Observation of water dissociation on nanometer-sized FeO islands grown on Pt(1 1 1)

Article abstract of DOI:10.1016/j.cplett.2010.09.080

Adsorption and dissociation of water on nanometer-sized FeO islands on Pt(1 1 1) substrate were investigated using scanning tunneling microscopy. It is observed that the adsorbed water molecules may spontaneously dissociate into hydroxyls on the step edge

Full text of DOI:10.1016/j.cplett.2010.09.080

Chemical Physics Letters 500 (2010) 76–81
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Chemical Physics Letters
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Observation of water dissociation on nanometer-sized FeO islands grown on
Pt(1 1 1)
⇑
Wen Wang, Hui Zhang, Weihua Wang, Aidi Zhao, Bing Wang , J.G. Hou
Hefei National Laboratory for Physical Sciences at the Microscale, University of Science and Technology of China, Hefei, Anhui 230026, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
Received 12 May 2010
In final form 30 September 2010
Available online 14 October 2010
Adsorption and dissociation of water on nanometer-sized FeO islands on Pt(1 1 1) substrate were
investigated using scanning tunneling microscopy. It is observed that the adsorbed water molecules
may spontaneously dissociate into hydroxyls on the step edges of the FeO(1 1 1) islands, even at 80 K,
which can be attributed to the active sites of coordinatively unsaturated Fe atoms at the step edges. These
hydroxyls are found to diffuse and form chains on the FeO terrace. The formation of the oxygen vacancy
chains on FeO islands indicates that the hydroxyls may desorb from the surface as H
temperature.
2 2
and H O at room
Ó 2010 Elsevier B.V. All rights reserved.
1
. Introduction
Parkinson et al. [13] investigated the interaction of Fe0 atoms with
2
D O layers on FeO(1 1 1) and found dissociation products of FeOD
Oxide surface plays an important role in the surface chemistry
and hydroxyl.
and heterogeneous catalysis. The chemistry of water on oxide sur-
faces has received considerable attention [1–6]. Water adsorption
on epitaxial films of iron oxides grown on Pt(1 1 1) substrate has
been investigated by thermal desorption spectroscopy (TDS), infra-
red reflection absorption spectroscopy (IRAS) and photoelectron
spectroscopy (UPS, XPS) [7–10]. Perfect oxygen-terminated
FeO(1 1 1) monolayer films are chemically inert [7–9]. Water
molecularly physisorbs through an attractive electrostatic inter-
action between the oxygen atoms of the adsorbates and the Fe
cations located on the second layer. The IRAS measurements show
that water is hydrogen bonded at low coverage even at 30 K, and
no evidence of isolated water monomers is found. A kinetic analy-
Ultra-thin FeO(1 1 1) films can be reduced after exposure to
atomic hydrogen at room temperature, leading to the formation
of triangularly-shaped oxygen vacancy dislocation loops at specific
sites [14,15]. Knudsen et al. [16] observed that water dissociates on
the most heavily reduced FeO
gen vacancy dislocation loops was resulted from the reduction of
2
FeO film [14–16], in which the hydroxyls desorb as H and H O
x
film. The presence of triangular oxy-
2
from the surfaces by either heating the hydroxylated surface to
500 K [14] or increasing the concentration of the hydroxyl to a
threshold of 12% ML [16]. Two types of oxygen vacancy dislocation
loops were observed [15,16]. The smaller one is always centered at
hcp domains with an edge length of approximately five Fe atoms,
and the larger one is always centered at the top domains with an
edge length of 12 Fe atoms.
ꢀ1
sis determined the isosteric heats of adsorption of qst = 52 kJ mol
,
15 ꢀ1
with a preexponential v = 3 ꢁ 10
s
for the monolayer and
ꢀ
1
15 ꢀ1
q
st = 47 kJ mol , v = 3 ꢁ 10
s
for the bilayer [9]. On Fe (1 1 1)
O
3 4
Peculiar catalysis of oxide nanoparticles has attracted many
surface exposing both iron and oxygen atoms, initial water adsorp-
tion is dissociative. The resulting OH group binds to the iron cations
and the H species to the neighboring oxygen sites. As the coverage
concerns, such as gold nanoparticles supported on TiO
particulated CeO [17]. For the Pt/oxide nanocatalysts, its activity
in the preferential oxidation (PROX) reaction at low temperatures
could be enhanced by Fe or FeO additives [18,19]. The interfacial
COads + OHads reaction to produce CO occurred facilely at the
2
and nano-
2
increases, coadsorbed water molecules bridge the OH and H groups
x
þ
forming a hydronium-ion-like structure OH –OH [10]. Joseph et al.
2
3
[
c
7,11] determined the heats of adsorption for the dissociated
-species (65 kJ mol ). A recent work by Cutting et al. [12] has dem-
Pt–oxide interface at low temperatures [20]. Generally, surface
defects strongly influence the surface chemistry of metal oxides.
Precisely monoatomic-height step edges at terraces constitute
some of the most common defects on the surface. Kim et al. [21]
showed that the alcohols dissociate primarily at FeO(1 1 1) step
edges. It is found that the step edges are also responsible for the
ꢀ1
onstrated that the saturation coverage of dissociated water on the
Fe (1 1 1) surface is limited to the number of surface Fe sites,
indicating that the metal sites are the active centers for water
dissociation. Using the ‘atom-dropping’ preparation technique,
3 4
O
2
CO oxidation [22]. Similarly, the anatase TiO (1 0 1) surface is
fairly nonreactive for water dissociated [23]; however, theoretical
calculations by Gong et al. [24] showed that both molecular and
dissociative H O adsorption can occur at the step edge.
2
⇑
Corresponding author. Fax: +86 551 360 2803.
E-mail address: bwang@ustc.edu.cn (B. Wang).
0
009-2614/$ - see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.cplett.2010.09.080

W. Wang et al. / Chemical Physics Letters 500 (2010) 76–81
77
In this Letter, we studied the effect of the edges of FeO islands
on the adsorption behavior of water molecules using scanning
tunneling microscopy (STM). The dispersed nanometer-sized FeO
islands were grown heteroepitaxially on Pt(1 1 1) substrates. The
adsorption behaviors of water on the islands were characterized
both at room temperature and at 80 K. The presence of surface
hydroxyls and oxygen vacancy chains on the islands after water
adsorption indicates that water is dissociative. We suggest that
the coordinatively unsaturated Fe atoms were the active centers
for water adsorption and dissociation.
2
. Experimental details
The STM experiments were performed using a low temperature
scanning tunneling microscope (OMICRON, SCALA), in an ultra-
high vacuum (UHV) analysis chamber with a base pressure of
ꢀ
11
ꢂ5 ꢁ 10
mbar. The Pt(1 1 1) single crystal sample was prepared
base pressure of
mbar. The Pt(1 1 1) surface was cleaned by cycles of
Ar sputtering (1 keV, 20 min) and annealing (flash to 1000 K,
0 min). The FeO islands were prepared by depositing submono-
layer of Fe at 150 K with an e-beam evaporator in O partial
pressure of 5 ꢁ 10 mbar. After the vacuum pressure recovered
in an UHV preparation chamber with
a
ꢀ
10
3
ꢁ 10
+
2
2
ꢀ
10
7
ꢀ
to about 5 ꢁ 10
mbar, the sample was then annealed to 410 K
for 1 min. Water (deuterium depleted, from Sigma–Aldrich) was
degassed in several freeze–pump–thaw cycles and introduced into
the STM by using a leak value. The water dosing was performed by
keeping the sample at room temperature or keeping the sample
onto the cryostat of the microscope at 80 K. All STM measurements
were performed at 80 K with
a constant current mode. A
chemically etched tungsten tip was used.
3
. Results and discussion
Figure 1a shows the image of nanometer-sized FeO islands dis-
Figure 1. (a) STM image of FeO islands grown on Pt(1 1 1) (acquired at 50 mV and
1.2 nA). (b) Plot of size distribution of FeO islands. (c) Atomic resolved image of the
bare Pt(1 1 1) substrate before FeO growth (acquired at 3 mV and 6 nA). (d) Image
of Pt(1 1 1) between the FeO islands after FeO growth (acquired at 50 mV and
persed on Pt(1 1 1). Overall, the islands are triangular but with
truncated corners. This shape is similar to FeO particles grown on
Au(1 1 1) [25]. The size distribution of FeO islands is plotted in
1.2 nA). (e) Atomic resolved image of an FeO island with two sets of edges A and B
(
acquired at 20 mV and 2.1 nA). The circles represent the centers of three different
domains of Fe on top sites (Fe–top), Fe on fcc sites (Fe–fcc), and Fe on hcp sites (Fe–
hcp) of Pt(1 1 1) surface. (f) Ball model (top view) corresponding to the FeO island in
(e). (g) Line profile for the label line in (e).
Figure 1b. The islands are mainly distributed between 20 and
2
4
0 nm in area. The moiré patterned feature in the islands is
similar to that in FeO(1 1 1) monolayer on Pt(1 1 1) [26–28]. It
is suggested that lattice mismatch between the hexagonal
Fe/O-lattice (3.1 Å) and the Pt(1 1 1) substrate (2.78 Å) as well as
a small rotation of the Fe/O-lattice relative to the substrate
is schematically given in Figure 1f. In the model, the centers of
the different domains are correspondingly labeled. We suggest that
the edge atoms of the FeO islands are coordinatively unsaturated
[22]. In the truncated triangular island, there exist nonequivalent
edges, as marked by A and B. In the edge A each outermost Fe atom
is bonded with two oxygen atoms (two-fold coordinated Fe atom),
while in the edge B each outermost Fe atom is only bonded with
one oxygen atom (one-fold coordinated Fe atom). An edge with
two-fold coordinated Fe atoms should be energetically more stable
than the one with only one-fold coordinated Fe atoms. Therefore,
the edge A with a longer lateral length is assigned to two-fold
coordinated Fe atoms, and the short edge B to one-fold coordinated
Fe atoms. There is some evidence that such coordinatively unsatu-
rated Fe atoms are responsible for the catalytically active sites for
CO oxidation [22]. The islands have slightly bright edges, but from
the line profile the step edges have almost the same height as the
terrace, as shown in Figure 1g.
(
ꢂ0.6°) leads to a characteristic moiré patterned structure with
ꢂ25 Å periodicity [29]. There are three different domains in the
FeO(1 1 1) monolayer, i.e., Fe on top sites (Fe–top), Fe on fcc sites
(
Fe–fcc), and Fe on hcp sites (Fe–hcp) of Pt(1 1 1) surface [30,29].
The FeO(1 1 1) monolayer consists of a hexagonal Fe-lattice sand-
wiched in between the Pt(1 1 1) substrate and a hexagonal surface
layer of O atoms. As shown in Figure 1c, the atomic resolved image
of the Pt(1 1 1) substrate was obtained, which is used to determine
the orientation of the islands. It is also noted that there exist dark
spots on Pt(1 1 1) substrate between the FeO islands (Figure 1d).
These dark spots have quite similar feature as the observation for
oxygen atoms on Pt(1 1 1) [31]. Therefore, we assign the dark spots
on Pt substrate to the residual oxygen atoms in our sample. The
coverage of oxygen is about 0.02 ML. Figure 1e shows a typical
atomic resolved image of an FeO island. The centers of the different
domains (Fe–top, Fe–fcc, and Fe–hcp) are labeled by circles in the
island. The edges of the islands approximately run along h1 1 0i
directions. According to the features of the orientations of the
island edges and the moiré patterned structure, such islands
should adopt the same structure as that for the FeO(1 1 1) mono-
layer [26–28]. As an example, the atomic model of the FeO island
Following, the sample was exposed to 10 Langmuir water
ꢀ7
(1.3 ꢁ 10 mbar for about 100 s) at room temperature. We
allowed the sample to be maintained at room temperature for
ꢀ
11
about 6 h with a vacuum pressure of about 5 ꢁ 10
mbar. Figure
2a shows a typical image of FeO islands. The images were acquired
at 80 K. Compared with the as-grown FeO islands (Figure 1a), the

7
8
W. Wang et al. / Chemical Physics Letters 500 (2010) 76–81
dislocation loops upon heating the hydroxylated surface to 450 K
16], caused by desorption of hydroxyls as H and H O [14]. As a
[
2
2
result, the remaining O atoms at one side of the oxygen vacancy
chain may shift to adjacent hollow sites, forming an edge disloca-
tion. However, the coordinatively saturated Fe atoms in the terrace
of FeO(1 1 1) are chemically inert for water dissociation [7–9],
therefore the dissociative reaction does not directly happen on
the terrace of the FeO islands. The source of hydroxyls should be
originated from other mechanisms.
It was reported that at low temperatures a well-ordered bilayer
of water can be formed in a hexagonal honeycomb structure on
Pt(1 1 1) [32,33]. The water molecules in the lower half bilayer
are bonded to the metal and to three neighbors in the upper layer
via hydrogen bonds, leaving the upper waters with one unsatisfied
hydrogen bond each. The structure of a full bilayer has been
p
p
determined to be 39 ꢁ 39R16.2° by LEED [34,35]. On oxygen
precovered Pt(1 1 1) surface, H
2
O is dissociative to form a mixed
p
p
layer of OH and H
2
O with 3 ꢁ 3R30° and (3 ꢁ 3) structures at
about 150 K [36–41]. Water desorbs between 150 and 170 K from
a pure water bilayer, while it desorbs around 200 K from the mixed
2
layer of OH and H O on an O-covered Pt(1 1 1) surface [42–45]. In
the latter case, the proton transfer is important to re-produce
water [39,46,47]. However, water does not tend to adsorb at
Pt(1 1 1) surface at room temperature [44], thus, the dissociative
water may be also restricted on oxygen precovered Pt(1 1 1) for
the water-dosed sample at room temperature. Moreover, in our
experiment the coverage of the residual oxygen on Pt(1 1 1) is rel-
atively low, with only about 0.02 ML (Figure 1d and the inset in
Figure 2a). It is insufficient to form a stable mixed layer of OH/
2
H O (or ‘OHx’) on Pt(1 1 1) [41], especially at room temperature.
It is noticed that the coverage of oxygen on Pt(1 1 1) surface is al-
most unchanged after water was dosed at room temperature in our
sample, which indicates that dissociative water on Pt(1 1 1) is, if
there were, not a main source for the hydroxyls occurred on FeO
islands. Moreover, it also indicates that the diffusion of oxygen
on Pt(1 1 1) may not be fast enough (with diffusion barrier of
2
Figure 2. (a) STM image of FeO islands after dosing H O (10 Langmuir) at room
temperature (acquired at 30 mV and 2.0 nA). The inset shows the Pt(1 1 1) substrate
with oxygen coverage of 0.02 ML. (b) Magnified image of a typical island (acquired
at 30 mV and 2.0 nA). The superposed grid shows the O lattice, and the white and
the dark arrows mark the bright chains and the dark chains, respectively. (c) Line
profiles for the lines 1 and 2 marked in (a). Profile 2 is shifted upward by 1 Å for
2
clarity. (d) Line profile for the line 3 marked in (b). (e) Image of the same H O dosed
0
.43 eV [31]) to the FeO islands to compensate the deficiency of
sample after annealing at 650 K. The upper left inset shows the image of Pt
substrate, and the right inset shows a magnified image of dark triangle on the FeO
terrace (20 mV and 2.0 nA). (f) Line profiles for the line marked in (e).
oxygen when the hydroxyls desorb as H and H O from the FeO is-
2
2
lands at room temperature. Compared with the coordinatively sat-
urated Fe atoms in the perfect FeO film, the coordinatively
unsaturated Fe atoms at the edge may be more active for adsorp-
tion and dissociation of water molecules, which is consistent with
the observation for alcohol dissociation [21] or CO oxidation [22].
We suggest that the water molecules prefer to adsorb at the
edges of the islands and undergo spontaneous dissociation at the
coordinatively unsaturated Fe atoms. This process is schematically
main difference is that there appear some bright protrusions and
dark rows inside the FeO islands, and some adsorbates at the island
edges. Statistically, the island edges become slightly rough. The
feature of Pt(1 1 1) substrate is almost kept unchanged, remaining
nearly the same coverage of oxygen, as shown in the inset of Figure
2a. Figure 2b gives a magnified STM image of an island. On the
2
depicted in Figure 3. A H O molecule may initially adsorb at the
island, it is observed that there exhibit chains of bright protrusions
on O lattice both at edge and on terrace (marked by the white
arrows) and dark chain (marked by the black arrow). The apparent
height is about 1.3 Å for the FeO islands, and the protruded chains
are higher than the FeO terrace by about 0.5 Å, as the line profiles
given in Figure 2c and d.
Since water desorbs from FeO(1 1 1) around 200 K [7], the
molecular water adsorption on the FeO islands for the water-dosed
sample at room temperature can be ruled out. The protrusions on
FeO islands in Figure 2a may be attributed to the species of disso-
ciative water, most likely hydrogens atop O atoms, forming
hydroxyls on FeO islands. Similar bright protrusions and dark rows
edge Fe atom site (Figure 3a), and then it spontaneously dissociates
into two hydroxyls (Figure 3b). In this mechanism, the number of
the coordinatively unsaturated Fe atoms is important since the
water dissociation is limited once the unsaturated Fe atoms are
exhausted. In the nanometer-sized islands, the ratio of the number
of the unsaturated Fe atoms at the step edge to the area of an island
can be much large. Knudsen et al. have pointed out that water can
dissociate on the corner sites of the dislocation loops (oxygen
vacancy sites) [16], on which the Fe atoms are coordinatively
unsaturated. In our experiment, since the as-prepared FeO islands
have sparse dislocations, we did not observe such phenomenon.
At room temperature, the hydroxyls (or H) may diffuse from the
edge into the FeO terrace. It is observed that the hydroxyl protru-
sions on FeO islands tend to form chains between domains of the
moiré patterned structure (Figure 2a and b). This may be due to
higher adsorption energy of hydroxyls at these sites. We notice
that these sites may be quite related to the formation of dislocation
loops in the FeO monolayer. In the work by Metre et al., after the
FeO monolayer was exposed to atomic hydrogen and subsequently
(
or triangles) have been observed in FeO(1 1 1) monolayer film on
Pt(1 1 1) after dosing atomic hydrogen [15]. Since H atoms prefer
to adsorb and form hydroxyls atop O atoms, the positions of
hydroxyls are signature of lattice O sites [15]. It was found that
the concentration of surface hydroxyls increases with exposure
time of atomic hydrogen at room temperature until a threshold.
The well-shaped triangles are assigned to the oxygen vacancy

W. Wang et al. / Chemical Physics Letters 500 (2010) 76–81
79
2 2
Figure 3. Schematic drawings of (a) H O adsorption at coordinatively unsaturated Fe and (b) H O dissociation into two hydroxyls.
flashed to 500 K, triangular dislocation loops were then formed,
though there still existed disorderedly some isolated residual
hydroxyls on FeO [15,16]. In this process, the formation of disloca-
tion loops should be resulted from desorption of hydroxyl chains as
the FeO islands acquired immediately after dosing almost kept
unchanged (Figure 4b), which indicates that the FeO islands do
not tend to adsorb H O on terrace even at 80 K. However, there
2
exhibited some bright spots at the edge of a few islands. The
occurred adsorbates at the island edges are then the aggregations
of molecular water or the dissociative species. It is noted that
the Pt(1 1 1) substrate was covered with disordered submonolayer
of adsorbates (inset in Figure 4b). After 1 h, more adsorbates
appeared at edges of FeO islands (marked in white circles shown
in Figure 4c), which is attributed to the aggregations of the diffu-
sive adsorbates from the Pt(1 1 1) substrate. It was reported that
water is adsorbed intact on bare Pt(1 1 1) surface below 180 K,
and in the presence of sufficient oxygen, water dissociates to form
hydroxyl species above 150 K [49]. However, at temperatures
lower than 80 K, water does not dissociate even in the presence
of oxygen [38]. By considering our experiment was performed at
80 K, the adsorbates on the Pt(1 1 1) substrate are attributed to
molecular water, even though there is oxygen on Pt(1 1 1) with a
coverage of about 0.08 ML (inset in Figure 4a). Therefore, the
aggregations at the edge of the FeO islands are initially in the form
of molecular water.
H
2
2
and H O after annealing at a relatively high temperature of
5
00 K [14], thus leaving oxygen vacancy chains at these sites on
FeO. The isolated residual hydroxyls on FeO may have higher
desorption energy. In our experiment, the partial oxygen vacancy
chains have been observed, as shown in Figure 2b, which indicates
2 2
that the hydroxyls have already desorbed as H and H O even at
room temperature. It is noted that the O lattices at both sides of
the dark chain are shifted from each other by about half lattice
distance, as marked by the superposed grid in Figure 2b. It is in
agreement to the process as that described in Ref. [14].
After the measurement, we again annealed the sample at 650 K.
The hydroxyl chains disappeared, leaving dark triangles on FeO
islands, as shown in Figure 2e. Due to the relatively high annealing
temperature, the islands coalesced into larger ones. In this case,
there is nearly no oxygen left on the Pt(1 1 1) substrate (the upper
inset in Figure 2e). The formation of much bright aggregations on
the FeO islands in Figure 2e is attributed to Fe clusters, which is
due to lack of oxygen compensation from the surface during
annealing, causing the reduction of FeO. The line profile for the
bright aggregations is shown in Figure 2f. The apparent height
for the bright aggregations is about 2.5 Å, which is in agreement
with the monoatomic steps of Fe islands [48].
To trace such water aggregations at the edges of the islands, we
acquired atomic resolved images of an island, as shown by the
magnified images in Figure 5. The bright protrusions appear at
2
the island edges immediately after dosing H O (Figure 5a), and a
bright protruded chain (marked by the arrow) even appears on
the terrace of the island after 1 h later (Figure 5b). The line profiles
of the protrusions are correspondingly shown in Figure 5c and d.
The apparent heights of such protrusions are quite similar to those
in the experiment performed at room temperature (Figure 2d),
typically in the range of 0.3–0.5 Å. A much brighter protrusion
occurs at the upper edge of the island (as marked by the larger
Figure 4 gives a set of STM images of FeO acquired in-situ with-
2
in the same area before and after dosing 1 Langmuir H O (exposing
ꢀ8
the sample to water at 1.3 ꢁ 10 mbar for about 100 s) at 80 K.
During water dosing, we retracted the STM tip from the surface
by about 5–10
lm to reduce the possible effect that the tip may
shadow the water dosing. Overall, the main feature for most of
2
Figure 4. A set of STM images acquired within the same area at 80 K, (a) as-grown sample before dosing H O (inset shows the Pt substrate with residual oxygen coverage of
ꢀ
11
0
8
.08 ML), (b) acquired immediately after dosing 1 Langmuir H
0 K (acquired at 0.2 V and 1.5 nA). The feature changes are marked by circles in (b) and (c).
2
O in-situ, and (c) acquired after 1 h by holding the H
2
O dosed sample at a pressure of 5 ꢁ 10
mbar and at

8
0
W. Wang et al. / Chemical Physics Letters 500 (2010) 76–81
Figure 5. (a) STM image of an FeO island acquired immediately after H
2
O dosing (acquired at 50 mV and 3.0 nA). (b) STM image acquired after 1 h later (60 mV and 2.5 nA),
measured in-situ at 80 K. (c–e) Line profiles of the lines 1, 2, and 3 marked in (a) and (b), correspondingly.
circle in Figure 5b, and its line profile is shown in Figure 5e), which
thus can be most likely attributed to the water molecule(s) from
the water adsorbates from the Pt surface. It is also observed that
some protrusions appear or disappear at some sites of the step
edges by comparing Figure 5a and b (marked by the small circles
and the ellipse).
that the protruded chain on the terrace of the FeO is quite similar
to those occurred on the terrace of the sample at room temperature
(Figure 2a). Such similarity may suggest that these chains have the
same origin, i.e., the hydroxyl chains from the dissociative water at
the island edges, which thus indicates that water may spontane-
ously dissociate at the step edges even at 80 K.
Since physisorbed molecular water and hydroxyl may exist on
FeO at 80 K [7,9,16], it is difficult to directly determine the exact
species of the adsorbates in the STM images. However, it is noticed
As a further confirmation, we prepared another sample with
larger FeO islands, which was annealed at 900 K. Figure 6 shows
the results for a larger FeO island (typical lateral size of about
6
0 nm) performed with 1 Langmuir water dosing, acquitted within
the same area in-situ measurement at 80 K. With almost one
monolayer of water adsorbed on the Pt(1 1 1) substrate, we only
observed a few adsorbates at the edges of this large FeO island.
From the size and height of the protrusions, it seems that these
adsorbates are nondissociated water molecules. The feature inside
the island nearly keeps unchanged. Further comparison with the
results from the small FeO islands seems to suggest that the island
size is also another factor for water dissociation on FeO islands. In
the large island, the ratio of the number of the coordinatively
unsaturated Fe atoms at the step edges to the island area becomes
small. In this case, only a small amount of hydroxyls can be pro-
duced and the feature of the island may not be obviously affected.
4
. Conclusions
In conclusion, we have observed spontaneous dissociation of
water into hydroxyls on the nano-sized FeO/Pt(1 1 1) islands, with
typical size of 5–10 nm. We found that after dosing water at room
temperature there exhibited bright protrusions and dark rows on
the terrace of the FeO islands. The bright protrusions were attrib-
uted to the hydroxyls, and the dark rows were attributed to the
oxygen vacancies because of further desorption of hydroxyls as
2 2
H and H O. The hydroxyls totally desorbed and left well-shaped
Figure 6. STM images of (a) before and (b) after H
and (c) and (d) corresponding magnified images with marked area in (a) and (b).
Images in (b) and (d) were acquired after 1 h later for 1 Langmuir H
sample. Acquired at 60 mV and 0.2 nA.
2
O dosed sample at 80 K in-situ,
oxygen vacancy triangular loops on the FeO islands after the
water-dosed sample was further annealed at 650 K. The presence
of surface hydroxyls and oxygen vacancies on the terrace of
2
O dosed

W. Wang et al. / Chemical Physics Letters 500 (2010) 76–81
81
FeO suggests that the water adsorbates may dissociate on the
nano-sized FeO islands. The experimental results obtained at
0 K show that molecular water may adsorb at the step edges of
[16] J. Knudsen et al., Surf. Sci. 604 (2010) 11.
[
[
[
17] A. Grirrane, A. Corma, H. Garcia, Science 322 (2008) 1661.
18] X.S. Liu, O. Korotkikh, R. Farrauto, Appl. Catal. A 226 (2002) 293.
19] M. Kotobuki, A. Watanabe, H. Uchida, H. Yamashita, M. Watanabe, J. Catal. 236
(2005) 262.
8
the FeO islands, which may undergo spontaneous dissociation even
at 80 K. The STM images revealed that the hydroxyls were diffusive
and formed hydroxyl chain on the FeO islands as a function of time.
We suggest that the outermost Fe atoms of the islands are coord-
inatively unsaturated. Such coordinatively unsaturated Fe atoms
act as the reaction centers for the water dissociation. On larger
FeO islands, say, with lateral size of about 60 nm, the feature inside
the islands was not obviously affected after exposure to water. It
suggests that the ratio of the number of coordinatively unsaturated
Fe atoms to the area of an island plays an important role.
[
[
20] L.S. Xu, Y.S. Ma, Y.L. Zhang, Z.Q. Jiang, W.X. Huang, J. Am. Chem. Soc. 131 (2009)
16366.
21] Y.K. Kim, Z.R. Zhang, G.S. Parkinson, S.C. Li, B.D. Kay, Z. Dohnalek, J. Phys. Chem.
C 113 (2009) 20020.
[
[
22] Q. Fu et al., Science 328 (2010) 1141.
23] G.S. Herman, Z. Dohnalek, N. Ruzycki, U. Diebold, J. Phys. Chem. B 107 (2003)
2788.
[24] X.Q. Gong, A. Selloni, M. Batzill, U. Diebold, Nat. Mater. 5 (2006) 665.
[
[
[
25] N.A. Khan, C. Matranga, Surf. Sci. 602 (2008) 932.
26] M. Ritter, W. Ranke, W. Weiss, Phys. Rev. B 57 (1998) 7240.
27] Y.J. Kim, C. Westphal, R.X. Ynzunza, H.C. Galloway, M. Salmeron, M.A.
VanHove, C.S. Fadley, Phys. Rev. B 55 (1997) 13448.
[
28] L. Giordano, G. Pacchioni, J. Goniakowski, N. Nilius, E.D.L. Rienks, H.J. Freund,
Phys. Rev. B 76 (2007) 075416.
Acknowledgements
[
[
29] H.C. Galloway, P. Sautet, M. Salmeron, Phys. Rev. B 54 (1996) 11145.
30] W. Weiss, M. Ritter, Phys. Rev. B 59 (1999) 5201.
This work was supported by the NSFC (Grant Nos. 50721091,
0921013, 10825415, 60771006, and 10874164) and the NBRP
Grant No. 2006CB922001) of China.
[31] J. Wintterlin, R. Schuster, G. Ertl, Phys. Rev. Lett. 77 (1996) 123.
[
32] H. Ogasawara, B. Brena, D. Nordlund, M. Nyberg, A. Pelmenschikov, L.G.M.
Pettersson, A. Nilsson, Phys. Rev. Lett. 89 (2002) 276102.
9
(
[
[
[
33] T. Schiros et al., J. Phys. Chem. C 114 (2010) 10240.
34] P.J. Feibelman, Phys. Rev. Lett. 91 (2003) 059601.
35] G. Zimbitas, M.E. Gallagher, G.R. Darling, A. Hodgson, J. Chem. Phys. 128 (2008)
References
0
74701.
36] C. Sachs, M. Hildebrand, S. Volkening, J. Wintterlin, G. Ertl, Science 293 (2001)
635.
[
[
[
[
1] M.A. Henderson, Surf. Sci. Rep. 46 (2002) 5.
2] W. Weiss, W. Ranke, Prog. Surf. Sci. 70 (2002) 1.
3] S.K. Shaikhutdinov, Y. Joseph, C. Kuhrs, W. Ranke, W. Weiss, Faraday Discuss.
1
[
[
37] G.S. Karlberg, G. Wahnstrom, J. Chem. Phys. 122 (2005).
38] K. Bedurftig, S. Volkening, Y. Wang, J. Wintterlin, K. Jacobi, G. Ertl, J. Chem.
Phys. 111 (1999) 11147.
(
1999) 363.
[
[
[
[
[
[
4] M. Salmeron et al., Faraday Discuss. 141 (2009) 221.
5] I.M. Brookes, C.A. Muryn, G. Thornton, Phys. Rev. Lett. 87 (2001) 266103.
6] H. Gronbeck, I. Panas, Phys. Rev. B 77 (2008) 245419.
7] Y. Joseph, W. Ranke, W. Weiss, J. Phys. Chem. B 104 (2000) 3224.
8] U. Leist, W. Ranke, K. Al-Shamery, Phys. Chem. Chem. Phys. 5 (2003) 2435.
9] J.L. Daschbach, Z. Dohnalek, S.R. Liu, R.S. Smith, B.D. Kay, J. Phys. Chem. B 109
[
[
[
[
[
[
[
39] M. Nagasaka, H. Kondoh, T. Ohta, J. Chem. Phys. 122 (2005) 204704.
40] T. Schiros et al., J. Phys. Chem. C 111 (2007) 15003.
41] C. Clay, S. Haq, A. Hodgson, Phys. Rev. Lett. 92 (2004) 046102.
42] S. Haq, J. Harnett, A. Hodgson, Surf. Sci. 505 (2002) 171.
43] J. Harnett, S. Haq, A. Hodgson, Surf. Sci. 528 (2003) 15.
44] A. Hodgson, S. Haq, Surf. Sci. Rep. 64 (2009) 381.
(
2005) 10362.
45] A. Picolin, C. Busse, A. Redinger, M. Morgenstern, T. Michely, J. Phys. Chem. C
[
[
10] M.E. Grillo, M.W. Finnis, W. Ranke, Phys. Rev. B 77 (2008) 075407.
11] Y. Joseph, C. Kuhrs, W. Ranke, M. Ritter, W. Weiss, Chem. Phys. Lett. 314 (1999)
1
13 (2009) 691.
46] G.S. Karlberg, F.E. Olsson, M. Persson, G. Wahnstrom, J. Chem. Phys. 119 (2003)
865.
47] M. Nagasaka, H. Kondoh, K. Amemiya, T. Ohta, Y. Iwasawa, Phys. Rev. Lett. 100
2008) 106101.
[
[
1
95.
4
[
[
12] R.S. Cutting, C.A. Muryn, D.J. Vaughan, G. Thornton, Surf. Sci. 602 (2008) 1155.
13] G.S. Parkinson, Y.K. Kim, Z. Dohnalek, R.S. Smith, B.D. Kay, J. Phys. Chem. C 113
(
(
2009) 4960.
[
[
48] D. Repetto et al., Phys. Rev. B 74 (2006) 054408.
49] G.B. Fisher, B.A. Sexton, Phys. Rev. Lett. 44 (1980) 683.
[
[
14] W.X. Huang, W. Ranke, Surf. Sci. 600 (2006) 793.
15] L.R. Merte, J. Knudsen, L.C. Grabow, R.T. Vang, E. Laegsgaard, M. Mavrikakis,
F. Besenbacher, Surf. Sci. 603 (2009) 15.