Journal of Natural Gas Chemistry 16(2007)217–226

Review

Chemical Reduction of CO2 to Different Products during

Photo Catalytic Reaction on TiO2 under Diverse
Conditions: an Overview

G. R. Dey∗
Radiation and Photochemistry Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085, India

[ Manuscript received May 29, 2007; revised July 4, 2007 ]

Abstract: The chemical reduction of CO2 remains G. R. Dey was born in 1962 at
a challenge with respect to the reversal of the oxidative Nuagram, Jharkhand (India). He
received his Ph.D. degree in 1995
degradation of any organic materials. The conversion of
from the University of Mumbai. He
CO2 into useful substances is essential in developing al- has worked in 1998 with Prof. O.
ternative fuels and various raw materials for different in- Brede at University of Leipzig,
dustries. This also aids in preventing the continuous rise Germany. During the period of
2000-2001, he was a postdoctoral
in tropospheric temperature due to the green house effect fellow with Prof. M. Mostafavi at
of CO2 . In this article an overview of the growth taken the Laboratoire de Chimie Phy-
place so far in the field of CO2 chemical reduction is pre- sique, Université Paris-Sud,
sented. The discussion comprises of photochemical meth- France. His current interests are
related to free radical chemistry in
ods for the development of different products, viz. CO, the field of radiation chemistry,
CH3 OH and CH4 , through chemical reduction of CO2 . photochemical studies in the presence of semiconductor pho-
This includes the use of photo catalysts, mainly TiO2 , tocatalysts and dielectric barrier discharge. Dr. Dey has pub-
lished more than 50 papers in peer-reviewed journals.
and the role of a hole scavenger (such as 2-propanol) for
this purpose. ners (separately/mixed/metal-doped forms) for this
Key words: CO2 chemical reduction; H2 ; CH4 ; CO; purpose [5,6]. Photo catalytic reactions using TiO2
TiO2 ; hole scavenger; photolysis
surfaces are of importance for their diverse applica-
tions in environment related problems. The prelimi-
1. Introduction nary step in TiO2 photo catalytic oxidation is under-
stood to be the formation of both hydroxyl radicals
1.1. General background
(· OH) and super oxide radical anions (O·−2 ) through
Making use of the photochemical technique to de- the reactions of photo-generated electron-hole, with
stroy organic pollutants through oxidation and to con- solutes present in the system (reactions 1−3) [3]:
TiO2 −−−−→ e− + h+ (electron-hole pair)
hν
vert them to a useful material by reduction is the (1)
best way to undertake pollution related environmen- h+ + H2 O −→ · OH + H+ + TiO2 (2)
tal problems [1−10]. The use of sunlight for such con-
In the presence of air,
version at accelerated rates with the help of a compar-
atively economical and non-toxic photo catalyst such e− + O2 −→ O·−
2 (3)
as TiO2 , etc. is an attractive alternative for refurbish- Therefore, the species, · OH (E o =2.72 V) [11,12],
ment of the deteriorated environment [2−7]. Various a strong oxidant, and O·− o
2 (E =−0.33 V) [13], a weak
photo catalysts, viz. TiO2 , ZnO, SnO2 , WO3 , Fe3 O4 , reductant, are produced during the above mentioned
CdS, and ZnS, have been employed in assorted man- photo catalytic redox processes. Rothenberger and
∗ Corresponding author. Fax: 91-22-25505151; E-mail: grdey@barc.gov.in
218 G. R. Dey/ Journal of Natural Gas Chemistry Vol. 16 No. 3 2007

his colleagues have monitored time-resolved absorp- warming due to the green house effect. Photo cat-
tion spectra of the trapped electron; a transient pro- alytic reduction of CO2 using photo catalysts of semi-
duced after picosecond laser light excitation of col- conductor powders have been studied before [18−31].
loidal TiO2 , and interpreted their results by a stochas- According to the various studies, the CO2 chemi-
tic kinetic model. The trapping of photo-generated cal reduction follows two different reaction pathways,
electrons (conduction band electrons) has been shown viz. CO2 → HCOOH → HCHO → CH3 OH → CH4
as a rapid process occurring within the leading edge of and CO2 → CO → C· → CH2 → CH4 , to yield
the 30-ps laser flash. The recombination coefficient the end product CH4 through different intermedi-
between the trapped electrons and the free holes ates. The former mechanism has been anticipated on
has been determined to be 3.2(±1.4)×10−11 cm3 ·s−1 the basis of the results obtained in condensed media
[14,15]. The generation of · OH (hydroxyl) radicals, a [21,26−36], while the latter has been proposed based
principal oxidant in photo activated TiO2 , has been on the findings in photo catalytic reduction of high
supported from the formation of hydroxylated in- pressure CO2 using TiO2 photo catalyst as a suspen-
termediates during the photo catalytic degradation sion in a 2-propanol solution, and also on electrolytic
of halogenated aromatic compounds. In addition, reduction of CO2 [9,23,37]. Therefore, the reaction
EPR studies have also confirmed the existence of hy- pathways understood for such a conversion are not
droxyl and hydro-peroxy radicals in aqueous solutions specific and depend mainly on the reaction condi-
of light-illuminated TiO2 [5,16,17]. In the absence tions. As of today there is a good debate about the
of oxygen, the · OH radical and e− having divergent reaction pathways through which the chemical reduc-
properties are the reactive species generated on the tion of CO2 executes.
photolysis of suspended TiO2 in an aqueous medium
[9,16,17]. In the presence of an · OH or h+ scavenger, it 1.3. 2-Propanol as a hole scavenger
is possible to convert a TiO2 suspended aqueous sys-
tem into a system with a reducing condition; whereas The use of 2-propanol as a hole scavenger in the
the system exhibits an oxidizing condition when a chemical reduction of CO2 is very few. However,
scavenger of the photo-generated e− is added. The its oxidation, photodegradation, photo-oxidation, cat-
overall processes are summarized in Figure 1. alytic oxidation, etc. are ample in the literature
[38−49]. Most of these reports deal with the min-
eralization of 2-propanol to CO2 through intermedi-
ate carbonyl compounds (acetone), which depends on
the experimental conditions. The information con-
cerning the formation of hydrocarbons through the
oxidation of alcohols is exceptionally limited in liter-
ature. Recently, the formation of CH4 has been re-
Figure 1. Primary steps in photo catalytic mecha- ported on photolysis of 2-propanol along with other
nism on TiO2 alcohols such as methanol and ethanol in aqueous so-
(1) formation of charge species electron (e− ) and hole (h+ )
lution containing TiO2 photocatalyst as a suspension
by a photon, (2) recombination of e− and h+ , (3) trapping
of a conduction band electron, (4) trapping of a valence band even under aerated or oxygenated conditions [18−20].
hole i.e. formation of surface adsorbed · OH radical in aqueous
system, (5) initiation of reduction reaction by photo-generated 1.4. Hydrogen formation
conduction band electron, (6) initiation of oxidative pathway by
photo-generated valence band hole i.e. mineralization pathway
The generation of H2 , a photolysis product
through the photo-catalytic effect of semiconductor
1.2. CO2 conversion in the presence of water is well known [10,50,51]. In
other words, this phenomenon is recognized as a water
Conversion of CO2 into useful materials, mainly splitting reaction. During the electro-photo catalytic
CH4 and/or other inorganic and organic substances process, H2 evolves usually at the counter electrode
such as CO, HCOOH, HCHO, CH3 OH, etc, is of (Pt) due to the participation of photo-generated e−
importance for the development of alternative fuel [10,50] whereas O2 generates at the surface of TiO2
sources or various raw materials for different indus- (acting as another electrode). The reactions (4−7)
tries. This conversion also assists in preventing global taking place at both of the electrodes [50] during the
 Journal of Natural Gas Chemistry Vol. 16 No. 3 2007 219

photo catalytic process are shown below: 175 nm and reaches a maximum value around 145 nm.
At the TiO2 electrode, The absorption band is more diffused with a low ab-
sorption coefficient value (∼15 cm−1 ) [52]. However,
2TiO2 −−−−−→ 2e− + 2h+ (similar to reaction 1)
2hν
being a linear molecule, CO2 is infrared active due to
(4) some of its vibrations, which produce an oscillating
dipole. There are two different kinds of IR active vi-
2h+ + H2 O −→ 1/2O2 + 2H+ + 2h (h = TiO2 )
(5) brations in the molecule, the stretching and bending
At the Pt electrode, (two each) modes, making a total of 4 (3n-5, where
n represents the number of atoms) types of vibra-
2e− + 2H+ −→ H2 (6) tions. A symmetrical stretching vibration does not
The overall reaction, produce any change in the dipole moment of the mole-
TiO
H2 O + 2hν −−−−2→ 1/2O2 + H2 cule and hence is inactive in the IR spectrum, whereas
(7) the asymmetrical stretching vibration causes active-
(water splitting reaction)
ness of the molecule, ensuing infrared spectrum in the
Similarly, a reaction mechanism has been pro- 2349 cm−1 region. The deformation vibrations (two
posed for H2 formation during the photolysis of bending vibrations) of CO2 having identical frequen-
methanol-water (ratio 50:50) systems containing Pt, cies are said to be degenerated and appear at the same
Pd, RuO2 or rhodium complex-TiO2 mixed photo region with doubly degenerated 667 cm−1 [1,53,54].
catalysts through reactions (8−10) [51]. Under this The heat of formation of CO2 from its constituent
study, photo-generated e− in the conduction band of atoms is 336 kcal/mol [55] and the electron affinity
the particle reduces protons in the solution resulting is −0.6±0.2 eV [56], which are useful in understand-
in additional H2 formation through reaction (6) [51]. ing the reduction processes shown below in different
2hν, Cat
equations through various steps.
CH3 OH −−−−−−−→ HCHO + H2 (8)
CO2 (aq) + 2H+ + 2e− −→ HCOOH (11)
HCOOH + 2H+ + 2e− −→ HCHO + H2 O (12)
2hν, Cat
HCHO + H2 O −−−−−−−→ HCOOH + H2 (9)
HCHO + 2H+ + 2e− −→ CH3 OH (13)
CH3 OH + 2H+ + 2e− −→ CH4 + H2 O (14)
2hν, Cat
HCOOH −−−−−−−→ CO2 + H2 (10)
From a thermodynamic perspective, to transform
Where ‘hν’ and ‘Cat’ represent the photo-light one mole of CO2 into one mole of HCOOH or HCHO
and the semiconductor catalyst, respectively. or CH3 OH or CH4 requires 2 or 4 or 6 or 8 electrons.
The formations of HCHO, HCOOH and CO2 (ox- The above equations (11−14) represent the reactions
idation products of methanol) have been observed due for the formation of all these products [21,34].
to the hole/photochemical reaction with methanol. The UV-VIS absorption spectra of CO2 [1,52] and
In this article, we have tried to summarize the 0.5 M 2-propanol in aqueous solution [19] suggest that
growth in the field of CO2 chemical reduction for the absorption at
300 nm due to both CO2 and 2-
the development of various useful products, viz. CO, propanol is negligible. As a result, the photochemical
HCHO, HCOOH, CH3 OH and CH4 , through photo- changes such as excitation, decomposition, degrada-
chemical means. This helps in preventing the rise tion, etc of both CO2 and 2-propanol without TiO2
in tropospheric temperature due to the green house are nil. This fact has been well established after ex-
effect. The overview presents mainly the use of TiO2 ecuting appropriate blank photolysis experiments on
as a photo catalyst and a hole scavenger (such as CO2 -purged system with and without 2-propanol in
2-propanol) for this purpose. aqueous solutions separately in the absence of TiO2
photo catalyst [18−20].
2. Discussion
2.2. Signif icance of photo light and the amount
2.1. Specif icity of CO2 of TiO2 on CO2 reduction

Carbon dioxide does not show any absorption in The amount of TiO2 used in photo catalytic stud-
the UV-VIS regions. The absorption spectrum of ies plays a crucial role in getting efficient changes in
CO2 exhibits a gradual increase in absorption beyond the reaction-product yield. Mostly, 0.1%−2% w/v
220 G. R. Dey/ Journal of Natural Gas Chemistry Vol. 16 No. 3 2007

of TiO2 has been used for such studies [18−20, 23, irradiation on single crystal TiO2 (100) and TiO2
26,33]. Recent studies indicate that 0.1% w/v TiO2 as (110) surfaces separately. The formations of CH4 and
suspension is adequate for the generation of maximum CH3 OH have been noticed in the gas phase while us-
amount of CH4 , a photolytic product of CO2 reduc- ing a TiO2 (100) surface, while only CH3 OH with
tion. Under this study, the minimum required amount a low yield has been observed on TiO2 (110) af-
of TiO2 to achieve its maximum efficiency with re- ter photo-irradiation of a mixture of CO2 and H2 O
spect to CH4 generation due to photochemical reduc- [37,61].
tion of CO2 has been reported to be
0.05% w/v [20]. Methane with a low yield has been noticed dur-
Polychromic light sources, such as Xe arc lamps, ing photo catalytic reduction of CO2 over TiO2 sus-
medium pressure mercury lamps and black light pended in an aqueous system [32]. Under this study,
bulbs, have been used in most of the photolysis ex- CH4 yield is higher on metal-doped TiO2 as compared
periments in the presence of a semiconductor photo to the pure TiO2 system. In a Pd doped TiO2 sys-
catalyst. In these systems, the quantum efficiency or tem, the CH4 yield has been reported to be the highest
photonic efficiency cannot be calculated accurately amongst the other metal-doped TiO2 (viz. Rh, Pt or
due to scattering/reflection of incident light by sus- Au) photo catalysts. However, a substantial amount
pended semiconductor photo catalyst particles [57]. of acetic acid (CH3 COOH) has been produced when
Interests in CO2 chemical reduction have been Cu-TiO2 and Ru-TiO2 photo catalysts were used in
growing owing to its potential use as C1 source, the photolysis experiments [32].
the increase of its concentration in air and CH3 OH, HCHO and a trace of HCOOH in liquid
efforts to mimic photosynthetic carbon assimila- phase and CO in the gas phase have been reported
tion [58,59]. Photo catalytic reduction of CO2 as products during photo catalytic reduction of CO2
on TiO2 semiconductor has been undertaken pre- on TiO2 suspension in water containing copper pow-
viously [19,20,23,24,26,33,36,60] for producing afore- der [26]. During the study, the generation of Cu (II)
mentioned various products. Some important results ions takes place through the oxidation of copper metal
are summarized below. by photo-generated holes. Low yield of CH4 has been
observed after a long illumination in KHCO3 contain-
2.3. Ef fects of dif ferent forms & surfaces of ing system. In this system, the matrix is more con-
photo catalyst structive for reduction due to the rapid transfer of
the excited electrons to the copper particles; as a re-
Using different forms of TiO2 (highly dispersed, sult the separation between holes and electrons has
anchored and finely powdered), Hirano and co- been enhanced. In this way the copper metal plays an
workers have studied the photo catalytic reduction important role in separating the reduction sites from
of CO2 in the presence of H2 O [26]. The forma- the oxidation sites (h+ ) of semiconductor surfaces on
tion efficiency of photo-reduction products, viz. CH4 , which the oxidation of copper metal by positive holes
CH3 OH and CO, depends on various aspects such as occurs [26].
the proportion of H2 O and CO2 , the type of photo CO originating reactions:
catalyst and the reaction temperature. The increase
in temperature and the ratio of H2 O to CO2 can en- CO2 + e− −→ CO·−
2(ads) (15)
hance catalytic activity; however, the excess of H2 O CO·− −
2(ads) + H + e −→ CO + OH
+ −
(16)
suppresses the reaction rate. A reaction mechanism
CO·− −
2 + CO2 + e −→ CO + CO3
2−
(17)
has been projected as per results observed in ESR
studies for the H· radical, and Ti3+ and CH·3 radical Generation/consumption of Cu(II) ions:
formations at a low temperature (77 K) [37]. It has
Cu + h+ −→ Cu+ + TiO2 (18)
also been proposed that the photo catalytic reduction
of CO2 with H2 O is interrelated with the formation of 2Cu −→ Cu + Cu
+ 2+ (19)
− −
reductive TiO2 surface sites on UV-irradiation and a +
Cu /Cu 2+
+ e /2e −→ Cu (20)
higher surface reactivity of the charge transfer excited
state (Ti3+ -O− )3 * of the tetrahedrally co-ordinated 2.4. Ef fects of CO2 concentration/pressure
TiO2 species formed on its surfaces.
The effect of catalyst surfaces on chemical reduc- Methane yield has been enhanced three times
tion of CO2 is showing its importance during photo- with respect to the dark reaction yield when 1 ml CO2
 Journal of Natural Gas Chemistry Vol. 16 No. 3 2007 221

(pCO2 =0.05 atm) and 12 ml H2 (pH2 =0.05 atm) mix- Reaction of 2-propanol with hole,
ture is photo-irradiated in the presence of Ru loaded
TiO2 (spread over the bottom of a flat pyrex ves-
sel) [60]. In this case, H2 acts as a hydrogen/proton
source. The mechanism suggested for the formation of
CH4 through photo-generated e− and hole reactions
with H2 and CO2 is shown in reactions (21−25).
Reduction of CO2 present as a solute,
During photo-irradiation,
+Ru
4e− + CO2 −−−−→ Ru-C + 2O2− (21)
2H2 + 4h+ −→ 4H+ (22)
4H+ + 2O2− −→ H2 O (23)
Ru-C + 2H2 −→ Ru + CH4 (24)
Whereas in darkness,
(CO2 )ads + 2(H2 )ads −→ Ru-C + 2H2 O (25)
Scheme 1. Mechanism for the formation of CH4
through C· radical
Thus, Ru-C species generated in darkness take
part in methane formation through reaction (24). In liquid CO2 , HCOOH has been reported as
At high pressures CO2 , CH3 COOH, CH3 OH, and a photolysis product in the liquid phase. No any
HCOOH in the liquid phase and CH4 as a major prod- gaseous products were noticed during the experiment.
uct, along with minor yields of ethane (C2 H6 ) and Under this study, CO·−2 generated in liquid CO2 dur-
ethylene (C2 H4 ) in the gas phase, have been observed ing photo-irradiation gets protonated on addition of
on the photolysis of TiO2 suspended in aqueous solu- water, a proton source (used for the extraction of pho-
tions. Under this condition the yield of methane in- tolysis products), and forms subsequently HCOOH
creases with the increase in CO2 pressure. The entire after further reduction [22].
yield of the gaseous products has been increased on
the addition of electrolytes like NaOH into the sys- 2.5. Chemical reduction of in-situ generated
tem. However, the yield of H2 decreases with the CO2
photolysis time. Hence, H2 produced initially due to
photochemical reduction of water has been consumed The ambient such as N2 , air, O2 and CO2 are
either by oxidation with a hole or by the reaction with important for chemical reduction of CO2 [20] in the
transient intermediates of CO2 reduction resulting in presence of 2-propanol. Both commercially available
the formation of hydrocarbons and alcohols [33]. CO2 and CO2 generated in-situ during photo oxida-
In different experiments on high pressure CO2 tion have been used separately for this study. The
systems, CO2 reduction does not produce CH4 in variation of the yields of CH4 in N2 , aerated, O2 and
the absence of any electron donors [23]. However, CO2 purged systems are presented in Table 1 for com-
in the presence of 1.0 mol·dm−3 2-propanol, a hole parison. A higher yield of CH4 has been reported
scavenger/electron donor, formation of methane has both in the aerated and CO2 -saturated systems in
been reported during photo catalytic reduction at contrast to O2 and N2 -purged systems. The presence
high pressure CO2 using suspended TiO2 photo cat- of 0.5 M 2-propanol is enough to scavenge h+ , an ox-
alyst. During photo-irradiation, the increase in CO2 idizing species, and produce subsequently a reducing
pressure enhances the formation of C· (carbon radi- organic radical ((CH3 )2 C· OH) through reaction (28).
cal), an intermediate detected in ESR measurements This amount (0.5 M 2-propanol) is adequate for a high
[23]. A proposed reaction mechanism is shown in the yield of CH4 during CO2 chemical reduction [20]. In
scheme (scheme 1) below to explain how the formation the N2 -purged system, the absence of oxygen prevents
of the C· radical takes place during the CO2 metha- the mineralization of 2-propanol to CO2 to a greater
nation process. extent. In other words, under this condition a small
hν amount of CO2 has been produced during photolysis
TiO2 −−−→ e− (Ti3+ ) + h+ (26)
(see Table 1). The mineralization of alcohols has been
hν
(Ti4+ − O2− ) −−−→ (Ti3+ − O− )∗ discussed earlier [38,62] and the process is enhanced
(27)
(Excited state species) with the modification of the photo catalyst. Thus,
222 G. R. Dey/ Journal of Natural Gas Chemistry Vol. 16 No. 3 2007

CO2 generated in-situ, due to the mineralization of In the oxygenated system, a part of e− reacts with
alcohol on the surface of the semiconductor, performs O2 through reaction (3) rather than with CO2 , (re-
an important role in the formation of CH4 under aer- action (30)), resulting in a lower yield of CH4 . In
ated conditions. In the case of the oxygenated system the aerated system, although the CO2 yield is lower
(∼100% oxygen), where the concentration of oxygen than that in the oxygenated system, relatively more
is ∼5 times higher than in the aerated system (20% e− is available for the photo-reduction of CO2 . The
oxygen), the CH4 yield is lower (see Table 1). This surface adsorption of CO2 is higher than that of O2
supports the noteworthy argument regarding the in- and the surface-adsorbed CO2 has a better chance of
volvement of photo-generated e− in CH4 formation. getting reduced to CH4 . Nevertheless, it is difficult
Hence, the yield of methane depends on the concen- to distinguish the surface-adsorbed CO2 from the in-
trations of both oxygen and the hole scavenger (2- situ generated CO2 at the surface of a photo cat-
propanol). The overall process has been explained alyst. In another set of experiments, the reduction
through the following mechanism [20]: of CH3 OH does not direct to the formation of CH4 ,
Organic radical (OR) + O2 −→ CO2 suggesting that the pathway for its formation is not
(29)
(mineralisation reaction) through the methanol route under this experimental
CO2 + e− −→ CH4 (methanation) (30) condition [20].

Table 1. The relative yields of CH4 , CO2 , CO and H2 (in µl) obtained after 10 h photolysis in dif ferent
ambient condition containing 0.1% w/v TiO2 suspension in water with and without 0.5 M 2-propanol
Photolytic yields in without or with 2-propanol
Ambient Without 2-propanol with 2-propanol
[CH4 ] CO2 [CO] [H2 ] [CH4 ] CO2 [CO] [H2 ]
Air 0 0 0 0 7.2 660 15.3 4.5
O2 0 0 0 0 5.0 1330 12.7 4.7
N2 0 0 0 2.1 4.2 165 8.0 27.1
N2 O 0 0 0 0 1.3 − 5.7 4.5
CO2 1.8 − 3.1 17.9 6.9 − 13.9 3.0

As discussed above, in a CO2 -purged TiO2 photo- very fast in condensed media (· OH+(CH3 )2 CHOH→
catalyst suspended aqueous system, the ambient is (CH3 )2 C· OH+H2 O; kbimol =1.9×109 M−1 ·s−1 ) [63]).
vital in controlling the system for the production of The high concentration of 2-propanol (0.5 M) makes
different photolytic products (CO, CH4 and H2 , etc.), the system more favorable under a reducing condi-
as shown in Table 1 for comparison. H2 yields are tion by rapid scavenging · OH [61] and subsequently
different in two different systems (with and without allows photo-generated e− to react with H+ through
2-propanol containing 0.1% TiO2 suspension in water) reaction (6) to yield more H2 . Similar mechanism
at different ambient conditions (Table 1). The yield has been explained above for CH4 formation during
of H2 is higher in the N2 -purged system containing the chemical reduction of CO2 . Due to the negligi-
0.5 M 2-propanol after 10 h photolysis as compared to ble reaction between e− and 2-propanol, the loss of
the system without 2-propanol. There is a significant e− is nil because of the 2-propanol. Low yield of H2
difference in H2 generation rates between these two in the system without 2-propanol has been explained
N2 -purged systems (without and with 2-propanol, due to the recombination reaction (reverse of reaction
the rates are 0.226 µl·h−1 and 5.8 µl·h−1 , respec- (1)), which is more favorable in the absence of any
tively) [18]. This has happened due to the presence of added hole scavenger. This agrees well with the ear-
2-propanol, a hole scavenger which resists the hole-e− lier views about the necessity of a hole scavenger for
recombination reaction (reverse of reaction (1) which the enhancement of the reduction reaction and the
is usually very fast and completed within 10−100 ns) product yields [20,23,64]. Also in the oxygen contain-
[5,57] by scavenging holes. Holes (as discussed above) ing systems, viz. both in the aerated and O2 -purged
are considered as · OH radicals or surface attached systems, H2 was not observed in the absence of 2-
·
OH radicals generated on TiO2 photolysis (reac- propanol, in contrast to a low H2 yields (∼5 µl after
tion (2) and Figure 1) under an aqueous matrix 10 h photolysis as listed in Table 1) in its presence
[16,17]. The · OH radical reaction with 2-propanol is [18]. In this case the O2 present in both the aerated
 Journal of Natural Gas Chemistry Vol. 16 No. 3 2007 223

and O2 -purged systems ranging from 0.2 to 1.2 mM either CO2 or both CO2 and 2-propanol itself, or its
is quite enough to scavenge the photo-generated e− photo degradation products, in addition to H2 regen-
through reaction (3), preventing reaction (6) to con- eration through the H-H recombination reaction.
tribute in the H2 formation. In this way, O2 present As discussed above, the methane yield decreases
in these systems acts as an e− scavenger. N2 O is when N2 or air or O2 is replaced with N2 O in 2-
also a well-known electron scavenger [63,65,66]. Re- propanol containing aqueous TiO2 suspended sys-
cently, we have observed that the methane yield de- tems [19]. This shows that the involvement of photo-
creases considerably, meanwhile changing the ambient generated e− in product (CH4 ) formation under photo
air or O2 or N2 or CO2 to N2 O [19]. The H2 yield catalytic reduction of CO2 . Methane formation in
is nil in the N2 O-purged system, but in the presence photo-irradiated and aerated/O2 -purged system con-
of 2-propanol its yield is comparable with other O2 taining 2-propanol has been explained previously [19].
containing (oxygenated and aerated) systems (Table In brief, the generation of methane via methyl rad-
1). This suggests that even in the presence of 0.5 M ical (CH·3 ) formation has been ruled out because:
2-propanol (having an efficient h+ scavenging proper- 1) Methane yield is higher in the aerated system
ties), a fraction of the photo-generated e− takes part in which CH·3 , if formed, should produce a perox-
in the reduction reaction, resulting in a low yield of H2 ymethyl radical (CH3 O·2 ) after its reaction with oxy-
other than its scavenging reaction due to O2 or N2 O. gen, and subsequently undergo mineralization to CO2
As mentioned above, H2 formation in the presence [10]. 2) As discussed above, 2-propanol has negligi-
of methanol is proceeding through photo catalytic re- ble absorbance at lights of
300 nm. Hence, the
actions of methanol (reactions (8−10)) [51]. In the experimental light, i.e. 350±50 nm, is not favoring
presence of 2-propanol, an alcohol like methanol, if CH·3 generation through direct photo-dissociation.
H2 generation is taking place following a similar reac- 3) In the N2 O-purged system the yield of CH4 de-
tion mechanism, then its yield in N2 O-purged system creases. 4) CH·3 , if generated, should react either
should not decrease. It should either remain the same with water or with alcohol present in the system to
or lead to a higher yield due to the conversion of the generate CH4 through the H-abstraction reaction.
e− into the · OH radical through the N2 O-e− reac- Since the generation of the CH·3 radical has been
tion (e− +N2 O→N2 +O·− ; kbimol =9.1×109 M−1 ·s−1 ) studied thoroughly in aqueous solution, therefore, its
and (O− +H2 O→OH− +· OH; k=9.4×107 s−1 ) [62]. reaction with water is either very slow or negligible
Hence, in this case, the H2 generation also takes [68,69]. On the other hand, H-abstraction reactions
place through the reduction of proton by the photo- of CH·3 with alcohols are very slow [19,68,69]. The
generated e− , not through the photochemical re- low reaction rate constant for CH·3 with 2-propanol,
actions (8−10). H2 generation has also been re- 3.4×103 dm3 ·mol−1 ·s−1 [68,69], is not favoring H-
ported in photo catalytic reduction of CO2 on TiO2 atom abstraction under the experimental condition
(0.5 g/80 ml) suspension in aqueous solution contain- (especially in the aerated/oxygenated system) to gen-
ing 4 M methanol, and its yield enhances on metal erate methane. Again, the possibility of CH4 forma-
powder addition [67]. The decrease in H2 production tion caused by the Photo-Kolbe reaction (the Kolbe
in photo catalytic reduction of CO2 (at high pres- reaction is a decarboxylation reaction of carboxylic
sure CO2 ) in the presence of 0.2 N NaOH has been acids, yielding hydrocarbons) has been ruled out,
explained previously due to the formation of hydro- because in this case, the CH·3 radical is produced
carbons [33]. The explanations for the decreasing and it undergoes dimerization to produce ethane,
trends of H2 in both the CO2 -purged systems with or abstracts H to yield CH4 , depending on the re-
and without 2-propanol are as follows: 1) in the ab- action conditions. The most significant part of the
sence of 2-propanol, H2 is consumed mainly for the Photo-Kolbe reaction is the ambient condition. Ac-
generation of other photo catalytic products such as cording to Kraeutler and Bard, the system should be
methane, etc. The yield of CH4 increases with pho- either in inert (helium atmosphere) or under high vac-
tolysis time under an identical condition [20]. 2) uum conditions [70−72]. Nevertheless, in the chem-
In systems both with and without 2-propanol, the ical reduction of CO2 in the presence of 2-propanol,
H2 yield reduces through h+ or · OH radical reac- different ambient, including the N2 -purged (an inert
tions (· OH+H2 →H2 O+H; kbimol =3.4×107 M−1 ·s−1 ) atmospheric condition) system, has been employed.
[63] and the generated H atom must be consumed by An interesting observation highlighted is the methane
224 G. R. Dey/ Journal of Natural Gas Chemistry Vol. 16 No. 3 2007

yield,which is higher, when the system contains air mediate (CO2 →CO→C· →CH2 →CH4 ). That is why
and oxygen, than the inert atmosphere (N2 in this the CO yield is higher than the end product CH4 (see
case). According to Kraeutler and Bard [71,72], traces Table 1). The generations of different products in di-
of oxygen suppress the hydrocarbon yield. Therefore, verse ambient conditions are explained by reactions
methane generation is not through the decarboxyla- (31−41):
tion of carboxylic acids produced as an intermediate In the absence of 2-propanol, and in the deoxy-
during the mineralization of alcohol (2-propanol). It genated system,
is noteworthy to mention here that if CH·3 is gen- 2e− + 2H+ −→ H2 (31)
erated, then a trace of ethane should also be ob-
In the aerated/oxygenated system,
tained in the gas phase. Since the observation is un-
likely, therefore, it is confidently concluded that the e− + O2 −→ O·−
2 (32)
methane is not generated through the CH·3 radical
intermediate under this condition. A very low yield O·−
2 + H3 O −→ HO2 + H2 O
+ (33)
of CH4 has been reported in photo catalytic redox
reaction of methanol in the presence of TiO2 under 2HO2 −→ H2 O2 + O2 (34)
diverse ambient conditions [19,20]. This pointed out In the CO2 -purged system,
that the methanol intermediate generating pathway
(CO2 →HCOOH→HCHO→CH3 OH→CH4 ) is not the e− + CO2 −→ CO·−
2 (35)
CO2 reduction route under this condition.
CO·− −
2 + CO2 + e −→ CO + CO3
2−
(36)
The formation rates [18] and the yields (Table 1)
of CO and CH4 are different in the N2 O-purged 0.5 M CO2 + e− −→ CH4 (via CO intermediate) (37)
2-propanol aqueous solution containing 0.1% TiO2
2CO·−
TiO
2
2 + 2H −→ (COOH)2 −−−−→ 2CO2 + H2
+
suspension. The higher formation rate and the higher
yield of CO, as compared to that of CH4 under identi- (38)
cal condition, indicate that all the CO generated dur- In the presence of 2-propanol,
ing CO2 reduction does not convert to CH4 instantly
[18]. The methane yield in the N2 O-purged system h+ + (CH3 )2 CHOH −→ (CH3 )2 C· OH(OR) + H+
(39)
is quite low as compared to the CO2 -purged, aer-
ated, oxygenated, and N2 -purged systems (see Table 2(CH3 )2 C· OH −→ (CH3 )2 CO + (CH3 )2 CHOH
1) [18,19]. In the CO2 -purged system containing 0.1% (40)
TiO2 suspension in water and containing 2-propanol, [OR represents organic radical]
the yields of CO and CH4 as well as their formation In the oxygenated/aerated system,
rates are higher than those obtained in the system OR + O2 −→ CO2 (mineralisation reaction) (41)
without 2-propanol [18]. CO generation is known pre- During photo catalytic studies on systems con-
viously in TiO2 systems, and also in other different taining 2-propanol, acetone has been observed as
systems, and the yields depend on the reaction condi- a photo catalytic product along with the above-
tion [20,73−75]. The generation of methane in these mentioned products (CO2 , CH4 , CO and H2 ). Or-
systems has been explained previously as due to free ganic radicals (OR) also contribute in the reduction
radical induced reduction of CO2 [18−20]. In the ab- reaction because of their high reduction potential
sence of 2-propanol, the yield of CH4 is less due to the (E o (CH3 )·2 COH/(CH3 )2 CO, H+ =−1.7 V) [76], but
prominent recombination reaction (reverse of reaction to a lesser extent due to its other successive decay re-
(1)) and a part of the photo-generated e− is only able actions. The formations of both CO and CH4 support
to react with CO2 , yielding CO and CH4 . In this the previously elucidated mechanism for the metha-
system the generation of CO reveals that it is an in- nation process through CO and C· radical [23,37].
termediate produced during the CO2 photo catalytic
reduction (the only source of carbon in the system) 3. Conclusions
through either the reduction or the photodecomposi-
tion reaction. The former process is more likely since Photo catalytic reduction of CO2 using TiO2 sus-
the latter process does not exist due to the negligible pension in aqueous solutions with and without 2-
absorption of experimental light (
350 nm) by CO2 . propanol as a hole scavenger leads to the formation
Therefore, the reaction route is through the CO inter- of CH4 . The yields of both CO and CH4 are higher
 Journal of Natural Gas Chemistry Vol. 16 No. 3 2007 225

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