Applied Surface Science 67 (1993) 166 178

North-Holland applied
surface science

The adsorption and dissociation of CO, on Rh

M . F . H . van Tol, A. G i e l b e r t a n d B.E. N i e u w e n h u y s
Department of Heterogeneous Catalysis, Gorlaeus Laboratories, Leiden UnivetMo', t'. O. Box 9502, 2300 RA Leiden, Netherlam£

Received 1(1 August 1992; accepted for publication 21 August 1992

The adsorption and dissociation of CO~ on Rh were studied at temperatures between 80 and 1200 K with field emission
microscopy. For this purpose a new microscope was used which is based on image processing. This DigiFEM has a vm,'y high spatial
resolution. Because of this high resolution the surface structure specificity of adsorption and dissociation could bc monitored in
detail. CO 2 adsorption at 80 K starts on 1211)) followed by adsorption on (111)), (321), 1221), (51 I) (71 I) and (310). At low surface
coverages CO 2 dissociation starts around 165 K on 1211)). A little below this temperature also CO 2 rearrangement over the surface
and some CO 2 desorption take place. Between 235 and 290 K CO recombines with O to form CO~ which desorbs leaving a clean
surface at 340 K. At higher coverages two processes take place simultaneously. Following CO 2 desorption around 121) K, ( ' 0 ,
dissociation starts around 190 K. Some CO 2 is desorbed after recombination of CO with O, but C O , dissociation continues to be of
importance. Oxygen formed at these higher temperatures and coverages is forced to diffuse into the bulk of Rh. CO desorption
takes place with 7~,~ = 451) K. O-atoms start to diffuse out of the bulk around 600 K. These O-atoms are desorbcd as O , or RhO,
between 1000 and 12110 K. In order to solve the processes taking place during the study of the interaction of ('O~ with Rh the
results obtained were compared with results obtained fl)r the adsorption and desorption of CO and ()~ on the same tip.

1. Introduction ciation has also been studied in detail using field

The CO2-surface interaction has been the
subject of many investigations to determine the
bonding and dissociation of this molecule on the
various transition metal surfaces. CO_~ dissocia-
tion is an important step in the route to more
valuable chemicals. For this reason the dissocia-
tion of CO, has attracted special attention. A
controversy exists concerning the question
whether or not CO, dissociation occurs on clean
Rh surfaces. Recently this controversy attracted
renewed attention in a review paper by Solymosi
[1]. For a detailed discussion on the adsorption
and reactions of C O , on a great number of
transition metals the reader is referred to this
paper. The adsorption and dissociation of CO,
on Rh will now be discussed.
As was already mentioned before, a contro-
versy exists whether CO. does dissociate on Rh
or not. The Somorjai group has found that CO,
is chcmisorbed dissociatively on Rh foils and on
R h ( l l l ) , (100), 1331) and (755) [2-6]. CO 2 disso-
emission microscopy (FEM) and thermal desorp-
tion spectroscopy (TDS) by our group [7,8]. It was
shown that CO, adsorption is very crystal face
specific; CO, is adsorbed especially on the open
crystal planes like (210), (320) and (531). Dissoci-
ation takes place on the stepped planes around
(111) and (100) and dissociation of CO, could not
be shown to occur on the smooth (100), (111) and
(110) crystal planes of Rh. Later also Kruse et al.
found a strong indication of the importance of
steps with a special structure for the dissociation
of CO, [9]. However, a field effect could not be
ruled out during the experiments where a high
positive voltage was applied when performing
pulsed field dcsorption mass spectrometry. On
the other hand, the Solymosi group does not
support the conclusion that CO~ does dissociate
on clean Rh surfaces and attributes the dissocia-
tion observed to impurities, like B, present on the
surfaces used [1,10].
The main problem in the arguments put for-
ward by authors in favour of CO, dissociation is

0169-4332/93/$1)6.110 (': 1993 - Elsevier Science Publishers B.V. All rights reserved
 M.F.H. can Tol et al. / The adsorption and dissociation of CO 2 on Rh
that only adsorbed CO and no adsorbed oxygen
could be detected as dissociation products.
Therefore, it has been suggested that the ad-
sorbed CO detected was due to adsorption of
residual CO and not to CO 2 dissociation.
As a new field emission microscope equipped
with image processing facilities became opera-
tional in our laboratory last year, which offers the
possibility to study adsorption, desorption and
reactions with a very high spatial resolution and
sensitivity, the CO 2 adsorption experiments were
taken up again and it was attempted to solve the
dispute concerning CO 2 dissociation on Rh.
2. Field emission microscopy
Field emission microscopy in its most basic
form consists of the application of a negative high
voltage V to an emitter tip (metal or semiconduc-
tor) under U H V conditions. At a certain applied
voltage electrons are emitted from this sharp
needle (r ~ 1000 ~,) due to the very high field
strength ( F = aV/r, with a being a constant for a
given emitter).
These electrons are accelerated towards a con-
ducting fluorescent screen positioned right in
front of the tip several cm away. The higher the
applied voltage, the higher the total current I of
electrons between tip and screen. The relation
between V and I is described by the simplified
F o w l e r - N o r d h e i m relation given below [11]:
I = A V 2 exp[(-Bd)3/2)/V],
where A is, amongst others, a measure for the
emitting surface area, B is, amongst others, a tip
shape- and radius factor and ~b is the work func-
tion of the tip material. From the slope a of a
graph displaying the variation of log(I/V 2) with
l / V , the work function of a tip with known
(bcl . . . . for example 4.80 eV for clean Rh, during
chemical processes like adsorption or reaction
can be calculated using eq. (2):
2/3
¢~p . . . . . . = ¢~clean(a clean/OL p . . . . . . )
where a is given by -Bqb 2/3. Ogclean depicts the
slope of the clean tip and a p . . . . . . of a tip which
167
is, for example, covered by adsorbate molecules.
Often A~b is used, which is defined as:
A(~ = ~process -- ~clean" (3)
In this study both ~ and the related applied
voltage required for maintaining a constant emis-
sion current will be displayed. Curves with V
displayed are usually smoother than curves where
the calculated values of ~b are used. Of course it
was checked carefully that no information was
lost when using V instead of & or A4~.
3. Experimental
A novel field emission microscope based on
image processing was used that was constructed
in 1990-1991 in our laboratories. All details about
the experimental set-up, hardware and software
used were reported earlier [12]. This set-up was
first applied succesfully to study the interaction
of 0 2 with W [12], Re and W / R e [13]. A short
description of the DigiFEM will be given below.
The microscope consists of a bakeable stainless
steel U H V chamber with a background pressure
better than 2 × 10 -~° Torr. The chamber is
equipped with a mass spectrometer for gas analy-
sis and partial pressure reading and an ion gauge
to determine the total pressure.
FEM images formed on a fluorescent screen
were recorded by an ultra-low light CCD camera.
The images were stored on video tape. The signal
(1) from the camera was also simultaneously digi-
tized by a Commodore Amiga computer equipped
with an 8-bits digitizer. In this way, the FEM
image is converted into a matrix of 256 × 320
pixels, each one representing a light intensity
between 0 and 127. The more intense a part of
the F E M image is, the lower the work function of
the corresponding surface area on the emitter.
The lower the work function ~h of a crystal plane
present on the emitter, the higher the number
that is attributed to the corresponding pixel.
Ranges of intensities can now be attributed a
, (2)
colour. In this way colour images can be dis-
played on a computer screen, photographed or
printed and studied in great detail by changing
168 M.F.H. van Tol et aL / The adsorption and dissociation o f CO 2 on Rh
colour settings and so on as will be shown in
detail later.
The most powerful feature of the DigiFEM
used is the possibility to subtract images. Images
obtained during two stages of an experiment can
be subtracted by computer and changes occurring
in, for example, a certain temperature range can
be visualised. Several examples of the use of this
unique possibility will be covered in this article.
All images were recorded at a constant emis-
sion current of 4 nA in order to allow comparison
of images obtained. The emission current was
measured on the fluorescent screen.
Rh tips were prepared by electrochemically
etching a Rh wire with a thickness of 0.10 mm in
a saturated solution of KOH. The radius of cur-
vature of the tips was about 2000 ,~. The emitters
were spotwelded to a Rh support wire with thick-
ness 0.25 mm. All Rh wires used had a minimum
purity of 99.95%. The purity of the CO 2 and 0 2
used was better than 99.995% and 99.998%, re-
spectively.
Determination of the temperature of the tip,
which could be heated resistively by applying a
current to the support wire, was performed by
measuring the change in resistance of the fila-
ment supporting the tip. The temperature was
calibrated using optical pyrometry for high tem-
peratures and by cooling of the filament by filling
the Dewar carrying the tip assembly with liquid
N 2. All exposures of the tip to adsorbing gas are
given in Langmuir units, a multiplication of pres-
sure and time of exposure: 1 L = 1 0 - 6 Torr • s.
4. Cleaning procedure
Due to the discussion whether or not the Rh
tips used in our earlier study were clean enough,
which we believed they were, special effort was
made to clean the Rh emitters used. They were
subjected to many cycles of heating in 0 2 (Po2 =
1 × 10 -8 Torr) followed by evacuation and flash-
ing in vacuum. During the flashing the tips were
heated to temperatures close to the melting point
of Rh. After extensive cleaning the cleanness of
Rh was checked in several ways. Heating of the
tip at temperatures between 300 and 1300 K in
U H V for a whole variety of durations up to
several hours did not result in any migration of
any impurity whatsoever. For the same argument
as that oxygen originating from CO 2 should be
visible [1] also small amounts of impurities, if
segregated to the surface, should be visible. The
resolution of the FEM set-up used was found to
be about 20 × 20 .~2 which makes it possible to
visualise even very small aggregates of impurities.
Never any indication of impurity segregation to
the surface was found. Another method is to
determine the saturation value of A4, of a given
molecule on Rh and check if this changes from
experiment to experiment. Our results could be
reproduced within the resolution in ~b of 0.03 eV
as had been determined before [12]. The purity of
the Rh tips used was carefully monitored
throughout the studies reported here. Therefore,
we can be almost sure that impurities cannot
cause the enormous effects discussed below.
5. Results
The results obtained will be presented in the
following order. First, the effects of exposure to
CO 2 at 80 K will be presented, followed by expo-
sure to CO 2 at 300 K. Secondly, the adsorption of
CO on Rh at 80 and 300 K will be evaluated for
sake of comparison. Next, the thermal desorp-
tion-like studies of CO 2 and CO will be covered
in detail. Finally, the results obtained during
heating of a Rh tip precovered with 0 2 will be
presented in order to be able to discuss the fate
of oxygen formed during CO z dissociation.
5.1. Exposure to CO 2 at 80 K
In fig. 1 the voltage required to yield a con-
stant emission current of 4 nA is displayed as a
function of exposure of the Rh tip to CO e at 80
K. The surface is not yet fully covered after
exposure to 4.8 L. It is known that under condi-
tions of low temperature CO 2 adsorption multi-
layer formation can occur [1,8]. In fig. 2 the
power of the new DigiFEM is shown. The filling
of the crystal planes can be followed as a function
of exposure. The picture in fig. 2a is that of the
 M.F.H. uan Tol et al. / The adsorption and dissociation of CO 2 on Rh 169

9.4
Table 1
92-
The filling of the various crystal planes during exposure to
9
CO 2 at 80 K; the change in work function upon CO 2 adsorp-
88
tion on Rh is based on ~dcan ah = 4.80 eV
~-86
~ 84 Exposure + zl~b Adsorption mainly on
~ 82
(L) (eV)
0 0
=CL 7 6 0.14 0.23 (210), (110), less on (311)
~74 0.37 0.39 (321)
72 0.62 0.46 (321), (221)
0.99 0.52 (321), (221), around (711)
68 2.9 0.61 (711), (511)
6.6
1
I I

2 31
I

4 4.8 0.80 (711), (551), (310), etc.

-~ exposure (L)
Fig. 1. Adsorption curve of CO 2 on Rh at 80 K.

applied voltage is lower at 300 than at 80 K. The

sticking probability of CO 2, however, is still quite
clean tip. When CO 2 is adsorbed the image
high. The images are different from those ob-
changes. Changes between two stages of an ex-
tained at 80 K. Some characteristic, subtracted,
periment are visualised in figs. 2b and 2c. The
images are displayed in fig. 4. The filling of the
crystal planes where CO z does adsorb are repre-
crystal planes is also different from that at 80 K.
sented in blue. The work function of these planes
CO 2 adsorption starts around (311) (fig. 4a), fol-
is increased due to CO 2 adsorption. Because of
lowed by (110) and surrounding surfaces like (331)
the fact that all images are recorded at the same
and (320) (fig. 4b). The adsorption spreads with
emission current the planes where ~b is increased
increasing exposure from (110) in the [111] direc-
less, probably due to a lower CO2-coverage, be-
tion on surfaces like (221) and (320).
come brighter (green). It can be concluded that
first (110), (210) and to a lesser extent (311) are
5.3. Exposure to C O at 80 K
occupied by CO 2. Finally (711), (310) and other
surfaces around (100) are occupied. In table 1 the
At 80 K CO is adsorbed with high sticking
filling of the different planes as a function of the
probability on Rh. The surface is entirely covered
exposure to CO 2 is given including (b values
after an exposure of 0.7 + 0.1 L.
based o n ~clean Rh = 4 . 8 0 e W .
The surface structure specificity of the adsorp-
tion of CO 2 indicates that it may be expected
8.8
that the weakly bound CO 2 molecule will diffuse,
8.6-
even at 80 K, to the most favourable sites avail- 8.4-
able. Although the dipole moment of the adlayer, 8.2-
and thus the effect of adsorption on the emission, 8-

does not necessarily have to be the same for all 7.8-

76-
planes, table 1 gives an indication of the variation
7.4-
of the heat of adsorption of CO 2 on the various
7,2-
crystal planes present on the emitter. 7-

6,8-

5.2. Exposure to C O 2 at 300 K 6.6-

6.4-
8.2
In fig. 3 the applied voltage is presented as a
function of exposure of Rh to CO 2 at 300 K. As --D.-exposure (L)
can be judged from figs. 1 and 3 the initial rise in Fig. 3. Adsorption curve of CO 2 on Rh at 300 K.
170 M.F.H. l,an Tol et al. / The adsorption and dissociation o f CO 2 on Rh

b C

Fig. 2.

a b

Fig. 4.
 M.F.H. can To/et al. / The adsorption and dissociation of CO 2 on Rh 171

10.5

j
10.5
10

10
~-93
9.5
g~
8"5 -
~8.5

El.
~8
7.5 7.5

6.5 f , r f I , , , , T , , r r , , r I 6,5
0.2 0.4 0.6 0.8 1 1.2 1.4 1.6 1.8
exposure (L) exposure (L)

Fig. 5. Adsorption curve of CO on Rh at 80 K. Fig. 6. Adsorption curve of CO on Rh at 300 K.

The adsorption curve of CO on Rh is given in 5.5. The desorption of CO pre-adsorbed at 300 K

fig. 5. The adsorption of CO was found to start at
(311) followed by (110). When the (110) surface is In fig. 8 the desorption spectrum of Rh ex-
filled, the areas around (100) and then (111) posed to 4.1 L CO at 300 K is displayed. Between
become populated by CO. This order of adsorp- 300 and 340 K a small increase in ~b is observed,
tion is different from CO 2. probably due to rearrangement of the adlayer.
Desorption is the exact reverse of the adsorption
5.4. Exposure to CO at 300 K order. CO desorption starts around (111) at about
350 K followed by the (221) and (110) planes.
At 300 K the adsorption of CO is slower than Finally, CO seems to be most tightly bound on
at 80 K as can be seen in fig. 6. The surface is (311). The surface is clean around 480 K.
almost entirely covered after exposure to 1 L, but
even then some CO can still be adsorbed around 5.6. The desorption of CO pre-adsorbed at 80 K
the (111) surface. The order of adsorption is
similar to that at 80 K. A series of subtracted In fig. 9 the desorption of 2 L CO adsorbed at
images is given in figs. 7a-7d. During the first 80 K is shown. After exposure to 20 L CO at 80 K
0.02 L exposure, CO is mainly adsorbed on and the system behaved similarly. There is no striking
around (311), followed by adsorption on (110), difference between desorption following adsorp-
spreading towards (111) (fig. 7c). Finally, adsorp- tion at 80 or at 300 K. The desorption starts
tion on surfaces around (111), like (221), takes around (111) followed by (221), (110) and finally
place. (311). The only slightly different behaviour is

Fig. 2. (a) DigiFEM image of a clean (111)-oriented Rh tip at 80 K. Colour intensity 0-17: black, 18-38: blue, 39-65: red, 66-99:
white, 100-117: green, 118-125: yellow. The higher the number the more electrons are emitted by that particular crystal plane. (b)
Subtracted image: image of (a) subtracted from the image obtained when 0.14 L CO 2 had been adsorbed at 80 K. Colour settings
0-80: dark blue, 81-117: light blue, 118-138: black, 139-199: dark green, 200-250: light green. In order to prevent "negative"
intensities 128 is added to the outcome of each subtraction. The colour settings are the same for all subtracted images used
throughout this paper. (c) The differences in F E M image occurring between an exposure of 1 and 4.8 L of C O 2 / R h at 80 K.

Fig. 4. (a) The effect of exposing Rh to 1 L CO 2 at 300 K on the F E M image. (b) The changes in F E M pattern between an
exposure of 1 and 6.8 L.
172 M.F.H. t,an Tol et al. / The adsorption and dissociation o f C O 2 on Rh

a b

C cl

Fig. 7. (a) The exposure of 0.02 L CO at 300 K. The blue areas are covered by CO. (b) The changes in emission pattern between an
exposure of Rh to 0.06 and 0.17 L CO at 80 K. (c) Changes between 0.17 and 0.32 L. (d) Changes between 0.32 and 1.2 L.

between 220 and 290 K where (111), (211) and
(533) emit slightly more intense, probably caused
by a rearrangement of the adlayer. This process is
continued between 290 and slightly below the
onset of desorption at about 380 K. Between 400
and 480 K desorption is very rapid with Tmax = 450
K.
5. 7. Heating o f Rh exposed to CO 2 at 300 K
A tip exposed to 6.8 L C O 2 a t 300 K
heated between 300 and 1100 K. Between
and 407 K no changes in the emission pattern
visible and the FEM pattern resembles that
tained after adsorption of CO. In fig. 10 the
effect of heating of the tip on the work function is
displayed. In figs. l l a - l l c some stages in the
desorption process are given. Between 407 and
453 K (110) and (311) become somewhat brighter
(fig. l l A ) . Between 453 and 479 K a very rapid
decrease in tb is observed. This sharp decrease
appears at the same temperature as found for
CO desorption described in section 5.5 and at a
much higher temperature than CO 2 desorption
was as will be discussed in section 5.8. At high tem-
300 peratures, between 500 and ll00 K (fig. llc),
are (210) increases in intensity, especially in the high
ob- temperature region. This behaviour was not ob-
 M.F.H. uan Tel et al. / The adsorption and dissociation of CO 2 on Rh 173

6 5.4
5.9
5.8 53
5.7
5.6 52
~" 5.5
5.4 ~ 51

Q-53

~ 5.2 5

5.1

5 4.9 (

4,9 j

, , , 4.8
4.8
300 400 soo 600 700 250 3k0 ,k0 5;0 ~50
-~ temperature (K) --=,- temperature (K)

Fig. 8. The effect on the work function of heating a Rh tip Fig. 10. The effect on the work function of heating a Rh tip
exposed to 4.1 L CO at 300 K. exposed to 6.8 L CO 2 at 300 K. Note the similarities with figs.
8 and 9.

served during a reference experiment during desorption behaviour of 0.24 L C O 2 adsorbed at

which the tip was heated between 300 and 1300 K 80 K is given. In fig. 12d the same spectrum is
in UHV. The high temperature and the images given after exposure to 2.2 L.
observed indicate O-diffusion from the bulk, fol- The images representing the desorption at low
lowed by desorption of O 2 a n d / o r RhO x. Proof ~9, 0.24 L, are given in figs. 13a-13c. Between 100
for these processes will be presented in section and 140 K the (110) planes start to emit some-
5.9. what stronger although the overall work function
remains relatively constant. According to Hen-
5.8. Heating of the tip following exposure CO 2 at
drickx et al. [7] this effect is caused by a rear-
80 K rangement of the adlayer. Between 165 and 235
K (fig. 13b) (110)-(221) become darker and also
The desorption of CO 2 pre-adsorbed at 80 K the areas connecting (111) with (100), the (711)-
will now be covered in some more detail. The
desorption behaviour of CO 2 is strongly depen-
dent on the surface coverage. In fig. 12c the 6.2
6.1
6
o shiftotg r a p h
59
6.2
5.8
6.1 - 0.2422L
L ~~ + ~ t ~ ~
5.7
6- B----_ >
59- 5.6
5,8 ZQ.5.S
o~L (c)
57 5.4
~" 5.6
oozL - - -m ~-" - ~
-~ ~- +04 ev
5.3
~ 55 5.2
~ 5.4 6.1
5.3
5
5.2
4.9 ~ 0ev
5.1 -
4.8
5- 2~o .~0 6~o
4.9
temperature (K)
4.8 , ,
200 400 600 Fig. 12. The effect of heating a Rh tip exposed to various
-~- temperature (K)
amounts of CO 2 at 80 K. Note that some of the graphs have
Fig. 9. The effect on the work function of heating a Rh tip been shifted for sake of clarity. Spectra were taken after
exposed to 2 L CO at 80 K. exposure to: 0.02 L (a), 0.10 L (b), 0.24 L (c) and 2.2 L (d).
174 M.F.H. t,an Tol et al. / The adsorption and dissociation of CO: on Rh

b b

Fig. 11. Some characteristic difference-images obtained when Fig. 13. Some characteristic changes occurring between 1{}0
a Rh tip exposed to 6.8 L CO 2 at 300 K was heated between and 140 K (a), 165 and 235 K (b), 235 and 290 K (c), after
407 and 453 K (a), 453 and 479 K (b), 500 and I100 K (c). exposing Rh to 0.24 L CO 2 at 80 K.
 M.F.H. van Tol et al. / The adsorption and dissociation of CO 2 on Rh 175

(311) surfaces, d a r k e n . T h e emission intensity o f a n d s u b s e q u e n t d e s o r p t i o n p r o c e s s c o n t i n u e s un-

(210) starts to increase. B e t w e e n 235 a n d 290 K
t h e (110) surfaces b e c o m e b r i g h t e r (fig. 13c).
T h e p r o c e s s e s o c c u r r i n g b e t w e e n 165 a n d 235
K can b e e x p l a i n e d by C O 2 dissociation on (210)
followed by m i g r a t i o n of C O to t h e m u c h less
p o p u l a t e d , b u t for C O a d s o r p t i o n i m p o r t a n t , (311)
a n d (221)-(110) surfaces. A s a result t h e l a t t e r
surfaces d a r k e n . B e t w e e n 235 a n d 290 K C O
r e c o m b i n e s with oxygen to form C O 2 which des-
orbs. This p r o c e s s starts at (110) b e c a u s e h e r e the
C O c o v e r a g e is r a t h e r high. This C O 2 f o r m a t i o n
til t h e tip is c l e a n a r o u n d 340 K. N o indications
of m u c h C O d e s o r p t i o n w e r e found. A s was dis-
cussed in section 5.6, Tm~x for C O d e s o r p t i o n lies
a r o u n d 450 K leaving a c l e a n tip above 480 K.
H e r e , the surface of the tip was a l r e a d y clean at
340 K.
A t h i g h e r e x p o s u r e s the b e h a v i o u r o f C O 2 is
s o m e w h a t different. A s an e x a m p l e , we will dis-
cuss the e x p o s u r e o f R h to 2.2 L C O 2 at 80 K. I n
fig. 12d the effect of h e a t i n g on this C O 2 - c o v e r e d
tip is given. B e t w e e n 90 a n d 135 K again a

Fig. 14. Some characteristic changes occurring between 190 and 218 K (a), 423 and 482 K (b) and 600 and 1200 K (c), after exposing
Rh to 2.2 L CO z at 80 K. As a reference-image to be compared with (c) the image representing the processes occurring while
heating a Rh tip exposed to 7 L 02 at 300 K between 1100 and 1200 K is given in (d). Just like in (c) the (210) areas have increased
in emission intensity.
176 M.F.H. van Tol et al. / The adsorption and dissociation o f CO 2 on Rh
rearrangement of the adlayer takes place, espe-
cially around (110), with probably some desorp-
tion of CO 2. Between 135 and 190 K no serious
changes are visible in the emission pattern. Some
of the more interesting stages during the heating
process are given in figs. 14a and b.
Between 190 and 218 K (fig. 14a) (110) and
(311) become relatively dark, caused by CO 2 dis-
sociation to COad ~ and O~ds, probably combined
with some CO desorption resulting in free sites
required for CO 2 dissociation. Maybe also some
CO desorbs, but the temperature is rather low for
such a process. Between 244 and 270 K the (110)
surfaces become brighter. This temperature is too
low for CO desorption to occur but, as was dis-
cussed for 0.24 L CO 2, CO recombination with O
to form CO2, followed by CO 2 desorption is
characteristic of this temperature range. Between
270 and 380 K ¢b increases by about 0.3 eV,
probably due to migration of CO to more
favourable sites. Also CO desorption starts to
occur around (111). The surface is not clean at
340 K like at low coverages but instead a very
rapid decrease in 4' is observed between 400 and
480 K and as can be judged from fig. 14b this
image is comparable to the CO desorption dis-
cussed earlier (section 5.6). CO 2 has already des-
orbed completely below 340 K, so all data indi-
cate that CO 2 is dissociated to form CO which in
turn desorbs between 400 and 480 K. The TDS
spectra of fig. 12d and fig. 8 do also indicate CO
desorption from CO 2 dissociation on Rh.
The dissociation of CO 2 to CO should also
result in oxygen atoms that cover the surface. It
was shown that at low temperatures CO and O
recombine to form CO 2 again. At high surface
coverages of CO2, CO does desorb leaving O on
the surface. As indicated in the introduction it
could never be shown unambiguously where the
oxygen atoms had moved to. With the DigiFEM,
oxygen was found to diffuse out of the bulk of the
Rh at high temperatures after high CO 2 expo-
sures. O diffusion out of the bulk starts already at
lower temperatures but the major part of the
oxygen can be shown to appear at the surface
around 1000 K. In fig. 14c the image obtained
when heating the CO 2 precovered tip between
600 and 1200 K is given. The (210) crystal face
appears to become bright due to desorption of 0 2
or maybe evaporation of R h O x. During a refer-
ence experiment at high temperatures under
U H V conditions, the clean Rh tip did not show
such an increase in (210) emission intensity.
5.9. Heating of a Rh tip precovered with 0 2 at 300
K
As a reference the Rh tip was exposed to 7.1 L
0 2 at 300 K. When the tip was heated between
1115 and 1183 K an image was obtained (fig. 14d)
which was very similar to that of fig. 14c. This
temperature is in excellent agreement with re-
suits published elsewhere and by our group [14-
16] for R h O X decomposition and evaporation.
This forms evidence for the dissociation of CO~
on Rh to COad s and Oads, resulting in bulk oxygen
formation at high precoverages of CO 2.
6. Discussion
It was shown that CO 2 adsorption takes place
on Rh at 80 and at 300 K. At 80 K the initial
sticking probability is higher that at 300 K. At 80
K the surface is almost saturated with CO 2 after
exposure to 4.8 L. At 300 K saturation occurs for
exposures above 12 L. At 80 K CO 2 is preferen-
tially adsorbed on the open planes like (210)
followed by (110), (321), (221) and planes with
(100) terraces and (111) steps like (711) and (511).
At higher exposures also planes like (310) are
covered. This is in general agreement with the
results reported earlier by Hendrickx et al. [7,8].
CO 2 adsorption at 300 K is found to be differ-
ent from that at 80 K. Due to the high spatial
resolution of the new DigiFEM it could be no-
ticed that not (210), but the (311) crystal plane is
most active in the CO 2 adsorption at 300 K.
Immediately after filling of (311), (110) and sur-
rounding areas like (331) and (320) are covered.
The adsorption spreads with increasing exposure
in the direction of (111) on surfaces like (221) and
(320).
The adsorption of CO at 80 K starts at (311),
and not on (210), as was reported earlier [7],
followed by (110). After filling of (110), areas
 M.F.H. van Tol et al. / The adsorption and dissociation of CO 2 on Rh 177

around (100) and (111) become occupied. The dissociation of C O 2 into C O a d s and Oads does
filling of the planes after adsorption of CO at 300 take place, but O is not forced to diffuse into the
K is basically the same as at 80 K, only the rate of bulk. Instead, the CO formed recombines with O
adsorption has slowed down. The adsorption of and desorbs as CO 2, leaving a clean tip at 340 K.
CO at 80 and 300 K is different from CO 2 ad- Another strong indication of CO 2 dissociation
sorption at 80 K but similar to CO 2 adsorption at comes from comparing the heating spectra after
300 K. This is a first indication of CO 2 dissocia- exposure of Rh to 0.24 L CO 2 adsorbed at 80 K,
tion at 300 K into CO and O atoms. The images after 2.2 L CO 2 at 80 K and after exposure to 2 L
obtained after CO 2 adsorption at 300 K resemble CO at 80 K. After exposure to 0.24 L CO 2 the tip
those obtained after CO adsorption, again indi- is clean at 340 K. After exposure to 2.2 L some
cating that CO 2 dissociation takes place. Also the CO 2 desorbs around this temperature but for the
images obtained after heating of a Rh tip precov- rest the behaviour upon heating is exactly the
ered with CO 2 at 80 K come to match CO images same as that of 2 L CO adsorbed at 80 K. A
at around 200 K due to CO 2 dissociation. At low strong desorption maximum is found around 450
initial CO 2 coverage CO recombines with O to K and the tip is only clean above 480 K.
form CO 2 between 235 and 290 K which desorbs
from the surface leaving a clean tip at 340 K. At
higher CO 2 coverages, CO 2 starts to dissociate 7. Conclusions
around 200 K. Again between 244 and 270 K CO
reacts with O and desorbs as CO 2 from the (110)
It was shown that CO 2 does dissociate on
surface. The tip is not clean but the images
clean Rh. Dissociation is highly surface structure
obtained are characteristic of CO which is still
specific. CO 2 dissociates starting on Rh(210). At
present on the surface. Migration of the CO
low surface coverage of CO 2, recombination of
formed to more favourable sites between 270 and
COad s and Oads formed through dissociation of
380 K results in an increase in 05. At these higher
CO 2 takes place followed by desorption of CO 2
temperatures CO starts to desorb as well. The
leaving a clean tip at 340 K:
maximum rate of CO desorption lies around 450
K which is in excellent agreement with both our CO 2 (ads) T>200K CO (ads) + O (ads)
data and data taken from the literature (ref. [7],
and references therein). T>240 K CO 2 (g)
At temperatures between 600 and 1200 K oxy-
At a high initial surface coverage of CO 2,
gen atoms, which were forced to diffuse into the
some CO 2 desorbs upon heating according to the
bulk of Rh at higher CO 2 exposures, reach the
above mentioned reaction. O atoms are forced to
surface by the kinetically controlled process of
diffuse into the bulk of the metal, and CO de-
diffusion. This diffusion is very rapid between
sorbs around 450 K. Oxygen atoms start to dif-
1000-1200 K. At these temperatures oxygen and
fuse out of the bulk at temperatures higher than
RhO x are evaporated from the surface leaving
about 600 K. This kinetically controlled process
the clean tip with the right value of 05clea,"
reaches a high rate between 1000 and 1200 K.
This process was checked by performing some
Oxygen desorbs around this temperature in the
reference measurements with O 2 and by heating
form of O 2 or as rhodium oxides.
of a clean tip in UHV. The latter experiments did
not result in a change in emission characteristics T > 200 K T > 240 K
CO 2 (ads) ~ C O (ads) + O (ads) ' C O 2 (g)
or 05 at high temperatures but from the reference
Tm = 450 K [T>300K
experiments with O 2 it was concluded that the
processes taking place between 1000 and 1200 K C O (g) 0bulk
involved oxygen. This could only originate from
CO 2 dissociation at higher exposures where O is
forced into the bulk. At a low coverage of CO 2,
IT = 600-1200 K

0 2 (g) a n d R h O x (g)
178 M.F.H. van Tol et aL / The adsorption and dissociation of CO: on Rh
A forthcoming paper will deal with a similar
study using a Pt tip. It will show that the interac-
tion of Pt with CO 2 is very different from that
reported here for CO 2 with Rh [17].
References
[1] F. Solymosi, J. Mol. Catal. 65 (1991) 337.
[2] L.H. Dubois and G.A. Somorjai, Surf. Sci. 88 (1979) LI3.
[3] B.A. Sexton and G.A. Somorjai, J. Catal. 46 (1977) 167.
[4] D.G. Castner and G.A. Somorjai, Surf. Sci. 83 (1979) 60.
[5] D.G. Castner, B.A. Sexton and G.A. Somorjai, Surf. Sci.
71 (1978) 519.
[6] L.H. Dubois and G.A. Somorjai, Surf. Sci. 91 (1980) 514.
[7] H.A.C.M. Hendrickx, A.P.J.M. Jongenelis and B.E.
Nieuwenhuys, Surf. Sci. 154 (1985) 503.
[8] H.A.C.M. Hendrickx, A.P.J.M. Jongenclis and B.E.
Nieuwenhuys, Surf. Sci. 162 (1985) 269.
[9] N. Kruse, G. Abend and J.H. Block, Surf. Sci. 211/212
(1989) 1038.
[10] F. Solymosi and J. Kiss, Surf. Sci. 149 (1985) 17.
[11] R.H. Fowler and L.W. Nordheim, Proc. R. Soc. London
A 119 (1928) 173.
[12] M.F.H. van Tol, F.A. Hondsmerk, J.W. Bakker and B.E.
Nieuwenhuys, Surf. Sci. 266 (1992) 529.
{13] M.F.H. van Tol, F.A. Hondsmerk, J.W. Bakker and B.E.
Nieuwenhuys, Surf. Sci. 266 (1992) 214.
[14] V.V. Gorodetskii, B.E. Nieuwenhuys, W.M.H. Sachtlcr
and G.K. Boreskov, Appl. Surf. Sci. 7 (19811 355.
[15] N.M.H. Janssen, M.F.H. van Tol and B.E. Nieuwenhuys,
to be published.
[16] H.A.C.M. Hendrickx and B.E. Nieuwenhuys, Surf. 8ci.
175 (1986) 185.
[17] M.F.H. van Tol, A. Gielbert, R.M. Wolf, A.B.K. Lie and
B.E. Nieuwenhuys, Surf. Sci., in press.