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2014 American Chemical Society 216 dx.doi.org/10.1021/jp5065159 | J. Phys. Chem. C 2015, 119, 216227
The Journal of Physical Chemistry C Article
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 Co(0001) surfaces were investigated rst. Then, based on the
components from Co/CuZnO catalysts using steady state results on the two surfaces, the role of Cu for C2 oxygenate
isotopic transient kinetic analysis (SSITKA) for CO hydro- synthesis is discussed. We expect this study will greatly improve
genation. The activity for Co/CuZnO catalysts found to be the understanding of this reaction and the subsequent design of
signicantly decreased compared to a Co/Al2O3 catalyst; high-performance catalysts.
however, the selectivity to oxygenates was enhanced owing to
blocking a signicant portion of active sites for hydrocarbon 2. COMPUTATIONAL METHODS
synthesis. Xiang et al.12 developed a highly selective CuCo 2.1. Surface Model. To simulate the structures of
catalyst that possesses a Co-rich core structure and a Cu- bimetallic catalysts, two kinds of models were widely adopted.
dominated mixed shell, and the selectivity to long chain The rst one is the bulk alloy or solid solution model, in which
alcohols has been found superior to traditional CuCo the two components are intimately mixed by forming a single
catalysts. This study indicates that the CoCu interaction, solid phase microstructure. It has been successfully applied to
especially in the near-surface region in which a Cu-rich surface the study of NOx decomposition over RhAg bimetallic
conguration is predominant, can play an important role in catalysts.39 The second one is the near surface alloy (NSA)
promoting the production of alcohols. Moreover, combining model, which has been widely used for investigating Pt-based
theoretical calculations and experimental study, Prieto et al.31 oxygen reduction electro-catalysts.40 In this model, the
identied a CuCo alloy phase with Co-rich compositions as the formation of alloy structure is expected to occur only at the
ideal catalyst surface for long-chain alcohols. near surface region, while the bulk region remains a pure phase.
Density functional theory (DFT) calculations have demon- In general, the choice of the model for bimetallic catalysts is
strated to be a powerful tool for elucidating kinetic determined by how intimately the two components interact
behaviors32,33 and gaining insight into the reaction mechanism. with each other.
Actually, the DFT method has been applied to investigate the For CoCu catalysts, it is well established that the bulk
F-T synthesis and oxygenate formation process over Co-based CuCo alloy does not exist due to the low solubility of one metal
catalysts.3438 It has been suggested that the oxygenate into the other.41 However, a simple mechanical mixing of two
synthesis process is initiated by CO dissociation through a H- metals did not change the cobalts selectivity.42 Actually, it has
assisted mechanism, in which CO is rst hydrogenated to been reported that alloying phenomena may exist at the
produce CHxO species, followed by a CO bond cleavage, nanoscale.43 Hence, the NSA model may serve as a feasible
resulting in the formation of CHx species. As for the chain choice. Furthermore, since Cu has a larger tendency to
growth toward higher oxygenates, a CO insertion model is the segregate to the surface compared to Co,44 a Cu-rich surface
most preferred, but more recent studies also propose that a conguration45 is observed when exposing to syngas atmos-
HCO insertion model may be an alternative mechanism. pheres. Additionally, Co atoms may either homogeneously
To the best of our knowledge, the theoretical study of the distribute or aggregate to form local ensembles on a Cu-rich
detailed reaction mechanism for this reaction system has been CuCo surface. To further identify the surface structure of a
rarely reported. In order to elucidate the eect of Cu on Cu CuCo catalyst, we perform calculations with dierent Co
Co catalysts, elementary steps involved in C2 oxygenate arrangements and reveal that Co atoms prefer to aggregate
formation from syngas on both pure and Cu-doped rather than homogeneously distribute on the Cu6Co3 surface in
217 dx.doi.org/10.1021/jp5065159 | J. Phys. Chem. C 2015, 119, 216227
The Journal of Physical Chemistry C Article
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 dierent pseudopotentials chosen (Chengs: norm-conserving;
CHxO (x = 13) and CHxOH (x = 03) species, except this work: PAW).
CH3OH, which is adsorbed at the top sites, prefer to bind at 3- 3.1.1.3. CHxCO (x = 13), CHxCHO (x = 13). CHxCO and
fold hollow site. Among CHxO (x = 13) species, CHO and CHxCHO species (x = 13) are the key precursors for the
CH2O prefer to bind via both C (bridge) and O (bridge/top) formation of C2 oxygenates. Both the adsorption geometries
atoms with a BE of 2.26 and 0.79 eV, respectively, while and BEs vary with an increase in x. CHCO and CH2CO species
CH3O tends to bind only via O atom with CO bond tend to bind via both C and C at the 3-fold hollow site, with
perpendicular to the surface, and the calculated BE is 2.88 eV. BEs of 3.46 and 1.14 eV, respectively. Nevertheless,
The adsorption geometry of COH is quite similar to CO, CH3CO only binds via the O atom at the top site with a BE
of 1.63 eV. The adsorption congurations of CHxCHO
namely, perpendicularly binding via its C atom, and the
species follow a similar trend. CHCHO and CH2CHO bind via
calculated BE is 4.39 eV. The other three CHxOH species (x
two atoms, C and O, to the surface at the hollow sites, while
= 13) have quite dierent adsorption geometries and BEs.
only the O atom at the top site is involved in the binding of
CHOH and CH3OH tend to bind only via one atom (C for the CH3CHO to the surface. The adsorption of CHxCHO species
former, while O for the latter) to the surface, whereas CH2OH is weakened with the increasing of x from 1 to 3, and the
is in favor of binding via both C (bridge) and O (top) atoms. corresponding BEs are 4.39, 2.01, and 0.33 eV,
The calculated BEs for CHOH, CH2OH, and CH3OH are respectively. These results agree well with the previous data
3.02, 1.62, and 0.28 eV, respectively. Cheng et al. have of Cheng et al.34 and Zhuo et al.56
investigated the formation of oxygenates on Co(0001) using 3.1.2. Comparison of the Results on Cu9 and Cu6Co3. After
DFT calculation34 and reported data are in good agreement summarizing the results of adsorption geometries and BEs of
with our results except for the BE of CHOH species, which has various intermediates on Co9, we make a comparison for these
a dierence of 0.80 eV. The discrepancy may arise from the intermediates between Co9 and Cu6Co3. On Cu6Co3, all the
219 dx.doi.org/10.1021/jp5065159 | J. Phys. Chem. C 2015, 119, 216227
The Journal of Physical Chemistry C Article
species tend to bind at the Co sites rather than the Cu sites. In possible pathways: (i) CO dissociation followed by hydro-
general, most of the species are adsorbed with the same genation (carbide mechanism), and (ii) CO hydrogenation
adsorption geometries on both surfaces, except for CO and followed by CO bond cleavage (H-assisted CO dissociation
HCO. CO prefers to bind at the Cotop site on Cu6Co3, instead mechanism). We carried out calculations for CHx formation
of the 3-fold hollow site on Co9, but interestingly, there is (R1R11) based on the above mechanisms (Figure 2) and the
almost no change in BE (1.81 eV vs 1.79 eV). Similarly, geometries of TS (Figure 3). The potential energy diagram for
HCO also undergoes a migration from the hollow site to the these reactions is displayed in Figure 4.
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, Figure 3. Top view of geometries of TSs involved in the formation of
it is obvious that the change in CoCo distance can directly CHx species on the Cu6Co3 surface (small gray, C; small red, O; small
aect the binding of those surface species at the hollow sites, as white, H).
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 The barrier of the CO dissociation (R1) on Cu6Co3 found as
no modication in the electronic structure of the individual Co high as 2.45 eV, being comparable with our result (2.55 eV on
atom upon the addition of Cu, which leads to similar BEs on Co9) and the reported data56,60 on pure Co surfaces. This
two surfaces. The dierences in the adsorption on two surfaces suggests that the direct CO dissociation or carbide mechanism
will denitely take eect on the reaction energetics and reaction is unlikely to occur on Cu6Co3. As for the H-assisted
pathways, which will be presented in the following section. mechanism, it is reported that the activation barrier for CO
3.2. Reaction Pathways on Cu6Co3. In this part, we bond cleavage is remarkably reduced after CO hydro-
investigated the thermodynamics and kinetics for the plausible genated.6163 Two hydrogenation pathways, hydrogenation of
elementary steps involving the formation of C2 oxygenate from CO to form formyl (HCO) and formyl-isomer (COH) were
syngas on both pure (Co9) and Cu-modied Co(0001) considered. For HCO formation, starting from the most stable
(Cu6Co3) surfaces. All the calculations were performed in the coadsorbed conguration, CO at the Co3hol site and H at a
low coverage condition (1/9 ML), and NEB calculations were neighboring Co1hol site, the activation barrier of 1.35 eV (R2)
performed for all initial and nal states within 0.2 eV of the was obtained. However, the activation barrier was reduced to
most stable coadsorbed conguration within a unit cell. Most of 1.01 eV at the Cu site. These results suggest that HCO
the coadsorption congurations are in favor of locating around formation at the Cu sites is the energetically favorable pathway
the Co3 ensemble with one stabilized therein while the other is from CO hydrogenation. The activation barrier and transition
in neighboring bimetallic sites. The eects of the pure Co sites, state structure for HCO formation is in good agreement with
Cu-modied Co sites (namely bimetallic sites), and pure Cu reported results in the range of 1.311.50 eV.34,56,63
sites on the reactions as well as the formation of key reaction The preferred CO hydrogenation product, HCO, can either
intermediates will be presented and discussed in more detail. directly dissociate into methylidyne (CH) and O (R4) or be
3.2.1. C2 Oxygenates Formation. 3.2.1.1. CO Hydro- hydrogenated to form formaldehyde (CH2O) (R5) or
genation and Dissociation (R1R11). Up to now, the CO/ hydroxymethylene (CHOH) (R6). As listed in Table 2, the
HCO insertion mechanism has been widely used for elucidating CO bond cleavage in HCO (0.98 eV) is facilitated
C2 oxygenate synthesis on Co-based catalysts. In this signicantly compared to that in CO (2.45 eV). The activation
mechanism, CO is assumed to be rst activated to produce a barrier and transition state structure are both in good
chain initiator or insertable monomer, CHx species, then agreement with reported results in the range of 0.901.00
followed by the insertion of CO/HCO species to form the eV.34,56,63 The facilitation can be explained by the fact that
precursors for C2 oxygenates. HCO binds to the surface via both C and O atoms, and the C
Formation of Insertable Monomers. According to the proposed O bond is largely elongated (1.289 in HCO vs 1.196 in
reaction mechanism, the key issue is to elucidate how CO is CO) which is an indicative of weakened CO binding.
activated to form the CHx species. In general, there are two Nevertheless, HCO dissociation is still less favorable than HCO
220 dx.doi.org/10.1021/jp5065159 | J. Phys. Chem. C 2015, 119, 216227
The Journal of Physical Chemistry C Article
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 monomers formed, and this process will be presented in the
formation of CH2O and CHOH are 0.65 and 0.83 eV, following part.
respectively. Thus, the preferred products from HCO should be 3.2.1.2. CO/HCO Insertion into CHx (x = 13) species
CH2O, which can further undergo two processes: dissociation (R12R17). As inspired by the homogeneous catalysis,64 the
into CH2 and O (R7), or hydrogenation to form methoxy insertion of the unsaturated carbonyl-containing species into a
(CH3O) (R8) or hydroxymethyl (CH2OH) (R9). carbonmetal bond of a CHx species has been widely adopted
The calculation results show that CH2O dissociates as the chain growth step on Co. Hence, we followed this
exothermically (0.07 eV) with a barrier of 1.05 eV, which is propagation mechanism for C2 oxygenate formation on
slightly higher than the barrier for HCO dissociation. As for the Cu6Co3, in which both CO and HCO were considered as the
hydrogenation products, CH3O and CH2OH, they possess unsaturated carbonyl-containing species for insertion.
formation barriers of 0.58 and 0.68 eV, respectively. Again, Dif f usion of CHx (x = 13) and HCO. Given that there are
dissociation is not preferred compared with hydrogenation. As three types of sites (Co sites, CoCu bimetallic sites, and Cu
a result, CH3O is more likely to be the preferred intermediate sites) on the Cu6Co3 surface, the reaction intermediates may
produced from the subsequent transformation of CH2O. thus undergo diusion among these sites, which can aect the
CH3O is very stable on the surface (Eb = 2.62 eV) and location of active centers for chain propagation processes. To
binds to the surface via its O atom. The barriers for CH3O expound on the eects of diusion on the bimetallic CoCu
dissociation and methanol (CH3OH) formation are 1.60 and surface, we have calculated the diusion barriers of the key
1.48 eV (Table 2), respectively. Consequently, both dissocia- reaction monomers involving this process including CHx (x =
tion (R10) and hydrogenation (R11) of CH3O is dicult to 13) and HCO species, and the diusion barriers are
occur on Cu6Co3. Accordingly, CH3 species is unlikely to be summarized in Table 3. CHx species are more likely to be
formed via CH3O dissociation. formed at the Co sites. Their diusion from initial Co sites to
On the basis of the above-mentioned results, we can Cu sites are all endothermic with overall barriers in the range of
summarize that the most favorable path for CO hydrogenation 0.681.39 eV (Table 3). We deduce that the CHx species
is CO HCO CH2O CH3O. After CO hydrogenation, produced is conned at the Co sites, where subsequent
the dissociation of HCO and CH2O to produce CH and CH2 reactions with neighboring reactive species may occur. On the
become competitive to the corresponding hydrogenation step, other hand, the key carbonyl-containing species, HCO, is
while the dissociation of CH3O to CH3 is unfavorable. Thus, produced at the Cu sites during the reaction. HCO can
two insertable monomers, CH and CH2, could be formed via undergo a barrierless diusion process to Co sites or bimetallic
the H-assisted CO dissociation mechanism. In addition, sites. The facile diusion of HCO species from Cu sites to Co
considering that the surface is covered by certain amounts of sites would increase the concentrations of these species at the
hydrogen under the reaction conditions, the formation channel bimetallic sites. In the next section, the CO/HCO insertion
of CHx upon hydrogenation should be involved. From R21 into the CHx species at the bimetallic sites was investigated and
R22 in Table 2, CH2 and CH3 can be easily formed via CH and summarized in Figure 5, and the corresponding TS structures
CH2 hydrogenation with barriers of 0.40 and 0.43 eV, (ts1217) are illustrated in Figure 6.
respectively. Thereby, CH2 hydrogenation could act as an CO Insertion (R12R14). We rst calculated the coad-
alternative route for CH3 formation. In summary, CH comes sorption of CHx (x=13) and CO species on Cu6Co3. As
from HCO dissociation, whereas CH2 and CH3 come from indicated in Table 2, the most stable coadsorption cong-
hydrogenation. Chain growth starts immediately once the urations for R12R14 are very similar, in which CHx tend to
221 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
Figure 5. Chain propagation processes on the Cu6Co3 surface. The corresponding TS structures are shown in Figure 6.
(iii) The RC(H)O bond cleavage of oxygenated Cu6Co3 surfaces. This material is available free of charge via the
intermediates is inhibited . The possibility of CO bond Internet at http://pubs.acs.org.
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
AUTHOR INFORMATION
Corresponding Author
moderate activation barriers (less than 1.10 eV) and exothermic *Phone: (+86) 21-64251928; fax: (86) 21-64251928; e-mail:
in thermodynamics. However, RCHO dissociation is yifanhan@ecust.edu.cn.
signicantly suppressed with the addition of Cu, which can
increase the selectivity to C2 oxygenates. It can be inferred that Notes
The authors declare no competing nancial interest.
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 ACKNOWLEDGMENTS
oxygenates with longer chains. Prieto et al.31 has also identied The authors are grateful to the support from the National
that Co-enriched surfaces are ideal for the selective production Science Foundation (21176071, 21106041, 21273070), the
of long chain alcohols. Notably, a larger ensemble could also Program for New Century Excellent Talents in university
increase the probability for the formation of hydrocarbons from (NCET-12-0852), Science and Technology Commission of
RCH species. Shanghai Municipality (11JC1402700), Innovation Program of
Therefore, this study allows us gain deep insight into Shanghai Municipal Education Commission (12ZZ051), and
optimizing CoCu-based catalysts to achieve higher productivity the Chinese Education Ministry 111 project (B08021).
and selectivity for oxygenates. Optimum CuCo oxygenate
synthesis catalysts should be prepared to contain enough REFERENCES
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