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ELSEVIER Applied Surface Science 82/83 (1994) 305-309
applied
surface science

CO adsorption on clean and atomic-layer-Cu-covered

ZnO(1010) surfaces
Qingfeng Ge, Preben J. Moller *,I
Department of Chemistry, H.C. Qrsted Institute, University of Copenhagen, 5 Uniuersitetsparken, DK-2100 Copenhagen, Denmark

Received 25 April 1994; accepted for publication 1 July 1994

Abstract

The adsorption at room temperature of CO on clean and atomic-layer-Cu-covered ZnO(lOi0) surfaces was studied by
temperature-programmed desorption (TPD). Submonolayer amounts of Cu on the surface enhance the ability of ZnO to
adsorb CO drastically. A small amount of CO, desorbed from the surface as a result of CO reaction with surface oxygen. A
desorption order of 2 and a desorption activation energy of about 60 kJ/mol were obtained for CO desorption from the
Cu-covered ZnO(lOi0) surface, which is in good agreement with the binding energy of CO adsorbed on Cu(100) surfaces.

1. Introduction near-edge-X-ray adsorption fine structure (NEXAPS)

Cu/ZnO is an important catalyst for the synthesis
of methanol and for the water-gas shift reaction.
Therefore, studies of CO interaction with ZnO and
Cu/ZnO are of great interest for understanding the
reaction mechanisms involved in the above-men-
tioned reactions. As model catalysts, Cu deposited
onto different ZnO single-crystal surfaces have been
studied extensively [l-4]. As for CO adsorption, the
experiments in ultrahigh vacuum (UHV) are usually
conducted at cryogenic temperatures. The CO coor-
dination to ZnO(lOi0) surface has been studied by
photoelectron spectroscopy (PES) [5], high resolution
electron energy loss spectroscopy (HREELS) [6] and
* Corresponding author. Tel.: (+45) 35320262; Fax: (+45)
35320299.
1Present address: Research Institute of Electronics, Shizuoka
University, Hamamatsu 432, Japan. Fax: (+ 81) 53 474 0630.
[7]. The results suggest that CO binds carbon end
down to the coordinatively unsaturated zinc site on
ZnO(lOiO> surface, and the CO bond in the CO/ZnO
surface complex is shorter and stronger relative to
the gas phase [8]. Temperature-programmed desorp-
tion (TPD) is the most frequently employed tech-
nique to study desorption kinetics in which the tem-
perature of the solid surface is raised as a function of
time. CO TPD spectra from Cu-covered ZnO(OOOl)-
0 surfaces were dominated by a peak at 220 K [9].
Reports on CO adsorption at room temperature to-
ward the clean and atomic-layer-Cu-covered ZnO
single-crystal surfaces have been rare [lo].
Here we present the results of temperature-pro-
grammed desorption (TPD) of CO from clean and
atomic-layer-Cu-covered ZnO(lOi0) surfaces. The
adsorption proceeded at room temperature under a
relatively high pressure. The results show that CO is
adsorbed on both clean and Cu-covered ZnO sur-
faces. The kinetic parameters were determined from

0169-4332/94/$07.00 0 1994 Elsevier Science B.V. AR rights reserved

SSDI 0169-4332(94)00233-9
306 Q. Ge, P.J. M@ller /Applied Surface Science 82 / 83 (I 994) 305-309

the experimental data and compared with that from
the adsorption of CO on Cu(100) surface.
2. Experimental details
The experiments were carried out in a, previously
described [ 111, multidetector ultra-high vacuum
(UHV) chamber. The base pressure in the chamber
was about 2 X lo-* Pa.
The ZnO sample was oriented by X-ray Laue
back-reflection technique to within 0.5”, followed by
cutting and polishing with i Frn diamond paste to a
mirror-like surface as checked by 200 magnification
optical microscopy. The clean ZnO surface was pre-
pared by Art sputtering and heat treatment in cycles
until it was free from contamination as checked by
AES and LEED.
The copper (purity 99.995%) was evaporated from
an electron beam evaporator (ESV-2) at a rate 0.06

~. L~~~..

360 370 380 390 400 410 420 430

Temperature (K)

(b)

320 330 340 350 360 370 380 390 400 410 420 430

Temperature (K)
Fig. 1. (a) TPD spectrum of CO from the clean surface after background subtraction. (b) Raw desorption spectra of CO from the clean
znO(loio) SurfaCc (A - A ) and the sample holder (0 - 0) after exposure to 100 Pa CO for 15 min.
 Q. Ge, P.J. M&r/Applied
nm/min. The amount of Cu deposition was moni-
tored by a quartz crystal microbalance (QCMul). The
pressure increased to 5 X lo-’ Pa during the Cu
deposition.
Heating of the sample was accomplished either by
focusing light precisely onto the sample for the
surface cleaning or by a tungsten filament that was
mounted behind the sample holder for the TPD
experiments. The temperatures were measured by a
thin chromel-alumel thermocouple attached onto the
sample front face. A heating rate of 2.5 K s-l was
used in the TPD measurements.
CO (purity 99.997%) adsorption was performed at
room temperature in a preparation chamber in order
to maintain the ultrahigh vacuum in the main UHV
chamber. The base pressure of the preparation cham-
ber prior to adsorption was 5 X 1Om8 Pa. After CO
dosing, the preparation chamber was evacuated and
the samples were transferred to the main chamber.
Upon moving the sample to the front of a quadrupole
mass spectrometer (QMS) head and heating with a
linear temperature increase, the TPD spectra were
obtained. Besides the gases released during the tem-
perature-programmed heating, the residual gas com-
ponents were also detected by the QMS.
3. Results and discussions
3.1. CO and ZnO(lOi0) interaction
The ZnO(lOi0) sample was cleaned routinely as
described in the above section. After being cleaned
the surface exhibits a sharp LEED pattern with
(1 X 1) structure and the contaminants are under the
detection limits of our AES which uses a cylindrical
mirror analyzer. The clean ZnO(lOiO> surface was
exposed to CO ambient in the preparation chamber.
The TPD spectrum from a sample was obtained after
background subtraction.
Fig. la gives the CO TPD spectrum from a clean
znO(lOi0) surface after exposure to 100 Pa CO
ambient for 15 min. For comparison, a CO back-
ground desorption spectrum from the sample holder
is shown together with that from the clean ZnO(lOi0)
surface in Fig. lb. The control experiments showed
that the surface was saturated after having been
exposed to 100 Pa CO for about 10 min. Further
Surface Science 82/83 (1994) 305-309 307
increasing the exposure time did not increase the
amount of adsorbed CO. Therefore, we chose 15 min
as the exposure time for all experiments. By monitor-
ing CO, at the same time, we can see that a small
amount of the adsorbed CO also desorbs as CO,,
which is a reaction product of CO with surface
oxygen since CO, desorbed at the same temperature
at which CO desorbed. This result is in contrast to
that of Hotan, GSpel and Haul [12]. The only ob-
served desorbing species was CO, in their TPD
experiment. A similar result has been observed in
laser-induced desorption of CO from a ZnO(0001)
surface [lo].
The CO TPD spectrum from the clean ZnO(lOiO>
surface peaked at 360 K with a tail to 410 K. This
long tail may be attributed to the heterogeneities of
the surface.
The clean and CO exposed ZnO(lOiO> surfaces
were also checked with HREELS. The CO loss
features were hardly distinguished from the over-
tones of znO(lOi0) surface phonons because of the
strong overlap between them. A little difference can
be observed in the region 230-260 meV between the
spectra from the clean and CO exposed surfaces,
which was attributed to C-O stretch vibration of
adsorbed CO [13]. To determine the stretching fre-
quency precisely, a deconvolution technique is
needed to remove the effect of the substrate. Addi-
tionally, the intensity of the elastic peak from the CO
exposed surface was one order of magnitude lower
than that from a clean ZnO(lOiO> surface. This may
provide further evidence for the occurrence of CO
adsorption on the ZnO(lOi0) surface.
3.2. CO and Cu/ZnO(lOiO) interaction
Cu deposition was performed at room tempera-
ture. The average thickness of the Cu deposited onto
the ZnO(lOi0) surface was read from the QCM.
Considering the similarity of the (lOi0) and (ll?O)
ZnO surfaces, the reading from the QCM was corre-
lated to the coverage with the reading of 0.2 nm
corresponding to monolayer (ML) coverage [4]. A
copper-substrate vibrational frequency at a low en-
ergy loss could hardly be distinguished from the
HREEL spectra after Cu deposition because of the
overlap from the elastic peak [13]. However, the
intensity of the elastic-scattered electron peak de-
creases.
308 Q. Ge, P.J. M@ller/Applied Surface Science 82 /83 (1994) 305-309

Fig. 2 gives the CO TPD spectra from the Cu-
covered ZnO(lOi0) surfaces after exposure to 100
Pa CO ambient for 15 min in the preparation cham-
ber. The CO TPD spectrum from the clean surface is
redrawn here for comparison. Comparing the desorp-
tion spectrum from the 0.3 ML Cu-covered surface
with that from the clean surface we can easily find
that the capacity of the Cu-covered surface towards
CO adsorption is increased drastically. By further
increasing the Cu coverage on the ZnO surface, the
intensity of the CO desorption does not increase
significantly.
By analyzing the TPD spectrum shown in Fig. 2
we find that the peak position shifted slightly and the
shapes of the spectra changed. The CO TPD spec-
trum from the 0.3 ML Cu-covered surface peaked at
363 K while the spectrum from the 1.5 ML Cu-
covered surface peaked at 370 K with the broadening
of the spectrum. The shoulder in the clean surface
spectrum still can be distinguished in the 0.3 ML
Cu-covered surface spectrum but it merged with the
broadened peak in the 1.5 ML Cu-covered surface
spectrum. The shift to a higher desorption tempera-
ture indicates that the binding of CO to the adsorbate
is becoming stronger because of the presence of Cu
on the surface. The broadening of the spectrum from
the 1.5 ML Cu-covered surface spectrum may sug-
gest an appearance of two different adsorption states
on the surface.
In the Polanyi-Wigner model it is assumed that
the rate of desorption of adsorbed species in state i
on a surface may be written in the form:
d Bi
--=
dt
where n, is the reaction order for desorption from
state i, vi is a frequency factor, Ei is the desorption
activation energy. For a single state, the rate equa-
tion is simply
d0 I E\
--=
dt
Assuming that v and E are coverage-independent,
we can obtain a set of values of v, II and E by
fitting this equation to the experimental data with the
technique proposed by Tronconi and Lietti [14]. In
the case of CO desorption from the 0.3 ML Cu-
covered ZnO(lOi0) surface, we obtain n = 2 and
E = 60 kJ/mol, i.e. the reaction order of desorption
from this Cu-covered surface is 2 and the activation
energy is 60 kJ/mol. This activation energy is in the
binding-energy range for CO on a Cu(100) surface
[15]. It may imply that CO binds to the finely
divided Cu cluster even though the Cu did not grow

320 330 340 350 360 370 380 390 400 410 420
I
430

Temperature (K)
Fig. 2. TPD spectra of CO from the Cu-covered Zn@lOiO) surfaces, with different Cu coverages, after exposure to 100 Pa CO for 15 min
(A- A, clean surface; O- 0, 0.3 ML Cu; 0 - 0, 1.5 ML Cu).
 Q. Ge, PJ. M@ller/Applied Surface Science 82 /83 (1994) 305-309 309

epitaxially on the ZnO(lOi0) surface. [2] S.V. Didziulis, K.D. Butcher, S.L. Cohen and E.I. Solomon,
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In summary, we present the results of TPD spec-
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[6] K.L. D’Amico, F.R. McFeely and E.I. Solomon, J. Am.
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The project is supported by the Carlsberg Founda- Catal. 141 (1993) 380.
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