50 Surface Science 256 (1991) 50-06

North-Holl.nd

Reactions of carboxylic acids on the Pd(111)-(2 × 2)0 surface"

multiple roles of surface oxygen atoms
J.L. Davis ~ and M.A. Barteau *
('enter for Catalytic Science and Tedmolo,w. Departments of ('hemistrv and Chemi,'al En,~ineering, University of Dekaware.
Newark, DE 10716. USA

Received 16 January 1991" accepted for publication 5 April 1991

The reactions of formic acid, acetic acid, and propanoi¢ acid were examined on the oxygen-dosed Pd(111) surface. Adsorption of
these ¢arboxylic acids on Pd(111 )-(2 × 2)0 at 170 K produced adsorbed carboxylate species via direct transfer of the acid hydrogen
to the oxygen adlayer, in addition, the presence of adsorbed oxygen suppressed the formation of the hydrogen-bonded catemers
observed for ¢arboxylic acids on the clean surface. The stability of carboxylate species on Pd(111) was found to depend upon the
substituent on the carboxvl group and upon the presence of adsorbed oxygen. Formate species were the least stable on Pd(111) and
decomposed primarily through a dehydrogenation pathway at 280 K, evolving CO 2 and releasing hydrogen atoms to the surface. The
temperature required for formate decomposition was 20 K higher on the oxygen-dosed surface than on the clean surface, suggesting
that the presence of oxygen adatoms stabilized the formate adlayer. Acetate decarboxylation occurred at 305 and 420 K on the
oxygen-dosed surface. The lower temperature acetate decomposition pathway was also observed for acetate species adsorbed on the
clean P d { l l l ) surface, and resulted in the desorption of primarily CO,. In contrast, the decomposition channel at 420 K was
a,,soc~atcd with acetate specie.,, stabilized by the prcscncc of ad.,,orbed ox? gen. Decomposition of oxygen-stabilized acetates released
(~*,, L t l ~,~,)()t~, and tt ,. Propanoate species produced fron, propanoic acid on the Pd(l 11 )-(2 × 2)O surface decomposed at 380 K,
25 K higher than on the clean ,,,urface. Th,? m,alliple role,~ of oxygen adatoms in ¢arboxylate formation and stabilization on P d ( l i l )
max be generalized both to the ;-eactlon,, of ~,ther oxygenates and to ~l~e reactivity of other group-Vlll ami -IB metals.

~. ~nm~aucfion participation of these intermediates in synthesis

Carboxy!ate species have been proposed as in-
levmediates in a number of catalytic processes.
Vor example, one mechanism proposed for
oxygenate synthesis from CO and H, over group-
VIII metal catalysts envisions the participation of
~,~vq,, carbox\lates tha~ undergo hydrogenation to
\'ield alcohols [1 ]. This mech~nism is supi~orl,'c~ b\,
!~A ,pe,qra shmving the. p,,.-.,,ence of f~,rmate [1]
mctha,~ol ,,nd clhanol s}~ntl~esis, respcc:ivcly, over
",t~op~tcd g~oup-V~]l[ nlcta~ c a l , t l \ : Is.
carboxvlale formation is clearly not the only path-
xxz~x tov oxvvcna~e s\'nthesis from ('O :.m.| H,. tee
' ~hc,~l*t ,tddvc,, M~qotola [iau. ~i)~) ~*csl %unti,.c BIxd. ~!
" I,, ,,~1~,~i!' ,', .ic,,[-,ondcnce sh~,tlld bc .idd,cv, cd.
reactions may be favorable for reactions occurring
on group-VIII metal catalysts supported on cer-
tain metal oxides [3].
Because of the ubiquity of carboxylales in
catalysis, a number of workers have examined the
synthesis and [eaction of these species on metal
surfaces. Formate decomposition has been studied
on single crystals of Pd [4,5], Pt [6,7], Ni [8,9], Fe
[10f Ru [11], Rh [12,13], Cu [14,151, Ag [16,171,
and Au [!8] The ac!iva~ion energies f~r decom-
position of formales adsorbed on g r o u p - V ~ and
'.\"bile gv,.mp-IB mct:~l surfaces can be correlated wi~h the
enthaloies of formatic ! of the respective metal
,,x~.,~s [I~)1. The mote negative the cnthalpy of
oxide f,~rmation, the greater is the activation bin-
tier for forrnate decomposition, and :bus the
grcalcr the ~hermal stability of the adsorbed for-
mate. A previously unrecognized aspect of such
 J.L. Davis, 14_4. Barteau / Reactions of carbo.,o'lic acids on Pd( l l l )-(2 × 2 ) 0
correiations, however, is that forn,ates on group-IB
m e t a s do not ..)bey the same correlation as those
on gloup-VIll metals [19]. Rather, acth, ation bar-
riers for formate decomposition on the IB metals
are ca. 10 kcal/mol higher than one would predict
from linear free-energy relationships based on the
reactivity of only the group-Vlll metals. This can
b: understood qualitatively in terms of metal-
oxygen and metal-hydrogen bond strengths on
thest, metals [20]. Higher metal-oxygen bond
strengths can be associated with greater formate
stability; higher metal-hydrogen bond strengths
increase the thermodynamic preference for de-
composition products and thus decrease formate
stability [20]. The relationships between metal-
oxygen and metal-hydrogen bond strengths differ
between the group-VIII and -IB metals.
Although ample data exist for formate species
adsorbed on metal surfaces, the stabilities of higher
carbox~lates, such as acetates and propanoates,
have not been as well characterized. Reactions of
acetate species have been studied on Pt(111 ) [21],
N i ( l l 0 ) [22], N i ( l l l ) [23], Fe(100)[10], C u ( l l 0 )
r'~L,4].Ag(110) [25], and Rh(111)[26] surfaces. Fewer
examples of the chemistry of propanoates on metal
.,,urtaces are extant [2i,27,28]. One of the goals of
~his work is to provide a systematic comparison of
tile behax'ior of carboxylate species adsorbed on
the P d l l l | ) surface in order to gain an undcr-
st:.nding of factors which influence carboxylatc
:aability. Surface carboxylates can be readily pre-
p'ued by the adsorption of carboxylic acids on
~,'ygen-dosed metal surfaces. Adsorbed oxygen
ha~ been observed to function as a Bronsted base.
abstracting acidic hydrogens from carboxylic acids
adsorbed on oxygen-containing surfaces of Pd(100}
[5]. Pt(lll)[6,7,211. R h ( l l l } [|2], Cu(110} [14.24i.
,\~1110) [16,17.25]. and Au(110) [18]. In addition.
adsorbed oxygen has been observed lo .,,tabilize
f~rmate species on the R h t l t l } . resu~tino in the
decomposition of formate.,, :~[ ,,ignificantlx higher
tcmp~eraturc, on the ox>gcn-doscd Rh{ 11 I i ,,urfacc
than on the clean surface [12]. In the presem w o r k
x~e compare the reactions of Iormic acid on clean
and oxygen-dosed Pd(l 1|} surfaces, a.,, \~cll as the
.,;labilities of C, (,~ carboxylate:, s\nthesized on
thi, surface in the presence of {x ~ \, o' ~u n adatoms.
A potential source of stabilit\ differences.
51
whether between homologous carboxvlates or re-
duced b3 coadsorbates, is the variation of
carboxylate configuration. In inorganic coordina-
tion chemistry, carboxylate specie~ have been
found to bind to the metal centers in one of three
configurations' (1) monodentate, (2) bidentate.
and (3) bridging between two metal centers. These
three types of carboxylate ligands can be dis-
tinguished on the basis of the splitting, A ob-
served between the v,(OCO) and v.(OCO) vibra-
tions of the carboxyl group [29]. For example, in
the free formate anion ( H C O O - ) , infrared spec-
troscopy places the u,(OCO) mode at 1351 cm I
and the u,,(OCO) mode at 1585 cm 1. Thus. 3 for
the formate anion is 234 cm-~. A similar value of
3 will be observed if the carboxylate ligand bridges
two metal centers. In contrast, A will be larger
than 234 cm -~ for monodentate carboxylate
ligands, and will be smaller than this value for
bidentate ligands. In addition, the selection rules
operative in HREELS require that the v,,(OCO}
mode become dipole-inactive for symmetrically
bound bidentate and bridging carboxylate species
adsorbed on metal surfaces. Thus. the presence of
the a,,,{OC()) mode near 1585 cm ~ would indi-
cate that the adsorbed carbox\,'late ligand ix mono-
dentate, or that the txvo metal oxygen bonds in
the bidcntate ~r brideina.. confi,2' "
EUF,A~,ICHlS ;.tFC itl-
cquixalcn~. Sxmtnetricall\ bound C:, carboxxlatc
..,pccie.., have been ubacl~,cci by l t l k L L L S iolkv,a~t~.
carboxylic acid adsorption on oxygen-dosed
surfaces of P t ( l l l ) [6,7,21], N i ( l l 0 ) [ 8 ] . and
Ru(001) [11]. In contrast, monodentate carboxy-
late ligands have been observed at low tempera-
lures on surfaces of Pd(100) [5], Pt(111) [7].
C u ( l l 0 ) [15]. and A g ( l l 0 ) [ t 7 1 . Hove'ever. anneal-
ing the monodentate carboxvlate ligands con~ert_,,
these specie., to S V R 1 R l e t r i c d l ] \ bound ~.arboxv~ates
on all of these metal.,,.
he e×penments ~ere c e n d u c ~ e d in p~o sep-
a r a t e stainless s~ect ultra-high vacL~um chamber.,,
which have been described previously [30.31]. De-
scription ~,, -" the ......... preparation and cleanina
prc, ccdv.res ha\c :fl,,o been reported rt:(pi. ~ , TPD
52 J.L Davis, M.A. Barteau / Reactions of carboxylic acids on Pd(l l l)-(2 X 2)0
spectra were recorded using a linear heating ramp
of 10 K / s . HREELS experiments were conducted
with a beam energy of 5 eV and a resolution of
64-72 cm-1 at F~VHM of the elastically scattered
beam. Oxygen (Matheson Extra Dry, 99.6%) and
deuterium (Matheson 99.5%) were obtained from
lecture bottles on a separate dosing manifold from
the carboxylic acids. These adsorbates were ad-
mitted to the chamber through a variable leak
valve equipped with a 1.6 mm stainless steel doser.
In the experiments discussed below, dioxygen was
dosed onto the P d ( l l l ) surface above room tem-
perature, resulting in the formation of a (2 × 2)
overlayer of oxygen adatoms (denoted below as
P d ( l l l ) - ( 2 × 2 ) O ) , as verified by LEED. The
oxygen atom coverage of the (2 × 2)0 overlayer is
one-quarte, monolayer. Upon cooling the crystal
to 170 K, the desired carboxylic acid was dosed on
the P d ( l l l ) - ( 2 × 2)O surface, and elmer H R E E L S
or T P D experiments were performed. A combina-
tion of AES, HREELS, and T P D was used to
monitor surface cleanliness during this study, and
no impurities were observed on the nominally
clean surface, within the detection limits of these
techniques.
The carboxylic acids used in these experiments
were stored on the dosing manifold described pre-
viously [30,31]. The H C O O H (Aldrich, 98%) sam-
ple was prepared under an N_, atmosphere in
order to reduce contanfination of tiffs hygroscopic
sample by ambient water vapor. The sample was
found to degrade in the sample reservoir over a
period of several days, and trace amounts of acetic
acid were detected among the contaminants. The
CH3COOH (Fischer, 99.7%), CH3COOD (Chem-
ical Dynamics, 99.5% D), CD~COOD (Chemical
Dynamics, 99.5%), and propanoic acid (Aldrich,
99 + %) samples were transferred directly from the
reagent bottles to the sample reservoir~, since these
compounds are less hygroscopic than formic acid.
ltn addition, there was no evidence for contamina-
tion of the acetic acid and propanoic acid samp]es
b~' reactions with the dosing line, in cop,tra,,;t t o
formic acid. All samples were purified by multiple
freeze p u m p - t h a w cycles and the purity was
checked by mass spectrometry. The formic acid
sample was initially observed i(; contain small
amounts of water (roughly 5~i), but tbc remaining
carboxylic acids were water-free. The carboxylic
acids were admitted to the chamber through a 1.6
mm needle that served as a molecular beam ~oser.
Unless otherwise mentioned, all doses were de-
livered with a carboxylic acid pressure of 100
mTorr at 298 K in the dosing line. The pressure in
the vacuum chamber rose no higher than ]0 -~'
Torr during the carboxylic acid exposure, and
rapidly returned to 10 - l ° Torr upon completion
of the dose. The carboxylic acid adsorption tem-
perature in all experiments was 170 K.
3. Results
3.1. Formic acid adsorption and decomposition on
the Pd(l 11) surface
The adsorption and reaction of formic acid on
the clean Pd(111) surface were greatly influenced
by hydrogen-bonding in the adlayer, which, as will
be shown below, did not occur on oxygen-dosed
surfaces. Following the adsorption of H C O O H on
the P d ( l l l ) surface at 170 K, unreacted formic
acid desorbed at 185 K as sbown in fig. 1. Formic
acid also dissociated to formate species. The de-
composition of formates on the clean P d ( l l l )
surface produced CO 2 (Tr, = 260 K), I-t 2 (Tp = 330
K), and CO ( T o = 490 K). Tim peak-shapes and
desorption temperatures for both H 2 and CO
were indicative of the evolution of these products
i I I i I I i I I I
HCOOH on Pd('111)
0 -'------
A
ct
0
(0 __ /'~
'FI,J:
150 250 350 450 550 650 750
TEMPERATURE (K)
Fig. 1. T P D ,~pemrum for the r e a c t i o n o f t t C O 0 t t on lhe d e a n
Pd( l I I ) ,~urface.
 J . L Davis, M.A. Barteau i' Reactions of carboxyfic acids on ,Pd(l l l)-(2 x 2)0
Table 1
Product yields for the reaction of H C O O H on P d ( ! l l )
Product Peak temperature (K) Absolute yield
( X 10 TM molecutes/~m 2 i
H 2° 180 0.5
HCOOH 185 2.1
CO 2 260 0.8
H2 330 1.6
CO 490 0.5
via desorption-limited processes. The CO 2 prod uct
was reaction-limited, since CO 2 was found not to
adsorb on the Pd(111) surface at these tempera-
tures. Thus, the CO 2 peak at 260 K indicates that
formate decarboxylation occurred at this tempera-
ture. Water accompanied the evolution of molecu-
larly adsorbed formic acid. However, this peak
was most likely due to the water impurity present
in the formic acid sample, rather than a product of
formic acid reactions on the Pd(111) surface. The
product yields observed in TPD experiments are
listed in table 1.
A HREELS examination of the adlayer pro-
duced by a saturation exposure of HCOOH a~ ,, 0
K provided evidence for a large degree of inter-
molecular hydrogen-bonding, as previously noted
for acetic and propanoic acids on the Pd(111)
surface [27]. HREEL spectra recorded following
formic acid adsorption on the Pdtl 11) surface are
shown in fig. 2. Formic acid adsorbed molecularly
on the P d ( l l l ) surface as evidenced by the ~,(C=O)
and ~,(C-O) vibrations at 1685 and 1240 cm -~.
respectively. The vibration at 945 cm-~ was as-
signed to the t~(OH) mode of formic acid catemers,
based on the high intensity of this loss and com-
parison with IR specmt of cD'staUine formic acid
I " I_
wntcn located this vibration at 947 cm 1 [32]. In
contrast, the 6(OH) mode was observed at 1229
cm 1 133] in iR studies of gas-phase formic acid
monomers and at 1395 cm-~ [34] in studies of
liquid-phase formic acid dimers. The strong vibra-
non appearing at 195 cm ~ in the spectrum ~:~t
formic acid on P d ( l l l ) is a translational mode
characteristic of strongly hydrogen-bon~ded species.
This vibration can be best described ~s the trans-
lation of one monomer unil with respect to
ar~othet. The corresponding mode was observed at
53
232 cm-1 in IR spectra of crystalline formic acid
catemers [32]. Additional support for extensive
hydrogen-bonding in the formic acid adlaver is
provided by the r'(OH) vibration at 2700 cm
According to the classification of Novak [35], the
frequency of this vibration is indicative of a strong
hydrogen-bonding interaction, consistent with the
formation of formic acid catemers. In addition, as
discussed further below, the vibration was red-
shifted from that observed for crystalline formic
acid because of the coordination of the formic
acid catemers to the P d ( l l l ) surface through the
hydroxyl oxygen lone pair. The assignment of the
vibrations of formic acid catemers closely parallels
that of crystalline formic acid and is summarized
in table 2.
Annealing the adlayer to 200 K resulted in the
disappearance of the vibrations of formic acid
catemers from the H R E E L spectrum, consistent
with the desorptio',l of formic acid at 185 K in
TPD experiments. The vibrational spectrum ob-
served after annealing t o 200 K can be readily
identified as that of surface formate species. The
t I I i I~-T"T-T-r-I i i 1 i o ~ ~
340 HCOOH ,
1355
1=4o-]~ I 200 K
[ 1 0 5 cps 168s
195 ~~
0 1000 2000 3000
Energy Loss (era -1)
Vi~,~ . . ~ . . -"~
. ~peclla for HCOOH adsorbed on the clean Pd~lll~
surface
54 d.t. Dat'is, M.A. Barteau / Reactions o/carbo?o'lic acids on Pd(! 11)-(2 × 2)0

Table 2 underwent decompositior! at 280 K, releasing CO 2

Vibrational assignn~ent.', for formic acid catemer.~ on I'd( 111) in a narrow peak ( F W H M = 20 K) at this temper-
Mode (t+C()()lt),,/Pd(! ! 1) IR (ttCO()tl),, [321 ature. The formate decomposition peak tempera-
v(CH) 2935 2960 ture was 20 K higher on the oxygen-dosed Pd(111)
v(OH ) 2700 2900 surface than on the clean surface, suggesting that
v(C=O) 1685 1620 coadsorbed oxygen increased formate stability.
8(CH) 1350 1370 The activation energy for formate decomposition
~,(C-O) 1240 1248
on Pal(Ill)-(2 × 2 ) 0 was calculated to be 16.5
8 (O H ) 945 947
8(0('0) 705 720 kcal/mol, assuming first-order desorption and a
Lattice 195 232 constant frequency factor of 10 ~3 s --~. The reac-
tion of formic acid on the Pd(111 )-(2 x 2 ) 0 surface
also yielded a small amount of adsorbed CO,
which evolved at 490 K with a peak-shape char-
vibration at 1355 cm I was assigned to the acteristic of first-order desorption. The observa-
v,(OCO) mode of adsorbed formates and the tion of CO desorption indicated tha: a portion of
8(OCO) vibration appeared at 780 cm 1. The the formates reacted via scission of the carbon-
intense vibration observed at 340 cm ~ was due to oxygen bond to produce adsorbed CO, oxygen
the v(Pd-O) stretch, of the formate adlayer. The and hydrogen atoms. The production of CO via
frequencies of these vibrations are in excellent the decomposition of the CO 2 generated at 280 K
agreement with those of a previous study of for- can be ruled out, since COz does not react on the
mates adsorbed on Pd(100) [51. Weak vibrations Pd(l 11) surface at the temperatures examined [36].
were also observed at 1820 and 500 c m I which The selectivity for formate decarboxylation was
are characteristic of the presence of adsorbed CO over 90% based upon the total amounts of CO2
a n d oxygen adatcmls, respectively. Thus, the de- and CO desorbed. The product yields obsm'ved in
composition of formic acid catemers between 170 TPD experiments are given in table 3. Desorption
and 200 K r~:aulied ill tlm dc,,,oiptio~ of fo~,|i~. of oxygen was not observed for saturation ex-
acid at 185 K in TPI) experiments and the forma- posures of formic acid on Pd(111)-(2 × 2)0, indi-
liOIl O f .%l.lr[dCC ~'orl'..ldteS. } e t ) l ' l l l d t C dcc,miposition cating that the oxygen adlayer was completely
~wcurrcd at 26{) K in FP]), rclcasiq,, ('(), at thi', consumed by reactions occurring during TPD.
temperature. In addition, a portion of the formate The production of water provided insights into
species decomposed to adsorbed CO and oxygen the effect of oxygen adatoms on the reaction of
adatoms.

! | | | I I | | | I |
3." Rea~'U+moS.formic acid +m the Pd(lll)-(2 X 2 ) 0
HCOOH on Pd(lll)-(2x2)O
su,:face

[ h e i2 × 2)() adktycr abstracted the acidic hv-

d r o x \ ' ] hydrogens of formic ach.t molcct, les to yield
fl~rmatcs on the F'd(lll) surface. The absence of CO
I I c°~ /-~
k---__ , 4
in fig. 3, indicated that the entire formic acid
,,

adsorption. Recent experiments on the oxygen-

.: 2
dosed Pal(]0/)) stir[|tee have dem,~|ls'.rated thal
_ I__A_ __[ [ _ I I
preston abxiraction from adsorbed f<,~rlnic actd ~s
150 250 350 450 550 650 750
[acilc c\cn at lcmpcralurcs as low as liii) K [51.
TEMPERATURE (K)
~:orm:~tc species produced b\ the reaction of [ o f }iV , 3 ' d } + +0," ",I'~CC~FUII~ [OF t!~.t.' [ C d C t i O I 1 ('~[ ,.! > , d [ U l ' d t l O t ' t CkDOY, tlFC
,z~i<_; acid c>lt ll~c ~,.\\~c~-d<~,sct~ t~tii [ 11 ) suri'iice of }l('()()l] ~m t h e P d ( 1 1 1 1 - ( 2 "-. 21() .',uH'acc.
 J.L. Daris. M.A. Barteau / Reactions of carhoxrlic acidv m, Pd( 111 )42 × 2 ~0 ~

Table 3 has been observed near 340 K in HREELS and

Product yield for H C O O H reaction of Pd(111 )-(2 x 2)0
Product Peal< temperature (K)
H 20 220
H ~O 280
CO~ 280
H2 350
CO 490
formic acid. Water desorbed at 220 and 280 K
following H C O O H adsorption on Pd(l I 1 )-(2 x 2)-
O. However, less than half of the original (2 x 2)-
O oxygen adlayer could be accounted for by the
water desorbed during TPD experiments, suggest-
ing that consumption of the oxygen ad!ayer to
form water must also occur during dosing of for-
mic acid at 170 K. The overall stoichiometry of
the desorption products w a s C H l . 2 O x . 9, suggesting
that a large amount of hydrogen was removed
from the surface before heating was initiated in
TPD experiments.
TPD studies of the reaction of adsorbed oxygen
and hydrogen atoms to form H2 ° on ti~e Pd(t i I}
surface are shown in fig. 4. Following the adsorp-
tion of H, on Pd(lll)-(2 × 2)0, water desorbed in
a broad peak centered at 270 K. The productic, n
of ~atcr at this ~cmpcrature was due to the recor~-
bination of oxygen and hydrogen adatoms, since
these were the only surface species present during
the experiments. A similar O(ad) + H(ad) reaction
O(a) .~ H(a) RECOMBINAT~ON
TPD experiments on the Pd(100} surface [371.
A b s o l u t e yield Based on these experiments, the ~ater produc~
( x 10 ~4 m o l e c u l e s / c m ~ ) evolved at 280 K during the reaction of formic
0.8 acid on the P d ( l l l ) - ( 2 x 2)0 surface can be at-
0.6 tributed to the recombination of adsorbed oxygen
3.1
and hydrogen atoms. The source of hydrogen
0.5
0.2 atoms for this water product was the formate
decomposition reaction which peaked at 280 K.
This reaction consumed the remainder of the
oxygen adlayer, resulting in a slight excess of
surface hydrogen which recombinea and desorbed
a s H 2 at 350 K. The onset of H 2 desorption in fig.
3 was 280 K, ca. 30 K higher than that observed
for desorption-limited hydrogen from the clean
P d ( l l l ) surface. These results clearly demonstrate
that the scavenging of hydrogen atoms by the
oxygen adlayer to form water was dominant at
temperatures between the onset of formate decom-
position at ca. 230 K and the onset of H2 desorp-
tion at 280 K.
The observation of H.:O desorption at 220 K
following formic acid adsorption on the Pdl] 11)-
(2 × 2)0 surface suggested that removal of the
hydroxyl hydrogen of adsorbed formic acid in-
volved the direct transfer of hydrogen u~ the
oxygen adlaver. As discussed above, the reaction
,~f adsorbed ,~x?,gcn and hydrogen atom> to pro-
duct \~alcr ~ccurs :it 27{} K. The ~n,~cl ~f lhi,,
reaction was observed to be 230 K in experiments
in which hydrogen atoms and oxygen atoms were
coadsorbed {fig. 4). The production of water be-
low this temperature can not involve hydrogen
atoms adsorbed on the Pd( ] 11 ) surface. Therefore.
the water product evoh'ed at 220 K in HC()C~H
TPD must have resulted from the dim:t transfer
nf the acidic hydroxyl hydrogen of ad.,orbed for-
mic a,.:id to the oxygen adlavcr. Thi:. hydrogen
~ransfer path'aay resulted in ~he for:mtiop of

jfifi/ ~2 =

IEMPERATURE
me=a2
as low as 100 K [5]. The water desorption product
l I 1 J _]_ __[ 1 ~_ _ observed at 220 K in TPD exl~:,:rimcn~s for
150 350 550 750 950
(K)
llCOG~; t,~: i : d { l t l H 2 × 2 ) O was a~tributed ~o
]:i.~ .-1 ]'!>]'~ "~[';2Cl;iil',; ,,~;',C~ ~,¢,3 l'O]]~v~in~. ~1 ,,:~uri~t=,,n ."*p~',~!rC the di.,,pn~portionation of surface h\'droxxl gnmp,
of ~ , ,,',n I ~' Pdil 1 t t-~2 ", 21() ,urO'acc at !7i,~ K. to form H~()Ig} and (){ad}. This reaction has been
56 J.L. Davis, M.A. Barteau / Reactio;ls of carboxylic acids on Pd(l l l)-(2 x 2)0

observed previously for hydroxyl species on I I I I I I I I I I I i I I i

3s0 HCOOH on Pd(l11)-(2x2)O
P d ( l l l ) [38] and also occurs between 230 and 250 ~< 1000
K for hydroxyls adsorbed on the oxygen-dosed
Pd(100) surface [37]. The presence of a pathway 200 K
involving the direct transfer of acidic hydrogen
atoms to surface oxygen is consistent with the
surface oxygen atoms functioning as Bmnsted
bases on P d ( l l l ) . Surface hydroxyls that reacted
with a second formic acid molecule to form H 2 0
during the adsorption of formic acid were ap-
parently removed from the surface during this e-
350
r-
process, as evidenced by the hydrogen and oxygen c lOO

deficits in the T P D product yields. I10 s cps

810
The synthesis of formate species on the
Pd(lll)-(2 x 2)O surface at 170 K was indicated 1355
clearly in H R E E L spectra. Following a saturation
170 K
exposure of HCOOH, only vibrations attributable
to symmetrically bound C2,, formate species and II 29~s
adsorbed hydroxyl groups were observed, as shown .==ol I .. =,.s /~, [
\ / ~ ,, loo0 W,,r~ u,J' ~ I
in fig. 5. An intense vibration corresponding to the
symmetric OCO stretch of the formate adlayer
/ \Y
I I I ! I I I I I I I I I ! I I I I
appeared at 1355 cm -~, and the /}(OCO) mode
0 1000 2000 3000
was observed at 810 cm -~ in the spectrum re-
corded at 170 K. There was no evidence for the Energy Loss (crn-1)
asymmetric OCO stretch of surface formates (e×- Fig. 5. HREEL spectra observed following the adsorption of
a saturation exposure of HCOOH on the P d ( l l l ) - ( 2 x 2 ) O
pected near 1585 cm -1 [29,39]), indicating that
surface.
these formates were bound to the surface in a
co~lfiguration with C:,, symmetry (i.e., either
bidcntate or bridging). Assignme~,t of the re-
mainder of the vibrational spectrum is relatively vibrational assignments of formate species pro-
straightforward. The v(Pd-O) mode of adsorbed duced by the adsorption of formic acid on the
formates produced a strong loss at 350 cm -~, Pd(111)-(2 × 2 ) 0 surface are given in table 4, along
while the v ( P d - O ) stretch of the oxygen adlayer with previously reported frequencies for formate
appeared as a weaker mode at 480 cm -~ The vibrations on other metals. Excellent agreement
C - H stretch of the formate adlayer was observed was observed between the vibrational frequencies
as a weak mode at 2915 cm -~ The loss at 172s of surface formates on the P d ( l l l ) - ( 2 × 2)O
cm-~ following formic acid adsorption on the surface and previous work. In addition, there was
Pd(111)-(2 × 2)O surface was assigned to a multi- no significant difference between the vibrational
ple loss feature involving the v,(OCO) mode at frequencies of formate species adsorbed on the
1355 cm-~ and the v(Pd-O) mode at 350 c m - ; P d ( l l l ) - ( 2 × 2 ) 0 and those of formates on the
Likewise, the weak mode observed at 2145 c m - ! clean surface. However, there was no evidence
\va.,. assigned to a multiple loss invohing the from either H R E E L S or TPD for the formation of
,,(OCO) mode at 1345 cm -~ and the 8(OCO) hydrogen-bonded formic acid catemers on the
m,~de at 810 cm -~. The first overtone of the Pd(lll)-(2 × 2 ) 0 surface at 170 K, in contrast to
vjOCO) mode appeared at 2.685 c m - : . These the behavior of the clean P d ( l l l ) surface. Thus,
combination bands have been ob:;erved in the presence of the oxygen adlayer suppressed
HREELS ~,~:~udies of formate species adsorbed on catcmer formation arid enhanced dissociation to
oxygen-dosed Pt(111) ~:urfaces as well [6,7]. The surface formates.
 J.L. Davis, M.A. Barteau /Reactions of carho.D,lw aci& on Pd(I /1)-(2 x 2)0 57

Table 4
Vibrational frequencies of formate species adsorbed on metal surfaces

Mode I R ( N a H C O O ) "~ O / P d ( l l l ) h~ O / P t { l l l ) ~~ Ni(llO) ,t~ RutO01) '~ AgtllO) t: CuriO0} *~

(cm - ~ ) (cm - ~) (cm - ~ ) (cm - ~ ) (cm - ~) Icm - ~ ) (cm- ~)

v(CH) 2841 2915 2920 2940 2917 2900 2870

2v,(OCO) 2685 2670
v,(OCO) + 6(OCO) 2145
P,(OCO) + v ( M - O ) 1725 1690
v,,(OCO) 1567 . . . . 1640 1660
v,(OCO) 1366 1355 1330 1370 1358 1340 1350
o(CH) 1073 . . . . 1050 1060
8(OCO) 772 810 780 790 807 770 760-790
v(M-O) 350 360 440 380 280 280-335

'u From ref. [291.

h~ From this work.
o From ref. [6].
a~ From ref. [8].
~ F r o m ref. [1 i].
f~ F r o m ref. [ 1 7 ] .
g~ F r o m ref. [ 1 5 ] .

Following formic acid adsorption at 170 K,
several vibrations were obaerved that can be at-
tributed to surface hydroxyl groups and molecu-
larly adsorbed water produced by the direct trans-
fer of hydrogen from formic acid to the oxygen
adlayer. Weak modes appearing as shoulders on
the peak at 810 cm '~ are most likely due to
iibrations of adsorbed water and the OH bendino
mode of ~urface hydroxyl groups. The ob~,crvation
of these vibrations provides spectroscopic evi-
dence for the direct transfer of acidic hydrogen
atoms to surface oxygen upon adsorption at 170
K, and supports the role of adsorbed oxygen as a
Bronsted base. A review of the vibrational fre-
quencies of H,O(a) and OH(a) on metal surfaces
has been given by Thiel and Made}, [40]. The
3(OH) mode of hydroxyl groups adsorbed on
metal surfaces is generally observed between 900
and 950 cm ~. Water adsorbed on the surfaces of
group-VIii metal,,, generally exhibits an HOH scis-
soring mode around 1600 c m ~ and ,~ hi~dcucd
i o t a t i o i / iit t h e r e g i o n 5 0 0 - 7 0 0
~ipon annealing the adlayer to 200 K, the in-
tensities of the formate vibrations remained con-
stant, while the vibrations of adsorbed water were
no longer resolvable. Slight downward shifts ( < 20
cm ~) were ob,,.erved in the frequencies of the
principal formate modes. No further chaages oc-
curred in the vibrational spectrum of surface for-
mates below 280 K. However, annealing the ad-
layer to 280 K resulted in the disappearance of
vibratiop, s of the formate adlaver and the ap-
pemance of a weak mode at 1805 c m - ~ d u e to the
CO stretch of molecularly adsorbed CO.
Thus, TPD and HREELS results demonstrate
~hat formic acid dissociated on the ox}gen-dosed
Pd(t 1 t ) ~,urfacc ~.o form ~,urfacc forma~ca, atopmarc
decomposition occurred at 280 K on the Pd(111)-
(2 × 2)0 surface and resulted in the desorption of
CO, and ~.he release of CO and hydrogen to the
surface. The decomposition temperature of for-
mate species adsorbed on the Pd(lll)-(2 × 2)0
was 20 K higher than observed for formates on
the clean surface, suggesting that the presence of
adsorbed oxygen stabilized the formate adlaver
slighdy. The dominant formate decompo.,dtion
pathv+'ay was decarboxylation, although some ~c-
tivitv for ('O production was also observed.
cm
su(f}we
The presence of surface oxygen facilitated the
production of acetate species from adsorbed acetic
acid by serxing as a Bronsted base. consistent wi~h
its behavior to,xard formic acid. Following a
 58 J.L. Dat'is, M.A. Bart,,au / Reactions of carbo.,o'lic acids on Pd(l l l)-(2 x 2)0

I I I I I I'^1 I I I I
][/ CHaCOOHon C O 2 occurred in two peaks at 305 and 420 K. A
J ~.~d(111)-(2.2 )0 CO, peak at ca. 300 K was also observed follow-
ing the adsorption of acetic acid on the clean
surface [27] and was assigned to the decomposi-
H~O
tion of adsorbed acetate species. The CO 2 peak at
420 K was accompanied by the desorption of
CHaCOOH and H20 with roughly the same
peak-shape and desorption temperature. HREELS
data discussed below indicated that these products
were also derived from acetate species. Oxygen
was clearly present on the surface at 420 K as
I I I I I I I I I I
150 250 350 450 550 650 750 evidenced by the desorption of H 2 0 at this tem-
TEMPERATURE (K) perature and the desorption of CO via the reaction
Fig. 6. T P I ) s p e c t r u m for the reaction of ( ' H ~ ( ' O O H o n the of C(a) and O(a) at 550 K. These reactions con-
Pd{ l 11)-{2 × 2 ) 0 surface. sumed the remainder of the oxygen adlayer, as the
desorption of molecular oxygen was not detected
in the TPD experiment of fig. 6.
saturation exposure of acetic acid on the P d ( l l l ) - The behavior of acetates adsorbed on P d ( l l l ) -
(2 × 2)0 surface at 170 K, virtually all of the (2 x 2)0 was somewhat different at low coverages
adlayer reacted to produce adsorbed acetate than that noted above for saturation coverages. In
species. Only a trace amount of acetic acid de- TPD experiments involving subsaturation acetic
sorbed at 215 K, as shown in fig. 6, indicating that acid exposures on Pd(lll)-(2 × 2)O, adsorbed
the vast majority of the adlayer was converted to oxygen was present in considerable excess, and
acetates below this temperature. Producl yields only the acetate decomposition channel at 420 K
observed for TPD of acetic acid on the Pd(l 11)- was observed. In contrast, in the absence of i~d-
(3
- × -R)surface are listed in table 5. The produc- sorbed oxygen, acetate decomposition occurred
tion of acetate species from acetic acid involved only at 300 K [27]. These observations provide
~hc direct lransfer of the acid hydrogen ~o ad- strong evidence that the acetate species that de-
sorbed oxygen to form surface acetates and hy- composed at 420 K were stabilized by the pres-
droxyl groups. These hydroxyls underwent dispro- ence of adsorbed oxygen atoms. In an analogous
portionation at 220 K, resulting in the desorption tashiom the presence of adsorbed oxygen has been
of H:O at this temperature. The desorption of reported to increase the decomposition tempera-
ture of formate species adsorbed on the R h ( l l l )
surface by up to 100 K [12].
Table 5
Acetate decomposition at 305 K resulted in the
Product yields for the reaction of ( ' H 3 C O ( ) H on P d { i l l t -
12 x 2R) surface desorption of only C O 2, while acetate decomposi-
tion at 420 K liberated CO,, CH3COOH, and
Pr.,~ducl Peak temperature Absolute yield
H20. For the lower temperature acetate decom-
(K) ( ~ 1(/14 molecules ,"CI~a:)
position reaction, the activation energy was calcu-
laled to be 18.0 kcal/moi, while E,, for the reac-
__{t 113)
lion al 420 K was 25.7 kcal/mol, assuming that
('t ~, 305 I. 1 both reactions were first-order with constant
('(l~ 420 "~ v
...,, ; frequency factors of 1013 s I. No other desorption
~.'11 d . ~ . ~ t ~ 42~! 3.3 products such as methane (CH4) or ketene
I~ ,{~ 421/ 0.5
(tI,C=C=O) were observed to accompany either
(-'( ~ 4S~,) l .()
acetate decomposition reactkm, in contrast to re-
~, {,Id) 0.7 3 3"
suits from other metal surfaces I10,,.4,,~]. De-
carbox,,lation of adsorbed acetate species Io pro-
 J.L. Dams, M.A. Barteau / Reactions of carboxvhc a~ Ms .n Pd(l 11H2 x 2)0 5~

duce C O 2 at 305 and 420 K would be expected to

~t0°° MeCOOH on Pd(111)-(2,2)0
release C, h y d r o c a r b o n species to the surface.
However, no hydrocarbon desorption products
were observed in TPD, suggesting that these C~ 305 ~~,'-~"~"~
hydrocarbons decomposed upon contact with the ,3
~~1 675 ~is 450 K
P d ( l l l ) surface. Decomposition of C~ hydro-
carbons produced by acetate decarboxylation re- A II =~,s
It / t .,ooo .,.-%.
leased hydrogen atoms to the surface which re-
acted with the oxygen adlayer to yield H20 near 400 K
300 K. Hydrogen atoms were also released to the
surface by acetate decarboxylation at 420 K and
either reacted with oxygen adatoms to l,roduce ICiO
C
705
water or with part of the acetate adlayer to yield
acetic acid at 420 K. Thus, the products de:~orbing
at 420 K were produced by sequential process
IlI
I 10 s cps
220
arising from acetate decomposition: (1) deca,'box-
ylation of surface acetate species to pro&tee CO., • ,000 ~A
•

and surface hydrocarbons; and (2) hydro.~enation U 68S

of the acetate adlayer by hydrogen atoms gener-
I

: te 495 ~l 820 -1445 170 K

ated by the decomposition of these hydro,:arbon 3005
species. Acetate species a d s o r b e d on the Pd(l 11 )-
-.. J
(2 x 2 ) 0 surface also exhibited slight activity for 2885
C O p r o d u c t i o n via c a r b o n - o x y g e n bond scission. 0 1000 2000 3000
A d s o r b e d C O produced d u r i n g acetate conversion Energy Loss (cm -1)
dcs,.~rbed at 480 K with a first-order peak shape. Fig. 7. tIRFt'.I, spectra for ( t t ~ ( ' O O H ad~,orbcd un ',he
P d ( l l 1 )-42 * 2)() ,,urla~.c ;.it 17~) K. Spectra d e n o t e d b\ higi~cr
consixtent wiiii desorption-limited evolution of this
[ClllpCTt!lklrC', tkCFC ~*}~[,tlltCd .lilCl ,ittltC{i!iI)E {[~C Ad]<t\Cf it} [hc
pro~luct. Based upon the total a m o u n t of acetate lildicalcd 1.cillpcl<lltirc,, i~qitv,~,t:d i',\ ~.l~tIlil,_' l~l l G l i K
s p o ie.,, present on the .,,urface. o n l \ 10ci of thc
a d l a y e r reacted to p r o d u c e molecular (.,O.
!tREELS demonstrated that formation of .,,urface acetate species. The vceaker loss observed
acetat : species cm Pd(i I1 )-(2 x 2 ) 0 oc, urred n p o n at
• 1775 cm ~ in the spectrum for C H ~ C ( ) O H was
adsorl_fion of acetic acid at 170 K. Further, in assigned to a multiple loss involving lhe v,(OCO}
a g r e e n e n t with results for formic acid, there v,:as and v ( P d - O ) modes. The absence of the as\'m-
no e~idence for the f o r m a t i o n of acetic acid metric O C O stretch expected near 1578 cm
t a l e , n e t s on the oxygen-dosed surface, t t R K E L .,uggests that lhe acetate .,pecies were adsorbed in
spectra recorded following adsorption of a .,,,,mmctric ( 2 , configuration. A .,ummarv c,f the
( ' t t g ' ( ) ( ) H on the o x y g e n - d o s e d Pd( 111 ) surface \'ibratior, al frcquencie.,, of acetates a d : o r b e d nn
arc sho~vn in fig. 7 as a function of surface tem- Pd(l I 1 )-( :."~ × _)() " is given in tablc 6. ~n addition to
perature. I t R I : E L S experiment.,, ~vcrc also con- t~.,,,,c.', a l t r i b u l a b t c Io surface acetate ~,pcc~c,,. ~
ductcd follo~vi,ag thc a d s o r p t i o n of ( ' I I : ( ( ) ( ) I ) \ l}]P{t~i{~tl~ \~ '.1' tlS{* {)}]kt:r, e(.t ,t1~ tt~2{} c~]~ ' ill the

and ('I)~('()()1) on lhc ox\gcn-do~cd ~ c l ( l l l )
surface, and the vibrational spectra ol thc,,,c ad-
sorbak:s v, ere similar to that observed folkvaino
( ' t { ~ ( ' ( ) ( ) l { adsorption. The adsorption of acetic
acid or,~ l!~e ' Pd(l l l )-(2 × .:)O
~ ,mrfacc at 170 K
p r o d u c e d ~l~tc't~.,,c dipole Ms.,,cs at 1,i45 cu~ 1
(,,.(()('())}. {,S:q cm ' (8~()('())). and 315 cm
t a'iPd (>)) ~vhich arc indicative of the presence ~t
t l~.tt)~t}l{ .,poe(rum :~t i74i .E. ,,thich x~:~, i~tc,,.~
ntke}v due to hvdroxvl ..<,r,mps. l o r m e d durtne~ ~i~c
production of .~cJrface acetates, as dascussed a b o \ e
for formic acid ad.,,orptkm.
A n n e a l i n g the surface to, t e m p e r a t u r e s up to
300 K resulted in ~irtuallv no c h a n g e in the vibra-
tional .,,pectrum. t4,~excr, a n n e a l i n g the adla~cr
to 4()0 K re>ulted in sm,~l shifts (rough{.x 40
 60 J.L. Davis, M.A. Barteau / Reactions of carboxylic acids on Pd(l i l).(2 X 2)0

Table 6 though C H 3 C O O D is also expected to have a

Vibrational frequencies of acetate species adsorbed c,n |he
small m / e = 60 cracking fragment. T h e r o l e = 61
P d ( l l l ) - ( 2 x 2 ) O surface at 170 K
cracking fragment was due to C H 3 C O O D . In-
Mode C H 3 C O O / P d ( 11 i ) - IR C 1 t 3 C 0 0 creasing the D 2 dose resulted in an increase in the
(2 x 2)0 [39]
amount of acetic acid desorbing b e t w e e n 300 and
v(CH 3) 3005 293~ 350 K vfia acetate hydrogenation. Following a 1
2v,(OCO) 2885 -
langmuir dose of D E, nearly 50% of the acetate
~,(OCO)+ v(Pd-O) 1775
~(OCO) 1445 1413 adlayer u n d e r w e n t hydrogenation to acetic acid.
8(CH 3 ) 1265 1344 Although d e u t e r i u m was in excess on the surface,
v(CC) 1025 920 there was some evidence for the r e c o m b i n a t i o n of
8(OCO) 685 650
v(Pd-O) 315 -
I I " I I I

cm ~l) to lower frequencies for the v ( O C O ) and o

6(OCO) vibrations. Smaller frequency shifts were II

observed for the acetate vibrations upon annealing E

=..-
to 350 K. Thus, after the first acetate decomposi- c:

tion reaction at 305 K, the properties of the re-

maining surface acetates changed, as reflected by _ O

the vibrational frequency shifts observed in

HREELS. Annealing the surface to 450 K resulted
in the complete disappearance of the vibrations of
adsorbed acetates and the a p p e a r a n c e of a weak
,'ibration at 1820 cm-~ attributable to the CO
! ....... ..,L ~ . L . ~
stretch of adsorbed CO. It is difficult to tell from 2OO 300 400 500
H R E E L S experimenls exactly when adsorbed CO TEMPERATURE (K)
was flr:~! produced, since the v , ( O C O ) + v(Pd)
combina~i,~n band occurred at roughly the same
frcquc.cy at ~.lle ~,(CO) vibraaon of adsorbed CO. ~r'------ ~'~-- i: ¸ ~ T - ' ~ ~
There were no vibrations of surface hydrocarbons
resolvable following acetate decarboxylation at 420 II

K, indicating that C~ hydrocarbons released to the

~ ________/ ~ c
=

surface by this reaction decomposed rapidly to c

al
atomic carbon and hydrogen, in agreement with
T P D results discussed above.
tn order to clarify the behavior of acetate
species coadsorbed with hydrogen and oxygen
atoms o~ the P d ( l l l ) surface, the following ex- g
p,?r;,-,o::t~ we're c o n d u c t e d . After adsorbing acetic
acid on the Pd(l~ It-(2 × 2}O surface at 170 K, the A

adlayer was annealed ~o 330 K to remove m~st of =L.~==J= . . . . . . ~=j. L L=_===~

the su;facc oxygen a.,, water. Upon cooling to 170
K, D:. was dosed and a T P D experiment con- TE~'IPERATURE (K)
ducted. The T P D spectra obtained for m / e 50 Fig. 8. Uncorrected TPD spectra for m/e = 60 and m/e = 61
~" ~u .

and 61 are shown in fig. 8 for ~hree different ,o,o~mg d~c adsorption of Dz on the Pd(111 )-I2 × 2)0 surface
Jeutcrium exposures. The m / e = 60 cracking f~ag- dosed with a saturation exposure of acetic acid. ~'he deuterium
mcn~ was dt~c to prcdomin,m~y CH3COOH, al- exposures in these experiments were: (a) 0.1 langmuir: ~b) 0.4
~angmuir: It) 1.0 kmgmuir.
 J.L. Dat,is. M.A. Barteau / Reactions of carboxvlic acids on Pd(l 11)-(2 x 2)0 6~

H(ad) with the acetates to produce acetic acid. Table 7

The fact that the acetic acid produced by acetate Product yidds for ~he reaction of propanoic acid on ~hc
Pd(i 11 )-(2 x 210 surface
hydrogenation in these experiments consisted of
both CH3COOH ( r e ~ e = 6 0 ) and CH~COOD Product Peak tempera- Absolute yield
( m / e = 61) provides additional proof that the hy- ture (K) ( x 10 ~'* molecules/
drocarbon species produced by acetate decarboxy- era: )
lation near 300 K liberate hydrogen adatoms. Some H20 240 0.4
H20 280 0.2
of these hydrogen adatoms were scavenged by the
CHxCH2COOH 310 0.1
acetate adlayer, resulting in the desorption of both CH3CH2COOH 370 0.7
C H 3 C O O H and CH3COOD in these co-dose ex- CO 2 380 0.5
periments. H20 400 0.4
CH3CH2COOH 400 0.2
Ha 420 0.1
3.4. Reaction of propanoic acid on the (2 x 2)0
H2 460 0.1
surface CO 470 0.5
C(ad) 0.3
Oxygen adatoms reacted with propanoic acid
on P d ( i i l ) to form surface propanoate species
and hydroxyl groups. Evidence for this reaction
was provided by the water product generated at shown in fig. 9. Product yields observed in TPD
240 K by the disproportionation of hydroxyl experiments for saturation coverages of propanoic
groups produced during propanoate formation, as acid on the P d ( l l l ) - ( 2 × 2)0 surface are given in
table 7. The absence of propanoic acid desorption
near 230 K indicated that the adlayer wa~: com-
I i I ~~l ) i i pletely converted to propanoate (CH ~CH 2 C O O ( a ) )
C 2 H s C O O H on
species upon adsorption at 170 K. The decomposi-
Pd(111)-(2~2}0 tion of these propanoates occurred at 380 K, as
CO
CO, was evolved at ~his temperature. Propanoate
decomposition also produced propanoic acid,
x~hich e,~ol~cd in tw~ pe:~,ks a~ 370 and 4{,)i) K. Iv~
contrast, propanoate decomposition occurred only
at 355 K on the clean Pd(l 11 ) surface and resulted
in the desorption of primarity CO and CO 2 [27].
Thus, the presence of adsorbed oxygen increased
the thermal stability of propanoa~.e species ad-
sorbed on Pd(111), as noted for formates and
acetates on this me~al, and altered the selectivi>,'

//
/
/
% of propanoate decom ;o.,d~.ion. The magnitude of
this oxygen-s~abiliza~ion was significantly less than
observed for acetate species, most likelx due ~o the

occurring at 380 K.
<
/
/ Bx ana}o:z', v,i~h ~.hc b c h a ~ i ~ ~,~i ~tlrfac,:
<
\,.EtCOOH
J acetates, decarboxylation of propanoate species
__..L I__L~._t.___~L_A. . . . . . would be expected to release C, hydrocarbon
150 250 350 450 550 650 750 fragments to the surface, which would decompose
TEMPERATURE (K)
to deposit carbon adatc~ms. Atomic hydrogen de-
}::g. g. ! P i ) spec',rum for the reaclion of propanoic acid on the rived from these C, hydrocarbons was removed
Pd(1 l I )-(2 x 210 surface. from ~he surface via three competitive pathways
62 J.L. Dat'is. M.A. Barteau ,/Reactions of carboxvlic acids on Pd(l 11)-12 × _)0

¢1) recombination and desorption as H, at 420 K: EtCOOH on Pd(111)-(2×2)O

(2) reaction with adsorbed oxygen to form water

above 300 K; and (3) hydrogenation of adsorbed
propanoate species between 300 and 410 K
Although the propanoic acid detected in TPD [ ' ' ' ' ' ' I, ' o,.
' ' '
experiments was generated by propanoate decom- 1400

position, its peak-shape was different from that of 655 ~1000

the other propanoate decomposition products, 29a0

H:O and CO,. The desorption peak maximum of

the first propanoic acid product at 370 K coin-
cided with the onset of H 2 desorption. Both the °~
(/)
r-
propanoic acid desorbing at 370 K and the onset
C x 1oo0 2950
of H 2 desorption at this temperature are indicative
of partial decomposition of the hydrocarbon
species released to the surface during p r o p a n o a t e b60
1000

decomposition. ~Iydrocarbon decomposition gen- 2950

erated hydrogen adatoms which were removed
frorn the surface by the three pathways mentioned
above. The relative rates of the three hydrogen
desorption channels depend upon the activation
energies for these processes. The observed H,O,
H , , and propanoic acid desorption behavior can
be explained by' assuming that the activation en-
ergy for the O ( a d ) + H(ad) reaction is slightly
greater than that of lhe p r o p a n o a t e hydrogenation
pathway. The activation energy for the recombina-
tion of adsorbed h\drooen. ~ a~mls appears to be
sufficicnll\ high that this reaction occurred only
after ~l~c ~xxScn ~dl:Lx,cr ~a~ bcc~ con_',umcd b3'
other reactions. As the surface temperature was
increased, the rate of the O(ad) + H(ad) recombi-
nation increased relative to that of the p r o p a n o a t e
hydrogenation reaction. As a re~,ult, the rate of
water desorp~ion rose steadily up to 41110 K, while
~he rate of propanoic acid desovption decreased
between 370 and 390 K. Complete co:~sumption of
the oxygen adlayer by 40ti K r,::~;ul~ed in an in-
crease in the rate of p r o p a n o a t , hydrogenation.
and yeas accompanied by increa.,,cd I--I2 desorption
diad ' ~ i~ "" r,,,i, ,,,; .... P:op;~r~oatc
.',pccics ,ld.,,~bcd on lhC Pd( | t ~"(~- ;< .,~,.,~';'~3;.ar~do"
.I I
2800
0 1000 2000 3000
Energy Loss (era -1)
Fig. i0. HREEL spectra for propanoic acid adsorption on the
oxygen-dosed P d ( l l l ) surface. The spectra were recorded after
adsorption of propanoic acid at 170 K, followed by annealing
to tile temperatures indicated.
tion ~vas ncarly 75%, thc sclcctiviLv to CO was
25%.
Consistent with the behavior described above
for acetic acid, H R E E L spectra obtained follow-
ing propanoic acid adsorption on Pd(l l 1 )-(2 × 2 ) 0
at 170 K were characteristic of surface carboxylate
species. The H R E E L spectra for propanoic acid
adsorption are shown in fig. 10 as a function of
temperature to which the adlayer ,,,,,'as annealed,
and assignment
,_ of the vibrations is ~,,b,'en in table
8. Propanoa~e species '`'`'ere characterized by in-
lcn:;c dipole losses at ]405,660, and 305 cm I due
Io the v, lOC'()L 811)('()), and p(Pd ()t modes,

~c>,pcctivciy. F h c [rcqucncics of t.hc.,,c vibration.,,

carbon oxygen bond scission, analogol.~s to behav-
ior observed ~or the other carboxvlates. Molecu-
[r,[~-]\~[~.d,Norbcd ('(} t!,eII"i\'cdf|'()[]'lsu[l'~.l~c pl('~p~.ll]-
~,',~t,,x dcsor!;.._'d at 470 K. indicative of the desorp-
li~p,-li~,~tc~{ cx~,tt~li<,n <~f ~.his product. l'hc scicc-
were in excelim~t agreement with those reported
previously for propanoates adsorbed on the
P u i t i ~ surface !211. Adsorbed propa.:~.oate species
also ga',c ri.,:c t~.~ k~sscs at 351t and i040 cm ~,
assigned ,.o ~he ~S(('('(')and r.,¢C('(') modes, re-
spcctivc0v In additi~m to viRwa~.ions as.,,igncd t~
 J.L. Daris, M.A. Barteau / Rca~tt,m.~ ,:f~,;rb+,xvh~ a,~,,¢.~ ,m Pd(111H2 x 2)~) ~3

Table 8
occurred al iemperaturcs nearly 100 K lox~cr ,~n
Vibrational assignments for adsorbed propanoate specie.,,
the clean surface than on the ox?,gen-d,;.,,ed ~urfacc
Mode EtCOO/ EtCOO/ iR At the temperatures at which propanoate decom-
Pd(11 ! ) Pt(111 ) "~ EtCOO h~
position occurred on the (2 x 2 ) 0 surface.
G(CH3), ~,(CH2) 2950 2960 2915 acetylide intermediates would already have disap-
Ik(CHx), v(CH 2 ) 2800 n.r. 2870
peared from the H R E E L spectrum on the clean
2v(OCO) 2800 -
l,,(OCO) + v(Pd-O) 1710 n.r. - surface. Thus these species were not isolated in the
v(OCO) 1405 1395 1429 course of propanoate d e c o m p o s i t i o n on the
G(CCC ) 1040 1090 1076 Pd(111 )-(2 x 2 ) 0 surface.
~(OC()) 660 660 618
~(CCC) 350 n.r. 300-500
i,(Pd-O) 305 270 -
4. Discussion
,,i From ref. [211; n.r. = not resolved.
,i From ref. [411,
The stability of c a r b o x y l a t e species on the
Pd(111 )-(2 × 2 ) 0 surface varied ,a'idel\,, depending
upon the substituent on the carboxyl group. The
presence of adsorbed oxygen was also found to
increase carboxylate d e c o m p o s i t i o n temperatures
propanoates, a loss was observed at 805 c m on Pd(111). Formate species produced by the re-
following adsorption of propanoic acid at 170 K action of formic acid on the o x y g e n - d o s e d Pdll 11 )
that was attributed to the presence of surface surface were the least stable and dec~xnposed a~
hydroxyl groups, as discussed above. 280 K to C O , CO., and h y d r o g e n adatoms. Acetate
Annealing the surface to 220 K rc.,,ulted in ihc :pecie.,, d e c o m p o s e d by t~vo difi,:rent reaction
disappearance of the vibrations of surfacc h;dr<~,,- t}.~2i> g~[ . ~{}q gtlld
. . . . ~ ~ ~ . . . . ~

vls, consistent with results from TPD. The ap-
D a r a n c e of the vibralional spectrum did not
change further for t e m p e r a t u r e s between 21)i} and
!Sl) K althouoh sn-al~ shifts of rc, ue.,hl\ 1~ ,,~
w.crc ob~er~,ed for 111o.~[ lOa~ea upon a n n e a l i n g to
350 K. W a r m i n g the a d l a y e r to 375 K resulted in
the disappearance of the p r o p a n o a t e ~'ibrations.
and the observation of weak vibrations due to
C O I a d ) and C 2 h y d r o c a r b o n species. 'i'he spec-
t r u m recorded after a n n e a l i n g to 375 K consisted
of \veak losses at 1385 (likely a broad e n v d o p e of
several modes), 670. and 315 cm 1 a~d a rela-
'ix'ely strong loss at 1810 cm ~ The vibrations
o b s c r \ c d at 1810 and 315 cm ~ \yore a.,,,,igned ~o
the r{('()) and v(Pd C()) vibrati~,ns of adsorh,:d
('(). These \ibration~ ~crc one\ o h , c ~ c d ~:~ ten>
pera,urc,, grcatcr lhan the p r o p a m , a t c dcv't,~np,,>~-
tttqi t c i t i p c r a t u r c , dc~l~o~t,-,tiJ.~.ittg ~.~eai~\ tt~at tO)
\%?.S 4 •r "",',~
............""' of the p r o p a n o a l e d e c o m p o s i t i o n
reaction. Propanoate d e c o m p o s i t i o n on the clean
Pd(] 1') surface gave ri:,e to a recogni::ab~c k;ss r__.~n
surf:ice acct\tide {('{'li~ :~pccie-. ;~, 72!) cm ~ in
addilion lo C ( ) [ 2 7 ] . Ho~vevcr, the d~.,,appearancc
of propap, t,atc lo.,,.,,c.,, from lhe HREt{i. spcctr~m
dccomp~siti~m was obserxcd at 3St} K. (1).n t!~c
clean Pd{ l I ] ) ,,urfacc fiwm:~lc.~ dcc~mp~scd a~ 2{-i)
K. 4 c c t a t C , , ,it ]tt)4} K, aF~cl pn~f~dTl~x~tcx ~1! 3<5 }<
["~j. ll~c rci,tti\ c ,l~thi)i~i<_., ~,! c;trh~,,,v t:ltc ,p~,,.~:-,
ox~ metai suriaces are dlscusseU below, along ~vt~h
the roles of surface oxvoe,~ in the reaction of
carbox\,llc acids on the Pd~ 111 ) surface.
There are two principal decomposition pa~h-
v a \ s for f o r m a t e species on metal surfaces ....'~d-
,orbed f o r m a t e s can cilher decompo.,,e via d e h \ -
drogenation to produce C(),{g) and surface hy-
drogen, or d e c o m p o ~ i t a m can o,-cur ~ia carbon
oxygen b o n d sc],,sion h~ ~>n~ducc ( ( ) ( 4 d ) and t] .()
(ncl deh\dra~i~m~. ] h c se~ccli~i~\ fiw thc,c p~.~}~-
\~4\'N ~,4ric', I { o ~ l MC{41 I0 Mct~4] dLIC {~ di{[crCl~cC',
a~d p i a ~ n u m t~zat arc charac~cn/.ca i--.\ rcia~.~xc:,.
~'eak met;~t-~x>>cn bonds M>o exhibit ii~llc activ-
i~\' for C - ( ) h o ~ d clca~aac ~f a~ls~,rhed c-arho\~lic
acids. In contrast, meiats \vhich exhibit hi~hcr
metal oxygen bond .,,trengths d{splay a gre:~ter
~endenc\ t~ ( ~) b<~nd ,_Ic:~,,4~c , , I - u r f a c c ik~r-
:hates Sign~ icant :tm~t~n_rs of ( ( } arc produc~.d
64 J.L. Davis, M.A. Barteau / Rest,ions of carbo.D'iic acids on Pd(l ,t 1)-(2 x 210
directly from adsorbed formate species during de-
composition reactions on Ni(110) [91, Ru(001 ) [11 ],
R h ( l l l ) [12,13], and Fe(100) [10]. Although some
of these metals may decompose formic acid upon
adsorption at low temperature [11], the majority
of the CO evolved in TPD of formic acid on these
metals dearly results from formate decomposition
reactions occurring above the adsorption tempera-
ture.
Analogous trends may apply for the decom-
position of higher carboxylates on metal surfaces.
However, there is a dearth of studies of acetate
and propanoate decomposition on metal surfaces,
making comparison of the behavior of these species
on other metals with that observed on P d ( l l l )
difficuit. The behavior of both acetate and pro-
panoate species on the oxygen-dosed P d ( l l l )
surface appears to be similar to that observed for
these species on P t ( l l l ) 121], although definitive
comparisons are not possible due to the incom-
plete characterization of carboxylate reac,ons on
platinum. Similar behavior has been observed on
the Ni(100) [22] and N i ( l l l ) [23] surfaces, where
acetate decomposition occurs between 430 and
450 K via competitive decarboxylation and dehy-
dration pathways. The chemistry of surface
acetates has been more fully characterized on the
,.aroup-lB metal.~. Acetate decompo,zition occur,"'; at
5~0 K on both clean and oxygen-dosed Cu(ll0)
[_4], and at 620 K on oxygcn-dot+cd Ag(ll0) [25].
Tiros, the stability of acetate species adsorbed on
surfaces of the group-IB metals is significantly
greater than on the group-VIII metals, consistent
with the trend for formate decomposition.
Oxygen adatoms served at least three roles dur-
ing the reaction of carboxylic acids on P d ( l l l ) .
Adsorbed oxygen functioned at a Bmnsted base to
facilitate the abstraction of the hydroxyl hydrogen
of adsorbed carboxylic acids and in doing ~
stppress:'d the formation of acid catemers. This
i~',dr.,,,.:,~, abstraction reaction im'ol\'ed the direct
~ran~,i'cr ~,~"hydrogen from the adsorbed carboxvlic
:~cid mtqcculcs to the oxygen adlaycr. Analogous
~:roton transfer reactions have been observed for
f,-rmic acid [5] and melhanol [42] on the oxygen-
d,~,~M Pd(100) surface, aad for alcohols on the
Pd(lll)-(2 × 2}O surface [38]. A second role per-
f~r~wd b\ ~x3gca adatoms was to control the
selectivity of higher carbox2~:ate reactions.
Whenever oxygen was in excess, only ca:'boxylate
decomposition reactions were observed in TFD.
However, when adsorbed hydrogen was present,
hydrogenation of the higher carboxylates to the
-orresponding carboxylic acids competed with de-
composition. The third role of surface oxygen in
these reactions was to increase the thermal stabil-
ity of carboxylate species relative to that observed
on the P d ( l l l ) surface. The decomposition of
-urface formates and propanoates occurred 20 to
25 K higlaer on the (2 × 2)0 than on the clean
P d ( l l l ) surface. Oxygen adatoms exhibized the
greatest stabilizing influence on adsorbed acetate
species. Acetate decomposition occurred oniy at
300 K on the clean P d ( ] l l ) surface [27]. On tile
oxygen-dosed Pd(ll 1) surface, acetate decomposi-
tion was observed primarily at 420 K, al&ough
some activity for acetate decomposition at 305 K
was also detected at high acetate coverages. It
should be noted that the concentrations of oxygen
atoms oresent at the ~emperatures of carboxylate
decomposition w~zre well below the initia' one-
quarter monolayer coverage prior to carboxylic
acid exposure. If one takes the yield of water at
280 K and above as indicative of the oxygen ato~
coverage in this temperature range, it is apparent
that for all three carboxylic acids, only about
15-20% of the ~nitial oxygen (i.e., ca. 4-5% of a
monolayer) v as still present. Taking this residual
oxygen concentration into acco,mt, and allowing
for the removal of some H20 during carboxylic
acid adsorption on the oxygen dosed surface at
170 K, the C : O stoichiometries of the products of
carboxylate decomposition above 250 K were
within ca. 20% of the expected value. C : H
stoichiomo .ties were somewhat less reliable. Again,
the 4-5% of a monolayer of oxygen atoms remain-
ing on the surface at the commencement of
carboxylate decomposition was apparently suffi-
cic--t to produce the increases in carboxylate sta-
bilities observed.
Although the TPD spcztra for carboxylate de-
composition on clean and oxygen-dosed P a ( ! l l )
were dramatically different, there were no signifi-
cant differences in the H R E E L spectra of
carbm:ylates on these two surfaces at low temper-
:~mrcs. For example, even though acetate species
 J.L. Davis, M.A. Barteau / Reactions of carboxylic acid:; ,m Pd(l l l)-(2 × 2)0
were stabilized hy 120 K on the Pd(lll)-(2 × 2)0
surface, the frequencies of the prinApai acetate
vibrations were the same (within + 10 c m - J ) on
both the clean and oxygen-dosed surfaces below
300 K. However, the vibratm,,al frequencies of
adsorbed acetates were consistently lower when
only the higher-temperature oxygen-stabilized
state was adsorbed, suggesting that the chemical
state of l,:he oxygen-.stabilized acetates may differ
from that of the acetates which decompose near
300 K.
The presence of adsorbed oxygen can also be
expected to influer, ce the transition state for
acetate decomposition, since the presence of
oxygen adatoms affects the electron density of the
mt-~ai substrate. Adsorbed oxygen withdraws e!ec-
t r o t , from the metal substrate, and raises the
Pd(111) work function by 0.6 eV [43]. The leduced
density of states of the r'd(ll 1)-(2 x 2)0 surface
may be responsible for the increased barrier for
carboxylate decomposition on Pd(l 11)-(2 x 2)0.
On group-VIII metals the influence of oxygen
adatoms on carboxylate stabilities, though varia-
ble in magnitude, is generally the same in sign"
oxygen stabilizes carboxylates. The extent of sta-
bilization is highly dependent on both the identity
of the metal and the chain length of the adsorbed
carboxylate. For example, oxygen atoms on
Rh(111 ) increase the formate decomposition tem-
perature by 100 K, but increase ti~e acetate de-
composition tempelature by only 35 K [26]. Con-
versely, as shown above, oxygen on P d ( ! l l ) shifts
acetate decomposition upward by 120 K but for-
mate decomposition only 20 K. A key difference
between carboxylate stabilities on the group-VlIl
and group-IB metals is the sign of the effect of
coadsorbed oxygen. Formate and acetate species
coadsorbed with oxygen exhibit greater therma!
stability on P d ( l l l ) and R h ( l l l ) [12], but hig'_~
concentrations of oxygen adatoms have been ob-
served to reduce the stability of formates and
acetates adsorbed on the Cu(110} [I:] and Ag(110)
[44] surfaces. This effect is due to 1he dir,~ct reac-
tion of oxygen atoms with carboxvlate species
adsorbed on Cu(110) and Ag(ll0) surfaces, rather
than a fundamental difference in the influence of
oxygen on the metal-carboxylate bond.
65
5. Conclusions
The reactions of carboxytate species produced
by the adsorption of formic acid, acetic acid, and
propanoic acid on P d ( l l l ) - ( 2 x 2 ) O were ex-
amined in TPD and HREELS experiments.
Carboxylates generated by the adsorption of these
carboxylic acids on Pal(l 11)-(2 x 2)0 decomposed
primarily through a decarboxylation pathway. The
temperature at which decomposition occurred
varied widely and depended upon the identity of
the carboxylatc species and the presence of ad-
sorbed oxygen. Surface oxygen served no fewer
:.han three roles in the reactions of carboxylic
acids on Pd(111)-(2 x 2)0. Oxygen adatoms served
as Bronsted bases, facilitating the formation of
carboxylates and suppressing the formation of acid
catemers by abstracting the acidic hydroxyl hydro-
gens from adsorbed carboxylic acids. Adsorbed
oxygen also influenced the selectivity of carboxy-
late reactions by scavenging hydrogen adatoms
which would otherwise be available for hydr')-
genation reactions. Oxygen adatoms also affected
the electronic properties of the subs~rate, resulting
in an increase in the thermal stabi:ily of carboxy-
lares adsorbed on Pd(111).
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