB path was then used as the initial guess for the site with a BE of 1.81 eV, via a CoC bond of 1.97 . CH,
transition-state structure, which was optimized by the Dimer CH2, and CH3 species are in favor of binding at 3-fold hollow
method along the potential energy surface to a saddle point. sites as well, with BEs of 6.43, 4.04, and 2.01 eV,
The Dimer separation was set at 0.01 , and the force on each respectively. These results agree well with previous DFT
atom was less than 0.05 eV/. The identied saddle points calculations on a Co(0001) surface.5658 Not surprisingly, CH4
were further conrmed by a vibrational frequency calculation, is very weakly bound (0.01 eV) on Co(0001) in a
in which only one imaginary frequency was obtained at the physisorption way, which is consistent with previous theoretical
saddle point. The activation barrier (Ea) was dened as the total calculations.57,59 The adsorption of C2H4 is also moderate, only
energy dierence between the transition state (TS) and initial with a BE of 0.25 eV, through a conguration with both C
state (IS). atoms bound at the top sites.
218 dx.doi.org/10.1021/jp5065159 | J. Phys. Chem. C 2015, 119, 216227
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Figure 2. Formation of insertable monomers (CHx species) from hydrogenation and dissociation of CO on the Cu6Co3 surface (small gray, C; small
red, O; small white, H). The activation barriers (left) and reaction energies (right) of the elementary steps are all shown in eV. The corresponding
TS structures are shown in Figure 3.
3.1.1.2. CHxO (x = 13), CHxOH (x = 03). In general, all of
CHxO (x = 13) and CHxOH (x = 03) species, except
CH3OH, which is adsorbed at the top sites, prefer to bind at 3-
fold hollow site. Among CHxO (x = 13) species, CHO and
CH2O prefer to bind via both C (bridge) and O (bridge/top)
atoms with a BE of 2.26 and 0.79 eV, respectively, while
CH3O tends to bind only via O atom with CO bond
perpendicular to the surface, and the calculated BE is 2.88 eV.
The adsorption geometry of COH is quite similar to CO,
namely, perpendicularly binding via its C atom, and the
calculated BE is 4.39 eV. The other three CHxOH species (x
= 13) have quite dierent adsorption geometries and BEs.
CHOH and CH3OH tend to bind only via one atom (C for the
former, while O for the latter) to the surface, whereas CH2OH
is in favor of binding via both C (bridge) and O (top) atoms.
The calculated BEs for CHOH, CH2OH, and CH3OH are
3.02, 1.62, and 0.28 eV, respectively. Cheng et al. have
investigated the formation of oxygenates on Co(0001) using
DFT calculation34 and reported data are in good agreement
with our results except for the BE of CHOH species, which has
a dierence of 0.80 eV. The discrepancy may arise from the
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dierent pseudopotentials chosen (Chengs: norm-conserving;
this work: PAW).
3.1.1.3. CHxCO (x = 13), CHxCHO (x = 13). CHxCO and
CHxCHO species (x = 13) are the key precursors for the
formation of C2 oxygenates. Both the adsorption geometries
and BEs vary with an increase in x. CHCO and CH2CO species
tend to bind via both C and C at the 3-fold hollow site, with
BEs of 3.46 and 1.14 eV, respectively. Nevertheless,
CH3CO only binds via the O atom at the top site with a BE
of 1.63 eV. The adsorption congurations of CHxCHO
species follow a similar trend. CHCHO and CH2CHO bind via
two atoms, C and O, to the surface at the hollow sites, while
only the O atom at the top site is involved in the binding of
CH3CHO to the surface. The adsorption of CHxCHO species
is weakened with the increasing of x from 1 to 3, and the
corresponding BEs are 4.39, 2.01, and 0.33 eV,
respectively. These results agree well with the previous data
of Cheng et al.34 and Zhuo et al.56
3.1.2. Comparison of the Results on Cu9 and Cu6Co3. After
summarizing the results of adsorption geometries and BEs of
various intermediates on Co9, we make a comparison for these
intermediates between Co9 and Cu6Co3. On Cu6Co3, all the
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species tend to bind at the Co sites rather than the Cu sites. In
general, most of the species are adsorbed with the same
adsorption geometries on both surfaces, except for CO and
HCO. CO prefers to bind at the Cotop site on Cu6Co3, instead
of the 3-fold hollow site on Co9, but interestingly, there is
almost no change in BE (1.81 eV vs 1.79 eV). Similarly,
HCO also undergoes a migration from the hollow site to the
bridge site when the surface switches from Co9 to Cu6Co3. On
the latter, HCO prefers to bind via its C (top) and O (top) at
two Co atoms with a BE of 2.13 eV, decreased by 0.13 eV
compared to that on Co.
The rest of the intermediate species shows the same
adsorption geometries on both surfaces. Nevertheless, their
BEs are dierent depending on the number of Co atoms
involved in the adsorption. One group of intermediates prefer
to bind at the 3-fold hollow sites with three surface Co atoms,
and their BEs vary in the range of 0.100.35 eV between two
surfaces. The other group of intermediates prefer to bind at the
top sites merely with one Co atom, and their BEs are nearly
unchanged on two surfaces. This contrary trend in the variation
of BEs could attribute to the following aspects: (i) the CoCo
distance is changed from 2.489 on Co9 to 2.433 on
Cu6Co3; (ii) according to the Bader charge analysis on Cu6Co3,
the average charge transfer between neighboring Co and Cu
atoms is only 0.05 e, in other words, there is no signicant
charge transfer between two components; (iii) the total
magnetic moments decreased upon Cu addition, which may
contribute to the weakening of adsorption. For the rst aspect,
it is obvious that the change in CoCo distance can directly
aect the binding of those surface species at the hollow sites, as
their adsorptions are merely dependent on the Co3 ensemble.
Thus, the energy dierence may arise from the contraction of
the ensemble. The second aspect indicates that there is nearly
no modication in the electronic structure of the individual Co
atom upon the addition of Cu, which leads to similar BEs on
two surfaces. The dierences in the adsorption on two surfaces
will denitely take eect on the reaction energetics and reaction
pathways, which will be presented in the following section.
3.2. Reaction Pathways on Cu6Co3. In this part, we
investigated the thermodynamics and kinetics for the plausible
elementary steps involving the formation of C2 oxygenate from
syngas on both pure (Co9) and Cu-modied Co(0001)
(Cu6Co3) surfaces. All the calculations were performed in the
low coverage condition (1/9 ML), and NEB calculations were
performed for all initial and nal states within 0.2 eV of the
most stable coadsorbed conguration within a unit cell. Most of
the coadsorption congurations are in favor of locating around
the Co3 ensemble with one stabilized therein while the other is
in neighboring bimetallic sites. The eects of the pure Co sites,
Cu-modied Co sites (namely bimetallic sites), and pure Cu
sites on the reactions as well as the formation of key reaction
intermediates will be presented and discussed in more detail.
3.2.1. C2 Oxygenates Formation. 3.2.1.1. CO Hydro-
genation and Dissociation (R1R11). Up to now, the CO/
HCO insertion mechanism has been widely used for elucidating
C2 oxygenate synthesis on Co-based catalysts. In this
mechanism, CO is assumed to be rst activated to produce a
chain initiator or insertable monomer, CHx species, then
followed by the insertion of CO/HCO species to form the
precursors for C2 oxygenates.
Formation of Insertable Monomers. According to the proposed
reaction mechanism, the key issue is to elucidate how CO is
activated to form the CHx species. In general, there are two
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possible pathways: (i) CO dissociation followed by hydro-
genation (carbide mechanism), and (ii) CO hydrogenation
followed by CO bond cleavage (H-assisted CO dissociation
mechanism). We carried out calculations for CHx formation
(R1R11) based on the above mechanisms (Figure 2) and the
geometries of TS (Figure 3). The potential energy diagram for
these reactions is displayed in Figure 4.
Figure 3. Top view of geometries of TSs involved in the formation of
CHx species on the Cu6Co3 surface (small gray, C; small red, O; small
white, H).
The barrier of the CO dissociation (R1) on Cu6Co3 found as
high as 2.45 eV, being comparable with our result (2.55 eV on
Co9) and the reported data56,60 on pure Co surfaces. This
suggests that the direct CO dissociation or carbide mechanism
is unlikely to occur on Cu6Co3. As for the H-assisted
mechanism, it is reported that the activation barrier for CO
bond cleavage is remarkably reduced after CO hydro-
genated.6163 Two hydrogenation pathways, hydrogenation of
CO to form formyl (HCO) and formyl-isomer (COH) were
considered. For HCO formation, starting from the most stable
coadsorbed conguration, CO at the Co3hol site and H at a
neighboring Co1hol site, the activation barrier of 1.35 eV (R2)
was obtained. However, the activation barrier was reduced to
1.01 eV at the Cu site. These results suggest that HCO
formation at the Cu sites is the energetically favorable pathway
from CO hydrogenation. The activation barrier and transition
state structure for HCO formation is in good agreement with
reported results in the range of 1.311.50 eV.34,56,63
The preferred CO hydrogenation product, HCO, can either
directly dissociate into methylidyne (CH) and O (R4) or be
hydrogenated to form formaldehyde (CH2O) (R5) or
hydroxymethylene (CHOH) (R6). As listed in Table 2, the
CO bond cleavage in HCO (0.98 eV) is facilitated
signicantly compared to that in CO (2.45 eV). The activation
barrier and transition state structure are both in good
agreement with reported results in the range of 0.901.00
eV.34,56,63 The facilitation can be explained by the fact that
HCO binds to the surface via both C and O atoms, and the C
O bond is largely elongated (1.289 in HCO vs 1.196 in
CO) which is an indicative of weakened CO binding.
Nevertheless, HCO dissociation is still less favorable than HCO
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Figure 4. Potential energy diagram for the formation of CHx species on the Cu6Co3 surface. The corresponding TS structures are shown in Figure 3.
hydrogenation, and the hydrogenation barriers for the
formation of CH2O and CHOH are 0.65 and 0.83 eV,
respectively. Thus, the preferred products from HCO should be
CH2O, which can further undergo two processes: dissociation
into CH2 and O (R7), or hydrogenation to form methoxy
(CH3O) (R8) or hydroxymethyl (CH2OH) (R9).
The calculation results show that CH2O dissociates
exothermically (0.07 eV) with a barrier of 1.05 eV, which is
slightly higher than the barrier for HCO dissociation. As for the
hydrogenation products, CH3O and CH2OH, they possess
formation barriers of 0.58 and 0.68 eV, respectively. Again,
dissociation is not preferred compared with hydrogenation. As
a result, CH3O is more likely to be the preferred intermediate
produced from the subsequent transformation of CH2O.
CH3O is very stable on the surface (Eb = 2.62 eV) and
binds to the surface via its O atom. The barriers for CH3O
dissociation and methanol (CH3OH) formation are 1.60 and
1.48 eV (Table 2), respectively. Consequently, both dissocia-
tion (R10) and hydrogenation (R11) of CH3O is dicult to
occur on Cu6Co3. Accordingly, CH3 species is unlikely to be
formed via CH3O dissociation.
On the basis of the above-mentioned results, we can
summarize that the most favorable path for CO hydrogenation
is CO HCO CH2O CH3O. After CO hydrogenation,
the dissociation of HCO and CH2O to produce CH and CH2
become competitive to the corresponding hydrogenation step,
while the dissociation of CH3O to CH3 is unfavorable. Thus,
two insertable monomers, CH and CH2, could be formed via
the H-assisted CO dissociation mechanism. In addition,
considering that the surface is covered by certain amounts of
hydrogen under the reaction conditions, the formation channel
of CHx upon hydrogenation should be involved. From R21
R22 in Table 2, CH2 and CH3 can be easily formed via CH and
CH2 hydrogenation with barriers of 0.40 and 0.43 eV,
respectively. Thereby, CH2 hydrogenation could act as an
alternative route for CH3 formation. In summary, CH comes
from HCO dissociation, whereas CH2 and CH3 come from
hydrogenation. Chain growth starts immediately once the
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monomers formed, and this process will be presented in the
following part.
3.2.1.2. CO/HCO Insertion into CHx (x = 13) species
(R12R17). As inspired by the homogeneous catalysis,64 the
insertion of the unsaturated carbonyl-containing species into a
carbonmetal bond of a CHx species has been widely adopted
as the chain growth step on Co. Hence, we followed this
propagation mechanism for C2 oxygenate formation on
Cu6Co3, in which both CO and HCO were considered as the
unsaturated carbonyl-containing species for insertion.
Dif f usion of CHx (x = 13) and HCO. Given that there are
three types of sites (Co sites, CoCu bimetallic sites, and Cu
sites) on the Cu6Co3 surface, the reaction intermediates may
thus undergo diusion among these sites, which can aect the
location of active centers for chain propagation processes. To
expound on the eects of diusion on the bimetallic CoCu
surface, we have calculated the diusion barriers of the key
reaction monomers involving this process including CHx (x =
13) and HCO species, and the diusion barriers are
summarized in Table 3. CHx species are more likely to be
formed at the Co sites. Their diusion from initial Co sites to
Cu sites are all endothermic with overall barriers in the range of
0.681.39 eV (Table 3). We deduce that the CHx species
produced is conned at the Co sites, where subsequent
reactions with neighboring reactive species may occur. On the
other hand, the key carbonyl-containing species, HCO, is
produced at the Cu sites during the reaction. HCO can
undergo a barrierless diusion process to Co sites or bimetallic
sites. The facile diusion of HCO species from Cu sites to Co
sites would increase the concentrations of these species at the
bimetallic sites. In the next section, the CO/HCO insertion
into the CHx species at the bimetallic sites was investigated and
summarized in Figure 5, and the corresponding TS structures
(ts1217) are illustrated in Figure 6.
CO Insertion (R12R14). We rst calculated the coad-
sorption of CHx (x=13) and CO species on Cu6Co3. As
indicated in Table 2, the most stable coadsorption cong-
urations for R12R14 are very similar, in which CHx tend to
dx.doi.org/10.1021/jp5065159 | J. Phys. Chem. C 2015, 119, 216227
The Journal of Physical Chemistry C Article

Table 2. Activation Barriers (Ea), Reaction Energies (H) Table 3. Diusion path and Barriers of CHx and HCO on
from DFT Calculations for Elementary Reaction Steps on Cu6Co3 Surface
Co9 and Cu6Co3
species diusion path overall barrier
EaCo9/ HCo9/ EaCu6Co3/ HCu6Co3/ CH 0.28eV 0.51eV 0.73eV 1.39 eV (Co3hol
no. reaction (eV) (eV) (eV) (eV) Co3hol Co2hol Co1hol Cu 3hol Cu3hol)

0.04eV 0.09eV 0.04eV
R1 CO*+*C*+O* 2.55 1.00 2.45 1.34
CH2 0.23eV 0.44eV 0.50eV 0.89 eV (Co3hol
R2 CO*+H* 1.42 1.14 1.35 1.00 Co3hol Co2hol Co1hol Cu 3hol Cu3hol)

HCO*+* 0.13eV 0.15eV 0.09eV
1.01 (Cu 0.85 (Cu CH3 0.30eV 0.31eV 0.56eV 0.69 eV (Co3hol
site) site) Co3hol Co2hol Co1hol Cu 3hol Cu3hol)

R3 CO*+H* 1.97 0.84 1.91 0.88 0.21eV 0.28eV 0.12eV
COH*+* HCO 0.19eV 0.67eV 0 0.86 eV (Co2brg
R4 HCO*+* 0.83 0.56 0.98 0.21 Co2brg Co1brg Cu 2brg Cu 3hol Cu3hol)

CH*+O* 0 0 0

R5 HCO*+H* 1.24 0.30 0.83 0.03

CHOH*+* that HCO insertion into CH, CH2, and CH3 is highly
R6 HCO*+H* 0.68 0.28 0.65 0.16 exothermic (1.11 to 1.15 eV) with nearly identical activation
CH2O*+*
barriers in the range 0.150.22 eV (Table 2).
0.52 (Cu 0.42 (Cu
site) site) In comparison with two insertion pathways, HCO insertion
R7 CH2O*+H* 0.57 0.61 0.58 0.52 shows a signicant superiority to CO insertion in both
CH3O*+* thermodynamics and kinetics. This superiority may arise from
0.32 (Cu 0.98 (Cu the smaller HOMOLUMO gap of HCO compared with CO,
site) site) which facilitates the charge transfer and hybridization with the
R8 CH2O*+H* 1.04 0.39 0.68 0.10 surface.65 But it should be noted that HCO formation is highly
CH2OH*+*
R9 CH2O*+* 0.78 0.65 1.05 0.07
endothermic, leading to a relatively low surface coverage, which
CH2*+O* may hinder it from serving as the main reaction channel toward
R10 CH3O*+* 1.44 0.03 1.60 0.22 C2 oxygenates. However, under realistic conditions, the
CH3*+O* presence of coadsorbed species as hydrogen may increase the
R11 CH3O*+H* 1.68 0.75 1.48 0.41 surface coverage of HCO,36,67 thus making the HCO insertion
CH3OH*+*
as a predominant channel. In general, both CO and HCO
1.17 (Cu 0.24 (Cu
site) site) insertion may serve as the reaction channels for the chain
R12 CH*+CO* 1.05 0.41 0.92 0.17 growth toward CHxC(H)O (x = 13), which are the
CHCO*+* precursors for C2 oxygenates.
R13 CH2*+CO* 0.83 0.17 0.89 0.13 3.2.1.3. CHxC(H)O Dissociation in CO Bond (R18R19).
CH2CO*+* The CHxC(H)O species formed may either desorb as the nal
R14 CH3*+CO* 1.79 0.95 1.66 0.51 oxygenate product or undergo further transformation to
CH3CO*+*
terminate the propagation process. As listed in Table 1,
R15 CH*+HCO* 0.41 0.49 0.15 1.15
CHCHO*+* CHCHO and CH2CHO both adsorb at the Cu6Co3 surface
R16 CH2*+HCO* 0.33 0.48 0.15 1.11 with high Bes (>1.99 eV). Therefore, those species should have
CH2CHO*+* a larger tendency to further react rather than desorb from the
R17 CH3*+HCO* 1.05 0.09 0.22 1.14 surface, while CH3CHO can desorb easily because of the low
CH3CHO*+* BE of 0.33 eV. Subsequently, CHCHO and CH2CHO may
R18 CHCHO*+* 0.79 0.83 1.18 0.16 either be hydrogenated to produce ethanol or break the CO
CHCH*+O*
R19 CH2CHO*+* 1.07 0.39 1.31 0.46
bond to generate CHxCH species, which can serve as insertable
CH2CH*+O* monomers for higher oxygenates or hydrocarbons. It is noted
R20 CH2*+CH2* 0.27 0.95 0.30 1.07 that the chain terminations by hydrogenation occur easily with
CH2CH2*+* barriers less than 0.8 eV,36 so the related hydrogenation steps
R21 CH*+H*CH2*+* 0.60 0.21 0.40 0.36 were not investigated in this study. Additionally, recent
R22 CH2*+H* 0.66 0.17 0.43 0.35 studies3537 on Co-catalyzed FischerTropsch synthesis have
CH3*+*
suggested that CHxCHO species may dissociate to produce
R23 CH3*+H* 1.05 0.05 0.85 0.18
CH4*+* CHxCH fragments through CO bond cleavage with moderate
activation barriers from 0.6 to 1.0 eV. We also carried out the
calculations of CO bond scission for two elementary steps,
bind at the Co3hol site, while associatively adsorbed CO is CHCHO (R18) and CH2CHO (R19) dissociation on
stabilized at the neighboring Co1hol site. By these cong- Cu6Co3 surface and the TS structures (ts18 and 19) (Figure 6).
urations, we found that the insertion of CO into CH, CH2 and CHCHO initially binds at the Co3hol site via its -C and O
CH3 are all endothermic with activation barriers of 0.92, 0.89, atom; then, the atop bonded O atom moves to a neighboring
and 1.66 eV, respectively (Table 2). Generally, the insertion of Co1hol site with CO bond largely elongated from 1.290 in IS
CO into CH and CH2 is more favored than that into CH3. to 1.827 in TS. The CHCHO dissociation is a slightly
HCO Insertion (R15R17). An alternative carbonyl-contain- exothermic process (0.16 eV) with a relatively high barrier of
ing species for insertion is HCO and the bimetallic sites are 1.16 eV. The reaction path for CH2CHO dissociation is quite
favorable for HCO insertion. The ISs for the R15-R17 are quite similar to that for CHCHO, but the dissociation with an
similar, in which the CHx species (x = 13) bind at the Co3hol activation barrier of 1.31 eV becomes more dicult. The
site, while the HCO species at the bimetallic sites. It was found calculations suggest that both CO bond cleavage in CHCHO
222 dx.doi.org/10.1021/jp5065159 | J. Phys. Chem. C 2015, 119, 216227
The Journal of Physical Chemistry C
Figure 5. Chain propagation processes on the Cu6Co3 surface. The corresponding TS structures are shown in Figure 6.
Figure 6. Top view of geometries of TSs involved in the chain
propagation processes on the Cu6Co3 surface.
and CH2CHO is not an energetically favorable process on
Cu6Co3 surface.
3.2.1.4. Summary of the C2 Oxygenates Formation. From
the above-mentioned results, we can summarize the formation
route for C2 oxygenate as follows. CO is rst hydrogenated to
223
Article
produce CHxO species (x=12), which then undergo CO
bond cleavage at the Co sites, leading to the formation of
insertable monomers, CH and CH2 species. Another insertable
monomer, CH3, is formed via CH and CH2 hydrogenation.
Upon CO/HCO insertion at the bimetallic sites, the CHx (x =
13) species are propagated to form the oxygenate precursors,
CHxC(H)O species, and then the chain growth will be
terminated by hydrogenation. Thus, it can be concluded that
single metallic Co and Cu sites act as the active centers for the
formation of two key intermediates, CHx (x = 13) and HCO
species, respectively, while the bimetallic sites are the active
centers for chain growth toward C2 oxygenates.
3.2.2. Formation of Methane (CH4), Ethylene (C2H4), and
Methanol (CH3OH). As suggested by the experimental results10
on oxygenate synthesis over Co/Cu-based catalysts, there are
mainly three undesired products formed in the process,
including methane, hydrocarbons, and methanol. Here, we
discuss the formation of these products and gain a more
comprehensive understanding of the whole process. Moreover,
C2H4 was chosen to be a representative of the hydrocarbon
product as it has been proposed to possess the smallest
formation barrier among the C2Hy (y = 26) species.66 The
potential energy diagram for the subsequent transformation of
CH2 species is shown in Figure 7.
CH4. Figure 2 shows that CH and CH2 are initially formed
through the H-assisted CO dissociation mechanism, and then
these species can undergo sequential hydrogenation processes
to produce CH4. The last hydrogenation step (CH3*+H*
dx.doi.org/10.1021/jp5065159 | J. Phys. Chem. C 2015, 119, 216227
The Journal of Physical Chemistry C
Figure 7. Potential energy diagram for the subsequent transformation
of CH2 species on the Cu6Co3 surface. All the initial states have been
supposed at the same position for clearer comparison, but the relative
stabilities (based on Eb) of the four coadsorbed species are in the
order: CH2(3.81 eV) > H(2.65 eV) > CHO(2.13 eV) >
CO(1.70 eV). The corresponding TS structures are shown in Figure
6 lower, and thus suppresses CHx coupling reactions. This is the
CH4) has the highest activation barrier (+0.85 eV), it desorbs
from the Cu6Co3 surface immediately once formed. Obviously,
CH4 is very likely to be formed as a major product for CO
hydrogenation on Cu6Co3.
C2H4. The monomer, CH2, is formed via the H-assisted C
O dissociation mechanism, then two CH2 species couples to
produce C2H4. The corresponding barrier for CH2 coupling is
only 0.30 eV, and the step is also highly exothermic (1.07
eV). From an energetic perspective, C2H4 formation at the
bimetallic sites is highly favorable, even more preferred than
CH4. However, as suggested in section 3.2.1, the surface
concentration of CH2 species decreases with a drop in the
amount of Co sites, and CH2 coupling will obviously be
restricted due to the limited supply of reactant monomers.
CH3OH. The formation of methanol may happen at both the
Co sites and Cu sites. Both of them proceed via the sequential
hydrogenation of CO. On bimetallic sites, the step with the
highest barrier for the formation of CH3OH is CH3O
hydrogenation (1.48 eV), even higher than that of CO
bond cleavage steps. Obviously, CH3OH formation is not
favored compared to CHx formation at the Co sites of Cu6Co3.
On Cu-rich sites, CH3OH formation is largely facilitated and
the highest barrier (in CH3O*+H* CH3OH) of the process
is reduced to 1.15 eV.
3.3. Role of Cu. 3.3.1. Comparison of the Reaction
Pathways with/without Cu. In order to clarify the role of Cu
in C2 oxygenate synthesis on CoCu catalysts, we make a
comparison of the reaction pathways for oxygenate formation
on Co catalysts with or without Cu. For the chain initiation, the
addition of Cu inhibits the CO bond cleavage steps
(CHxO*+* CHx*+O* in R4 and R9) signicantly, while
the hydrogenation steps to form CHxO species (CHxO*+H*
CHx+1O*+* in R2, R6 and R7) are enhanced slightly.
Notably, the hydrogenation of CHxO to CHxOH (x = 03)
and hydrogenation of CHx species (x = 13) are largely
224
Article
enhanced upon alloying with Cu. The propagation steps behave
dierently according to the monomer chosen. CO insertion is
slightly enhanced, while HCO insertion is largely enhanced and
even becomes more favorable than CH2 coupling, which is the
most energetically favorable propagation step on Co9. Finally,
the CO bond cleavage of CHxCHO species (x = 12) is
signicantly inhibited. In general, CO dissociation and CO/
HCO insertion steps are sensitive to the addition of Cu, while
hydrogenation steps are generally unaected.
3.3.2. The Eects of Cu. Clearly, upon alloying with Cu, the
selectivity to C2 oxygenate is improved signicantly over Cu
Co catalysts. Herein, discussions on the role of Cu will be
conducted based on the comparison between Cu6Co3 and Co9.
(i) The CO dissociation at the Cu-modied Co sites
(bimetallic sites) is suppressed, and thus reduces the probability
for hydrocarbon formation. It is well-known that Cu alone is
inactive in breaking the CO bond, which is the prerequisite
for initiating the carbon chain growth. As suggested in section
3.2, with the addition of Cu, the CHxO (x = 13) bond
cleavage steps are all inhibited both in kinetics and
thermodynamics, which means that the addition of Cu can
weaken the ability of Co in breaking CO bond (dilution
eect). This is consistent with experimental results that CuCo
catalysts generally show lower CO conversion than pure Co
catalysts.14,30 Due to the inhibition of CO bond cleavage, the
surface concentration of coupling monomers, CHx species, gets
reason why CuCo shows poor selectivity to hydrocarbons.
(ii) CoCu ensembles serve as reservoirs for undissociated
CO and HCO species. CO/HCO insertion into CH x
monomers is always the key step for the formation of C2
oxygenate. On the pure Co surface, CO/HCO tends to
dissociate rather than stay as undissociated species. However,
with the addition of Cu, the undissociated CO/HCO species
can exist at the less active Cu sites, then diuse to the bimetallic
sites and insert into the CHx species, which formed at the more
active Co sites. By this way, Cu mainly serves as reservoirs for
the key intermediates (CO/HCO), which is consistent with the
Dual-Site mechanism20,24 to some extent. However, besides
stabilizing the CO species on Cu sites, the addition of Cu was
also found to play prevalent roles in enhancing the production
of C2 oxygenates by facilitating HCO insertion in our study.
With this facilitation, the relative rate of the CO/HCO
insertion channel could be expected to be more favorable
than that of CHx formation based on the calculated activation
barriers and reaction energies, which is also similar to those
results on RhCu16 and Rh.65 In addition, HCO formation at the
Cu sites (in section 3.3.1) is more favorable than that at the Co
sites, and HCO can easily diuse to the bimetallic sites, which
will increase the surface concentrations of HCO compared to
pure Co. As a result, Cu is not only a diluter or stabilizer for
undissociated CO, but also provides the active center for the
formation of key intermediates (HCO), which may be the
origin of the high selectivity to oxygenates.
Based on discussions above, the bimetallic sites play an
important role in determining the reactivity of the CuCo
surfaces. Either electronic eects or geometric eects have been
proposed to explain how the interaction between two
components aects the catalytic behaviors for bimetallic
catalysts. The Bader charge analysis shown in section 3.1.2
indicates that only negligible charge transfer (0.05e) occurs
between Co and Cu. Thus, the addition of Cu takes eect on
the geometry of ensembles rather than electronic property.
dx.doi.org/10.1021/jp5065159 | J. Phys. Chem. C 2015, 119, 216227
The Journal of Physical Chemistry C
(iii) The RC(H)O bond cleavage of oxygenated
intermediates is inhibited . The possibility of CO bond
cleavage in CHxC(H)O species is another factor that inuences
the selectivity of C2 oxygenates. From the results on Co9,
RCHO dissociation is actually easy to happen with a
moderate activation barriers (less than 1.10 eV) and exothermic
in thermodynamics. However, RCHO dissociation is
signicantly suppressed with the addition of Cu, which can
increase the selectivity to C2 oxygenates. It can be inferred that
on the surfaces with larger Co ensembles, the RCHO bond
cleavage may be facilitated, leading to the formation of RCH
species, which can undergo CO/HCO insertion to produce
oxygenates with longer chains. Prieto et al.31 has also identied
that Co-enriched surfaces are ideal for the selective production
of long chain alcohols. Notably, a larger ensemble could also
increase the probability for the formation of hydrocarbons from
RCH species.
Therefore, this study allows us gain deep insight into
optimizing CoCu-based catalysts to achieve higher productivity
and selectivity for oxygenates. Optimum CuCo oxygenate
synthesis catalysts should be prepared to contain enough
bimetallic sites, which require the intimate mixing of the two
components; meanwhile, aggregated Co and Cu ensembles
should also exist to provide active sites for the formation of
propagation monomers. Notably, an increase in the surface
cobalt ensemble size may also lead to a shift of the product
distribution toward oxygenates with longer chains. Future
improvements may require a microkinetic simulation to gain
more insights into the promotional eects of Cu as well as the
kinetic behaviors of the involved species in realistic reaction
conditions, which are still ongoing in this group. Obviously, this
work will provide insights and prediction for the improvement
of the catalytic performance of CoCu catalysts and other
related catalytic systems.
4. CONCLUSIONS
In summary, we have used periodic DFT to study the reaction
mechanism of C2 oxygenate formation from syngas on both
pure and bimetallic Co(0001) surfaces. On the Cu6Co3 surface,
H-assisted CO dissociation mechanism is preferable to the
direct dissociation mechanism for the formation of CHx (x =
13) species. Starting from the insetable monomers, we have
studied both CO/HCO insertion and CHx coupling. The CO/
HCO insertion has found to be the favorable pathway for chain
propagation to generate the precursor of C2 oxygenate.
Furthermore, a mechanism has been proposed to explain the
eects of Cu on the C2 oxygenate formation on CoCu
surfaces. First, the addition of Cu can control the Co ensemble
size and block the active sites for CO bond cleavage, resulting
in inhibition of CHx coupling at the Co sites. Second, Cu can
provide undissociated CO/HCO at the Cu sites as well as
reduce the barriers for HCO insertion at the bimetallic sites.
Combining the mechanistic study and charge analysis on the
CuCo surface, we conclude that Cu can greatly modify the
geometry of active sites. We believe that the insight derived
from this study can be valuable for both the catalyst design of
oxygenate synthesis and other F-T related catalytic systems.
ASSOCIATED CONTENT
*
S Supporting Information
Additional table and gure for dierent CuCo surfaces and the
preferred adsorption congurations, corresponding BEs and
bond lengths of surface intermediate species on Co9 and
225
Article
Cu6Co3 surfaces. This material is available free of charge via the
Internet at http://pubs.acs.org.
AUTHOR INFORMATION
Corresponding Author
*Phone: (+86) 21-64251928; fax: (86) 21-64251928; e-mail:
yifanhan@ecust.edu.cn.
Notes
The authors declare no competing nancial interest.
ACKNOWLEDGMENTS
The authors are grateful to the support from the National
Science Foundation (21176071, 21106041, 21273070), the
Program for New Century Excellent Talents in university
(NCET-12-0852), Science and Technology Commission of
Shanghai Municipality (11JC1402700), Innovation Program of
Shanghai Municipal Education Commission (12ZZ051), and
the Chinese Education Ministry 111 project (B08021).
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