Article

pubs.acs.org/JPCC

CO Oxidation over Strained Pt(100) Surface: A DFT Study

Fuzhu Liu,† Chao Wu,*,‡ Guang Yang,§ and Shengchun Yang*,†,⊥
†
School of Science, Key Laboratory of Shaanxi for Advanced Materials and Mesoscopic Physics, State Key Laboratory for Mechanical
Behavior of Materials, Xi’an Jiaotong University, Xi’an 710049, People’s Republic of China
‡
Frontier Institute of Science and Technology, Xi’an Jiaotong University, Xi’an 710054, People’s Republic of China
§
Electronic Materials Research Laboratory, Key Laboratory of the Ministry of Education & International Center for Dielectric
Research, Xi’an Jiaotong University, Xi’an 710049, People’s Republic of China
⊥
Collaborative Innovation Center of Suzhou Nano Science and Technology, Suzhou Academy of Xi’an Jiaotong University, 215000,
Suzhou, People’s Republic of China
*
S Supporting Information

ABSTRACT: The oxidation of CO on strained Pt(100) surface was studied

using periodic density functional theory (DFT). Unlike the uniform response of
global properties (e.g., d-band center) to strain, the localized nature of
adsorption leads to complex site-dependent and adsorbate-dependent responses,
invalidating the generally believed statement of “tension strengthens binding”.
Moreover, the complex responses of reaction energetics to strain require direct
study of the reaction under strain rather than extrapolating the known behaviors
of individual adsorbates under strain or reaction energetics on unstrained
surfaces. We show that the tensile strain lowers the reaction barrier of CO
oxidation over the Pt(100) surface. This work provides a theoretical basis of
utilizing strain to improve the Pt catalysts with a higher tolerance toward CO
poisoning.

A number of important chemical reactions catalytically

occur on transition metal surfaces. Various methods,
including alloying/dealloying,1 surface masking with heter-
oatoms,2 morphology control, or defect engineering,3 have
been developed to improve their catalytic performance by
modifying the surface structure. In almost all the methods,
surface strain of the catalysts is introduced and/or varied
through mechanisms like local deformation of a single metal
phase,4 epitaxial metal overlayers,4−6 defects,7 and lattice
mismatch between core and shell.8,9 The geometric and
electronic structures of surface atoms are perturbed, and
consequently, surface catalytic reactions are affected.10−12 In
the past decade, an emerging field of strain engineered catalysis,
aiming at regulating the catalytic performance of transition
metals through strain, has attracted a lot of attention.3,7,13−18
Strasser and co-workers observed high catalytic activity of
dealloyed Pt−Cu core−shell nanoparticles in oxygen-reduction
reaction (ORR), which is attributed to surface strain induced by
lattice mismatch of the core and shell metals.1 Yang group
reported that icosahedral platinum alloy (Pt−Au/Ni/Pd)
nanoparticles presented higher ORR activity than octahedral
ones, as the tensile strain in the former facilitated the reaction
while the compressive strain in the latter hindered it.3
Several theoretical studies have successfully provided a
concise and insightful description of the strain effects on
catalysis by correlating reactivity and strain via the d-band
center shift of the catalyst.3 Nørskov et al. demonstrated that
for Ru(0001) tensile strain leads to surface lattice expansion
and upshift of its d states, in accordance with the enhanced CO
dissociation reactivity.4 Yu et al. further showed that the
continuous shift of the d-band center away from the Fermi level
triggers the weakening of O adsorption on the compressed
Pt(111) and Pt skins of Pt3Co(111) alloy compared with the
unstrained surface.19 Gradually, “tension strengthens binding”
summarized from theoretical predictions become a widely
accepted trend. 20 However, this rule is not always
observed.21−23 For example, Liu’s group found that the
response of chemisorption of CO on the Au(001) and
K(001) surfaces to external strain is site-dependent:24 for
either metal surface, two oppositely going linear relationships
between the CO adsorption energy and strain exist for the on-
top and hollow sites, respectively. Similarly, Groß et al.
discovered that for the same type of site on low-index surfaces
of different metals like Pd5 and Cu6 the H adsorption energy
and tensile strain exhibit opposite linear relationships.
In principle, strain adds an additional dimension of tunability
on top of the traditional catalytic variables including the types
of metals, surfaces, and surface sites, whose different responses
to strain may be utilized to regulate the catalytic reactions. In
this work, as an example, we try to solve or at least mitigate the
well-known problem of “CO poisoning” over Pt utilizing strain.
CO poisoning takes place in many catalytic systems, such as
Received: May 11, 2015
Revised: June 6, 2015
Published: June 8, 2015

© 2015 American Chemical Society 15500 DOI: 10.1021/acs.jpcc.5b04511

J. Phys. Chem. C 2015, 119, 15500−15505
The Journal of Physical Chemistry C
polymer electrolyte fuel cells and direct methanol fuel cells,12
which is caused by strong adsorption of CO on Pt surfaces,
blocking the active sites and reducing the catalytic activity of Pt.
Thus, an important and urgent issue is how to readily remove
CO from Pt surfaces or how to improve the tolerance of CO
poisoning at Pt surfaces? Based on the idea of surface strain
engineering, several techniques such as local deformation7 and
epitaxial metal overlayers25−27 have been developed to regulate
the binding strength of CO. However, a number of questions
about the atomistic behaviors of the relevant adsorbates still
remain unclear. (1) How does strain affect multiple species
involved in CO oxidation (e.g., O, CO) at multiple sites? (2) Is
CO−Pt binding strength the only key parameter to control?
(3) For the coadsorption of CO and O, required during CO
oxidation, how does the adsorption of one species affect the
other? (4) Whether the tolerance of CO poisoning at Pt
surfaces can be improved by strain?
Here we use the system of CO oxidation over the Pt(100)
surface as an example model to study the strain effects. First,
using the periodic density functional theory (DFT), we
systematically investigate the adsorption behaviors of key
species (e.g., O and CO) at multiple sites (e.g., top, bridge,
and 4-fold hollow sites) under compressive and tensile strains
(−3% to 3%). Next, we check if the response of coadsorption
to strain can be expressed as a linear combination of the
responses of each involved species. Finally, we probe the
variation of the energetics of CO oxidation under strain, thus
verifying if the higher tolerance of CO poisoning at Pt surfaces
can be achieved through surface strain engineering.
The spin unrestricted density functional theory (DFT)
calculations were carried out using the Dmol3 program
package.28,29 The generalized gradient approximation (GGA)
with the Perdew and Wang-91 (PW91) formulation of the
exchange-correlation functional was employed.30,31 The self-
consistent PW91 density was determined by iterative
diagonalization of the Kohn−Sham Hamiltonian.32 The valence
electron wave functions were expanded into a set of atomic
orbitals composed of the double numerical plus d-functions
(DND) basis set. Brillouin-zone integrations were performed
on a grid of (8 × 8 × 1) Monkhorst−Pack k-point mesh. The
width of the Fermi smearing of the Kohn−Sham states was set
to kBT = 0.005 hartree. The Pt(100) surface was modeled by
using a (2 × 2) five-layer slab supercell with the bottom three
layers frozen. Each slab was separated by a vacuum of 15 Å to
minimize the interactions between images. The convergence
criteria for geometry optimization were set to 10−5 hartree,
0.002 hartree/Å, and 0.005 Å for energy, force, and
displacement, respectively. Compressed and tensile strain
ranging from −3% to 3% was imposed in parallel to the
surface plane by changing the lattice constant of the unstrained
Pt(100) surface. This approach has been shown to yield
accurate estimates of adsorption energies on strained transition
metal surfaces.11 The calculated equilibrium lattice constant of
3.924 Å for Pt was in agreement with the experimental value of
3.920 Å.33 O2 and CO molecules were relaxed by placing them
individually in a rectangular cuboid box with a vacuum space of
at least 15 Å in all three directions to minimize image
interactions. The bond lengths were 1.224 Å (O2) and 1.140 Å
(CO), very close to the experimental values of 1.210 Å19 and
1.120 Å,4 respectively. To investigate the minimum-energy
pathway for O adatom diffusion and CO oxidation on the
strained Pt(100) surface, linear synchronous transit/quadratic
synchronous transit (LST/QST) approaches were invoked.34
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To interpret the strain effects on binding strength, the d-band
center model was employed.35−37 In addition, the adsorption
energy is defined as ΔE = E(ads/metal) − E(metal) − E(ads),
where E(ads/metal), E(metal), and E(ads) are the energies of
the adsorbate−slab system, the slab, and the adsorbate,
respectively.
Adsorbates and surfaces mainly interact through mixing the
valence orbital of the adsorbates and the d states of the surfaces.
The latter is concisely represented by the d-band center model
with the d-band center energy denoted as εd.38 The d-band
center model has been widely used to rationalize the catalytic
activity trends of transition metals and alloys,4,19,39,40 which is
also employed here to explain how strain modifies the
electronic structure of the Pt(100) surface and subsequently
its interactions with adsorbates.
The d-band center (εd) of the Pt(100) surface rises linearly
with the increasing tensile strain (Figure 1). As the atoms are
Figure 1. The d-band center of the Pt(100) surface as a function of
surface strain. The solid line only serves as a guide for eye. Top insets:
top views of the electron density plots of the −3% compressed (left),
equilibrium (middle), and 3% stretched (right) Pt(100) surfaces. The
color bar from red to blue indicates the reduction of the electron
density. Bottom inset: top view of the Pt(100) surface. The top (t),
bridge (b), and 4-fold (4f) sites are marked by the dark red circles.
Dark and light gray circles represent the sublayer and toplayer Pt
atoms, respectively.
moved away from their stable positions by the tensile strain, the
overlaps of the d states among atoms are reduced and the d-
bandwidth becomes narrower. Subsequently, the d-band shifts
upwardly,15,20 which is evidenced in the electron density plots10
(Figure 1, insets). The εd shift range is ∼0.2 eV from −3% to
3% strain, suggesting a fairly wide tunability of the surface
electronic structure; thus, it is interesting to see how the
adsorbates (e.g., O and CO) respond to this wide εd change.
Strain may cause various responses among different
adsorbates. The stronger binding of O atom, CO, and NO
molecules over stretched Ru(0001) surface was observed
experimentally,7,41 while the reduction in binding strength of
O atom on compressed Pt(111) was rationalized as a result of
the shift of d-band center away from the Fermi level.19 The
adsorption sites on the Pt(100) surface are defined in the
bottom inset of Figure 1. For O adatom, our calculations show
that the 4f site is the most stable site, the b site takes second
place, and the t site is less stable(Table S1), confirming the
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Figure 2. O adsorption energy at the 4f and b sites on the Pt(100) surface versus strain. (a) O adsorption energy at the 4f and b sites. Insets: top
views of O adsorption configurations. The t site O is unstable and migrates to the 4f site (indicated by the black arrow in the bottom left inset). (b)
CO adsorption at the t, 4f, and b sites. Insets: top views of CO adsorption configurations. The solid lines only serve as a guide for eye. The color
coding of the circles is as in Figure 1.

previous studies.42,43 As illustrated in Figure 2a, with the adsorption energy increases along with the rising tensile strain.
increase of the tensile strain, the O adsorption energy difference Particularly, for the latter (the t site), the tensile strain
between the 4f and b sites decreases from 0.29 eV at −3% strain introduces evident nonlinear response of the adsorption energy.
to 0.14 eV at 3% strain. For the b site, the O adsorption energy However, an opposite trend appears for the b site, quite
and the tensile strain (or the lattice constant expansion) different from the previous report of Au(001) and K(001)
relationship is monotonic: more exothermic adsorption systems,24 which may be caused by the different d-states of the
corresponds to larger tensile strain, which needs two linear metal surfaces at the Fermi level.36 The calculation results also
segments with similar slopes for compressed and stretched reveal that the Pt(100) surface, like the stepped Cu(211) and
regions to describe accurately. For the 4f site, the flat line in the Ni(211) surfaces, exhibits complex CO binding response to
compressive strain range reflects the insensitiveness of the 4f external strain, emphasizing the oversimplicity of the rule of
site to compression. Usually, O adatoms prefer a large “tension strengthens binding”.20
coordination number when adsorbed on a metal surface.42 The CO oxidation over the lateral strained Pt(100) surface
For the 4f site, tensile strain counteracts the lateral contraction follows the Langmuir−Hinshelwood (L−H) mechanism,44
caused by the O adsorption and thus weakens the adsorption. which requires the coadsorption of CO and O. We focused
For the b site, tensile strain promotes the O adatom’s bridging on the coadsorption energy (ECO+O(ε)) as a function of tensile
coordination to the Pt atoms, where the distance between the strain (ε) on the Pt(100) surface (eq 1).
O and Pt atoms decreases from 2.027 to 2.024 Å, strengthening
the adsorption from −3.639 to −3.678 eV (Table S1). The very ECO + O(ε) = E0 + k × ε (1)
different responses of O adatom at the 4f and b sites to strain
E0 represents the coadsorption energy of CO and O at zero
might serve as a handle for strain engineered catalysis.
strain and k is the slope. ECO+O can be obtained from either
Next, we studied the CO adsorption on the Pt (100) surface
direct DFT calculations of coadsorbed configurations or by
at the 4f, t, and b sites (Figure 2b and Table 1), where the C−
summing up the individual adsorption energies of CO molecule
and O atom over the strained surface.
Table 1. CO Adsorption Energy (Ead) and the C−O Bond The directly calculated coadsorption energy (Figure 3a, the
Length (d(C−O)) on the Pt(100) Surface black line and squares) becomes more exothermic linearly with
4f site b site t site the rising tensile strain. The summed-up coadsorption energy
strain d(C−O) d(C−O) d(C−O)
can be computed using the most stable adsorption site of each
(%) Ead (eV) (Å) Ead (eV) (Å) Ead (eV) (Å) individual adsorbate, i.e., the b site for CO and the 4f site for O
−3 −1.509 1.189 −1.589 1.169 −1.200 1.152 (Figure 3a, the dashed blue line and triangles). For the
−2 −1.512 1.190 −1.608 1.170 −1.207 1.153 summed-up coadsorption energy and strain, the opposite trend
−1 −1.517 1.189 −1.624 1.171 −1.210 1.153 is observed. The values of E0’s are markedly different by over
0 −1.516 1.189 −1.638 1.171 −1.217 1.153 ∼0.4 eV, with the directly calculated E0 being the higher one.
1 −1.502 1.190 −1.644 1.171 −1.241 1.153 Apparently, the adsorption energy of coadsorbed species is not
2 −1.481 1.190 −1.646 1.171 −1.212 1.153 a simple linear combination of that of each adsorbate at its most
3 −1.466 1.188 −1.650 1.172 −1.199 1.154 stable site. In fact, on Pt(100), the most stable coadsorption
configuration of CO and O before oxidation occupies two
neighboring b sites. At the presence of CO, the O adatom is
Pt coordination is favored and the b site is the most stable pushed away from its most stable 4f site by repulsive lateral
binding position, in agreement with the previous study.12 interactions. It implies that O adatoms could be easily relocated
Overall, the CO adsorption is much weaker than that of the O with the help of CO molecules.45−47 Therefore, selecting
adsorption by ∼2.3 eV. Calculations reveal that the CO adsorption energy at the b site for O adatom instead of that at
adsorption energy at different sites changes very differently with the 4f site is more reasonable for the summing-up scheme. This
strain. All sites show slight rises in adsorption energies (less time, the summed-up coadsorption energy (Figure 3a, the red
exothermic) to compressive strain, suggesting a weakened line and dots) presents the same trend as the directly calculated
adsorption. For the 4f and t sites on a stretched surface, the ones.
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Figure 3. Coadsorption of CO and O on Pt(100) surface with tensile
strain. (a) Coadsorption energies (ECO+O(ε)) versus strain. ECO+O(ε)
are calculated using coadsorbed configuration (Directly calculated,
black), using both b-site adsorption energies for CO and O (Summed-
up (b+b), red), and using 4f site and b site adsorption energies for CO
and O (Summed-up (4f+b), blue). (b) Extracted CO and O lateral
interactions versus strain. Directly subtracted (E1CO+O − E2CO+O, red)
and indirectly subtracted (black). To get the latter, two steps are
involved. (1) The individual adsorption energy is calculated by
freezing the relaxed coadsorption structures and removing one
adsorbate (keeping the other) at a time. (2) The lateral interaction
is obtained by subtracting these energies from the total coadsorption
energy. Note: the coadsorption configuration of CO and O on the
Pt(100) surface is presented in Figure S1.
Furthermore, the lateral interactions of coadsorbed CO and
O can be extracted (Figure 3b). A rough estimation can be
done (the dashed red line) by directly subtracting the summed-
up coadsorption energy using the b-site adsorption energies for
both CO and O (Figure 3a, the red line and dots) from the
directly calculated ones. The lateral interactions are ∼0.2 eV
repulsive, and they drop slightly as the tensile strain rises. A
more accurate way (“the indirect subtraction”) to obtain the
lateral interactions is by using the frozen structures under strain
with either CO or O removed, whose energies are used to
extract the lateral interactions (Figure 3b, the dashed black line
and dots). Both curves in Figure 3b have the same trend and
quantitatively close (differ by ∼0.03 eV). These results suggest
that the trend of coadsorption energy can be quantitatively
reproduced by the linear combination of the adsorption energy
of individual components at the near coadsorption config-
uration rather than the most stable configuration by itself.
At least at low O coverage, O2 automatically dissociates on
low-index Pt surfaces such as (111), (100), and (321).48−50
Although O adsorption is much stronger than CO adsorption,
their coadsorption has exemplified the change of favorable
binding site of O. Thus, the mobility of O adatoms over
strained surface may be crucial in many reactions including CO
oxidation.42 The diffusion of an O adatom from one 4f site to a
nearby 4f site is investigated under different strains. Similar to
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H diffusion on the TiN(100) surface, there are two typical
migration pathways for O adatoms to move over the surface:
the 4f−4f and 4f-b-4f paths (Figure 4a).51 For unstrained
Figure 4. Diffusion pathways of an O adatom on the Pt(100) surface.
(a) On the unstrained surface, diffusion pathways from a 4f site to its
neighboring 4f site (black) directly or via the b site (red). Insets: top
views of the diffusion paths. Dashed-open, pink-filled, and solid-open
circles represent the initial, transition (TS), and final states,
respectively. The color coding of other circles is as in Figure 1. (b)
Minimum-energy paths (4f-b-4f) on the −3%, 0%, and 3% strained
Pt(100) surface.
surface, the diffusion barrier via the 4f−4f path is 0.275 eV
higher than that of the 4f-b-4f path by 0.048 eV. A local
minimum appears in the latter when the O adatom moves onto
the b site, thus lowering the barrier than directly crossing the b
site. The minimum-energy paths of O diffusion under strains
are plotted in Figure 4b (for details see Table S2). A distinct
decrease in transition barrier by ∼0.165 eV is observed when
the tensile strain increases from −3% to 3%, consistent with the
tensile strain induced weakening of O adsorption at the 4f site
mentioned above. However, for the coadsorption case, the
most stable configuration has CO and O both adsorbed at two
neighboring b sites, and the relocation of the latter from the 4f
to b site is necessary (Figure 4); thus, an easier diffusion of O
atom could facilitate the reaction of CO oxidation under tensile
strain.
The lack of unanimous response of local properties (e.g.,
adsorbates at various sites) to the perturbation introduced to
global properties (e.g., strain or the d-band center shift) is
expected to alter the energetics of a reaction path. Figure 5
sketches the potential energy profiles of CO oxidized by O
adatoms via the L−H mechanism44 on the strained Pt(100)
surfaces. The activation energy barrier from the initial state to
the transition state for the stretched surface (3%) is below that
of the unstrained one by ∼0.29 eV, while the barrier of the
compressed surface (−3%) is higher by ∼0.57 eV. For the
transition state of the stretched surface (3%), the O atom
moves slightly to the 4f site compared with the originally
DOI: 10.1021/acs.jpcc.5b04511
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The Journal of Physical Chemistry C
Figure 5. Energy profiles of CO oxidation on the Pt(100) surface. IS,
TS, and FS refer to the initial, transition, and final states, respectively.
The activation energies are labeled. Insets: the geometry of the key
states during the CO oxidation on the −3%, 0%, and 3% strained
Pt(100) surface. The color coding of the circles is as in Figure 1.
favored b site in the initial state, whereas the CO molecule tilts
about 19° relative to the vertical configuration. The distance
between the C atom and the O adatom is 2.712 Å, which is
smaller than the initial state by 0.328 Å (Figure 5, inset). The
big variation in reaction energetics is the collective results of
different responses of the adsorbed O and CO to strain,
invalidating the simple statement that all adsorptions are
strengthened by tensile strain. In addition, our results are in line
with the experimental and theoretical observations that the
activity of nanoparticles with tensile strained surface is higher
than that of compressed surface.3,7
In summary, we have studied CO oxidation over the Pt(100)
surface under surface strain (−3% to 3%) using the periodic
DFT calculations. Through investigating this model system, we
hope to utilize strain to help solve the problem of CO
poisoning over Pt. Our main observations are summarized as
(i) in contrast to the single linear relationship between the
upward shift of the d-band center and the increasing strain
(from compressive to tensile), the adsorption energies of key
reactants (e.g., O adatom and CO molecule) exhibit bi- or
multisegment correlations to strain. These complex site-
dependent responses of different adsorbates to strain are
rooted in the localized nature of adsorption events. For
example, the adsorption strengths of O adatom and CO
molecule on their most stable binding sites present opposite
changes over the same strained surfaces. (ii) For coadsorption
of CO and O, the lateral interactions relocate the O away from
its most stable binding site; thus, linearly combining the
information on each involved adsorbate at its most stable
binding site does not qualitatively reproduce the coadsorption.
(iii) The O diffusion barrier decreases on the tensile strained
surface, which may facilitate the CO oxidation. (iv) The
activation energy of CO oxidation on the strained Pt (100)
surface is evidently reduced compared to unstrained surface,
which is desired for curing the CO poisoning. (v) The complex
responses of reaction energetics to strain require direct study of
the reaction under strain rather than extrapolation of known
behaviors of individual adsorbates under strain or reactions on
unstrained surfaces. We have shown that the tensile strain can
be utilized to enhance the reactivity of CO oxidation over the
Pt(100) surface; thus, strain is a useful handle to remedy or
even solve the CO poisoning problem.
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■
*
ASSOCIATED CONTENT
S Supporting Information
Adsorption energy of O atom and O2 and the bond length of
O2 (Table S1); the energy difference and diffusion barrier of O
atom under strained surface (Table S2); the configuration of O
and CO coadsorption on Pt surface (Figure S1). The
Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.jpcc.5b04511.
■ AUTHOR INFORMATION
Corresponding Authors
*E-mail: ysch1209@mail.xjtu.edu.cn (S.Y.).
*E-mail: chaowu@mail.xjtu.edu.cn (C.W.).
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work is supported by National Natural Science
Foundation of China (No. 51271135, 21203143), the program
for New Century Excellent Talents in university (No. NCET-
12-0455), the Fundamental Research Funds for the Central
Universities, the Natural Science Foundation and the project of
Innovative Team of Shanxi Province (No. 2015JM5166 and
2013KCT-05).
■
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DOI: 10.1021/acs.jpcc.5b04511
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