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surface science

ELSEVIER Surface Science 343 (1995) 261-272

A theoretical study of the adsorption of oxalic acid on TiO 2

Adil Fahmi a,1, Christian Minot a,,, Patrick Fourr6 b9 Patrice Nortier b
a Laboratoire de Chimie Organique Thdorique, Universit~ P. et M. Curie, Bolte 53, URA 506 CNRS, 4 Place Jussieu, F-75252 Paris Cedex
05, France
b Service de Synth~se Mindrale, RhSne-Poulenc Recherches, 52 rue de la Hale Coq, F-93308 Aubervilliers, France

Received 7 February 1995; accepted for publication 31 July 1995

Abstract

This paper presents results of periodic Hartree-Fock calculations on the adsorption of oxalic acid on rutile and anatase
TiO 2 structures. One dimensional polymers are used as models for TiO 2 bare surfaces. Oxalic acid undergoes dissociative
adsorption leading to the oxalate bonded to two adjacent Ti atoms, which seems to be the most stable form of oxalic acid on
TiO 2 surfaces. The adsorption is stronger on the anatase polymer than on the ruti!e polymer and thus the crystal growth of
TiO 2, in the presence of oxalic acid, leads to the rutile structure.

Keywords: Ab initio quantum chemical methods and calculations; Carboxylic acid; Low index single crystal surfaces; Titanium oxide

1. Introduction growth is therefore oriented towards the faces that


interact weakly with the additive. In the case of the
The effect of foreign substances on the growth of competition between the formation of two polymor-
crystals is a well-known phenomenon [1-3]. There phic structures (for instance rutile and anatase struc-
are several possible mechanisms by which an addi- tures for TiO2), the growth is oriented towards the
tive can inhibit the crystal growth reaction. Two least active structure. Here rises the molecular recog-
main mechanisms are often used to describe the nition phenomenon at inorganic surfaces [5] that has
inhibitory effect [4]: in the first one, the additive the potential to provide control over crystal growth
forms stable complexes with one of the precipitating processes. A detailed understanding of recognition
ions and decreases solution supersaturation; in the processes leads to the choice of the additive which
second one, the additive is adsorbed on the active can direct the growth towards the desired crystalline
growth sites. During this later process, the additive structure.
poisons the surface where the adsorption takes place. This work was stimulated by the neefi for more
The adsorption inhibits the growth on that face pre- effective chemicals to control the titanium dioxide
venting the deposition of the crystal molecules. The crystallization. Rutile and anatase are the main crys-
tal structures of TiO 2, rutile is the most stable one
[6]. During TiO 2 crystallization, some carboxylic
* Corresponding author. acids [7] are preferentially adsorbed on futile and the
Present address: Eindhoven University of Technology, De-
partment of Inorganic Chemistry and Catalysis, P.O. Box 513, growth is oriented toward~ a~atase. However, the
5600 MB Eindhoven, The Netherlands. rutile formation is still observed in presence of ox-

0039-6028/95/$09.50 © 1995 Elsevier Science B.V. All rights reserved


SSDI 0039-6028(95 )00813-6
262 A. Fahmi et al. / Surface Science 343 (1995) 261-272

alic acid. The same trend was found in the TiO 2 our previous studies [6,12,13], a PS-31G [14] basis
sol-gel process [8]. It is therefore suggested that set for the oxygen and the carbon atoms and the
oxalic acid is preferentially adsorbed on anatase, standard 4-31G basis set for the hydrogen atom. For
blocking the anatase growth. the titanium atom the basis set consists of five d
In this paper we present a theoretical study of the primitives contracted to a (4/1) basis set and a
adsorption of the oxalic acid on bare rutile and single 4sp shell with an exponent of 0.484; the 4sp
anatase surfaces. The structure of the oxalic acid on shell is almost vacant for the titanium ions. These
TiO., is analyzed. The crystal growth orientation will basis sets were optimized for the TiO 2 bulk structure
in principle be found by the comparison of the [6]. One might think that they are of medium quality.
adsorption energies of the oxalic acid on the two However, this represents for a periodic calculation a
structures. We first present the oxalic acid molecule better level than it would be for a molecular calcula-
(HOOC-COOH), the hydrogen oxalate (HOOC- tion. Indeed, very diffuse orbitals are not required as
COO-) and the oxalate (C.,O42-) ions (Sections for a molecular calculation, since they are responsi-
3-5). We discuss the gas phase acid-base properties ble for the basis set linear dependence [15].
of the oxalic acid (Section 6) and we present the
models for the bare TiO,. surfaces (Section 7). Next,
we report the results of the molecular adsorption 3. The oxalic acid molecule
(Section 8). The various dissociative adsorptions are
analyzed in Sections 9 and 10. The last section is The oxalic acid has a planar geometry. According
devoted to oxalic acid decomposition in the gas to hydrogen atoms orientation, two conformations
phase and on the TiO2 surface. are very close in energy (see Scheme 1). For the first
one, the hydrogen bonding takes place within each
carboxyl group, while for the second one, hydrogen
2. Method of calculation atoms connect different carboxyl groups. The first
one (conformation A) is more stable by 1.7 kca|/mol
The calculations are carried out at the SCF level with the PS-31G basis sets.
with a restricted Hartree-Fock hamiltonian using the The conformation B, with hydrogen bonding (O-
core pseudopotential from Durand-Barthelat [9]. For O 2.7 and H . . . O ~ 2.29 ,g,) is believed to be the
the gas phase properties of oxalic acid, we use the most stable according to electron diffraction [16] and
MONSTERGAUSS [10] program to optimize the spectroscopic analysis [16,17]. Despite of numerous
geometry of the various free anions which can be theoretical studies, the most stable conformation is
generated by the oxalic acid. Next we use the CRY~,- still controversial [18-20]. The use of ab initio all
TAL [11] program to compute the electronic prope~'- electron calculations shows a very small energy dif-
ties o: the optimized molecules and also for the ference between the two conformations. At the
adsorption studies. The basis sets are the same as in MP2/4-31G level [19] the conformation A is more

Table 1
Optimized geometrical parameters of the oxalic acid (in ,~ and deg), the hydrogen oxalate and the oxalate ions
Bond length Oxalic acid Hydrogen oxalate Oxalate Oxalate
or angle ("A"conformation) (planar) (orthogonai) (planar)
C=C 1,504 (1,536) 1,556 1,530 1.596
C=O 1,206 (1,202) 1,212 - -
C-O 1,33 (1,291) 1.361-1,239-1,268 1,274 1.269
O=C-C 124,7 (121,7) I i !.8 117.5 117.7
O-C-C ! 11,5 (112) 127,7-11 l,l-118 117.5 117.7

The experimental values [21] arc indicated in parentheses. The three values for the CO bond in the hydrogen-oxalate correspond to single
bonds (the first one is that of the hydroxyl group, the last one is cis with respect to that group). The same convention is used for the OCC
angles,
A. Fahmi et al./ Surface Science 343 (1995) 261-272 263

lation is 0.048. The optimized parameters for the


0 O--H planar conformation are shown in Table 1.

.-d -
\H 5. The oxalate ion, C20 z-
conformation A conformation B
Using the 6-31G, and 6-31 + G basis sets, De-
Scheme 1.
war et al. [22] found that the orthogonal D2d geome-
try of the oxalate is more stable than the planar D2h
geometry. By a metal-cation complex the geometry
can be modified towards the planar oxalate. The
stable by 0.8 kcal/mol and at the M P 2 / 6 - 3 1 G , energy difference between the two conformations are
level [20] the conformation B is more stable by 2.5 4.9 (6-31G,) and 6.3 (6-31 + G) kcal/mol. With
kcal/mol. the PS-31G basis sets, we found the same trend, a
The optimized parameters for the conformation A stabilization of the D20 geometry by 2.9 kcal/mol.
with the PS-31G basis sets are shown in Table 1. The optimized parameters are shown in Table 1. The
The overall agreement with experimental data [21] is C - C bond length is longer for the planar geometry
satisfactory except the position of the hydrogen atom because of the oxygen-oxygen repulsion.
that gives errors of 0.1 A for the O - H bond length
and 10° for the C - O - H angle. Errors of the same
magnitude were found by other authors [19].
6. Gas phase properties of oxalic acid

4. The hydrogen oxalate ion, HOOC-COO- 6.1. Gas phase proton affinities

The hydrogen oxalate ion has a planar geometry. 1here are two basic sites in the oxalic acid: a
The hydrogen atom is oriented in the way that allows carboxylic and a hydroxylic oxygen atom. When a
ydrogen bonding (O-O = 2.52 and H . . . O - - 2 . 0 4 single proton interacts with the oxalic acid molecule,
) between the two carboxyl groups (see Scheme 2). the first proton affinity is involved:
This bonding is strong because of the negative charge HOOC-COOH + H + ..o HOOC-C 0 (OH) 2,
on the oxygen atom.
The energy difference between the planar and the A Hc,,i,: = - 180.5 kcal/mol
orthogonal conformations is 9.9 kcal/mol. This later
value can be considered as an estimation of the (the proton is attached to a carbonyl group),
hydrogen bonding energy. The O . . . H overlap popu-
HOOC-COOH + H + --* HOOC-CO(OH 2 ) +'

AHc.~lc = - 168.2 kcal/mol

(the proton is attached to a hydroxyl group).

/--\
io oxxo___,,,o The proton is located on a carbonyl group, the
most basic site. Since the second COOH group is an
%. o attractor substituent, the oxalic acid proton affinity is
small with respect to that of the formic acid (A H -
- 184.1 kcal/mol; experimental value: - 182.8
kcal/moi [23]) or that of water ( A H = - 1 8 2 . 5
planar conformation orthogonal conformation kcal/mol; experimental value: - 1 7 3 kcal/mol
Scheme 2. [23,24]).
264 A. Fahmi et ai./ Surface Science 343 (1995) 261-272

When two protons interact with the oxalic acid, less endothermic than that of formic acid or that of
the best protonation mode also involves the carbonyl water:
groups: H20 -* H O - + H +, AHcalc- 423.8 kcal/mol
HOOC-COOH + 2H + --* (HO)2C+-C + (OH)2, (experimental value: 390.8 kcal/mol [25,26]),
AHcatc -- - 244.1 kcal/mol HCOOH -* H C O O - + H +,
(protonation of two carbonyl groups), AHcalc - 356.7 kcal/mol
(experimental value: 345.2 kcal/mol [26]),
HOOC-COOH + 2H + --* + ( H 2 0 ) O C - C + (OH)e,
HCOO-OOCH -* H O O C - C O O - + H +,
A Helle = - 231.4 kcai/mol
AHc~alc- 328.8 kcal/mol.
(protonation of one hydroxyl and one carbonyl The second acidic cleavage of oxalic acid is very
groups), endothermic:
HOOC-COOH + 2H + --* + (H20)OC-CO(OH~,) +, H C O O - O C C - ---, - O O C - C O O - + H +,
AHcalc = - 218.3 kcal/mol AHcalc - 459.5 kcal/mol.

(protonation of two hydroxyl groups).


From these results we expect several modes for
7. Models for the TiO z surfaces
the molecular adsorption of oxalic acid on TiO2. The
mode that should be the best involves two carbonyl
We model the TiO 2 surfaces by one dimensional
groups.
polymers [6,12]: a linear polymer for rutile and a
zigzag polymer for anatase (see Scheme 3). These
6.2. Acidic cleavages of oxalic acid models have been checked by a study on the clean
surface [27]; it is concluded that atoms from the
Since the COOH group is an attractor, the hydro- TiO 2 polymers do not differ by much from the bulk
gen oxalate ion, HCOO-COO =, is more stable than and are still bound objects relative to the free atoms.
the formate, HCOO =, or hydroxide, HO °, ions, We have already used this model for the studies of
Therefore, the first acidic cleavage of oxalic acid is adsorption on the TiO 2 surfaces [12,13,28].

J 11 11 11
0 C O 0 G 0

j o--T --o
~ ~ o

ruble polymer anatasc polymer


_ . presentedas undistortedsys~m
~ormc optimizedsuucture, Ti-O-Tiis 152°.
Scheme 3.
A. Fahmi et al./ SurfaceScience 343 (1995) 261-272 265

The rutile polymer is made of rectangular pieces oxygen atom in the polymer plane. We will consider
with a long edge (3.0065 A, the c parameter of the the adsorption of one molecule of oxalic acid on a
bulk) in the direction of the chain and a short one cell of two TiO 2 units of L~e polymer. Adsorption
(2.4875 A) in theoperpendicular direction. The Ti-O energies have been calculated according to the ex-
distances, 1.951 A, are the equatorial distances from pression:
the bulk structure. For the anatase polymer, the
Ead s ffi ETiO2 4" EH2C20, -- E(H2C202/TiO2),
Ti-Ti translation vector is the a parameter of the
bulk, 3.7629 A. This latter system involves both where E(H~C204/TiOe) is the total energy of the ad-
equatorial Ti-O bonds, 1.939 A, along the axis of sorbate/substrate system, ETi02 is the total energy
the polymer and apical ones, 1.995 A, in the perpen- of the substrate and Eu2c204 is the total energy of
dicular direction. These parameters are taken from the free oxalic acid molecule in its equilibrium ge-
the optimized bulk structures [6]. The coordination of ometry. A positive Eads value corresponds to a stable
the Ti atoms is four and is the same for the two adsorbate/substrate system.
polymers. For the oxygen atoms, the coordination is For the geometry of adsorbed oxalic acid, the
two in the linear polymer, while, in the zigzag following methodology has been used. We first per-
polymer, half of them is singly-coordinated and the formed a molecular calculation of the adsorbate
other half is triply-coordinated. On real surfaces, the species (without the substrate) using the MONSTER-
coordination of the Ti atoms is usually five (it is four GAUSS program. The adsorbate species is defined
on the (001) surface of ruffle) and that of the oxygen as the oxalic acid molecule plus one or two protons
atoms is most often two or three. Previous studies simulating the Ti metal cations. Positions of oxygen
[12,13] have shown that the reduction of the coordi- atoms by which the oxalic acid is attached to the
nation of the atoms in the polymer models contribute surface and those of protons are fixed; the positions
to overestimate the adsorption energies. The energy of all the other atoms are optimized. Finally, this
shift is comparable for various adsorption modes and geometry is transferred to the CRYSTAL calcula-
thus does not affect the relative stabilities. tions. The Ti-O distances between the oxalic acid
These polymers are obviously far from being a and the surface are taken from water adsorption [12]
complete representation of crystallographic faces al- ( T i - O - 2.12 ~. for the molecular adsorption and
though they are significantly better than a cluster Ti-O = 1.81 A for the dissociative adsorption). The
model. However, they contain titanium and oxygen study of the formic acid adsorption shows that these
atoms with the oxidation numbers + IV and -11, parameters, optimized for H20, are transferable to a
respectively. The linear polymer can be recognized carboxylic acid [29].
as the main feature of the ruffle (110) and (100)
faces; it contains the linearity of the TiO 2 sequence
that is specific of rutile. The zigzag polymer can be 8. Molecular adsorption on futile
found on the anatase (100) and (010) faces. We
consider that the study of the polymer models should Titanium dioxide is an amphoteric compound,
give information about the activities of the TiO2 endowed with acidic Ti(+IV) and basic O ( - I I )
surfaces. sites. Surface chemistry may thus involve Lewis and
The ruffle polymer is more stable than the anatase Brcnsted acid-base reactions. Bare TiO 2 surfaces
polymer; the calculated total bonding energies are 83 dissociatively adsorb water to form surface hydroxyl
and 68 kcal/mol, respectively [12]. The water ad- groups [12]. These surfaces correspond to the real
sorption study [12] shows that the metal cations from catalytic species more often than bare surfaces. The
the ruffle polymer are the best Lewis acidic sites and first step in the interaction of a carboxylic acid
the singly-coordinated anions from the anatase poly- (RCOOH) with TiO 2 surfaces is the formation of the
mer are the best basic sites. carboxylate (RCOOads) [30-34]. The proton is trans-
A basic adsorbing species would approach the ferred to an oxygen atom of the surface. The second
titanium atom perpendicularly to the polymer plane step is the decomposition of the carboxylate. The
and an acidic adsorbing species would app~::oach the structure of the carboxylate and the thermodynamic
266 A. Fahmi et al./ Surface Science 343 (1995) 261-272

H~~ .........',,,,~:)...,,,I,
H Lewis acid-base reaction, the Lewis acid is the
metal cation and the Lewis base is an oxygen atom
from the oxalic acid. There is a correlation between
the molecular adsorption and the gas phase proton
affinity of the carboxylic acid. The oxalic acid can
interact with the surface by one or two carboxyl
groups. These two adsorption modes are investi-
gated.

(a) 8.1. Adsorption by one fimction

This function can be either a carbonyl group (Fig.


la) or a hydroxyl group (Fig. lb). The geometry of
the adsorbed oxalic acid corresponds to that of
.... "m,llll~..,,,lill H H O O C - C(OH) + species (a model for the adsorp-
tion through the carbonyl) or to that of H O O C -
H CO(OH:) + species (a model for the adsorption
through the hydroxyl), where the proton simulates a
metal cation of the polymer. The best conformations
for the adsorbed oxalic acid are the orthogonal ones
where the non-adsorbed carboxyi group is parallel to
the polymer plane. In these conformations, the oxy-
(b) gen-oxygen repulsion is the weakest.
As expected from the gas phase proton affinities
Fig, 1, Molecular adsorption of the oxalic acid through a single
function: (a) the ¢arbonyl group, and (b) the hydroxyl group,
of oxalic acid, the adsorption by the carbonyl is more
favourable than that by the hydroxyl. The adsorption
energies are respectively 23.0 and 7.0 kcai/mol
of the reaction leading to its formation are not well (exothermic adsorptions). The molecular adsorption
determined. of the oxalic acid is weak in comparison with that of
in this section we d,~al with the molecular adsorp- the formic acid (31.2 and 26.2 kcal/m01 for the
tion: the oxalic acid is not dissociated on the surface. adsorption by the carbonyl and by the hydroxyl
The molecular adsorption can be described as a respectively). The deconjugation in the orthogonal

H H

(a) (b)
Fig, 2, Molecular adsorptionof the oxalic acid through two functions:(a) two carbonyl groups, and (b) the carbonyl group and the hydroxyl
group,
A. Fahmi et al./ Surface Science 343 t1995) 261-272 267

conformation of the oxalic acid increases the differ- O = 3.0065 ,g, (the translation parameter of the poly-
ence expected from the proton affinities. mer). The adsorption energy is weak, 25 kcal/mol.
At higher coverage (one oxalic acid per 2 TiO 2
8.2. Adsorption by two Jimctions units), the two adsorbed functions are either two
carbonyl groups (Fig. 2a) or one carbonyl and one
From the gas phase proton affinities (Section 6.1), hydroxyl groups (Fig. 2b). Adsorption energies are
we have seen that the protonation of two hydroxyl similar, 48.1 k c a l / m o l for the first adsorption mode
groups is less favourable than that involving two and 48.0 k c a l / m o l for the second one.
carbonyl groups. Thus, the corresponding adsorption The adsorption through two functions for both
should be less favourable than that involving car- modes is more favourable than the adsorption through
bonyl groups. Because of the proton-proton repul- one function.
sion between two nearest oxalic acid molecules, the
calculation of the adsorption by two hydroxyl groups
requires the use of a low coverage (one oxalic acid 9. Dissociative adsorption on futile
per 4 TiO 2 units). The geometry of the adsorbed
oxalic acid corresponds to that optimized for The dissociative adsorption can be described as a
(HO)2C+-C+(OH)2 species with the constraint O - Br0nsted acid-base reaction where the proton is

~
H
'.,,*,i**lllll~ .... Illll H

(a) (b)

(c)
Fig. 3. Various adsorption modes of the hydrogen oxalate: (a) The hydrogen oxalate is adsorbed through a single oxygen atom (CO), the
conformation is orthogonal. (b) The hydrogen oxalate is adsorbed through the two oxygen atoms of the carboxylategroup, the conformation
is planar. (c) The hydrogen oxalate is adsorbed through two oxygen atoms, one from the carboxylate group and the other one from qle
carboxyl group, the conformation is planar.
268 A. Fahmi et aL /Surface Science 343 (1995) 261-272

transferred tO an oxygen atom of the oxide (a


Br¢nsted base) and the carboxylate is adsorbed on a
metal cation. On the contrary to molecular adsorp-
tion, dissociative adsorption involves simultaneously
the acidic and basic properties of both the oxalic acid H
and the T i O 2 surface.

9.1. Adsorption of the hydrogen oxalate ion,


HOOC-CO0 -
Fig. 4. Adsorption of tile oxalate in a twisted conformation, the
The adsorption of the hydrogen oxalate ion can be twist angle is 15° .
seen as the result of a dissociative adsorption of the
oxalic acid molecule on the TiO_, surface (HOOC- cleavages. The oxalate is complexed in a twisted
C O O H a d s ~ H O O C - C O 0 ~ + H ads)"
+ The hydrogen geometry by two metal cations; the twisted angle is
oxalate is adsorbed on a Ti ion and the proton goes 15°. The protons are transferred to oxygen atoms of
to a bridged oxygen atom of the polymer. When the the polymer (Fig. 4). The complexation of the ox-
hydrogen oxalate is adsorbed through a single oxy= alate ion by two metal cations was found on hematite
gen atom from the carboxylate group (see Fig. 3a, [36,37], no data are available for TiO 2.
the carboxyl group is parallel to the polymer plane), There are different modes for the protonation of
the adsorption energy is very small, 18.7 kcal/mol. the polymer as already found for the dissociative
When the other oxygen atom of the carboxylate is adsorption of water [12]. In the best proton distribu-
also adsorbed (see Fig. 3b), the adsorption energy is tion, protons alternate on each side of the polymer.
83 kcal/mol. This adsorption mode is general for The adsorption energy of the oxalate is 101.7
monocarboxylic acids such as the formic acid [29,35]. kcal/mol; it is larger than that of the hydrogen
The heat of adsorption is slightly inferior to that of oxalate.
the formic acid, 85 kcal/mol, because of the attrac- We have also calculated the adsorption of the
tive effect of the COOH group. Since the oxalic acid oxalate ion through the two oxygen atoms of the
is a diacid, the adsorption may involve the carbonyl same CO, group. This adsorption is not favourable,
of the carboxyl group instead of that of the carboxyl- the adsorption energy is only 44.0 kcal/mol. This
ate (see Fig. 3c). Then, the adsorption energy be- system should be unstable and decompose into two
comes slightly larger, 85.7 kcal/mol. CO, molecules). The CC Mulliken overlap popula-
in this later adsorption mode, the geometry of the tion is very negative, O P - -0.15; this value sug-
adsorbate is planar with a strong internal hydrogen gests a repulsion between the two CO, groups. The
bonding. The oxygen-hydrogen distance is 2.1 A adsorption of the oxalate by one CO, group,
with a Mulliken overlap population, OP--0.023. (TiO)2C-CO 2, shows similarities with the (HO).,C-
From this OP, we expect a high value for the hydro- CO., system obtained by a proton transfer in the
gen bonding. For instance, in the water dimmer oxalic acid molecule; such system is unstable and
(H,O), [12] the hydrogen bond has an OP of 0.017 undergoes decarboxylation as found from previous
and a bonding energy of 7.3 kcal/mol. calculations [ 19].
Clearly, the best adsorption mode for the hydro- From these calculations, we conclude that the
gen oxalate involves two oxygen atoms. These oxy- oxalate is more stable than the hydrogen oxalate on
gen atoms can be either from the carboxylate group TiO, surfaces.
or from the carboxylate and the carboxyl groups.
9.3. Adsorption formally resulting from basic
9.2. Adsorption of the oxalaw ion, C20 ~ - cleavages, HOOC- +CO and OC +- +CO

The formation of the oxalate on the TiO 2 surface The heterolytic dissociation of an acid can be
can be seen as the result of two successive acidic either acidic (O-H cleavage) or basic (C-OH cleav-
A. Fahmi et a l . / Surface Science 343 (1995) 261-272 269

P gas phase, such cleavage is less endothermic than the


acidic cleavage by 35 kcal/mol:
HOOC-COOH --->HOOC-CO ÷+ H O - ,
A H = 294.13 kcal/mol.
© The adsorption energy is 44.4 kcal/mol. When
the adsorption is by one function, the basic cleavage
(Fig. 5a) is more favourable than the acidic cleavage
I ....0
(Fig. 3a) (see Section 9.1). However, while the
H'2~44A singly-coordinated carboxylate that results from an
acidic cleavage leads to the adsorption of a second
a) function (Figs. 3b and 3c) and to an increase of the
adsorption energy by a factor of five, the absence of
similar possibility for the basic cleavage makes this
process unfavourable.
The adsorption of the dication +OC-CO + that
results from two successive basic cleavages is un-
/H favourable (Ead s = 34.8 kcal/mol). The correspond-
,o--I- I- ing gas phase reaction is highly endothermic:
O ~ Ti 0]/// Ti
f HOOC-CO + ~ +O C - C O + + HO -,
AH = 510.9 kcai/mol.
b) Finally, we have considered the adsorption of the
Fig. 5. (a) Dissociative adsorption of the oxalic acid associated - O 2 C - C O + species that results from the dehydra-
with a basic cleavage(HOOC-COOH ~ HOOC-CO~., + HO~). tion of the oxalic acid (acidic and basic cleavages).
HOOC=+ CO is adsorbed in a bridging position. (b) Dissociative
adsorption of ~heo×alicacid associatedwith two cleavages(acidic This would be a possibility to have the adsorption of
and basic: HOOC=COOH~ H,,d,, + + - 02C-CO,,,*t,,+ HO,~,). two functions, one of them resulting from a basic
Since the C=C bond is elongated, this adsorption mode leads to cleavage. The corresponding geometry IS shown in
the decompositionof the oxalic acid on the surface. Fig. 5b. The corresponding gas phase reaction is less
endothermic than two acidic or basic cleavages.
HOOC-COOH ~ -O2C-CO+ + HO- + H +,
A H = 418.2 kcal/mol.
age). The basic cleavage of the oxalic acid on a TiO 2 The calculated adsorption energy is 71.6
surface leads to a doubly-coordinated carboxylate kcal/mol; this value is inferior to that obtained for
and a singly-coordinated hydroxyl group (Fig. 5a). the oxalate. As the - O 2 C - C O + species is a charged
There is an internal hydrogen bonding in the carbox- representation of the CO2-CO complex, this adsorp-
ylate; the oxygen-hydrogen distance is 2.44 A and tion mode raises the question of the decomposition
the overlap population is 0.011. of the oxalic acid on the surface. We shall discuss
Avoiding to speculate on the validity of a mecha- this matter in Section 11.
nism involving a basic cleavage for an acidic species,
we can conceive this adsorption mode simply as an
alternative distribution of fragments that may be
generated from an acidic cleavage followed by an 10. Adsorption of the oxalate on anatase
exchange between the OR and OH groups on the
surface. Let us note however in favour of a basic Since the oxalate is more stable than the oxalic
cleavage mechanism, that, for the oxalic acid in the acid or the hydrogen oxalate on the futile polymer,
270 A. Fahmi et al. / Surface Science 343 (1995) 261-272

that the anatase formation is inhibited. The adsorp-


tion on rutile is weaker than on anatase, whence the
crystallization leads to rutile structure.
C~o H~°
!/ 11. Decomposition of oxalic acid

11.1. Gas phase decomposition

In the gas pi~as~, the thermal decomposition of


H
oxalic acid yields CO_, + HCOOH [38]. The study of
Fig. 6. Dissociative adsorption of the oxalic acid on the anatase UV photolysis [39] suggests that two processes oc-
polymer. The geometry of the oxalate is planar and the protons are
cur, yielding CO, + HCOOH and CO 2 + CO + H 2O.
in the polymer phme.
The calculated enthalpies for these reactions, in
agreement with previous calculations [19], show
exothermic reactions:
we limit our discussion in this section to the oxalate
adsorption. Dissociative adsorption of the oxalic acid HOOC-COOH --* CO 2 + HCOOH,
on the zigzag chain of anatase involves the protona- AHcalc = - 12.1 kcal/mol
tion of singly-coordinated oxygen atoms (which are
more basic than doubly-coordinated oxygen atoms of (experimental value: - 9 . 6 kcal/moi [40]; AHc.qc =
the rutile polymer [12]). The protons are in the - 1 6 . 6 kcal/mol when intermolecular interactions
polymer plane (Fig. 6). The geometry of the oxalate between products are allowed),
is planar. The oxygen-oxygen distance when the HOOC-COOH ~ CO., + CO + H 2O,
oxygen atoms lie above the titanium atoms is long A Hc,,ic - - 7.2 kcal / mol
(3.10 ~) as compared with that of the rutile case
(3.01/~, the c parameter from the bulk) and closer to (experimental value: - 3.3 kcal/mol [40]; AH~,,i,, --
that of the oxalate in the gas phase (2.14 J.). 16.0 kcal/mol when intermolecular interactions
The adsorption energy, 128.2 kcal/mol, is larger between products are allowed).
than that on the rutile polymer by 26.5 kcal/mol.
The anatase structure appears to be more reactive 1i.2. Decomposition on the Ti02 surfaces
because of the basicity of the singly-coordinated
oxygen atom [ 12]. The distortion of the oxalic acid is In order to estimate the enthalpies of these two
not the driving force. Indeed, the adequation of the reactions on TiO., surfaces, we first calculate adsorp-
oxalic acid to the surface is not better on the anatase tion energies of all the products, H 20, HCOOH, CO,
surface than on the rutile one. On the contrary, on and CO., independently. For such calculations, we
the futile polymer the oxalate is twisted and the O-O used the rutile polymer and consider the best adsorp-
distance becomes close to that of the oxalate in the tion mode for each adsorbate: dissociative adsorption
gas phase. Such an adaptation is not possible on the for water ( H , O ~ H,ds + OHad~) and formic acid
anatase polymer since the molecule remains planar. (HCOOH ~ H,id,~ + HCOO, d,~) at saturation ( 0 - 1).
The large O - O distance in the adsorbate is however For water, the hydroxyl group is adsorbed above a Ti
not that destabilizing, since the calculated adsorption atom and the proton is transferred to an oxygen atom
energy is large. of the polymer [ 12]. For formic acid, the carboxylate
The difference in reactivity between the two is adsorbed between two Ti atoms and the proton is
phases allows us to explain the crystallization pro- transferred to an oxygen atom of the polymer [29].
cess of TiO, in presence of oxalic acid. Since the For CO [13] and CO 2 [28] the best adsorption modes
adsorption is stronger on anatase, the oxalic acid is correspond to perpendicularly adsorbed molecules
adsorbed on the first crystallites of anatase and by above Ti atoms. We have considered both the 0 - 1
A. Fahmi et aL / Surface Science 343 (1995) 261-272 271

Table 2 12. Conclusion


Adsorption energies in kcai/mol for various molecules on the
rutile polymer at 0 = 1 and 0 = 1 / 2 coverages
Adsorbed system 0= 1 0 = 1/2 In this paper, we have presented a periodic
H 2Odiss 63 a _
Hartree-Fock ab initio calculation of the adsorption
HCOOHdiss 85 b _ of the oxalic acid on TiO 2 surfaces. We have used
CO 15.2 c 19.3 c polymers as models for rutile and anatase surfaces.
CO 2 10.4 d 19.0 d Various adsorption modes for oxalic acid molecule,
CO., + HCOOH diss 95.4 104.0 hydrogen oxalate and oxalate ions were investigated.
CO 2 + CO + H20 diss 88.6 101.3 The best adsorption modes always involve two oxy-
gen atoms of the adsorbate. The dissociative adsorp-
H 2C204 diss 101.7 -
tion is more favourable than the molecular adsorp-
The subscript "diss" refers to dissociatively adsorbed species. tion; our results clearly show that the oxalate com-
a Ref. [12]. plexed by two metal cations is the most stable form
b Ref. [29].
c Ref. [13].
of the oxalic acid on TiO 2 surfaces. This is a study
d Ref. [281. of the thermodynamically stable adsorption. We rec-
ognize that kinetics may limit the accessibility of the
stable configurations. The decomposition reactions
of the oxalic acid that are exothermic in the gas
and 0 = 1 / 2 coverages. The various heat of adsorp- phase are not favoured by the adsorption on the
tions are given in Table 2. The sum of these adsorp- oxide surface. The comparison of the adsorption
tion energies give numbers that are very close to the energy of the oxalate on rutile and anatase polymers
value for the adsorption energy of the oxalate, 101.7 explains crystallization experiments of TiO 2 in pres-
kcal/mol. From these values and the gas pha~se ence of oxalic acid. The adsorption energy is larger
values, we derive the following values for the disso- on anatase. Therefore, the oxalic acid is adsorbed on
ciation on the surface: the growing anatase preventing the formation of the
bulk structure. The adsorption on ruffle is weaker
HOOC-COOHdiss - , CO 2 + HCOOHoiss, and the crystal growth leads to the ruffle structure.
AH~a~ = - 5 . 8 kcal/mol ( - 14.4 at 0 = 1/2)
(to be compared with - 16.6 kcal/mol),
HOOC-COOHdi~ -~ CO 2 + CO + H 2Odi.~,,, References
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