19 August 2002

Chemical Physics Letters 362 (2002) 181–184

www.elsevier.com/locate/cplett

Spectroscopic detection of CO dissociation on defect sites on

Ru(1 0 9): implications for Fischer–Tropsch
catalytic chemistry q
Tykhon Zubkov, Gregg A. Morgan Jr., John T. Yates Jr.*
Department of Chemistry, Surface Science Center, 234 Chevron Science Center, University of Pittsburgh,
Pittsburgh, PA 15260, USA

Received 11 March 2002; in final form 29 May 2002

Abstract

Dissociative chemistry of CO on an atomically stepped single crystal Ru(1 0 9) surface was studied using the com-
bination of vibrational spectroscopic and thermal desorption measurements. CO molecules on stepped Ru are by
desorption and dissociation together upon heating to 480 K. Contrary to the atomically smooth Ru(0 0 1) surface, the
step defect sites on the Ru(1 0 9) surface facilitate CO dissociation. Adsorbed atomic O and C then recombinatively
desorb near 520 K. This low-temperature mobile carbon species is likely to be an intermediate in the Fischer–Tropsch
synthesis on Ru. Ó 2002 Elsevier Science B.V. All rights reserved.

Metallic Ru surfaces are known to effectively
catalyze the production of linear alkanes from CO
and H2 in the Fischer–Tropsch (FT) reaction [1,2],
and it is very likely that a primary step in this re-
action is the dissociation of the CO bond in the
chemisorbed CO species. The formation of carbon
on the surface is followed by reaction with chem-
isorbed H atoms produced by H2 dissociation on
the surface. We have combined reflection-absorp-
tion infrared spectroscopy (RAIR) with tempera-
ture programmed desorption (TPD) and isotopic
q gas, and in ultrahigh vacuum. Fig. 2 shows the
Work supported by the Department of Energy, Office of
Basic Energy Sciences.
*
Corresponding author. Fax: +1-412-624-6003.
E-mail address: jyates@imap.pitt.edu (J.T. Yates Jr.).
mixing techniques to investigate the behavior of
the CO reactant molecule. Using the Ru(1 0 9)
single crystal surface, which contains periodic
double Ru atom height step defect sites, separated
by 10 atom wide smooth Ru(0 0 1) terraces, we
have determined that the CO dissociation reaction
preferentially takes place at relatively low tem-
peratures (
480 K) on the atomic step defect sites.
Fig. 1 shows the structure of the Ru(1 0 9) surface,
as determined by low energy electron diffraction
measurements [3]. This crystalline surface was
cleaned by conventional methods involving Arþ
bombardment, followed by annealing in oxygen
RAIR spectrum of 13 C18 O on this surface where
the C–O vibrational frequency at low coverage is
observed at 1884-1891 cm (for 12 C16 O at 1973–

0009-2614/02/$ - see front matter Ó 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 0 9 - 2 6 1 4 ( 0 2 ) 0 0 8 9 5 - 3
182 T. Zubkov et al. / Chemical Physics Letters 362 (2002) 181–184
Fig. 1. Schematic of the Ru(1 0 9) surface showing step and
terrace sites. The region of the step sites is circled.
1980 cm1 ). By comparison with other RAIR
studies of the atomically smooth close-packed
Ru(0 0 1) surface [4], we find that the bonding of
CO is similar and corresponds to a single coordi-
nated on-top species. Thermal depletion of ad-
sorbed CO causes the infrared band to decrease in
Fig. 2. RAIR detection of chemisorbed 13 C18 O species on
Ru(1 0 9) following heating in ultrahigh vacuum. The rate of
heating to the designated temperature is dT/dt ¼ 2 K/s. The
initial coverage of CO is 5:3  1013 CO=cm2 .
absorbance and shifts the terrace-CO frequency
downward which reflects the decreasing vibra-
tional coupling on the terraces than on the steps)
[5]. Upon heating to about 480 K, RAIR shows
that both CO is completely removed. Fig. 3a
shows the TPD spectrum of CO, where surpris-
ingly it is seen that some CO desorbs above 480 K.
This CO desorption process above 480 K must
result from the recombination of C(a) and O(a),
since the RAIR experiment indicates that undis-
sociated CO is not present above 480 K. To check
that CO dissociation is followed closely by
C(a) + O(a) recombination, we chemisorbed
equimolar amounts of 13 C18 O and 12 C16 O, and
Fig. 3. (a) TPD of CO from Ru(1 0 9). The initial coverage is
1:3  1014 CO=cm2 ; (b) fraction of isotopic mixing, fm , between
CO isotopomers, as determined by multiplex mass spectrometry
during TPD:
X13 C16 O
fm ¼ ;
ðX13 C16 O þ X13 C18 O ÞðX13 C16 O þ X12 C16 O Þ
where Xi is the mole fraction of the ith isotopomer in the de-
sorbing CO. In both cases, dT/dt ¼ 1.9 K/s.
 T. Zubkov et al. / Chemical Physics Letters 362 (2002) 181–184
measured the fraction of isotopic mixing between
the species during TPD. These results are shown in
Fig. 3b, where it may be seen that isotopic mixing
occurs extensively only during the high-tempera-
ture CO desorption process. For comparison, no
high-temperature CO desorption feature and no
isotopic mixing were observed on a smooth
Ru(0 0 1) surface [6,7]. These results demonstrate
conclusively that the sites associated with the Ru
atomic steps are selectively responsible for CO
dissociation near 480 K. Therefore, the well-
known catalytic activity of Ru for the FT reaction
is likely due to the special behavior of Ru atoms
with low Ru coordination numbers and/or due to
the special steric environment at the step vicinity
that facilitates the CO dissociation. Similar pref-
erential behavior has been seen for NO dissocia-
tion and N2 dissociative chemisorption on step
sites on Ru surfaces [8–10]. This is consistent with
the known electronic properties of low coordina-
tion number sites on metal surfaces leading to
enhanced reactivity [11]. If the CO dissociation is
rate-limiting, the above considerations imply that
the FT reaction is structure-sensitive, as reported
for supported Ru catalysts [12–16]. No evidence of
structure sensitivity was reported for methanation
over two different Ru single crystal faces, (0 0 1)
and (1 1 0) [17]. However both surfaces may lack
the Ru ensembles of the proper geometry for being
active.
In addition, on the early transition metals
[18–26], CO has been observed to dissociate, but
C(a) + O(a) recombination processes occur at
much higher temperatures than on the stepped Ru
surface. Since atom recombination must involve
surface mobility, it is possible that the special FT
catalytic activity of Ru may be due to low tem-
perature CO dissociation coupled with C(a) or
O(a) atom mobility at temperatures near 500 K.
By forcing CO dissociation on a stepped Ru sur-
face with high CO exposures at 501 K, Tamaru
et al. [7] have also observed effects attributed to C–
O bond scission at the steps. However, their TPD
data differ considerably from ours, and their ul-
traviolet photoelectron spectra (UPS) mainly in-
dicate that CO can be forced to dissociate at high
temperatures and CO exposures, blocking CO
adsorption at the step sites.
183
In summary we have shown that Ru atomic step
defect sites exhibit enhanced CO dissociation ac-
tivity compared to smooth (0 0 1) terrace sites, and
also that C and/or O atomic mobility near 500 K
leads to recombination and desorption of CO.
Fischer–Tropsch chemistry most likely involves
the interaction of C(a) and O(a) species with
adsorbed H to form linear alkane products and
water.
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