Energy-efcient regeneration of ketones from oximes using semiconductor

photocatalysts
K. Muthu, K. Selvam, B. Krishnakumar, M. Swaminathan*
Department of Chemistry, Annamalai University, Annamalainagar 608002, India
1. Introduction
One of the main principles of green chemistry is to replace
environmentally hazardous processes by energy-efcient routes.
The semiconductor photocatalysts work as environmentally
harmonious catalysts at room temperature in a clean manner
using light as an energy source in contrast to resource-burning
energy sources. The application of photocatalytic systems converts
inexpensive solar energy into chemical energy [15].
Oximes of carbonyl compounds are important, because of
their use in the purication and characterization of carbonyl
compounds and also their use in organic synthesis [68]. So far, a
large number of methods have been developed for the
regeneration of carbonyl compounds from oximes [915].
However most of these methods suffer some disadvantages
such as long reaction times, higher reux temperatures,
difculties in isolation of products, low yields etc. Deoximation
of ketoximes [16] and aldoximes [17] on irradiated TiO
2
using UV
light has been reported. But more than 2 h of irradiation time was
used and no study was carried out with different catalysts using
UV and solar light. Ag-doped TiO
2
has been developed and
characterized [18] in our laboratory. This Ag-TiO
2
was found to
be more efcient, particularly in solar light, for the toxic chemical
degradation and in organic synthesis [19]. This stimulated our
interest to test the efciency of this nano Ag-TiO
2
and other
semiconductor oxides in the deoximation of ketoximes.
Photocatalysis is a non-selective process in aqueous medium,
since the electrons and holes react with H
2
O and oxygen,
producing hydroxyl radicals which oxidize the compounds non-
selectively. But in acetonitrile, photocatalysis is found to be
selective [1]. In this paper we report the deoximation of some
ketoximes using TiO
2
(anatase), TiO
2
-P25 and Ag-TiO
2
photo-
catalysts in acetonitrile medium.
2. Experimental
2.1. Materials and methods
Benzophenone, 4-chlorobenzophenone, 4-methylbenzophe-
none, acetophenone, 4-hydroxyacetophenone, nano-sized ZnO
(Aldrich Chemicals), hydroxylamine hydrochloride, sodium acet-
ate (SD Fine Chemicals) and cyclohexanone (Merck) were used as
received. A gift sample of TiO
2
-P25 was obtained from Degussa
(Germany). It is an 80:20 mixture of anatase and rutile. It has a
particle size of 30 nm and a BET specic area of 56 m
2
g
1
. ZnO
(Merck) has a particle size of 0.14 mm and surface area
12.16 m
2
g
1
.
Titanium dioxide (anatase) with a BET surface area of
21.53 m
2
g
1
and perchloric acid were obtained from Merck.
Silver nitrate (analytical grade) from Merck was used as silver
Applied Catalysis A: General 358 (2009) 259263
A R T I C L E I N F O
Article history:
Received 8 January 2009
Received in revised form 11 February 2009
Accepted 15 February 2009
Available online 27 February 2009
Keywords:
Photocatalysis
Titanium dioxide
UV-A light
Ag-TiO
2
Deoximation
Solar light
A B S T R A C T
The regeneration of carbonyl compounds from ketoximes on various semiconductor oxides and Ag-
doped TiO
2
using solar and UV-A light was investigated. The order of activities of the photocatalysts are
found to be TiO
2
(anatase) > Ag-TiO
2
> TiO
2
-P25 > ZnO (nano) > V
2
O
5
> ZnO > CdS > Fe
2
O
3
> SnO
2
>
ZnS. The mechanism of photocatalysis is proposed. The deoximation was efcient and almost complete
in 30 min with the catalysts TiO
2
(anatase), TiO
2
-P25 and Ag-TiO
2
both in UV-A and solar light.
2009 Elsevier B.V. All rights reserved.
* Corresponding author. Tel.: +91 4144 225072; fax: +91 4144 225072.
E-mail address: chemres50@gmail.com (M. Swaminathan).
Contents lists available at ScienceDirect
Applied Catalysis A: General
j our nal homepage: www. el sevi er . com/ l ocat e/ apcat a
0926-860X/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2009.02.023
source for the preparation of Ag-doped TiO
2
photocatalysts. The
other chemicals CdS, Al
2
O
3
, V
2
O
5
, SnO
2
, Fe
2
O
3
, ZnS were obtained
from Sd Fine Chemicals and used as received. Other organic
solvents of LR grade were distilled prior to use. The Ag-doped TiO
2
(anatase) catalyst was prepared by photoreducing Ag
+
ions to Ag
metal on the TiO
2
surface as per the procedure reported earlier
[20]. The Ag-TiO
2
catalyst used in this study has the Ag
+
concentration of 1.5% atomic percentage in relation to TiO
2
. The
oximes of the corresponding ketones were prepared as per the
literature procedure [21].
2.2. Apparatus
A Heber multilamp photoreactor model HML-MP 88 (Fig. 1) was
used for photoreactions. This model consists of eight medium
pressure mercury vapour lamps (8 W) set in parallel and emitting
365 nm wavelength. It has a reaction chamber with specially
designedreectorsmadeof highlypolishedaluminiumandabuilt-in
cooling fanat the bottom. It is providedwitha magnetic stirrer at the
centre. An open borosilicate glass tube of 50 mL capacity, 40 cm
height and 20 mm diameter was used as a reaction vessel with the
total light exposure length of 330 mm. The irradiation was carried
out using four lamps in open-air condition. The UVpower of the four
lamps is 32 Wandtheir intensityis I = 1.381 10
6
einstein L
1
s
1
.
The solution with catalyst was continuously aerated by a pump to
provide oxygen and to mix the reaction solution completely.
For GC analysis, a Perkin-Elmer GC-9000 with a capillary
column of DB-5 and a ame ionization detector was used.
For solar experiments, all photocatalytic deoximations have
been carried out under similar conditions on sunny days of
different months of 2007 between 11 AM and 2 PM. During the
illumination time, the volatility of the solvent was compensated
periodically. The intensity of solar light was measured using a LT
Lutron LX-10/A digital Lux meter. The intensity was found to be
1100 100 lux and was nearly constant during the experiments.
2.3. Deoximation procedure
The photocatalytic deoximation was carried out using the
following procedure. Appropriate amounts of (50 mg) catalyst,
100 mg of oxime and 25 mL of acetonitrile (CH
3
CN) were taken in
long reaction tubes. Each mixture was irradiated. The progress of
the deoximation was monitored using TLC. After completion of
each reaction, the catalyst was removed by centrifugation and
ltration and the ltrate was subjected to GC analysis for the
determination of the yield. The ketone formation was also
conrmed by comparing the GC and FT-IR spectrum of the
products with those of ketone.
3. Results and discussion
A preliminary study on the photocatalytic oxidation of
benzophenone oxime in acetonitrile by TiO
2
-P25 in the presence
of air was carried out; the results are given in Fig. 2. No product is
formed on irradiation without catalyst. About 97% conversion of
benzophenone oxime to benzophenone was observed for 30 min of
irradiation with TiO
2
-P25. To nd out the optimum conditions for
maximum efciency of photocatalytic deoximation we carried out
various experiments.
3.1. Photocatalysis with different solvents
The deoximation of benzophenone oxime on TiO
2
-P25 with UV
light was investigated in a number of solvents; the results are given
in Table 1. The percentages of benzophenone formed are 99.6, 94.1,
91.3, 88.8, 83.2, 80.6 and 46.0 in dichloromethane, acetonitrile,
carbon tetrachloride, benzene, chloroform, dichloroethane and
nitrobenzene respectively. The variations may be due to the
differences in adsorption of oxime on titania and the differences of
dissolved oxygen content in these solvents. The variation of
product formation with the solvent may also be due to the band
bending at the semiconductor solution interface [22]. In the
alcoholic solvents like methanol, ethanol and isopropyl alcohol,
Fig. 1. Schematic diagram of photoreactor.
Fig. 2. Percentage of benzophenone formed under different conditions. Photolysis of
a solution of benzophenone oxime (100 mg in 25 mL of acetonitrile) (A) with UV
light (l = 365 nm) in the absence of TiO
2
-P25, (B) with TiO
2
-P25 in the absence of
light and (C) with TiO
2
-P25 under irradiation of UV light.
Table 1
Percentage of benzophenone formed in various solvents.
Solvents Percentage of benzophenone
Dichloromethane 99.6
Acetonitrile 94.1
Carbon tetrachloride 91.3
Benzene 88.8
Chloroform 83.2
Dichloroethane 80.6
Nitrobenzene 46.0
[Benzophenone oxime] = 100 mg/25 mL; TiO
2
-P25 = 50 mg/25 mL; time of irradia-
tion = 30 min; airow rate = 8.1 mL s
1
; I = 1.381 10
6
einstein L
1
s
1
.
K. Muthu et al. / Applied Catalysis A: General 358 (2009) 259263 260
benzophenone was not formed as the solvents underwent
oxidation.
Among these solvents, dichloromethane and acetonitrile are
most efcient and nitrobenzene is least efcient for conversion of
oxime to ketone. Nitrobenzene undergoes reduction by TiO
2
and
this decreases the activity of the catalyst. Dichloromethane, being a
low boiling solvent, is highly volatile at room temperature.
Acetonitrile is less volatile and is inert to light radiation; hence,
we used acetonitrile solvent for deoximation processes.
3.2. Inuence of catalyst and oxime concentrations
Keeping all other factors constant, we investigated the inuence
of the amount of TiO
2
-P25 on the photooxidation. For the same
concentration of benzophenone oxime, the amount of catalyst was
varied from25 to 150 mg. An increase in the percentage conversion
from 85 to 94.1% was observed with increasing amount of catalyst
from 25 to 50 mg/25 mL. Above 50 mg of the catalyst there is no
change in the conversion efciency. The percentage of product
formation in relation to amount of TiO
2
-P25 is presented in Fig. 3.
This indicates that the saturation is attained with 50 mg of TiO
2
-
P25. We had also carried out studies about the effect of catalyst
loading with TiO
2
anatase and Ag-TiO
2
on the deoximation of
benzophenone oxime. We found that the maximumconversion for
TiO
2
anatase (97%) and Ag-TiO
2
(95%) occurred even with 25 mg/
25 mL and it is nearly constant up to 150 mg/25 mL of the catalyst.
Therefore, the optimum concentration of catalyst for the photo-
catalytic oxidation of 100 mg/25 mL of oxime is taken as 50 mg.
The effect of different initial concentrations of benzophenone
oxime on photocatalytic deoximation was studied under similar
conditions. The amount of benzophenone formed decreases with
the increase of initial concentration of benzophenone oxime
(Table 2). Though the conversion efciency is maximum (99.4) at
50 mg/25 mL, there is no signicant decrease in efciency for
100 mg/25 mL of oxime (94.1). Hence we had taken 100 mg/25 mL
of oxime for further study.
3.3. Effect of various photocatalysts
The deoximation of benzophenone oxime with UV (365 nm)
light using various photocatalysts was carried out under identical
conditions; the results are given in Table 3. The order of activities of
the photocatalysts are TiO
2
(anatase) (band gap energy, E
g
3.2 eV) > Ag-TiO
2
(3.2 eV) > TiO
2
-P25 (3.2 eV) > ZnO (nano)
(3.2 eV) > V
2
O
5
(2.8 eV) > ZnO (3.2 eV) > CdS (2.4 eV) > Fe
2
O
3
(2.2 eV) > SnO
2
(3.6 eV) > ZnS (3.6 eV). ZnS and SnO
2
have higher
band gap energies (3.6 eV) and so the irradiation by 365 nmlight is
not efcient. Though CdS (2.4 eV), V
2
O
5
(2.8 eV) and Fe
2
O
3
(2.2 eV)
have lower band gap energies when compared to TiO
2
-P25, the
electronhole recombination may be faster and hence they are less
efcient. The lower efciencies of ZnOnano and ZnOmay be due to
that the BET surface areas, 15 and 12.16 m
2
g
1
, which are smaller
than that of TiO
2
-P25 (56 m
2
g
1
). Though the BET surface area of
Ag-TiO
2
is around 18 m
2
g
1
[18], this catalyst is efcient because
Ag doping inhibits the electronhole recombination. Furthermore,
Ag-TiO
2
has extended absorption in the visible region [18]. Since
three forms of TiO
2
viz., TiO
2
(anatase), Ag-TiO
2
and TiO
2
-P25, were
more efcient than the other photocatalysts, we had carried out
the deoximation using these three catalysts in acetonitrile under
optimum conditions with UV and solar light.
3.4. Deoximation of various ketoximes with UV light and solar light
The oximes of benzophenone, 4-methylbenzophenone, 4-
chlorobenzophenone, acetophenone, 4-hydroxyacetophenone
and cyclohexanone were irradiated with UV light using TiO
2
(anatase), Ag-TiO
2
, TiO
2
-P25 for 30 min under optimum condi-
tions; the results are shown in Table 4. For all the oximes, the
percentage conversion for 30 min is around 90% and above. TiO
2
(anatase) is slightly more efcient than TiO
2
-P25 and Ag-TiO
2
in
UV light. The photocatalytic deoximation was not effective with 4-
Fig. 3. Percentage of benzophenone formedunder different catalyst concentrations in
acetonitrile. [Benzophenone oxime] = 100 mg/25 mL; time of irradiation = 30 min;
airow rate = 8.1 mL s
1
; I = 1.381 10
6
einstein L
1
s
1
.
Table 2
Effect of [benzophenone oxime] on the photocatalytic conversion in acetonitrile.
Concentration of benzophenone
oxime (mg/25 mL)
Percentage conversion
50 99.4
100 94.1
150 65.0
TiO
2
-P25 = 50 mg/25 mL; time of irradiation = 30 min; airow rate = 8.1 mL s
1
;
I = 1.381 10
6
einstein L
1
s
1
.
Table 3
Effect of various photocatalysts on deoximation of benzophenone oxime in
acetonitrile.
Catalysts Percentage conversion
TiO
2
(anatase) 97.3
Ag-TiO
2
95.9
TiO
2
-P25 94.1
ZnO (nano) 86.9
V
2
O
5
82.3
ZnO 81.7
CdS 78.1
Fe
2
O
3
69.3
SnO
2
65.2
ZnS 61.3
[Benzophenone oxime] = 100 mg/25 mL; catalyst suspended = 50 mg/25 mL; time
of irradiation = 30 min; airow rate = 8.1 mL s
1
; I = 1.381 10
6
einstein L
1
s
1
.
Table 4
Percentage conversion of various ketoximes with different forms of TiO
2
using UV
light in acetonitrile.
Ketoximes TiO
2
(anatase) (%)
TiO
2
-P25 (%) Ag-TiO
2
(%)
Benzophenone oxime 97.3 94.1 95.9
4-Methylbenzophenone oxime 96.1 91.1 94.0
4-Chlorobenzophenone oxime 92.6 90.3 92.0
Acetophenone oxime 96.1 92.1 93.0
Cyclohexanone oxime 99.5 99.5 99.5
[Oxime] = 100 mg/25 mL; catalyst suspended = 50 mg/25 mL; time of irradia-
tion = 30 min; airow rate = 8.1 mL s
1
; I = 1.381 10
6
einstein L
1
s
1
.
K. Muthu et al. / Applied Catalysis A: General 358 (2009) 259263 261
hydroxyacetophenone. This reveals that the presence of a hydroxy
group inhibits the photocatalytic deoximation. Such a hydroxyl
group may react with TiO
2
and thus the deoximation is not
effective. In the case of cyclohexanone oxime (alicyclic ketone
oxime), the conversion efciency is almost 100%. Cyclohexanone
oxime under direct photolysis gives predominately Beckmann-
rearranged product [23]. Hence the semiconductor photocatalysis
offers the best method of deoximation for this oxime. As the dialkyl
ketones are volatile, their oximation and deoximation could not be
carried out at room temperature.
Since the saturation conversion (above 90%) was observed in
30 min for all the three catalysts with different oximes, we had
carried out an experiment to compare the efciencies of these
catalysts. The percentages of conversion of benzophenone oxime
with the catalysts, TiO
2
-P25, TiO
2
anatase and Ag-TiO
2
at different
times of UV irradiation are shown in Fig. 4. A steady increase in
efciency is observed for TiO
2
anatase and TiO
2
-P25. In case of Ag-
TiO
2
, the conversion efciency is very low up to 15 min and then it
increases sharply, reaching a maximum at 30 min of irradiation.
Initially TiO
2
anatase and TiO
2
-P25 are more efcient than Ag-TiO
2
.
But the maximum conversion is attained in 30 min with all the
catalysts.
Generally in photocatalysis, the electrons formed on irradiation
combine with oxygen molecules forming a superoxide ion radical
(O
2

). This radical is mainly responsible for the deoximation. In

case of Ag-TiO
2
, Ag acts as an electron trap. This may be the reason
for the lower efciency of deoximation initially. After some time
the electrons formed may be available for deoximation and then
the conversion efciency increases.
The deoximation of these ve ketoximes were carried out with
solar light under the conditions used for UV light. During the
experiment, the light intensity was almost constant. All the three
catalysts are efcient in the regeneration of carbonyl compounds
from their corresponding oximes (Table 5). The trend observed in
solar light is similar tothe one inUVlight, but insolar light Ag-TiO
2
is
found to be slightly more efcient. This may be due to its increased
absorption of visible light whencompared to TiO
2
anatase and TiO
2
-
P25 [18]. The deoximation of 4-hydroxyacetophenone was not
signicant in solar light also. The reason for this is discussed earlier.
3.5. Mechanism of photocatalytic deoximation
Titanium dioxide on irradiation with UV or solar light produces
an electron in the conduction band and a hole in the valence band
(Eq. (1)).
TiO
2
!
hn
e

CB
h

VB
(1)
These electrons and holes can react with the electron acceptors,
electrondonors or substrates before undergoingrecombination. The
following mechanismis proposed for the deoximationof ketoximes.
The holes react with the ketoximes forming cations
(2)
Oxygen is a good electron acceptor and it absorbs the electron,
forming oxygenradical anion[O
2

]. This superoxide anionis a good

oxidizing agent and it oxidizes the ketoxime cation into a ketone.
O
2

RR
0
CNOH

! RR
0
CO HNO
2
(3)
A similar mechanism for the conversion of an aldoxime to
aldehyde had been reported earlier [17].
4. Conclusions
The photocatalytic deoximation process is more efcient in
acetonitrile and dichloromethane and least efcient in nitro-
benzene. Acetonitrile, being less volatile and nonreactive, is the
best solvent for this process. The optimumcatalyst concentration
for the deoximation for 100 mg of oxime in 25 mL is found to be
50 mg.
Among 10 semiconductors tested for the deoximation of
benzophenone oxime, TiO
2
(anatase), TiO
2
-P25 and Ag-TiO
2
are found to be most efcient.
In both UV and solar light all three forms of TiO
2
are more or less
equally efcient and deoximation is almost complete in 30 min
of irradiation.
Since cyclohexanone oxime undergoes complete (99.5%) con-
version in 30 min without undergoing rearrangement, semi-
conductor photocatalysis is the best method for the deoximation
of this oxime.
A mechanism involving the oxidation of oximes by superoxide
O
2

(oxide radical anion) is proposed. As the photocatalytic

deoximation is completed in 30 min and is also efcient in solar
light, this process becomes an energy-efcient green chemical
process.
Acknowledgements
The authors thank Degussa (Germany) for the gift sample of
TiO
2
-P25. One of the authors, K. Selvam is thankful to CSIR, New
Delhi, for the award of a Senior Research Fellowship.
Fig. 4. Percentage of benzophenone formed in acetonitrile with TiO
2
-P25, TiO
2
anatase and Ag-TiO
2
at different irradiation times. [Benzophenone oxime] = 100 mg/
25 mL; catalyst 50 mg/25 mL; airow rate = 8.1 mL s
1
; I = 1.381 10
6
einstein L
1
s
1
.
Table 5
Percentage conversion of various ketoximes with different forms of TiO
2
using solar
light in acetonitrile.
Ketoximes TiO
2
(anatase) (%)
TiO
2
-P25 (%) Ag-TiO
2
(%)
Benzophenone oxime 96.1 92.0 98.9
4-Methylbenzophenone oxime 91.4 90.1 94.5
4-Chlorobenzophenone oxime 92.0 90.0 92.9
Acetophenone oxime 91.0 88.0 92.0
Cyclohexanone oxime 99.4 99.4 99.5
[Oxime] = 100 mg in 25 mL; catalyst suspended = 50 mg/25 mL; irradiation
time = 30 min; airow rate = 8.1 mL s
1
.
K. Muthu et al. / Applied Catalysis A: General 358 (2009) 259263 262
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