Applied Surface Science 476 (2019) 115–122

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Applied Surface Science

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Full Length Article

The synergistic effect between crystal planes and promoters on Ag-catalyzed T

ethylene epoxidation
⁎ ⁎
Lin Zhua, Haoxiang Xua, Yang Nanb, Yuan Xieb, Jiqin Zhua,c, , Daojian Chenga,
a
State Key Laboratory of Organic-Inorganic Composites, Beijing University of Chemical Technology, Beijing 100029, China
b
Lanzhou Petrochemical Research Center of PetroChina, Petrochemical Research Institute, PetroChina, LanZhou 730060, Gansu, China
c
State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China

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

Keywords: It is well-known that the promoter can enhance the selectivity to ethylene oxide (EO) of Ag catalyzed ethylene
Ag catalysts epoxidation. However, the selectivity enhancement on different crystal planes of Ag catalysts derived from
Promoters various promoters is still indistinct. In this work, in order to get an atomistic insight into the synergistic effect
Crystal planes between crystal planes and promoters on catalytic performance of Ag catalysts, we study ethylene epoxidation
DFT calculation
on Ag (1 1 1), (1 1 0) and (1 0 0) surfaces with the promoters of Re, Cs and Cu by density functional theory
Ethylene epoxidation
calculations. It is found that selectivity enhancement introduced by the promoters on Ag (1 1 1) surfaces is more
Selectivity
obvious compared with that on Ag (1 1 0) and (1 0 0) surfaces. The sequence of EO selectivity on Ag (1 1 0)
surfaces is Re < no promoter < Cs < Cu while it is Re < no promoter < Cu < Cs on Ag (1 1 1) and (1 0 0)
surface. The adsorption strength of oxametallacycle intermediate works as a selectivity descriptor and has a
negative correlation with valence electron depletion of surface Ag atoms. Therefore, the promoters can cause
charge redistribution of Ag crystal surfaces and lead to the corresponding effect on the selectivity toward EO. In
addition, the synergistic effect between promoter and crystal surface would affect the eletrophilicity of the
surface atomic oxygen. We believe that this works would provide guidance to enhance the EO selectivity of Ag
catalyzed ethylene epoxidation by rationally choosing suitable promoter for specific Ag crystal surfaces.

1. Introduction oxidation of ethylene has been proposed based on various observations

Due to the wide application of ethylene oxide (EO) in industry
[1–3], the ethylene epoxidation which can selectively generate the EO
is a significant chemical reaction. Ag-based catalysts have attracted a
great deal of interest experimentally and computationally [4–8]. Based
on the previous works [4,9–12], the reaction pathways of ethylene
epoxidation involve the formation of an oxametallacycle (OMC) inter-
mediate, as well as further isomerization of OMC through two compe-
titive pathways to form either EO or acetaldehyde (AA). In order to
enhance the selectivity to EO, many approaches have been employed to
enhance the catalytic selectivity of Ag-based catalysts, including the
synergistic effect between the Ag and oxide carriers (TiO2, SrTiO3,
MgTiO3) [13–16], and the application of sliver oxide and so on [17].
Moreover, it is well-known that the performance of Ag catalysts can be
improved by adding trace amounts of foreign species named as pro-
moters [18,19]. The effect of promoters on Ag catalyst for the ethylene
epoxidation has drawn attention and been studied extensively. It is
noted that the promotion of the EO selectivity during the partial
[20–25].
It has been demonstrated that the promoters added during the
preparation of Ag catalysts, such as Cs and Re, can enhance the se-
lectivity to EO [20–23]. As found in previous work [26], the moderate
addition of Cs can enhance the selectivity to EO while adding too much
Cs may result in a decrease of the activity. The most prevailing view on
the role of promoter is that various promotes (for example Cs) can affect
the EO selectivity via introducing electric field [22]. In addition, the
steric effect of Cs by inhibiting the adsorption of O atom onto the in-
herently less selective sites is responsible for the enhancement of EO
selectivity [26,27]. Nevertheless, it contradicts other works, which
claimed that the enhancement of EO selectivity introduced by Cs is
related with the strengthened interaction between surface and reaction
species containing oxygen [28,29]. As for Re employed as the promoter,
the selectivity to EO would be lower than that of pure Ag catalysts due
to the higher tendency of isomerization of the adsorbed EO to AA [30].
Moreover, it is discovered that the adjunction of Cu into the Ag catalyst
would enhance EO selectivity and the catalytic species was identified as

⁎
Corresponding authors.
E-mail addresses: zhujq@mail.buct.edu.cn (J. Zhu), chengdj@mail.buct.edu.cn (D. Cheng).

https://doi.org/10.1016/j.apsusc.2019.01.076
Received 7 November 2018; Received in revised form 28 December 2018; Accepted 8 January 2019
Available online 09 January 2019
0169-4332/ © 2019 Elsevier B.V. All rights reserved.
L. Zhu et al.
the AgeCu alloy [31]. However, a phase separation of AgeCu alloy
with high Cu content (above 1% [32]) would reduce the selectivity of
the catalyst at typical temperature and pressure used in industrial
production (T ≈ 500–600 K, p ≈ 1–10 atm). Therefore, it is significant
to control the addition of Cu to a small concentrate so that Cu can be
doped into the lattice of Ag and act as promoter to enhance the se-
lectivity [31]. Until now, most of theoretical works only focused on the
effect of promoter on the close-packed plane of Ag (1 1 1) surface
[33–35]. Actually, Ag (1 1 0) and (1 0 0) surfaces have also gained more
and more attention and been proved to possess higher selectivity to EO
than Ag (1 1 1) surface [8,35,36]. However, the synergistic effect be-
tween crystal planes and promoters on the catalytic selectivity of Ag
catalysts for ethylene epoxidation still remains unclear.
In this work, various promoter-modified Ag surfaces are constructed
through pairwise coupling between crystal surfaces (Ag (1 1 1), (1 1 0)
and (1 0 0)) and promoters (Cs, Re, Cu). The ethylene epoxidation on
these promoter-modified Ag surfaces are comprehensively explored by
density functional theory calculation. The adsorption intensity of OMC
intermediate is identified as selectivity descriptor and negatively cor-
relates with valence electron depletion of surface Ag atoms. The elec-
tron redistribution of Ag catalysts caused by promoter is found to be
facet-dependent, which leads to various enhancement of EO selectivity
on different combination of Ag surfaces and promoters during the
ethylene epoxidation.
2. Computational methods and models
The structural optimizations were performed by using first-principle
calculations within the framework of spin-polarized density functional
theory (DFT), as implemented in Plane-Wave Self-Consistent Field
(PWSCF) of the Quantum ESPRESSO package [37]. The exchange-cor-
rection energy was considered by using Perdew-Burke-Ernzerhof (PBE)
[38] functional. Ultra-soft pseudo potentials was used to represent the
interaction between ions and electrons. The kinetic energy cutoffs of 45
and 450 Ry were employed to depict the wave function and electronic
density, respectively. The theoretical lattice constants of bulk Ag is
4.16 Å, which is consistent with the experimental value (4.09 Å) and
previous studies (4.14 and 4.19 Å) [8,39]. The supercell methods were
employed to investigate Ag (1 1 1), (1 1 0) and (1 0 0) surfaces. The Ag
surfaces were modeled with a five-layers slab where a 15 Å region
thickness between two slabs was inserted in the z direction. A
3 × 3 × 1 k-mesh sampling of the Brillouin zone was used in the geo-
metry relaxation while 9 × 9 × 1 k-mesh was employed for the elec-
tronic structure calculations. In calculations the bottom two layers were
keep fixed, where all other Ag atoms were relaxed. The Gaussian
function procedure with a broadening constant of 0.002 Ry was applied
for electronic levels.
We define the adsorption energy (ΔEads ) as follows
ΔEads = Etotal − EAg surface − Eadsborbate
where Etotal denotes the energy of the system including catalyst and
adsorbate, EAg surface and Eadsorbate correspond to the energies of Ag cat-
alyst and adsorbate, respectively.
We define the formation energy (ΔE form ) of replacing Ag atom by
promoter as follows
ΔE form = EAgsurfacewithpromoter + EAgatom − EAgsurface − Epromoter
where EAgsurfacewithpromoter denotes the energy of the promoter-modified
Ag surface, EAg atom , EAg surface and E promoter correspond to the energies of
free Ag atom, Ag surface and free promoter atom, respectively.
To investigate the minimum-energy pathways (MEP), the climbing
image (CI-NEB) method was employed. Eight configurations including
endpoints were employed to depict the reaction path while the force
orthogonal must be less than 0.02 eV/Å. Vibrational frequency calcu-
lations have been done to verify the translation states (TSs) by ensuring
that the transition state has only one imaginary vibrational frequency.
Applied Surface Science 476 (2019) 115–122
The energy barrier (ΔEa ) for the element reaction step was calcu-
lated as follows
ΔEa = E TS − EIS (2)
where IS is the initial state. The value of ΔΔEa is used to measure the EO
selectivity while it is calculated as follow
ΔΔEa = ΔEa(AA) − ΔEa(EO) (3)
A larger value of ΔΔEa suggests that the selectivity to EO(ads) is
higher.
The center of d-orbital was calculated through analyzing the pro-
jected density of states (pDOS) as follows
+∞
∫−∞ ρDOS EdE
εd = +∞
∫−∞ ρDOS dE (4)
where the εd represents the d-band center, E denotes energy level and
ρDOS is the pDOS of d-orbital.
Recent studies [8,17,35,40–42] proposed that under ethylene
epoxidation conditions, the adsorbed atomic oxygen would induce the
reconstruction of silver surface to ultrathin oxide overlayer or oxide-
like complexes. In this work, however, we employed the single crystal
surfaces remaining essentially metallic state to model silver surfaces,
coinciding with previous model [22,31,43], which excludes the influ-
ence of surface reconstruction in order to focus on the synergistic effect
between crystal planes and promoters. In, addition, previous studies
[44,45] also demonstrate that metallic surfaces covered by atomic
oxygen can still be regarded as reasonable surface models at certain
environment, such as low oxygen regime, low temperatures or ultra-
high vacuum, since the O-reconstructions are kinetic limitation, where
the unreconstructed atomic oxygen also participate in the partial oxi-
dation of ethylene.
Previous studies [46–50] show that even small amounts of Cs would
induce the reconstruction of Ag (1 1 0) surface at 300 K. However, the
Ag (1 1 0) surface would not reconstruct the entire surface into (1 1 1)
facet until the oxygen coverage is larger than 0.20 ML [51]. Moreover,
the reconstruction of metal catalysts induced by Cs prefers to take place
when the temperature is higher than 80 K [47,51,52]. In present work,
we employ single promoter atom adsorbed on the silver surface to study
the ethylene epoxidation under the condition of ultra-high vacuum and
0 K, which was adopted in previous DFT works [22,31,43,53], and pay
emphasis on the cooperative effect between promoter and crystal sur-
faces. Therefore, the reconstruction of Ag surfaces induced by promoter
is not considered in this work.
3. Results and discussion
3.1. Location of promoter
(1)
To investigate the synergistic effect between various promoter and
crystal surfaces on adjusting selectivity to EO during ethylene epox-
idation, it is necessary to identify the thermodynamically preferable
location of each promoter on different surfaces. The possible position
for promoter includes the binding to surface Ag atoms as an adsorbate
and incorporation into the Ag surface as a dopant. Available adsorption
sites for promoters (Cs, Re, Cu) on Ag (1 1 1), (1 1 0) and (1 0 0) surfaces
are plotted in Fig. 1, and the corresponding adsorption energies of
promoters are summarized in Table S1. Three adsorption sites for
promoter on Ag (1 1 1) includes bridge (B), hexagonal-close packed
(hcp), and face-centered cubic (fcc) sites. Promoters prefer to adsorb at
fcc site. Ag (1 1 0) surface also contains three adsorption sites, namely
four-folds hollow (4F), longer and shorter bridge (LB and SB)) sites. Cs,
Re and Cu as promoters all tend to adsorb at 4F site. Only B and 4F sites
are available for the adsorption of promoter, and the 4F site is the most
preferable for the adsorption of promoters on Ag (1 0 0) surface. The
substitution sites for promoters (Cs, Re, Cu) on Ag (1 1 1), (1 1 0) and
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Table 1
The adsorption energies of atomic oxygen, OMC, C2H4 + O, EO and AA on pure
and promoted Ag (1 1 1), (1 1 0) and (1 0 0) surfaces.
O C2H4 + O OMC EO AA

Ag (1 1 1) surface
pure −3.28 −3.56 −3.86 −0.06 −0.06
Cs −6.26 −5.69 −12.04 −2.45 −2.45
Re −6.24 −10.53 −11.54 −3.12 −3.14
Cu −6.31 −6.14 −14.28 −2.48 −2.50

Ag (1 1 0) surface
pure −3.23 −3.51 −3.98 −0.06 −0.10
Cs −5.32 −5.40 −8.35 −1.88 −1.78
Re −7.32 −12.79 −8.75 −2.81 −3.23
Cu −6.19 −6.34 −8.57 −2.01 −2.01

Ag (1 0 0) surface
pure −3.36 −3.68 −3.86 −0.10 −0.07
Fig. 1. Top and side views of (a) Ag (1 1 1), (b) Ag (1 1 0) and (c) Ag (1 0 0)
Cs −6.13 −5.73 −8.52 −2.22 −2.23
surfaces. The blue spheres represent the Ag atoms in the first, fourth and fifth
Re −6.83 −8.05 −8.35 −3.06 −2.56
layer. The yellow and purple spheres are employed to present the Ag atoms in Cu −6.34 −6.09 −8.49 −2.02 −1.98
the second and third layers. Surface adsorption sites for promoter or atomic
oxygen are given as follows. fcc, face-centered cubic site; hcp, hexagonal-close
packed site; B, bridge site; L(S)B, the longer (shorter) bridge site; 3F, 3-fold
hollow site; 4F, 4-fold hollow site.

(1 0 0) surfaces considered in this work contains Ag atoms in first and

second layers (Fig. 1), the corresponding formation energies of repla-
cing Ag atom by promoter are summarized in Table S2. Compared with
the data in Tables S1 and S2, all promoters prefer to adsorb on Ag
surface rather than substitute Ag atom to form alloy on all studied Ag
surface models. Therefore, Ag surface with promoter pre-adsorption at
most favorable sites is adopted as the surface model of promoter-
modified Ag catalyst. There is a debate on whether promoter metal
atom turns to oxide or promoter do not form chemical bond with O
atom under industrial reaction conditions [27,54]. However, we focus
here on model catalysts where Ag surface and promoter are metal state,
which allows us to gain insight into the synergistic effect between
promoter and crystal surfaces that govern selectivity at atomic scale,
with a reasonable computational effort [22,27,31].

3.2. Adsorption on promoter-modified Ag surfaces

Recent studies shows that adsorbed atomic oxygen is the significant

active species [55–58]. Therefore, the adsorption of atomic oxygen is
studied on clean and promoted Ag surfaces. O atom inclines to adsorb
on fcc site on pure Ag (1 1 1) surface while 4F site is the most en-
ergetically favorable on pure Ag (1 1 0) and (1 0 0) surfaces. As shown
in Fig. S1, the possible adsorption sites of atomic oxygen on promoted
Ag surfaces have also been tested to find out the most stable adsorption
site, and corresponding results are listed in Table S3. The adsorption
energies of atomic oxygen adsorbed at the most stable adsorption site
are summarized in Table 1 and plotted in Fig. 2a. The binding energies
of atomic oxygen on pure Ag surfaces are close to each other (−3.28,
−3.23 and −3.36 eV on pure (1 1 1), (1 1 0) and (1 0 0) surfaces, re-
spectively). The adsorption of atomic oxygen becomes more stable due
to the presence of promoters. That is, the promoters can enhance the
adsorption of the atomic oxygen. The promoter Cs leads to a greater
stability of atomic oxygen on Ag (1 1 1) and (1 0 0) surfaces compared
with that on Ag (1 1 0) surface, while the enhancement effect on atomic
oxygen adsorption derived from Re follows the order of Ag
(1 1 1) < (1 0 0) < (1 1 0). The enhancement of stability of O atom
caused by Cu is almost the same on different Ag surfaces. We also
calculated the coadsorption of the C2H4 and O atom, the adsorption of
oxametallacycle (OMC) intermediate, ethylene oxide (EO) and acet-
aldehyde (AA). As shown in Fig. 2b, the co-adsorption of the C2H4 and
O is more stable on promoted Ag surfaces than that on pure Ag surfaces.
The sensitivity of Ag surfaces to Cs and Cu promoter in improving
coadsorption strength is less obvious than that to Re promoter. As seen
Fig. 2. The adsorption energy of (a) O, (b) C2H4 + O and (c) OMC intermediate
on Ag (1 1 1), (1 1 0) and (1 0 0) surfaces with and without promoters.
in Fig. 2c, the adsorption of OMC intermediate would be more stable on
promoted surfaces compared with that on pure Ag surfaces, which in-
dicates that the presence of the promoters can also lead to a more stable
OMC intermediate. All promoters would enhance the stability of ad-
sorbed OMC more obvious on Ag (1 1 1) surfaces than that on Ag (1 1 0)
and (1 0 0) surfaces. Likewise, the presence of the promoter can en-
hance the adsorption of EO and AA (see Table 1). Therefore, the sen-
sitivity of Ag surfaces to different promoters would affect the stability of
adsorbed reactant, intermediate and products, which may accordingly
have impact on the ethylene epoxidation reaction.
3.3. Ethylene epoxidation on promoter-modified Ag surfaces
Once the ethylene molecule and atomic oxygen are co-adsorbed on
the catalyst surfaces, they would interact with each other and form the
OMC intermediate. Table 2 and Figs. 3–5 show the energy barriers of

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L. Zhu et al. Applied Surface Science 476 (2019) 115–122

Table 2 products. The value of ΔΔEa which are shown in Table 2, are used to
The energy barriers for the reactions of (a) C2 H 4 + O → OMC, (b)OMC → EO qualitatively assess the selectivity toward EO on studied Ag catalysts. As
and (c) OMC → AA , as well as barrier difference (ΔΔEa) between reaction (b) shown in Figs. 3–5, we studied the OMC isomerization on clean Ag
and (c) on pure and promoted Ag (1 1 1), (1 1 0) and (1 0 0) surfaces. (1 1 1), (1 1 0) and (1 0 0) surfaces. Energy barrier for OMC → EO on
Pure Ag Cs Re Cu Ag (1 1 1) is higher than that on clean Ag (1 1 0) and (1 0 0) surfaces
while the energy barrier of OMC → AA is lower compared with that on
Ag (1 1 1) surface
clean Ag (1 1 0) and (1 0 0) surfaces [5]. ΔΔEa on Ag (1 1 1) surface
(a) C2 H 4 + O → OMC 0.49 0.51 0.60 0.53
(b) OMC → EO 0.81 0.79 0.68 0.88
(0.08 eV) is consist with preview works [59] and is smaller relative to
(c) OMC → AA 0.89 1.56 1.62 1.43 that on clean Ag (1 1 0) and (1 0 0) surfaces. Therefore, Ag (1 1 0) and
ΔΔEa 0.08 0.77 0.94 0.55 (1 0 0) surfaces achieve higher EO selectivity than Ag (1 1 1) surface,
Ag (1 1 0) surface which is consistent with other theoretical studies [60–62]. The activa-
(a) C2 H 4 + O → OMC 0.30 0.40 0.40 0.24 tion barriers of the OMC intermediate isomerization to produce the
(b) OMC → EO 0.78 0.40 0.40 0.15 desired product (EO) on clean Ag (1 1 0) surface is lower compared with
(c) OMC → AA 1.02 0.68 0.66 0.45
that on clean (1 1 1) and (1 0 0) surfaces. Therefore, as summarized in
ΔΔEa 0.24 0.28 0.26 0.30
Table 2, not only the selectivity but also the catalytic activity on clean
Ag (1 0 0) surface Ag (1 1 0) surfaces is superior to that on clean (1 1 1) and (1 0 0) sur-
(a) C2 H 4 + O → OMC 0.53 0.23 0.30 0.31
faces.
(b) OMC → EO 0.79 0.62 0.65 0.30
(c) OMC → AA 0.97 1.14 0.93 0.68 As shown in Fig. 3, the presence of promoters can enhance the se-
ΔΔEa 0.18 0.52 0.28 0.38 lectivity. The selectivity to EO on Ag (1 1 1) surfaces complies with the
sequence of clean Ag < Cu < Cs < Re. As seen in Fig. 4, the se-
lectivity to EO is also enhanced on studied Ag (1 1 0) surfaces. Never-
OMC intermediate formation on studied Ag surfaces. OMC intermediate theless, the promotion impact introduced by promoter on selectivity on
formation on pure Ag (1 1 0) surface proceeds more easily with lower (1 1 0) surfaces is not so obvious compared with that on (1 1 1) surface.
energy barrier relevant to that on clean Ag (1 1 1) and (1 0 0) surfaces. For example, the value of ΔΔEa was improved to be 0.77 from 0.08 on
The energy barriers of OMC formation are higher on promoted Ag Cs promoted Ag (1 1 1) surface while it was only increased by 0.02
(1 1 1) surfaces compared with that on clean Ag (1 1 1) surface. On the (from 0.24 to 0.28) on Cs promoted Ag (1 1 0) surface. ΔΔEa on pro-
contrary, the formation energy on promoted Ag (1 0 0) surfaces is lower moted Ag (1 0 0) surfaces also increases relative to that on pure Ag
than that on clean (1 0 0) surfaces. Among all studied surfaces, Cs (1 0 0) surface (see Table 2). This indicated that the promoter can also
promoted Ag (1 0 0) surface can catalyze the formation of OMC inter- enhance the selectivity to EO on Ag (1 0 0) surfaces. Likewise, the
mediate most efficiently. That is, the sensitivity of surfaces to the pro- promotion effect of the promoters on Ag (1 0 0) surfaces is less obvious
moters would affect the formation of the OMC intermediate. than that on Ag (1 1 1). For instance, on Ag surfaces with Cu promoter,
OMC intermediate would isomerize to form desired and undesired the value of ΔΔEa only increases by 0.20 on Ag (1 0 0) surface while it

Fig. 3. Energy profiles of OMC formation and two competitive pathways starting from OMC intermediate during ethylene epoxidation on (a) pure and (b) Cs, (c) Re
and (d) Cu promoted Ag (1 1 1) surfaces. The blue, grey, red, white, cyan, silver and orange spheres represent the Ag, C, O, H, Cs, Re and Cu atoms, respectively.

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L. Zhu et al.
Fig. 4. Energy profiles of OMC formation and two competitive pathways starting from OMC intermediate during ethylene epoxidation on (a) pure and (b) Cs, (c) Re
and (d) Cu promoted Ag (1 1 0) surfaces. The blue, grey, red, white, cyan, silver and orange spheres represent the Ag, C, O, H, Cs, Re and Cu atoms, respectively.
increases by 0.47 on (1 1 1) surfaces.
Ag particles approximately consist of 80% (1 1 1) facet [28]. We
compared our theoretical results on Ag (1 1 1) surfaces with previous
experimental results in Fig. S2. It can be found that the order of se-
lectivity to EO is Re < clean Ag < Cs in previous studies [28,63]. We
further focus on the competition between isomerization and desorption
of adsorbed EO, since the adsorbed EO becomes more stable on the
promoted Ag surfaces (see Table 1). The value of ΔΔEb is the energy
barrier difference between the reactions of EO(ads) → AA and EO(ads) →
EO (g), as listed in Table S4. Positive value of ΔΔEb means that the ad-
sorbed EO inclines desorb from surfaces instead of isomerizing to AA, so
the competition between isomerization and desorption of adsorbed EO
would not influence the final selectivity toward EO on studied catalysts
except Re promoted Ag catalysts. That is, the selectivity toward EO on
clean and Cs (or Cu) promoted Ag (1 1 1) is determined by the se-
lectivity of OMC isomerization (ΔΔEa). Conversely, the adsorbed EO
inclines to isomerization to AA on Re-promoted Ag surfaces. Despite of
the higher tendency of isomerization of OMC to EO (corresponding to
larger ΔΔEa), the selectivity toward EO on Re promoted Ag surface may
be lower compared with that on clean Ag surface due to high tendency
of EO isomerization. Therefore, the selectivity toward EO on (1 1 1)
surfaces will change to comply with the sequence of Re < pure
Ag < Cu < Cs, which agrees well with the previous studies
[26,28,30,54,63–66]. Likewise, the adsorption of EO becomes more
stable on promoted (1 1 0) and (1 0 0) surfaces. Therefore, desorption of
EO may also affect the selectivity to EO on promoted (1 1 0) and (1 0 0)
surfaces. As shown in Table S4, clean and Cs (or Cu) promoted Ag
(1 1 0) and (1 0 0) surfaces prefer to desorb EO, while isomerization is
prior to desorption for of adsorbed EO on Re promoted surfaces. Hence,
Re promoted Ag surfaces perform badly in selectivity to EO relative to
pure Ag surface due to the high tendency of isomerization of adsorbed
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Applied Surface Science 476 (2019) 115–122
EO, which is consistent with the previous studies [28,67–69]. To be
noticed, Re as single promoter might have no positive effect on EO
selectivity in the absence of other promoters. Accordingly, Re is the
indispensable component of multiple promoters for high selectivity to
EO, where Re can further enhance EO selectivity when it works to-
gether with other promoters, such as Cs, Mo, Nb and so on [28,70,71].
From above, the promotion effects of the promoters on three Ag sur-
faces are different. The selectivity to EO on (1 1 0) surfaces complies
with the sequence of Re < clean Ag < Cs < Cu while the order is
Re < pure Ag < Cu < Cs on Ag (1 1 1) and (1 0 0) surfaces. The
promotion impact of promoters on Ag (1 1 1) surface is more obvious
than that on the promoted Ag (1 1 0) and (1 0 0) surfaces.
3.4. The synergistic effect between crystal planes and promoters
3.4.1. Adsorption intensity of OMC intermediate
As a significant species in ethylene epoxidation reaction, OMC in-
termediate has been demonstrated that it can affect the selectivity to-
ward EO [72–74]. To have a better description about the configuration
character of adsorbed OMC intermediate, a series of geometric con-
stants are constructed (shown in Fig. 6a), containing the lengths of
C1 - C2 (d (C1 - C2)) , C1 - C2 (d (C1 - C2)), C1 - O (d (C1 - O)) , Ag - O (d (Ag - O))
bonds and ∠O - C1 - C2 . The structural parameters of OMC intermediate
when it adsorbed at the energetically most favorable site on studied Ag
surfaces are summarized in Table 3. As summarized in Table 3, the
values of d (C1 - C2) , d (C1 - O) andd (Ag1 - O) are 1.52, 1.44, 2.24 and 2.26 Å,
respectively, which agrees with other theoretical works [33,34]. The
angle of O - C1 - C2 (115.93°) is consistent with the previous results
(116°) [33].
The values of ΔEads /dAg −O (φOMC) (Fig. 6a) has been used to quantify
the adsorption intensity of OMC intermediate [75]. Fig. 6b–e show the
L. Zhu et al.
Fig. 5. Energy profiles of OMC formation and two competitive pathways starting from OMC intermediate during ethylene epoxidation on (a) pure and (b) Cs, (c) Re
and (d) Cu promoted Ag (1 0 0) surfaces. The blue, grey, red, white, cyan, silver and orange spheres represent the Ag, C, O, H, Cs, Re and Cu atoms, respectively.
relationship between the value of φOMC and ΔΔEa on studied surfaces.
The selectivity of OMC toward EO on different Ag crystal planes with
same promoter decreases linearly with the value of φOMC. As shown in
Fig. 6b, the value of φOMC would be diverse among different Ag sur-
faces. Ag (1 1 1) processes the highest adsorption ability of OMC in-
termediate among these surfaces. The OMC adsorption intensity on
clean Ag surfaces complies with the sequence
(1 1 0) < (1 0 0) < (1 1 1), which agrees well with the sequence of the
ΔΔEa. That is, a stronger adsorption strength of OMC intermediate leads
to larger value of ΔΔEa, which is consistent with previous works
[11,75]. Similarly, as plotted in Fig. 6c, the adsorbed OMC intermediate
on Cs promoted Ag (1 1 0) surface is more stable relative to that on
other Cs promoted Ag surfaces. The order of OMC adsorption intensity
on Cs promoted Ag surfaces is (1 1 1) < (1 0 0) < (1 1 0), and it can
coincide with the sequence of selectivity of OMC to EO. Likewise, se-
lectivity of OMC to EO on Re promoted Ag surfaces and Cu promoted
Ag surfaces also positively correlate with the OMC adsorption strength
in Fig. 6d–e. Therefore, tuning the OMC adsorption strength can control
the value of ΔΔEa so that it (φOMC) can be identified as a selectivity
descriptor. To gain an original understanding of the sensitivity in cat-
alytic selectivity of Ag crystal surfaces to the promoter, it is essential to
explore the origin of the diversity of the value of φOMC.
3.4.2. Electron charge redistribution
The binding strength of adsorbate to metal atom was demonstrated
to be influenced by the valence electrons in d-orbital of metal atoms
[76]. The electronic states of the metal atom interact with that of ad-
sorbate, and their hybridized energy levels would split into two groups.
One is the bonding states that are generally occupied under the Fermi
level, and the other is the anti-bonding orbital that lies above the Fermi
level. A change in the adsorption strength is due to the anti-bonding
Applied Surface Science 476 (2019) 115–122
states, that is, a lower location of d-band center (more electrons in the
d-orbital) of the metal atoms makes the anti-bonding states with lower
level and higher occupancy, leading to the weaker interaction between
the adsorbate and metal surface, and vice versa. Consequently, we in-
troduce the d-band center by calculating the projected density of states
(pDOS) of the d-orbital of Ag atoms which will interact with OMC in-
of termediate (see Figs. S3–S5). As shown in Fig. 7a, weakened binding
strength of OMC intermediate and a decrease of electron depletion of
Ag atoms are observed simultaneously with a shift of d-band center to
low energy level, which is consistent with the bond formation analysis
above. It can be seen that the φOMC is directly proportional to the d-
band center while it is inversely proportional to the electron depletion
of Ag atoms on studied Ag surfaces, so the OMC adsorption intensity has
a negative correlation with valence electron depletion of Ag atoms
which will interact with OMC. Combining with the relationship be-
tween φOMC and catalytic selectivity above, it can be concluded the
charge redistribution of Ag catalysts brought about by promoters leads
to the sensitivity of catalytic selectivity of Ag surfaces to different
promoters.
3.4.3. Eletrophilicity of surface atomic oxygen
Although it is accepted that the OMC intermediate is an important
intermediate in ethylene epoxidation [4,74], the adsorbed atomic
oxygen is also significant [77,78]. There are two different atomic
oxygen species, where 'covalent' (electrophilic) oxygen is benefit to
selective EO formation while 'ionic' (nucleophilic) is active in com-
bustion [28,66,79,80]. We study the valence electron distribution of
adsorbed atomic oxygen on clean and promoted Ag surfaces in Fig. 8
and analyze their eletrophilicity. The adsorbed atomic oxygen on Re-
promoted Ag (1 1 1) surface accepts the fewest electron corresponding
to the largest value of ΔΔEa while the atomic oxygen adsorbed on pure
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L. Zhu et al. Applied Surface Science 476 (2019) 115–122

Fig. 7. The adsorption strength of OMC intermediate (φOMC) and electron de-
pletion of surface Ag atoms as a function of d-band centers of surface Ag atoms
which will interact with OMC on pure and promoted (a) Ag (1 1 1), (b) (1 1 0)
and (c) (1 0 0) surfaces.

Fig. 6. (a) Definition of the adsorption strength of OMC intermediate on Ag

surfaces. (b–e) ΔΔEa as a function of adsorption strength of OMC intermediate
(φOMC) on (b) pure, (c) Cs, (d) Re and (e) Cu promoted Ag surfaces.

Table 3
Structural parameters of the adsorbed OMC intermediate on pure and promoted
Ag (1 1 1), (1 1 0) and (1 0 0) surfaces. The values of α present the angle of
∠OeC1eC2 while d(c1-c2), d(c1-O), α (deg), d(Ag1-O) and d(Ag2-O) are the length (in
Å) of C1eC2, C1eO, Ag1eO and Ag2eO bonds, respectively. The values of
φ = ΔEads /dAg − O are employed to measure the adsorption strength of OMC in-
termediate.
d(c1-c2) (Å) d(c1-O) α (deg) d(Ag1-O) d(Ag2-O) ΔEads (eV) φ

Ag (1 1 1) surface
Pure 1.52 1.44 115.93 2.24 2.26 −3.86 −1.71
(1 1 1)a 1.52 1.44 116.00 2.24 2.26 / /
(1 1 1)b 1.52 1.49 / 2.23 2.24 / /
Cs 1.53 1.42 117.45 2.30 2.31 −9.46 −4.17
Re 1.51 1.42 117.84 2.27 2.27 −12.04 −4.95
Cu 1.52 1.44 117.05 2.25 2.53 −8.95 −3.98
Fig. 8. The number of accepting electrons of adsorbed O atom and the value of
Ag (1 1 0) surface
pure 1.51 1.34 118.06 2.21 2.21 −3.98 −1.76 ΔΔEa as a function of Ag surfaces with different promoters.
Cs 1.52 1.44 118.76 2.28 2.28 −8.35 −3.66
Re 1.51 1.43 118.62 2.28 2.28 −8.75 −3.60
Ag (1 1 1) surface accepts the most electrons corresponding to the
Cu 1.52 1.44 118.96 2.27 2.26 −8.57 −3.78
minimum ΔΔEa value. The electron-accepting number of adsorbed O
Ag (1 0 0) surface
atom on studied Ag (1 1 1) surfaces follows the order of Re < Cs <
pure 1.53 1.42 117.79 2.23 2.23 −3.86 −1.73
Cs 1.53 1.40 119.96 2.29 2.22 −8.52 −3.84 Cu < clean Ag. That is, O atom adsorbed on Re promoted Ag (1 1 1)
Re 1.55 1.43 118.34 2.26 2.28 −8.35 −3.66 surface is more electrophilic and would correspond to a larger value of
Cu 1.53 1.42 119.27 2.22 2.24 −8.49 −3.80 ΔΔEa than other studied Ag (1 1 1) surfaces. Equally, the electron-ac-
a
cepting number of adsorbed O atom follows the order of Cu < Cs <
Ref. [33].
b Re < clean Ag and Cs < Cu < Re < clean Ag on studied Ag (1 1 0)
Ref. [34].
and (1 0 0) surfaces, respectively. As seen from Fig. 8, there are

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remarkable negative relevant relations between the electron-accepting
number of adsorbed O atom and the value of ΔΔEa. Therefore, the sy-
nergistic effect between crystal planes and promoters would affect the
eletrophilicity of the adsorbed atomic oxygen, which can accordingly
influence the selectivity to EOads on catalysts.
4. Conclusion
In conclusion, we systematically study the adsorption of atomic
oxygen, oxametallacycle, AA and EO as well as the reaction of ethylene
epoxidation on Cu, Cs and Re promoted Ag surfaces by using density
functional theory (DFT). The promoters have obvious impact on the
adsorption of the adsorbate, which can therefore influence the se-
lectivity to EO. The promotion impact of promoter to selectivity on
different Ag surfaces is different, where the enhancement of selectivity
on promoted Ag (1 1 1) surfaces is more obvious compared with that on
promoted (1 1 0) and (1 0 0) surfaces. The order of selectivity toward
EO on (1 1 0) surface is Re < pure Ag < Cs < Cu while it is
Re < pure Ag < Cu < Cs on (1 1 1) and (1 0 0) surfaces. We identify
the adsorption intensity of OMC intermediate (φOMC) as a descriptor,
which has a positive correlation with selectivity to EO. The adsorption
intensity of OMC intermediate is found to have a negative correlation
with valence electron depletion of surface Ag atoms. Moreover, the
synergistic effect between crystal planes and promoters also have im-
pact on the eletrophilicity of the surface atomic oxygen. Therefore, the
synergistic effect between crystal planes and promoters on catalytic
performance of Ag catalysts is concluded that promoters cause charge
redistribution of various Ag crystal surfaces to different extent and leads
to the corresponding promotion effect on the selectivity toward EO. We
believe that our works would provide approach to improve the se-
lectivity to EO by rationally choosing suitable promoter for specific Ag
crystal surface.
Acknowledgements
This work is supported by the National Natural Science Foundation
of China (21822801, 21576008, 91634116) and PetroChina Innovation
Foundation (2016D-5007-0505).
Appendix A. Supplementary material
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.apsusc.2019.01.076.
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