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Abstract
In this study the different processes occurring on the TiO2 and Pd and Cu doped TiO2 surfaces during the photocatalytic formic
acid degradation in the presence or absence of S2O82 or H2O2 have been investigated. FTIR studies have shown the relevance of
the H-bounded hydroxyl groups. It has been observed that formate molecules interact simultaneously with the dopants and
surfacial Ti atoms yielding an intermediate species which plays an important role in the phototacatalytic degradation
mechanism. Also, it has been determined that Pd or Cu oxides may act as receptors or transmitters of the TiO2 photogenerated
electrons and thus modify the degradation mechanism. Different redox reactions have been proposed according to the obtained
results.
# 2004 Elsevier B.V. All rights reserved.
0169-4332/$ – see front matter # 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.apsusc.2004.04.039
J. Araña et al. / Applied Surface Science 239 (2004) 60–71 61
Fig. 1. Results from the formic acid degradation with bare-TiO2 (D), Pd–TiO2 (&) and Cu–TiO2 (*). (1) Experiments with only the catalysts.
(2) Experiments with the catalysts þ S2 O8 2 ions. (3) Experiments with the catalysts þ H2 O2 .
J. Araña et al. / Applied Surface Science 239 (2004) 60–71 63
Without additives the highest efficiencies in two These sulphate radicals may yield OH through:
hours (as TOC reductions percentage) are obtained by
bare-TiO2 and Cu–TiO2, 67.7 and 49.8%, respectively SO4 þ OH ! SO4 2 þ OH (4)
(Fig. 1(1)). On the contrary, in presence of S2O82 ions or directly oxidise organic compounds.
the highest degradation is obtained by Cu–TiO2 In this study the effect of the presence of these ions
(75.3%) while bare-TiO2 efficiency (49.7%) is notably depends on the catalyst used. Hence, adding H2O2
reduced (Fig. 1(2)) with respect to that obtained with- sometimes improves the catalytic performance and
out additives. other the effect is the opposite.
Furthermore, the addition of H2O2 (Fig. 1(3)) gives The formic acid photocatalytic degradation may
the best catalytic behaviour which is that of Cu–TiO2 start by its reaction with a hole [26]:
(93.9%). Conversely, this is not the case for Pd–TiO2
HCOO þ hþ ! CO2 þ H (5)
that shows the highest efficiency in presence of S2O82
ions (49.7%) being similarly lower with H2O2 or with- or by means of a OH radical attack:
out additives (about 22%). Bare-TiO2 þ H2 O2 shows a HCOO þ OH ! HCOO þ OH (6)
slightly lower efficiency (56.6%) than that without the
peroxides. HCOO þ O2 ! CO2 þ HO 2 (7)
In addition to this, degradation studies with only For those processes in which the H2O2 presence
H2O2 or S2O82 ions and with H2O2 or S2O82 ions in improves the catalytic behaviour a degradation
presence of Cu2þ or Pd2þ ions were performed to mechanism based on the formation and reaction of
determine the catalyst and dopant influence on the
OH radicals (Reaction (2)) may be suggested (i.e.
process. Only in the experiments with H2O2 and Cu2þ Cu–TiO2). On the contrary, in those experiments in
ions a significant degradation (79.8%) was obtained, which no effect is observed after adding H2O2 but the
though lower than that from the experiment with Cu– presence of S2O82 ions improves the catalytic activ-
TiO2 under the same conditions. In the other cases ity, Reaction (5) may be favoured (i.e. Pd–TiO2).
much lower efficiencies than those with the catalysts Furthermore, when using bare-TiO2 the addition of
have been obtained. H2O2 does not improve the organic degradation, while
These experiments have shown quite different cat- the presence of S2O82 ions worsens it.
alytic behaviours depending on the presence of H2O2, To determine the reason of these different beha-
of S2O82 ions and the metal used. viours, FTIR studies have been conducted about the
As already described in the bibliography, UV-irra- effect of irradiation and the presence of H2O2 and
diated TiO2 is able to generate OH radicals by the S2O82 ions on the acid molecule–catalyst surface
following Reactions [20,21]: interaction.
)
hn
TiO2 !hþ þ e 3.3. FTIR studies
(1)
hþ þ OH ! OH
Catalysts were impregnated with 200 ppm formic
Hydrogen peroxide may also generate these radicals acid, 200 ppm of formic acid þ 400 ppm of H2O2 and
by accepting the photochemically generated electrons 200 ppm formic acid þ 200 ppm of S2O82 ions aqu-
[22,23]: eous solutions. Then, filtered, dried at room tempera-
ture and placed between two CaF2 windows in a
H2 O2 þ e ! OH þ OH (2) proper cell to be FTIR-analysed. Once the spectrum
Consequently, adding H2O2 might favour surfacial was obtained the cell was irradiated and analysed
oxidation processes. However, the effect of the per- every 10 min. This way, the evolution of the adsorbed
oxide addition highly depends on the catalysts used. formic acid and surfacial hydroxyl groups was studied
Persulphate ions may also react with the generated in the absence–presence of H2O2 and/or S2O82 ions
electrons to give SO4 radicals [24,25]: under irradiation. FTIR spectra have been obtained in
regions between 4000 and 2500 cm1 and 2000–
S2 O8 2 þ e ! SO4 (3) 1000 cm1.
64 J. Araña et al. / Applied Surface Science 239 (2004) 60–71
Fig. 2. FTIR study from the formic acid interaction and evolution under irradiation with bare-TiO2 in the 4000–2500 cm1 (1) and 2000–
1000 cm1 (2) regions.
3.3.1. Formic acid–water FTIR studies 3.3.1.2. Pd–TiO2 þ formic acid. Fig. 3 shows the
Figs. 2–4 show FTIR the spectra from the formic spectra from the formic acid–PdTiO2 interaction
acid interaction with the different catalysts. before and after irradiation. In the before irradiation
spectrum two bands located in the hydroxyl group
3.3.1.1. Bare-TiO2 þ formic acid. Fig. 2 shows the region (Fig. 3(1)) and centred at 3668 and 3000 cm1
spectra from the formic acid–bare TiO2 interaction may be observed. During the first 20 min of irradiation
before and after being irradiated. During the first the band at 3668 cm1 is shifted towards 3698 cm1,
20 min of irradiation the intensity of the bands corre- while the 3000 cm1 band intensity is reduced. During
sponding to H-bounded hydroxyl groups (between the subsequent irradiation period the 3698 cm1 band
3500 and 3150 cm1) is reduced (Fig. 2(1)). Also, is progressively shifted to lower wavenumbers (3668–
in the 2000–1000 cm1 region a slight intensity reduc- 3646 cm1) and the 3000 cm1 band to higher ones
tion of the bands attributed to formates, 1590, 1381 (3126 cm1). Also, a subtle darkening of the catalyst
and 1358 cm1, ns ðCOO Þ, nðCHÞ and nas ðCOO Þ is observed during these studies.
vibrations, respectively [8,27] may be observed The band centred at 3698 cm1 is attributed to
(Fig. 2(2)). After this, no band evolution was isolated hydroxyl groups coordinated with Ti4þ atoms.
noticed. However, some authors have indicated that this band
Similar reductions of the bands attributed to the H- shift towards lower wavenumbers is due to a Ti4þ atom
bounded hydroxyl groups have been described in other charge defect [29,30]. Thus, it may be concluded that
experiments [28]. Consequently, these groups might initially (at t ¼ 0) Ti4þ atoms have a charge defect
be responsible of the formation of OH radicals which is eliminated during the first 20 min of irradia-
needed in Reactions (1) and (6). tion.
J. Araña et al. / Applied Surface Science 239 (2004) 60–71 65
Fig. 3. FTIR study from the formic acid interaction and evolution under irradiation with Pd–TiO2 in the 4000–2500 cm1 (1) and 2000–
1000 cm1 (2) regions.
However, after these initial moments it seems that erated in this reaction could attack formic acid
charge defects increase, considering the observed band molecules adsorbed on the catalyst surface, to give
shift towards lower wavenumbers (3646 cm1). The the formaldehyde detected.
3000 cm1 band is attributed to physisorbed water
HCOO þ 2H þ Hþ ! HCHO þ H2 O (8)
molecules and the observed band shifts may also be
explained by Ti atom redox state changes. Thus, the lower efficiency obtained with this cata-
Furthermore, in the 2000–1000 cm1 region lyst (Fig. 1(1)) might be explained by these counter-
(Fig. 3(2)) new bands at 1490 and 1445 cm1 are acting processes, by which formic acid can be oxidised
obtained in addition to the formate proper bands at to CO2, and reduced to formaldehyde, with similar
1582 and 1352 cm1, but slightly shifted with respect reaction rates.
to those obtained with bare-TiO2. These new bands
show increasing intensities during the first 30 min of 3.3.1.3. Cu–TiO2 þ formic acid. Fig. 4 shows the
irradiation and correlate quite well with n(CH2) vibra- spectra from the formic acid interaction with Cu–TiO2
tions observed in other experiments with formalde- before and after irradiation. In the hydroxyl region of
hyde-methanol adsorbed on this catalyst. At this same the before irradiation spectrum (Fig. 4(1)) and simi-
time a short intensity reduction of the bands attributed larly to the observed with the catalyst Pd–TiO2, two
to formates is noticed. main bands centred at 3673 and 3000 cm1 are
When the catalyst is irradiated Pd oxides may act as observed. In this case no band shifts, but slight mod-
receptors and transmitters of the photogenerated elec- ifications of the band intensity are visible after irra-
trons favouring Reaction (5). H radicals photogen- diation. It must be pointed out the absence of
66 J. Araña et al. / Applied Surface Science 239 (2004) 60–71
Fig. 4. FTIR study from the formic acid interaction and evolution under irradiation with Cu–TiO2 in the 4000–2500 cm1 (1) and 2000–
1000 cm1 (2) regions.
H-bounded hydroxyl groups, similarly to the obtained catalyst with respect to bare-TiO2 could also be
with Pd–TiO2. In the 2000–1000 cm1 region of explained by the absence of H-bounded hydroxyl
the before irradiation spectrum (Fig. 4(2)) new group. Thus, Reaction (5) would be favoured. FTIR
bands attributable to physisorbed formic acid are studies also show the presence of reduced species
found at 1720 and 1213 cm1, in addition to bands from formates as obtained from studies with
attributed to formates which appear at slightly differ- Pd–TiO2, probably from H radicals generated in
ent wavenumbers from those obtained with bare-TiO2 Reaction (5).
(1581, 1382, 1350 cm1). After 10 min of irradiation Some authors have indicated that in formic acid
these bands disappear, those from formates are aqueous solutions containing TiO2 and Zn2þ ions, the
increased and new ones at 1660 and 1140 cm1 acid interaction with the catalyst surface differs from
attributable to physisorbed formaldehyde [15] are that with only TiO2, suggesting a simultaneous inter-
observed. Within the following few minutes of irra- action of the acid molecule with both metals [31]. The
diation the formate-band intensity is reduced. Then, shift of formate nðCOO Þs and nðCOO Þas vibration bands
no change in the spectra is noticed. Similarly to the and those from isolated hydroxyl groups observed in
observed with Pd–TiO2, the catalyst grows darker studies with Pd–TiO2 and Cu–TiO2 may be explained
during irradiation. by a similar interaction.
The slight band shift of isolated OH groups
towards lower wavenumbers may also be indicative 3.3.2. Formic acid þ S2O82 FTIR studies
of Cu oxide interactions with formate molecules, but Figs. 5 and 6 show the FTIR spectra from the formic
at a lower intensity than that observed with Pd. In this acid interaction with the catalysts in the presence of
case, the lower catalytic efficiency obtained with this S2O82 ions.
J. Araña et al. / Applied Surface Science 239 (2004) 60–71 67
Fig. 5. FTIR study from the formic acid þ S2 O8 2 interaction and evolution under irradiation with bare-TiO2 in the 4000–2500 cm1 (1) and
2000–1000 cm1 (2) regions.
3.3.2.1. Bare-TiO2 þ formic acid þ S2O82. Fig. 5 bands from physisorbed water (1640 cm1) and from
shows the spectra from the formic acid interaction S2O82 ions disappear, but those from SO42 ions are
with bare-TiO2 þ S2 O8 2 ions, before and after irra- increased. Also during this time, formate band inten-
diation. In the OH group region (Fig. 5(1)) the before sity is progressively reduced and new bands appear at
irradiation spectrum is quite similar to that obtained 1505 and 1432 cm1 which might be attributed to
with the catalyst doped with Pd and Cu in studies with carbonates [15].
only formic acid. In this spectrum a remarkable The hydroxyl group band shift towards 3730 cm1
intense band attributed to isolated OH groups at observed during the first minutes of irradiation is
3668 cm1 and a band at 3000 cm1 attributed to attributable to the Ti4þ atom reduction [14]. Also,
physisorbed water are observable. Furthermore, dur- S2O82 ions are progressively eliminated and formate
ing the first 40 min of irradiation the oscillation molecules degraded. From these results the following
between 3730 and 3668 cm1 of the band attributable mechanism may be proposed for the first minutes of
to isolated OH groups is also shown. Then, these bands irradiation:
are progressively shifted towards lower wavenumbers hn
(3648 cm1). In the 2000–1000 cm1 region of the TiO2 !hþ þ e (9)
before irradiation spectrum new bands appear at 1289, 4þ
Ti OH þ e ! TI OH 3þ
(10)
1134 and 1054 cm1 in addition to bands from phy-
sisorbed water (1640 cm1) and formates (1590, 1382 S2 O8 2 þ Ti3þ OH ! SO4 þ SO8 2 þ Ti4þ OH
and 1355 cm1). Bands at 1289 and 1054 cm1 are (11)
attributed to S2O82 ions, while the one at 1134 cm1
2
to SO42 ions. After the first 40 min of irradiation SO4 þ HCOO ! SO4 þ HCOO (12)
68 J. Araña et al. / Applied Surface Science 239 (2004) 60–71
Fig. 6. FTIR study from the formic acid þ S2 O8 2 interaction and evolution under irradiation the 2000–1000 cm1 region with Pd–TiO2 (1)
and Cu–TiO2 (2).
(4000–2500 cm1), is dominated by a wide band and (13)). On the contrary, Cu–TiO2 could be inhibit-
centred at 3430 cm1 in the 4000–2500 cm1. After ing these reactions and favour a degradation mechan-
irradiation this band intensity becomes slightly reduced. ism based on the attack of OH radicals generated by
Furthermore, in the 2000–1000 cm1 region (Fig. 6(2)) Reactions (1) and (4).
physisorbed acid formic molecules may be observed
(1705 cm1) in addition to typical formate bands (1590 3.3.3. Formic acid–H2O2 FTIR studies
and 1357 cm1). The S2O82 ion band at 1289 cm1 is Fig. 7 shows FTIR spectra from the formic acid
not clearly seen. After the first 10 min of irradiation the interaction with the catalysts in the presence of H2O2
physisorbed formic band (1705 cm1) disappears and in the 2000–1000 cm1 region. Since bands from
that from sulphate ion increases. Formate and S2O82 hydroxyl groups are not well defined this region is
ion band intensity are slightly reduced at larger reaction not shown.
times. In this case, Cu oxides may be also reacting with
photogenerated electrons to enhance the yield of SO4 3.3.3.1. Bare-TiO2 þ formic acid þ H2O2. Fig. 7(1)
ions. The high H-bounded hydroxyl concentration on shows the formic acid–bare-TiO2 interaction spectrum
the catalyst surface may enhance their interactions with between 2000 and 1000 cm1. In the before irradiation
S2O82 ions promoting Reaction (4) and the formation (t ¼ 0) spectrum bands at 1705 and 1213 cm1 are
of radicals by means of Reaction (1). The fact that attributed to physisorbed formic acid, and bands at
formate vibration band is not shifted may indicate that 1590, 1389 and 1357 cm1 are typical from formate.
the interaction is only taking place with Ti atoms. During the first 20 min of irradiation formate bands
Probably, this is why Reactions (12) and (13) are not become smaller, and later new bands attributed to
taking place. carbonate appear (1510 and 1428 cm1). After
Results from this section suggest that formic acid 30 min of irradiation these bands become slightly
degradation by bare-TiO2 and Pd–TiO2 in the presence increased. No subsequent modifications were detected.
of S2O82 ions, may be mainly controlled by the acid During the first minutes of irradiation formates may
reaction with holes or SO4 radicals (Reactions (12) be degraded by OH radicals generated by Reactions
Fig. 7. FTIR study from the formic acid þ H2 O2 interaction and evolution under irradiation in the 2000–1000 cm1 region with TiO2 (1), Pd–
TiO2 (2) and Cu–TiO2 (3).
70 J. Araña et al. / Applied Surface Science 239 (2004) 60–71
(1) and (2). However, also H2O2 could be reacting with by the presence or absence of certain dopants, H2O2 or
holes to give O2 molecules which are able to produce S2O82 ions.
carbonates (Reaction (14): From the numerous and complex processes
H2 O2 þ 2hþ ! O2 þ 2Hþ (15) observed it has been determined that:
O2 þ e ! O2
(16) The formic acid interaction with the catalyst surface
modifies the surfacial hydroxylic group distribution
This may explain why this catalyst shows a slightly
by different ways depending on the presence of
worse behaviour in the presence of H2O2 in comparison
H2O2 or S2O82. This determines the catalytic
with that obtained in its absence (Fig. 1(1) and (3)).
degradation efficiency.
The formic degradation by OH radicals seems to
3.3.3.2. Pd–TiO2 þ formic acid þ H2O2. Fig. 7(2)
be directly related with the sufacial concentration of
shows the spectra from the acid interaction with
H-bounded hydroxyl groups.
PdTiO2 þ H2 O2 , before and after irradiation in
The simultaneous formate bonding to Ti and Pd or
the 2000–1000 cm1 region. In these spectra new
Cu atoms in each case, may favour the formic acid
bands at 1687, 1479 and 1141 cm1 are obtained in
degradation by the organic reaction with holes.
addition to those from formates and carbonates.
Pd and Cu oxide deposits on catalyst particles act as
In this case, Pd oxides may scavenger the photo-
receptors and transmitters of electrons photogener-
generated electrons thus avoiding their reaction with
ated by TiO2.
H2O2 molecules. The reaction of the latter with the
The combination of catalyst doping (i.e. Cu–TiO2)
holes (15) will produce O2 which gives carbonates
with the addition of oxidising compounds notably
(Reaction (14)). Formaldehyde–methanol intermedi-
improves the bare-TiO2 photocatalytic efficiency.
ate species (bands at 1687, 1479 and 1141 cm1)
would be generated by the same way as that in
experiments with only formic acid. These processes Acknowledgements
may explain this catalyst low activity (Fig. 1(3)).
We are grateful to the Spanish Ministry of Science
3.3.3.3. Cu–TiO2 þ formic acid þ H2O2. Spectra and Technology for providing research funding
from these experiments are shown in Fig. 7(3). In (BQU2001-3872-CO2-02 and programa Ramón y
the 2000–1000 cm1 region of the before spectrum Cajal 2003) and to the Education Council of the
bands from formates are very short compared with Canarian Regional Government (Consejerı́a de Edu-
those from adsorbed water (1630 cm1) and quickly cación del Gobierno Autónomo de Canarias) for the
disappear under irradiation. project ref. PI2001/131.
Results from this section seem to indicate that in the
presence of H2O2 formic acid degradation by bare-
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