J. Phys. Chem.

1981, 85, 2543-2546 2543

Determination of I R Extinction Coefficients for Linear- and Bridged-Bonded CO on

Supported Palladium

M. Albert Vannice‘ and S-Y. Wang

Department of Chemlcal Englneerlng, The Pennsylvania State University, University Park, Pennsylvania 16802
(Received: March 3 1, 198 1; In Final Form: June 2, 198 1)

Infrared spectra were obtained of CO adsorbed on Pd dispersed on four supports: 7-A1203,SO2,Si02-A1203,

and Ti02. All catalysts were characterized by both H2 and CO chemisorption which allowed the calculation
of the surface coverages of both linearly adsorbed CO, which gives a band above 2000 m-l,and the bridged-bonded
form, which produces a band below 2000 cm-’. From these values, integrated absorbances, A, and extinction
coefficients, e, have been determined for each adsorbed species on Pd for the first time. For individual catalysts,
absorbances and extinction coefficients were always much higher for the bridged-bonded CO than the linearly
adsorbed co, i.e., average values were Ab = 85 X lo’ cm mol-’, A, = 3.3 X 10’ cm mol-’, €b = 4.1 X lo6 cm2
mol-’, and €1 = 0.36 X lo6 cm2mol-’. Because a specially designed IR reactor cell was utilized, spectra were
also taken under steady-state CO hydrogenation reaction conditions to form CH4. The A1203-, SO2-,and
Si02-A1203-supportedPd catalysts still exhibited strong CO bands; however, Pd/Ti02 wafers exhibiting SMSI
(strongmetal-support interactions)showed no detectable CO bands although they were the most active catalyst.
Using the E values obtained in this study, we estimated the maximum surface coverage on Pd to be less than
1%for the linear species and 0.1% for the bridged species.

Since the first application of IR spectroscopy by Eis-
chens and co-workers to study supported catalysts,’ this
technique has been in the forefront of approaches to study
adsorbed molecules on metal surfaces. Although numerous
papers have dealt with CO adsorption on group VI11
metals, few studies have quantitatively related the inten-
sities of the observed spectra for adsorbed CO with surface
Only Pt and Rh have been examined
until now, and no such studies have been reported for
palladium. Undoubtedly this is a consequence of the re-
quirement that accurate CO concentrations on the metal
must be known at the time the spectrum is recorded, and
the design of most IR cells has not allowed these uptake
results to be obtained. In addition, many CO spectra have
been obtained after evacuation, which can alter surface
coverage and complicate the determination of CO surface
concentrations.
More than one IR band for adsorbed CO frequently
occurs on metal surfaces, and typically a high-frequency
(HF) band exists between 2000 and 2100 cm-l along with
a low-frequency (LF) band between 1800 and 2000 cm-’
which is apt to be much broader and may appear to con-
tain several p e a k ~ . ~ pThe
~ J ~HF band is usually associated
with linearly adsorbed (single site) CO whereas multiply
coordinated CO is assumed to give rise to bands in the LF
region.’J’ It would be especially informative if extinction
(1)Eischens, R. P.; Francis, S. A.; Pliskin, W. A. J. Phys. Chem. 1956,
60,194.
(2) Eischens, R. P.; Pliskin, W. A. Adu. Catal. 1958, 10,1.
(3) Darensbourg, D. J.; Eischens, R. P. “Catalysis”; Hightower, J. W.,
Ed.; North Holland: Amsterdam, 1973; p 371.
(4) Heyne, H.; Tompkins, F. C. Trans. Faraday SOC.1967,63, 1274.
(5) Shigeishi, A.; King, D. A. Surf. Sci. 1976, 58, 379.
(6) Seanor, D. A.; Amberg, C. H. J. Chem. Phys. 1965, 42, 2967.
(7) Vannice, M.A.; Twu, C. C.; Moon, S. H. Submitted for publica-
tion.
(8)Duncan, T. M.; Yates, J. T., Jr.; Vaughn, R. W. J. Chem. Phys.
1980,73,975.
(9) Little, L. H.“Infrared Spectra of Adsorbed Species”; Academic
Press: New York, 1966.
(10)Hair, M. L. “Infrared Spectroscopy in Surface Chemistry”;Marcel
Dekker: New York, 1967.
coefficients, associated with band maxima, and integrated
absorbances, which are related to the area under each
band, could be obtained for each of these two major bands.
Such individual values have been published only recently
for CO adsorbed on Rh and Pt,‘ls and values for other
group VI11 metals have not yet been reported, principally
because of the difficulty in determining the representative
fractions of linearly adsorbed CO and of multiply bonded
CO, which is most likely to be the bridged-bonded (2-fold
coordination) species. In a recent study, we obtained IR
spectra for CO chemisorbed on Pd dispersed on four dif-
ferent support materials (7-A1203,Si02, Si02-A1203and
TiOJ and each catalyst was carefully characterized by both
CO chemisorption and hydrogen chemisorption measure-
ments.12J3 This allowed the calculation of fractional
coverages of linear- and bridged-bonded CO and the es-
timation of extinction coefficients and integrated absor-
bances for each CO band. The influence of Ti02 on CO
adsorption on Pd was of special interest because of SMSI
behavior which can be induced in this catalyst system.14
This paper reports these results.
Experimental Section
The Catalysts were prepared with aqueous impregnation
techniques by using PdClz (Ventron Corp.), and after im-
pregnation the samples were dried in air at 393 K for 16
h, bottled, and stored in a desiccator. The support ma-
terials used were Grade 57 SiOzand Grade 979 Si02-A1203
(Davison Chemical Co.), P-25 TiOz (Degussa Co.), and
7-A1203donated by Exxon Research and Engineering Co.
The H2 (99.999%), CO (99.99%), and He (99.9999%), all
from the Linde Co., were further purified before use. A
Deoxo unit (Engelhard) and an Oxy-trap (Alltech Assoc.)
were used for hydrogen, an Oxy-trap was employed for the
helium, and the CO was passed through a molecular sieve
(11)Bradshaw, A. M.;Hoffmann, F. M. Surf. Sci. 1978, 72,513.
(12) Wang, S-Y., Ph.D. Thesis, Pennsylvania State University, 1980.
(13) Vannice, M. A.; Moon, S. H.; Wang, S-Y. J. Catal. In press.
(14) Tauster, S. J.; Fung, S. C.; Garten, R. L. J.Am. Chem. SOC.1978,
100,170.

0022-3654/81/2085-2543$01.25/0 0 1981 American Chemical Society

2544 The Journal of Physical Chemistry, Vol. 85, No. 17, 1981 Vannice and Wang

trap. Weight loadings were determined by using neutron I I I I I I

activation analysis. Details on the materials and prepa-
rative technique are provided elsewhere.13J5
Adsorption measurements were performed in a con-
ventional, mercury-free, glass adsorption system capable
of achieving an ultimate vacuum near 4 X torr (5.3
X Pa). Pressures during adsorption runs were mea-
sured with a Texas Instruments precision pressure gage.
This system has been described previo~s1y.l~The IR
spectra were obtained in a specially designed cell which
could be heated above 700 K to allow in situ pretreatment
(reduction) in Hz and could also be operated as a differ-
ential, plug-flow reactor, if desired, to obtain spectra of CO
adsorbed on a catalyst surface under reaction condi-
tions.l3Js All spectra were recorded on a Perkin-Elmer
580 dual-beam spectrophotometer in which a pure support T

wafer was placed in the reference beam and the supported

catalyst wafer was placed in the sample beam. The re-
corded spectra represent the difference in transmission
between the beams passing through these two wafers, and
this technique very efficiently minimized or eliminated
contributions of gas-phase CO and CO physically adsorbed
on the support surface because identical gas mixtures were
flowed through each cell. As a result, spectra under CO
pressures as high as 500 torr could easily be obtained;
however, all results reported here were at a constant CO
pressure of 190 torr (0.25 atm). The total pressure in the
cell was 1atm (101 kPa) with the balance composed of He.
The wafers normally weighed 50-60 mg and were 0.2 mm
thick after being pressed into the stainless steel cylinder
which comprised the cell. The cell design forced gas flow
through the wafer, and high space velocities with low I I L I I I
22011 21100 1800
pressure drops could be attained. Precise details of the
design of this cell and the IR system have been previously w (an-')

published. l6 Figure 1. Transmittance spectra of CO adsorbed on Pd at 300 K, P,

The Pd/A1203,Pd/Si02, and Pd/SiOZ-Al2O3catalysts
were reduced 1 h at 673 K in flowing H2in the adsorption
system following a specified pr0~edure.l~ Two different
Pd/Ti02 catalysts were prepared by using the two re-
duction procedures of Tauster et al.;14 i.e., reduction at 448
K provided a Pd/Ti02 catalyst with normal adsorption
behavior while reduction at 773 K produced an SMSI state
which markedly suppressed Hz and CO ads0rpti0n.l~
Hydrogen and CO uptakes were measured by using the
dual isotherm technique of Benson, Hwang, and Boudart17
to determine chemisorbed hydrogen at 300 K, and the
method of Yates and Sinfelt'* was employed to determine
irreversibly adsorbed CO at 300 K. With the exception
of Pd/Ti02, these pretreated catalyst powders were used,
after passivation in air, to press the wafers for the IR study,
and the wafers, including the reference wafer, were then
reduced in situ at 548 K. After this reduction step, ad-
sorbed hydrogen was removed by flowing He through the
cell a t 548 K. The absence of H2 in the gas phase was
determined by using a gas chromatograph to analyze the
exit stream from the IR cell. The wafers were then cooled
under flowing He to 300 K and a baseline was obtained
in pure He before CO was introduced into the gas stream.
The Pd/Ti02 wafer was pressed from fresh, unreduced
catalyst powder and IR spectra were obtained after an in
situ reduction at 448 K. The wafer was then further re-
duced at 773 K to induce SMSI behavior and cooled in He
to 300 K, and the spectra were obtained.
(16)Palmer, M. B., Jr.; Vannice, M. A. J. Chem. Tech. Biotechnol,
1980, 30, 205.
(16)Vannice, M. A.; Moon, S. H.; Twu, C. C.; Wang, S-Y. J. Phys. E.
1979, 12, 849.
(17) Benson,J. E.; Hwang, H. S.;Boudart, M. J.Catal. 1973,30,146.
(18) Yates, D. J. C.; Sinfelt, J. H. J. Catal. 1967, 8, 348.
= 190 torr, P, = 570 torr: (A) 1.98% Pd/A1901, (B)1.86% PdITIO.
(448 K), (C) 1.53% Pd/SI02; (0) 2.12% Pd/&Ai20~, (E) i.86./0'
Pd/TI02 (SMSI).
TABLE I: CO Bands in He at 300 K
HF LF
(A) 1.98% Pd/s-A1,0, 2085 1970 (s), 1930
(B) 1.86% Pd/TiO, 2096 1926,1890 (s)
(C)1.93% Pd/SiO, 2085 1985,1938
( D ) 2.12% Pd/SiO,-Al,O, 2098 1965
(E) 1.86% Pd/TiO, (SMSI) 2058 1925
Results and Discussion
The spectra obtained at 300 K (and higher tempera-
tures), along with baseline behavior in the absence of CO,
are reported elsewhere,13but the transmittance spectra are
shown again in Figure 1 for comparison purposes. The
narrower HF band and the broader, more dominant LF
band typically found for supported Pd catalysts are clearly
evident. The baseline intensity, To,for each support was
superimposed on the CO spectra in the region between
2100 and 2600 cm-', and relative intensities, TIT,, were
calculated on this basis. The CO peak positions in Figure
1 are listed in Table I.
Small shifts (5-10% T )were sometimes observed in the
baseline obtained in pure He and that measured during
the spectrum for adsorbed CO, which introduced some
uncertainty in the absorbance values. The integrated form
of the Beer-Lambert law is a(v) = (Cl)-' In T o / T ,where
a(v)is the absorption coefficient, which can be dependent
on the radiation frequency, v, C is the molar concentration
of CO in the sample, I is the distance through the sample
through which the IR beam penetrates, and T and Toare
the transmitted radiation intensities in the presence and
Linear- and Bridged-Bonded GO on Supported Palladium The Journal of Physical Chemistty, Vol. 85, No. 17, 198 1 2545

TABLE 11: Extinction Coefficientsa and Integrated Absorbancesb for CO Adsorbed on Pd at 300 K
chemisorption on
used sample,
pmol g-’ 10-7x 10-7x io-’X 10-6 x x
A, Al, Ab, fbC EbrC
catalyst H* CO col/cob cm/mol cm/mol cm/mol cm2/mol cm*/mol
1.98% Pd/q-Al,O, 19 23 0.53 25 6.7 35 0.66 2.1
1.93% Pd/SiO, 6 11 10 19 1.4 190 0.16 9.3
2.12% Pd/SiO,-Al,O, 16 27 4.4 6.9 1.9 29 0.26 0.87
1.86% Pd/TiO, (448 K) 16d 41d 6.8
7.6
1.86% Pd/TiO, (SMSI) 2.0 7.0 9.2
1.86% Pd/TiO, (SMSI) 1.5e 5.0e 14
average 14 3.3 85 0.36 4.1
gas-phase CO (ref 21) 0.042 0.00018
E = log (T,/Tmax)/(CZ). A =J u dv/(CZ). At band maxima in Figure 1. Based on fresh, reduced catalyst. e Up-
takes at 548 K.

absence of the adsorbate, respectively. From a plot of In

(To/T)vs. v, such as those shown in Figure 2, the total
intensity of a given band was obtained by graphical inte-
gration using a planimeter. For each catalyst, an overall
integrated absorption coefficient, A = ~,,‘a(v)dv, was
obtained based on all adsorbed CO species under both
bands using CO uptakes per gram determined in the ad-
sorption experiments and the diameter of the wafer (di-
ameter = 15.9 mm). The sample thickness, 1, is not needed
because C1= Um/A where U is uptake in mole of CO g-l,
m is the wafer mass, and A is the cross-sectional area of
the wafer.
Integrated absorption coefficients for the HF band, A,,
and the LF band, Ab, and extinction coefficients deter-
mined at the frequencies corresponding to these two band

-
maxima, el and q, where E = 1/C1log (To/T-), cannot be
determined unless the fractions present as linearly ad-
sorbed CO, COI,and bridged-bonded CO, cob, are known.
The assumption that these two forms of adsorbed CO
predominate on Pd is supported by the model of Bradshaw
and Hoffmann, which proposes that CO in threefold or
higher coordination should have frequencies below 1880
cm-l.ll Since intensities are quite low below 1880 cm-l
(Figure I), this assumption seems justified; however, this
is the only assumption which allows an estimation of these <El

four parameters. Because hydrogen adsorption was also 2100 2000 1900 1800
measured on these catalysts and its adsorption stoichiom- u (Cm-1)

etry is established, i.e., H,d/Pd, is near unity,” where Pd,

is a surface Pd atom. This technique provides a value for
the total number of surface Pd atoms (Xp,J. It is assumed
that a surface Pd atom interacts with no more than one
CO molecule, either in the bridged form (COb/Pd, = 1/2)
or in the linear form (COl/Pd, = 1). The assumption that
only one- and two-site CO adsorption occurs produces two
straightforward algebraic equations involving CO and H2
uptakes from which surface fractions of linear and
bridge-bonded CO can be determined, i.e.
2(Hz uptake) = Xpd,
[cob]+ [CO,] = CO uptake
The values of AI, Ab, E,, and tb based on these fractions
are listed in Table 11. Because some decrease in the Pd
surface area occurred during the course of these studies,
adsorption values on used samples, listed in Table 11, were
employed in these calculations. The altered state of ad-
sorption on Pd/Ti02 samples, especially H2 adsorption on
the SMSI sample, prevented calculation of values for in-
dividual bands and only an overall A value could be de-
termined for these two catalysts.
Figure 2. Absorbance of CO adsorbed on Pd at 300 K, P,, = 190
torr, PHe= 570 torr: (A) 1.98% Pd/Ai,03, (B) 1.86% PdlTIO, (448
K), (C) 1.93% Pd/SiO,, (D) 2.12% Pd/Si02-Ai,03, (E) 1.86% Pd/TlO,
(SMSI).
The overall integrated absorbances, A , are in good
agreement, vary by a factor less than four, and have an
average value of 14. Considering that adsorption on the
used Pd/Ti02 sample reduced at 448 K should be some-
what lower than on the fresh sample, the actual A value
for this catalyst is probably a little higher than that re-
ported. The similarity of these A values indicates that no
dramatic differences seem to exist in the interaction of
adsorbed CO with incident IR radiation in these different
Pd catalyst systems. In addition, it is clear that A and E
values for adsorbed CO are orders of magnitude greater
than those for gas-phase CO, a fact which has been rec-
ognized2p9and which facilitates the application of this
spectroscopic technique to characterize CO adsorption on
metal surfaces.
Integrated absorbances and extinction coefficients could
be calculated for both the HF and LF species of CO on
the three catalysts exhibiting “normal” adsorption be-
havior. For the HF band, A1 values showed a fourfold
variation while a larger spread occurred in Ab values. The
2546 The Journal of Physlcal Chemistry, Vol. 85, No. 17, 198 1
I I I I I I
1890
I 1 I I 1 I
2200 2000 1800
v (cm-1)
Figure 3. IR spectra of CO adsorbed on Pd under reaction conditions;
, = 190 torr, PH = 570 torr: (A) 1.98% Pd/AI O3 ( N
T = 548 K, P
= 3.3 X s-‘); (6)1.86% $d/TiO, (448K) ( N = 2.0 X lo3 s-‘);
(C)1.93% Pd/SiO, ( N N 0.1 X lo-’ s-I), (D) 2.12% Pd/S102-Ai203
( N = 1.8 X s-’), (E) 1.86% Pd/TiO, (SMSI) ( N = 40 X s-’).
The number N in parentheses represents the turnover frequency of
methane formation (molecules (Pd site)-’ s-‘) occurring during the
recording of the spectrum.
unusually high value of Ab for Pd/Si02 may well be due
to the very low surface fraction calculated for the
bridged-bonded species. Gas uptakes were low on this
catalyst and even a small error in the Hz uptake would
create a large variation in the calculated amount of C o b
However, the major finding of this study is that Ab values
are always much greater than AI values, and 6b is much
higher than €1 for any particular catalyst. This conclusion
is true even if more than one form of multiply coordinated
CO comprise the LF band; however, the Ab values calcu-
lated here represent an average of all the species producing
the LF band. This is the first quantitative determination
of these values for each of the two major CO species on
Pd and it confirms the estimate of Palazov, Chang, and
Kokes that the extinction coefficient of the LF CO species
on Pd is about an order of magnitude higher than that for
the H F species.lg Doyen and Ertl found that multiply
coordinated CO species on Pd have a stronger metal-
carbon adsorption bond, i.e., a higher heat of adsorption
than linearly adsorbed C0,20and a lower C-0 stretching
(19) Palazov, A,; Chang, C. C.; Kokes, R. J. J. Catal. 1975, 36, 338.
(20) Doyen, G.; Ertl, G. Surf. Sci. 1974, 43, 197.
Vannice and Wang
frequency2J1V2lis therefore expected for the multiply
bonded CO.
This picture was supported by desorption experiments
during which the HF band always disappeared first.12
Carbon monoxide is invariably assumed to chemisorb via
an interaction between the carbon atom and the metal
surface,2*22and, as a consequence, a stronger adsorption
bond might result in a larger dipole moment derivative and
produce a larger extinction c o e f f i ~ i e n t . ~Based
~ on this
argument the predicted order of extinction coefficients
would be 6b > el >> which is the trend found in this
study.
The usefulness of these values for A and 6 is demon-
strated by in situ studies in which simultaneous kinetic
data and IR spectra were obtained for Pd methanation
catalysts under well-defined, steady-state reaction con-
ditions after H2was substituted for flowing He at 548 K.13
High band intensities similar to those at 300 K were ob-
served for typical Pd catalysts under reaction conditions
at 548 K, indicating high surface coverages of CO; however,
the Pd/Ti02 (SMSI) catalyst exhibited markedly different
behavior, no IR bands were detectable under reaction
conditions, as shown in Figure 3, despite its high activity.
The results in Table I1 show that A values are very similar
for CO adsorbed at 300 and 548 K and are not strongly
dependent on temperature. Therefore, if the average q and
€b values in Table I1 are also assumed not to be strongly
dependent on temperature or on adsorbed hydrogen,
maximum surface coverages on Pd under reaction condi-
tions can be estimated. The first assumption is supported
by the spectrum of CO in He obtained 548 K for the
Pd/Ti02 (SMSI) catalyst. The CO uptake was 5.0 pmol
g-l at 548 K resulting in an A value of 14 X lo-’, as shown
in Table 11, which is very close to values obtained a t 300
K. The second assumption is supported by the study
Conrad, Ertl, and Latta, which showed that essentially no
interaction occurs between adsorbed CO and hydrogen on
Pd single-crystal surfaces.24 With a minimum sensitivity
of 1%transmittance for each peak, the minimum de-
tectable coverage of linearly adsorbed CO is 0.39 pmol g-l
and the minimum coverage of bridged-bonded CO is 0.033
pmol g-l. Assuming the total Pd surface area measured
after the 448 K reduction is not changed by the 773 K
reduction, less than 1% of the Pd surface is covered by
the HF CO species and less than 0.1% is covered by the
LF CO species. The evidence that Pd surfaces of very
active methanation catalysts, such as Pd/Ti02 in the SMSI
state, can have very low CO coverage has led us to conclude
that only a small fraction of Pd surface atoms constitute
“active sites” for methane formation,26and illustrates the
usefulness of in situ IR characterization of catalysts under
well-defined reaction conditions.
Acknowledgment. Equipment used in this study was
purchased under Contract No. EG 778-02-4463, Depart-
ment of Energy, Division of Basic Energy Sciences. Ad-
ditional funds were provided by a grant from the Research
Corporation. Support for S-Y. Wang was provided by the
government of the Republic of China in Taiwan.
(21) Twu, C. C., Ph.D. Thesis, Pennsylvanic State University, in
progress.
(22) Blyholder, G.; Allen, M. C. J. Am. Chem. SOC.1969, 91, 3168.
(23) Norton, P. R.;Goodale, J. W.; Selkirk, E. B. Surf. Sci. 1979,83,
189.
(24) Conrad, H.; Ertl, G.; Latta, E. E. J. Catal. 1974, 35, 363.
(25) Wang,S-Y.; Moon, S. H.; Vannice, M. A. J . Catal. In press.