Article

pubs.acs.org/JPCC

Thermally Activated Interaction of Co Growth with ZnO(1010)

Surface
Shu Hsuan Su, Hsin-Hsien Chen, Tsung-Hsun Lee, Yao-Jane Hsu, and J. C. A. Huang*,,,

Department of Physics, National Cheng Kung University, Tainan 701, Taiwan

Advanced Optoelectronic Technology Center, National Cheng Kung University, Tainan 701, Taiwan

Center for Micro/Nano Science and Technology, National Cheng Kung University, Tainan 701, Taiwan

National Synchrotron Radiation Research Center, Hsinchu 30076, Taiwan

S Supporting Information
*

ABSTRACT: The nucleation and sintering characteristics of Co on ZnO(1010) during

annealing were investigated by scanning tunneling microscopy (STM). The extent of
coverage and annealing temperature were varied to modify the size of the Co nanoclusters.
Temperature-dependent X-ray photoemission spectra of the Co chemical state reveal that
metallic Co dominates the annealing procedure on ZnO(1010) and is more thermally stable
than Co on both ZnO(0001) and ZnO(0001). The eects of annealing time and the
distribution of Co adatoms were elucidated by STM. The results have potential implications
for the thermal stability of Co/ZnO(1010) in real catalytic processes.

INTRODUCTION
The use of metal supported on ZnO catalysts in the steam
reformation of ethanol (SRE),14 methanol synthesis,510 and
FischerTropsch synthesis11,12 is of interest. Metal adatoms at
the surface of oxides have been proposed as the active species
in several catalytic reactions.1315 This phenomenon is the
ultimate extension of the well-known size eect.16 The nature
of the metaloxide surface interface is believed to inuence the
chemical activity of the supported metal clusters. For example,
the number of active sites varies with the extent of sintering or
agglomeration of the clusters during heating as well as with the
initial wetting capacity of the metal on the oxide surface.1719
Recent research has demonstrated that catalysts based on
cobalt are promising candidates for SRE reaction, and they have
been reported to exhibit activity and selectivity that are
comparable to those of precious metals such as Rh and Pd.2024
One of the most challenging aspects of the catalytic behavior of
the metal/ZnO materials is their chemical and structural
sensitivity to heating. In the SRE reaction, the stability and
activity of Co supported on ZnO or CeO2 are greater than
those of Co on other oxide supports.20,25,26 One key advantage
of ZnO over CeO2 is that Co/ZnO exhibits higher selectivity in
low temperature operations (<700 K).2527, Llorca et al.20
reported that the selectivity of Co supported on ZnO toward
H2 and CO2 at 723 K was 91% for high ethanol-to-steam ratios,
but that of Co supported on MgO or TiO2 was 52%.
Additionally, most thermodynamic and transport phenomena
that have important technological applications depend on the
electronic and chemical properties of the metaloxide interface.
2013 American Chemical Society

To elucidate the chemistry of Co metal supported on ZnO as a

potential new catalyst, a fundamental understanding of its
growth behavior upon heating is required. The literature cannot
yet provide a detailed understanding of the growth and heating
behavior of Co on ZnO(1010). This fact motivates this study.
We previously reported the coverage-dependent growth
structure and chemical state of Co on ZnO(1010) at 300
K.28 To elucidate the aect of the postannealing of Co on
ZnO(1010), scanning tunneling microscopy (STM) and X-ray
photoelectron spectroscopy (XPS) were utilized to study the
morphology and chemical state of Co that was deposited on
ZnO(1010) as functions of Co coverage, annealing temperature, and annealing time.

EXPERIMENTAL METHODS
The experiments herein were performed in an ultrahighvacuum (UHV) system (JSPM-4500 A/S; JEOL Ltd.) with a
base pressure of 2.0 108 Pa. The system is composed of a
sample preparation chamber and an STM measurement
chamber.28,29 ZnO(1010) single crystal (Techno Chemic,
Inc.) was rst treated in an ultrasonic acetone bath and then
introduced to the sample preparation chamber. A clean surface
was obtained by cleaning the ZnO(1010) surface by cycles of
Ar+-ion sputtering at 1.5 keV using an ion current of 0.50.7
A for 15 min and then annealing at 700 C in UHV for 15
Received: April 16, 2013
Revised: July 31, 2013
Published: August 1, 2013
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Figure 1. STM images of (a) 0.5 ML Co deposited on ZnO(1010 ) at 300 K (30 30 nm2); (b) annealing 0.5 ML Co to 400 K (60 60 nm2); (c)
annealing 0.5 ML Co to 600 K (80 80 nm2); (d) annealing 0.5 ML Co to 800 K (80 80 nm2); (e) 1 ML Co deposited on ZnO(1010) at 300 K
(20 20 nm2); (f) annealing 1.0 ML Co to 400 K (30 30 nm2); (g) annealing 1.0 ML Co to 600 K (100 100 nm2); (h) annealing 1.0 ML Co to
800 K (100 100 nm2) ; (i) 3 ML Co deposited on ZnO(1010) at 300 K (100 100 nm2); (j) annealing 3.0 ML Co to 400 K (100 100 nm2),
(k) annealing 3.0 ML Co to 600 K (80 80 nm2); (l) annealing 3.0 ML Co to 800 K (100 100 nm2). Images show dierent regions of the surface.
The insets show magnication of STM images (inset images of (a) 7 7 nm2; (b) 15 15 nm2; (c) 23 23 nm2; (d) 24 24 nm2; (f) 11 11
nm2; (g) 30 30 nm2; (h) 40 40 nm2; and (l) 28 28 nm2). The size distribution of Co nanoclusters is shown in the Supporting Information.

min. The typical morphology of the clean ZnO(1010) surface is

shown in Figure S1 of the Supporting Information. The
temperature of the sample was measured by a K-type
thermocouple located behind and very close to the sample
holder. In addition, we also used an infrared thermometer
(Cyclops 100B, AMETEK Land, Inc.) to calibrate the sample
temperature. Cobalt was deposited on the ZnO(1010 ) surface
from a Co rod (diameter 2 mm, 99.995%) by electron
bombardment in a water-cooled commercial evaporator
(Omicrometer EFM 3). The deposition rate was calibrated
using a quartz crystal microbalance located close to the sample
holder. The Co growth rate was determined to be
approximately 0.1 /s. The concentration of the deposited
metal was produced in the monolayer equivalent (ML),
corresponding to a Co packing density of 1.8 1015 Co
atoms/cm2 when proceeding along the growth plane of
(0001) . However, for a growth plane of (1010), the atomic
density of 1 ML Co was approximately 1 1015 atoms/cm2,
which is quite close to the sum of the atomic densities of O and
Zn in ZnO(1010 ), 1.2 1015 atoms/cm2.28 The pressure
during Co deposition remained below 5 108 Pa, which was
only slightly higher than the background pressure. After
deposition at 300 K, the sample was postannealed at a series
of increasing temperatures, each of which was held for 10 min.
After being cooled to room temperature, the sample was
immediately introduced into the STM measurement chamber.
STM experiments were conducted at room temperature. STM

data were collected in a constant current mode at a positive

sample bias voltage of 2.53.0 V and with a tunneling current
of 0.30.6 nA. High-resolution topographic STM images were
then captured using electrochemically etched 0.3 mm tungsten
wires. Before the ZnO substrate was imaged, the tip was placed
a few m away from a silicon substrate that had been heated to
1200 C, indirectly heating and cleaning the tip. Next, the tip
was cleaned by applying voltage pulses during STM operation.
XPS measurements were performed using a VG SCIENTA
R3000 surface analysis system equipped with Al K radiation
(1486.6 eV) at the National Synchrotron Radiation Research
Center, Taiwan.28,30 The XPS measurements were made at a
base pressure of below 1.0 107 Pa with an energy step of
0.025 eV. The XPS spectra are referenced to the Zn 2P3/2 peak
at 1021.7 eV. The reported average height and diameter in each
experiment were determined by measuring the sizes of 100
clusters in line prole mode using scanning probe imaging
software. The STM tip is known to inuence the size and
structure of the clusters. To minimize any artifact from the tip
and STM electronics, the images that are presented in this
study were selected only following repeated scans of the same
surface region and the evaluation of various similar obtained
images. The reported sizes of the metal clusters in this study
may be overestimated because of tip convolution and the
dierence between the electronics of the ZnO substrate and the
Co metal clusters, but the results are self-consistent.
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RESULTS
First, we describe the eects of postannealing on the
morphology and chemical state of 0.5, 1, and 3 ML Co that
are deposited on ZnO(1010). Figure 1 displays the STM results
concerning Co deposited on ZnO(1010) at 300 K with various
coverages and subsequently annealed to elevated temperatures
of 400, 600, and 800 K . When 0.5 ML Co was deposited on
ZnO(1010) at 300 K, well-ordered structures were established
on the ZnO(1010), as shown in Figure 1a. The atomic
resolution STM (inset in Figure 1a) reveals that 0.5 ML Co
exhibits ordered (2 1) structures, as reported in our previous
investigations.28 When the surface is annealed to 400 K, the Co
atoms aggregate to form disordered clusters and the (2 1)
structures are eliminated. Some of the ZnO(1010) surface that
is originally covered by (2 1) structures is re-exposed
following the agglomeration of Co atoms (shown by the highermagnication STM image in the inset in Figure 1b). After this
surface was subsequently annealed to 600 K, bright protrusions
were observed mostly on the terraces (Figure 1c); these are
thought to be the disordered clusters that have further
agglomerated to form Co nanoclusters (NCs). The average
size of the Co NCs is about 1.02 nm in diameter and 0.25 nm
in height. Moreover, the inset in Figure 1c presents a signicant
increase in the exposed area of ZnO(1010) surface. After the
surface is further annealed to 800 K, more of the ZnO surface is
re-exposed (Figure 1d). Notably, the number density of Co
NCs is signicantly reduced upon annealing, and the average
diameter and height of Co NCs are slightly increased to 1.25
and 0.40 nm, respectively. Because the possibility of desorption
of Co atoms at this temperature (800 K) can be excluded, the
decrease in the number of Co NCs with increasing temperature
is likely caused by the diusion of Co atoms into the ZnO
substrate.
When 1 ML of Co was deposited on the ZnO(1010) surface
at 300 K, the striped Co structure with some missing Co
defects was observed (Figure 1e). After the surface was heated
to 400 K, the agglomeration in the Co striped structure was
observed in Figure 1f as bright protrusions. The re-exposed
ZnO(1010) surface following the agglomeration in the Co
striped structure is fuzzy in the inset in Figure 1f. Subsequent
annealing of the surface to 600 K caused larger Co NCs to be
formed because of the increase in surface diusion at high
temperature (Figure 1g). The average size of Co NCs is 2.32
nm in diameter and 0.87 nm in height. Moreover, the inset in
Figure 1g shows the some uncovered ZnO(1010) surface is
distorted, which is caused by the diusion of partial Co atoms
into the ZnO substrate. Figure 1h displays a striking change in
the surface morphology upon annealing to 800 K. In particular,
the Co adatoms grow laterally and form a large unreconstructed
rectangular wetting layer with sides along the [1210] and
[0001] directions of the underlying ZnO(1010) substrate. The
appearance of some voids, where the wetting layer is still
observed, is due to incomplete overlayers of the Co (Figure 1h,
inset). Furthermore, some Co NCs appear above the wetting
layer with an average diameter and height of 2.63 and 0.80 nm,
respectively. At 300 K, as the Co coverage increases to 3 ML,
three-dimensional Co clusters are formed (Figure 1i). Heating
the surface to 400 K causes the coarsening of Co NCs (Figure
1j). Because it is covered by the Co wetting layer, however, the
underlying ZnO(1010) substrate is not visible. Notably, a
bimodal distribution of Co NC cluster size was observed. Large
Co clusters with an average diameter of 4.65 nm and height of

0.85 nm as well as small clusters that are 2.66 nm in diameter

and 0.40 nm in height are present on the surface; the size
distribution of Co clusters is shown in Figure S2 of the
Supporting Information. After the sample was further annealed
to 600 K, disordered and rugged wetting layers formed. Some
Co NCs with an average diameter and height of 3.36 and 0.75
nm, respectively, formed above the Co wetting layers, and the
bimodal distribution of cluster sizes in Figure 1k vanished.
Subsequent annealing to 800 K substantially changes the
surface morphology. Figure 1l presents the formation of Co
rectangular islands and chains with sides along the principal
crystalline azimuth of ZnO(1010). The chain structures are
directed along the [1210] direction of the underlying
ZnO(1010) substrate (Figure 1l, inset).
To understand the eect of annealing on the chemical state
of Co that was deposited on ZnO(1010), the samples were
examined using XPS. Panels a and b of Figure 2 show the 2p

Figure 2. XPS spectra of Co 2p for various annealing temperatures:

(a) 1 ML Co and (b) 3 ML Co on ZnO(1010). Annealing
temperature-dependent energy shift of (c) Zn 2p3/2 and (d) O 1s;
negative values suggest that the band bends upward with respect to the
band of a clean ZnO(1010) surface. (e) O(1s)/Zn(2p) ratio as a
function of annealing temperature for 1 and 3 ML Co on ZnO(1010).
(f) Zn(2p)/Co(2p) ratio as a function of annealing temperature for 1
and 3 ML Co on ZnO(1010).

XPS core level spectra of Co with 1 and 3 ML of coverage,

respectively, following annealing to 400, 600, and 750 K. The
Co 2p XPS region contains the spinorbit spilt doublets of
2p3/2 and 2p1/2. The solid and dotted lines represent the Co
oxidation3136 and metallic states,3134 respectively. One ML
Co 2p3/2 exhibits a binding energy of 778.1 eV at 300 K, which
declines to 778.0 eV at 400 K and to 777.8 eV at both 600 and
800 K. The Co 2p3/2 binding energy is consistent with the
reported value for the Co metallic state.3134 The XPS spectra
of 1 ML Co on ZnO(1010) demonstrate that the Co metallic
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Figure 3. STM images of Co adatoms on ZnO(1010) surface following steps subsequent to annealing at 600 K for (a) 5 min (100 100 nm2), (b)
10 min (150 150 nm2), (c) 15 min (150 150 nm2), (d) 20 min (150 150 nm2), (e) 30 min (150 150 nm2), and (f) 60 min (150 150
nm2). Images display dierent regions of the surface. The insets show magnied STM images (inset images: (b) 69 69 nm2, (c) 100 100 nm2,
(e) 30 30 nm2, and (f) 60 60 nm2).

systems.45,46 A plot of the Zn (2p)/Co (2p) ratio as a function

of annealing temperature for 1 and 3 ML Co coverage on
ZnO(1010) reveals a signicant change in cobalt structure
upon heat treatment (Figure 2f). The Zn/Co ratio of 1 ML Co
increases remarkably with the annealing temperature. The Zn/
Co ratio for 1 ML Co increases much more abruptly upon
heating to 400 K, indicating the signicant agglomeration of the
Co adatoms into Co NCs, causing more of the ZnO substrate
surface to be re-exposed. Annealing of 1 ML Co at 750 K
slightly reduces the Zn/Co ratio, corresponding to the lateral
spreading of Co NCs to form a two-dinensional (2D) wetting
layer on ZnO(1010) and/or diusion of Co and Zn at the
interface. For 3 ML Co on ZnO(1010), the Zn/Co ratio shows
only slight variation upon annealing, suggesting that only a
small proportion of Co adatoms agglomerate into larger NCs
upon annealing. The XPS results are consistent with the STM
observations. For comparison, the Zn/Co ratio for the 2 ML
Co lm on the ZnO(0001) surface increases upon annealing to
700K, while the drop in the Zn(2p)/Co(2p) ratio upon heating
to 800 K is caused by the reaction of the Co with ZnO to form
CoO, which covers the surface.34 These results demonstrate
that the interaction of metallic Co with ZnO(1010 ) is much
stronger than that with ZnO(0001), resulting in a relatively
stable lm.
In an attempt to elucidate more thoroughly the thermal
stability of Co deposited on ZnO(1010), 1 ML Co that can
sustain annealing at a temperature of 600 K is annealed for
various times, as shown in the STM images in Figure 3. As the
annealing time is increased from 5 to 10 min, Co clusters
appear to ripen and become distributed randomly on the
surface (Figure 3a,b). As the annealing time is increased from

state dominates and is mixed with a small amount of the Co

oxidation state. A slight drop in the Co binding energy upon
annealing to elevated temperatures is attributed to the change
of the size in the Co NCs3742 as indicated by the STM results.
Concurrently, the Co 2p intensity decreases slightly upon
annealing because of the agglomeration of Co adatoms.
However, the Co 2p3/2 peak (778.1 eV) is almost xed in the
metallic state for 3 ML Co coverage throughout the annealing
procedure. Therefore, the annealing of 3 ML Co up to 750 K is
concluded not to result in Co oxidation and therefore diers
considerably from the annealing of Co on ZnO(0001).34 Panels
c and d of Figure 2 plot the Zn 2p3/2 and O 1s energy shifts,
respectively, as functions of annealing temperature. The Co
deposition on ZnO at 300 K results in the shifts of the Zn 2p3/2
and O 1s peaks to 0.30.4 eV lower binding energies with
respect to those of a clean ZnO surface. This phenomenon is
explained by the upward band bending that is induced by the
Co covering the ZnO(1010) surface.28 Furthermore, when the
sample is annealed to 400750 K, both the Zn 2p3/2 and the O
1s peaks shift to a 0.40.6 eV lower binding energy than those
of the clean ZnO(1010) surface. A plot of the O 1s/Zn 2p ratio
as function of annealing temperature for 1 and 3 ML Co
coverage on ZnO(1010) reveals a signicant increase with
increasing annealing temperature (Figure 2e). The trend
indicates that the accumulation of O atoms occurs at the
interface upon the annealing treatment and that these atoms
migrate from the bulk ZnO as the sample is heated to a high
temperature. Therefore, we deduce that the annealing-induced
upward bending eect is induced by the accumulation of O
atoms at the interface. Similar behaviors have been observed in
V/TiO 2(001),43 alkali metal/ZnO, 44,45 and clean ZnO
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observations of the Co/ZnO(0001) system suggest that the 1

nm Co grown on ZnO(0001) at 300 K aggregate into
nanometer scale clusters. When annealing remains below 700
K, the Co clusters coalesce into larger islands and remain
metallic. In the annealing temperature range between 700 and
780 K, the metallic and oxidized cobalt coexist. Co became fully
oxidized at annealing temperatures above 850 K. In comparison
to the above systems, these results suggest that the exchange of
oxygen between the ZnO(0001) and ZnO(0001) support and
Co is easier than that between the less reducible ZnO(1010)
and Co. The Co on ZnO(1010) system is more thermally
stable than the Co on ZnO(0001) and on ZnO(0001) systems.
One factor that is proposed for the thermal stability of Co is the
density of the O atoms exposed to various ZnO planes.
However, other factors such as the surface structure of the
supports, heats of formation of metal oxides on the surface,
thermodynamic equilibrium, growth modes, charge state of
metal overlayers, and so on also aect the thermal stability of
metal supported on oxide surfaces.52,53 Therefore, further
experiments are necessary to determine the mechanism
governing the thermal stability of Co on the ZnO surface.
The Co that is deposited on ZnO(1010 ) has characteristics
dierent from the other metal adatoms that are deposited on
the ZnO(1010), including those on Cu/ZnO(1010),50,54 alkali
metal(K, Na, and Cs)/ZnO(101 0 ), 44,45,56 and Ag/
ZnO(1010).49 For a Cu/ZnO(1010 ) system, Cu adatoms
grow at room temperature (RT) exclusively as three-dimensional clusters at step edges that are oriented perpendicular to
the ZnO [1210] direction,54,55 implying that the diusion rate
of Co on ZnO(1010) at RT is lower than that of Cu on
ZnO(101 0 ). Furthermore, annealing the Cu-covered
ZnO(1010) surface to 670 K coarsens the clusters, whereas
thermal treatment up to 770 K leaves the Cu in the metallic
state.50 Similar results are also obtained for Co on ZnO(1010):
Co clusters are coarsened and the Co remains in the metallic
state upon annealing up to 750 K. Angle-resolved photoelectron spectroscopy (ARPES) observations of the Ag/
ZnO(1010) system suggest that Ag islands formed with an
ordered structure at low coverage. When the Ag-covered
surface was annealed at 900 K, the Ag islands are sintered with
an ordered structure that is strongly inuenced by the surface
structure of the ZnO(1010) substrate.49 In the alkali metal (K,
Na, and Cs) on ZnO(1010) system,44,45,56 initial downward
bending at RT is observed because of the charge transfer
between the metal and ZnO. When the surface is annealed, the
thermally induced migration of the bulk O atoms and the
resultant increase in the number of O atoms on the surface are
responsible for upward bending on the annealed surface. Heat
treatment also causes the formation of an ordered overlayer. K
is adsorbed on ZnO(1010) in a 2D disordered fashion at RT,
whereas c(2 2) and (3 1) ordered structures are formed
when the K-covered surface is annealed at 9501050 and
11001200 K, respectively.45,56 However, the deposition of Na
on ZnO(1010) at RT produces the disordered overlayer with
any coverage; the (1 3) ordered structure emerges on the
surface that is annealed to 825 K. The ordered structure is
considered to arise from the Na adatoms that form atomic
chains along the ZnO dimer rows.44 The upward band
bending observation and chains structure of Co on ZnO(1010)
upon annealing are similar to those of the alkali metal (K, Na,
and Cs) on ZnO(1010) reported elsewhere. Another important
implication of the use of Co support catalysts is that the
support can signicantly aect reactivity. The catalytic activity

15 to 20 min, the tendency of the Co adatoms to order in the

[1210] direction becomes apparent (Figure 3c,d). As the
annealing time is extended to 30 min, the morphology changed
remarkably (Figure 3e). Most of the Co clusters migrate to
form elongated chains that are directed preferentially along the
[1210] direction (Figure 3e, inset). When the sample is
annealed for 60 min, the morphology becomes rugged wormlike islands (Figure 3f, inset) and the alignment with the
principal azimuth of the ZnO(1010 ) substrate is lost (Figure
3f). Accordingly, Co adatoms migrate to form chains in the
ZnO [1210] direction, indicating that Co diusion occurs
mainly along the [1210] direction because the energy barrier is
lowered. This result is consistent with the theoretical results for
Cu on ZnO(1010),47,48 which predict that the migration path
with the lowest barrier is along the [1210] direction. As a result,
the migration of Cu adatoms along the [1210] direction is
easier than that in the [0001] direction. Figure 4 plots the

Figure 4. Plots of average diameter and height of Co clusters as

functions of annealing time.

average diameter and height of Co clusters as functions of

annealing time. Both the average diameter and height of Co
clusters strongly depend on the annealing time. The initially
rapid increase in average diameter and height of Co clusters is
followed by a slow increase as the annealing time increases. The
results demonstrate that large Co islands can be grown by the
consumption of Co adatoms that have diused across the
surface from small clusters.

DISCUSSION
The STM and XPS results of this study provide further insight
into the structural and chemical evolution of a Co deposited on
ZnO(1010) surface in terms of coverage versus annealing
temperature. Nucleation growth and diusion characteristics of
Co on ZnO(1010) upon heating are observed. The Ostwald
ripening process induces a modication of Co NCs. The Co
NCs are dispersed on the terraces of ZnO(1010) , and this
nucleation is not preferred on the step edge or at the defects.
Moreover, the heat treatment results in the reappearance of the
ZnO(1010) surface by causing the coalescence and ripening of
Co adatoms because of the high mobility of Co adatoms at
elevated temperatures. Cu-covered and Ag-covered
ZnO(1010)49,50 have been observed to behave similarly. The
XPS spectra reveal that most Co remains in the metallic state
during annealing. When Co was deposited on the ZnO(0001)
surface, it was found to exhibit approximately layer-by-layer
growth at 300 K, but it agglomerated into clusters when
annealed to 700 K. When the sample is annealed to between
700 and 800 K, Co oxidizes as a result of a reaction with the
ZnO support. Annealing above 800 K results in the
incorporation of Co into the ZnO support.34 Furthermore,
the thermally activated processes of Co on the ZnO(0001)
surface have been reported by Dumont et al.51 Their XPS
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nanoclusters upon annealing. This material is available free of

charge via the Internet at http://pubs.acs.org.

toward surface metal adatoms and the selectivity of the

supported catalyst can depend strongly on the size of clusters
below 6 nm.17,5760 Furthermore, metal clusters are frequently
sintered under catalytic reaction conditions. Sintering reduces
activity or selectivity mainly by reducing the number of exposed
metal atoms but also by eliminating the smallest clusters, which
may have electronic properties that make them especially
reactive.17,18 In this work, optimal Co coverage and annealing
treatment are inferred to give rise to the Co clusters that are
supported on ZnO(1010) with an average size of less than 6
nm, which is appropriate for catalytic activity. Additionally, the
Co-based catalysts can exhibit SRE selectivity toward CO2 and
H2 in excess of 90% at relatively low temperatures with CH4,
CH3CHO, C2H4, and (CH3)2CO as the primary side
products.20,61 In the SRE reaction, the selectivity of Co
supported on ZnO toward H2 and CO2 at 723 K was 91% for
high ethanol-to-steam ratios.20 Specically, on metallic cobalt,
the primary reaction pathway for decarbonylation to produce
CO, H2, and methyl group adsorption was found in the
catalyst.3,20,62 Catalysts containing metallic cobalt particles
often show a signicant enhancement of the catalytic
performance in SRE reactions. In comparison to Co on both
ZnO(0001) and ZnO(0001), Co supported on ZnO(1010) can
remain in the metallic state upon similar annealing treatment,
which is valuable for remaining active in ethoxide decarbonylation and thus useful for forming CO, H2, and adsorbed
methyl groups under typical SRE conditions. This study is
useful in the design of nanostructured materials for catalytic
applications.

Corresponding Author

*Tel: +886-6-2757575, ext. 65266. Fax:+886-6-2747995. Email: jcahuang@mail.ncku.edu.tw.

Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS

REFERENCES

The authors thank the National Science Council of the

Republic of China, Taiwan, for nancially supporting this
research under Contracts NSC 99-2120-M-006-003 and NSC
100-2112-M-006-018-MY3. Funding was also received from the
Headquarters of University Advancement at National Cheng
Kung University, which is sponsored by the Ministry of
Education, Taiwan, ROC. Ted Knoy is appreciated for his
editorial assistance.

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CONCLUSION
In conclusion, the thermally induced structural and chemical
changes in Co deposited on ZnO(1010) were investigated by
STM and XPS. Low coverage of Co (0.5 ML) on ZnO(1010)
at room temperature produces the well-ordered (2 1)
structure, whereas annealing treatment forms Co NCs. The Co
in the striped structure of 1 ML Co on ZnO(1010)
agglomerates to form nanoclusters following annealing to 600
K. Heating to 800 K resulted in the formation of a rectangular
wetting layer with sides along the [1210] and [0001] directions
of the underlying ZnO(1010) substrate. Annealing of 3 ML Co
deposited on the ZnO(1010) surface at 400 K produces Co
clusters with a bimodal size distribution. The Co rectangular
islands and chains directed along the crystalline azimuths of the
ZnO(1010) substrate are formed upon further annealing to 800
K. The Ostwald ripening process induces the observed sintering
behavior of Co adatoms, which depend on the Co coverage.
The temperature-dependent measurements of the Co chemical
state indicate that the Co remained in the metallic state during
the annealing procedure, and was more thermally stable than
Co on both ZnO(0001) and ZnO(0001) . The upward band
bending in XPS is ascribed to the accumulation of the O atoms
on the surface via segregation of the bulk O atoms on the
annealing surface. When the surface is annealed to 600 K, the
Co atoms migrate to form chains along the [121 0] direction.
The cluster size increases with the annealing time. This study
provides insights into the rational design of the Co/ZnO
catalyst for SRE and other catalytic processes.

AUTHOR INFORMATION

ASSOCIATED CONTENT

S Supporting Information
*

The STM image of the clean ZnO(1010) surface, schematic

model of the ZnO(1010), and the size distribution of Co
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