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Fe(III)-photocatalytic partial oxidation of benzyl alcohol to benzaldehyde

under UV-solar simulated radiation

Article  in  Photochemical and Photobiological Sciences · September 2013

DOI: 10.1039/c3pp50210d · Source: PubMed

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Fe(III)-photocatalytic partial oxidation of benzyl alcohol

to benzaldehyde under UV-solar simulated radiation
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Cite this: DOI: 10.1039/c3pp50210d

Danilo Spasiano,*a Raffaele Marotta,a Ilaria Di Somma,b Roberto Andreozzia and

Vincenzo Caprioa

Received 3rd July 2013,
Accepted 19th August 2013
DOI: 10.1039/c3pp50210d
www.rsc.org/pps
A great deal of interest is recorded among researchers in the identification of new catalytic systems that
make possible the selective oxidation of organic species in the presence of non-toxic solvents, primarily
water, through the use of inexpensive catalysts. The possibility to selectively oxidize benzyl alcohol to
benzaldehyde is studied in the present work by using ferric ions as homogeneous catalysts and oxygen
as an oxidant under UV-solar simulated radiation. Due to the possibility that Fe(III) aquo-complex photo-
lysis could generate undesired reactive OH radicals with the consequent occurrence of side reactions,
most of the runs are carried out at pH = 0.5 at which these events have a reduced incidence. The results
indicate that benzyl alcohol can be partially converted into benzaldehyde with yield and selectivity
values higher than 40% and 80% respectively for the conditions adopted, with a minor occurrence of
benzoic acid formation. Reaction schemes to account for the experimental observations are provided.

Introduction
The use of solar radiation to drive organic transformations
provides a sustainable pathway for “green processes” and has
gained significant interest during the last decade.1,2 In this
sense, the possibility to carry out partial photooxidations thus
avoiding the use of some typical toxic oxidants such as per-
manganate or dichromate is very attractive in the context of
“green chemistry”.
Since water is the “greenest” solvent among all those
industrially adopted, a photocatalytic reaction in water with
the achievement of high selectivity for some specific com-
pounds is of great importance.
Moreover, most of the chemical reactions, whether sustain-
able or not, require catalysts allowing them to proceed under
milder conditions or ensuring the achievement of the desired
product.3 Right now, catalysts typically mean precious or rare
(earth) metals (Ru, Te, Pd, Rh, Au, Pt, Re, Os, and Ir), which
are expensive, in some cases toxic, and either destined to be
depleted or coming exclusively from a few countries.4,5
Therefore, it is highly desirable to replace the established
precious/rare metal catalysts used for industrial processes with
more Earth-abundant, inexpensive and environmentally com-
patible base metals such as iron and copper.6
a
Dipartimento di Ingegneria Chimica, dei Materiali e della Produzione Industriale,
Università di Napoli “Federico II”, p.le V. Tecchio, 80-80125 - Naples, Italy.
E-mail: danilo.spasiano@unina.it; Fax: +390815936936; Tel: +390817682968
b
Istituto di Ricerche sulla Combustione (CNR), P.le V. Tecchio, 80-80125 - Naples,
Italy
In this sense, due to the urgent need for new sustainable
industrial methods for chemical transformations, the design
of alternative oxidation processes, i.e. employing solar light,
oxygen and aqueous media at mild temperatures, is a current
field of investigation.7–9
These selective processes can be also performed in the pres-
ence of non-toxic and cheaper heterogeneous10,11 or homo-
geneous catalysts in aqueous phase.12
As regards the homogeneous catalysis, previous studies
demonstrated that ferric ions are able to promote a selective
phototransformation of “hydrated” carbohydrates,13 benzylic
methylene groups14 and alcohols15,16 to higher value-added
chemicals. Among these processes, the partial oxidation of
alcohols to the corresponding carbonyl compounds is a
pivotal reaction for organic and industrial chemistry.18 In
particular, the conversion of benzyl alcohol to benzaldehyde
is noticeably attractive. In fact, benzaldehyde, by quantity,
is the second most important aromatic molecule (after
vanillin) used in the cosmetics, flavor and perfumery indus-
tries. Synthetic benzaldehyde is industrially produced by the
hydrolysis of benzalchloride derived from toluene chlorination
or through the toluene oxidation route.17
The main concerns related to the listed processes
are the use of catalysts that are rather expensive and
often harmful to the environment, severe operating
conditions (high temperatures and pressures), costs related
to the recovery of catalysts for environmental and economic
reasons and those for systems to ensure a good level of plan
safety (highly flammable mixtures, ignition phenomena,
etc.).19

This journal is © The Royal Society of Chemistry and Owner Societies 2013 Photochem. Photobiol. Sci.

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Therefore, much attention has been devoted to the develop-
ment of catalytic reactions in place of classical oxidation pro-
cesses that require large quantities of inorganic oxidants.20–22
However, from these reviews, it appears that the most com-
monly used catalysts consist of noble or rare earth metals.
Consequently, some attempts at converting benzyl alcohol
to benzaldehyde have been made in aqueous media under
mild conditions using cheaper homogeneous or hetero-
geneous catalysts or photocatalysts.
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With regard to heterogeneous photocatalysis, Augugliaro
and coworkers performed the oxidation of benzyl alcohol
using home-prepared TiO2 catalysts achieving selectivities
three- to seven-fold higher than those of commercial TiO2
catalysts.23,24
The authors recently investigated the possibility to convert
liquid benzyl alcohol to benzaldehyde through an acidic sus-
pension of titanium dioxide in the presence of cupric in-
organic salts under an inert atmosphere and solar irradiation
at a laboratory scale and in a pilot plant.25,26 The influence of
different operating conditions such as TiO2 type and load, the
nature of the inorganic anions, Cu(II) concentration and pH
has been investigated. The best result found, in terms of yield,
was 35% for benzaldehyde with respect to the initial benzyl
alcohol concentration.
Instead, very poor and qualitative information is given on
the possibility of using homogeneous photosystems based on
more inexpensive metals for the partial oxidation of benzyl
alcohol in aqueous solution.17 These authors studied the
photooxidation of primary alcohols to the corresponding alde-
hydes by aqueous ferric ions and concluded, on the basis of
qualitative observations, that the reaction proceeds through
the formation of alkoxy radical species.
The present study is therefore carried out to:
• determine the yield of benzaldehyde in the homogeneous
Fe(III) ion assisted partial photocatalytic oxidation of benzyl
alcohol under aerobic conditions in aqueous solution at
varying pHs;
• better clarify the mechanism of oxidation as a preliminary
step for the development in the future of a detailed mathemat-
ical model able to simulate the kinetic behaviour of the
process.
Experimental
Photoreactor unit
Photocatalytic runs have been carried out in a batch cylindrical
glass jacketed reactor (280 ml) with an outer diameter of
6.5 cm and a height of 40 cm wrapped with an aluminium foil.
At the top, the reactor had two inlets for feeding reactants or a
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Fig. 1 Photoreactor unit.
gaseous stream and an outlet for withdrawing samples. The
reactor was equipped with a 125 W ( power input) high-
pressure solar UV lamp (Helios Italquartz) mainly emitting at
305, 313 and 366 nm enclosed in a glass sleeve, immersed in
the solution in the center of the reactor. The reactor has been
thermostated at 25 °C. A scheme of the experimental device is
shown in Fig. 1.
Experimental procedure
For all the experiments, the pH has been regulated with
perchloric acid and monitored by means of an Orion 420A+
pH-meter (Thermo). During the oxidation runs, the reactor is
open to the air. For the experiments performed in the absence
of air, the solution has been preventively purged with nitrogen
to remove the dissolved oxygen and the photocatalytic run
has been carried out under a nitrogen atmosphere without
bubbling it in the solution to prevent the stripping of the benz-
aldehyde produced.
Analytical methods
The concentrations of benzyl alcohol (BA), benzaldehyde
(BHA), benzoic acid (BAC) and their hydroxylated derivatives
(HO-S), at different reaction times, have been evaluated by
HPLC analysis. For this purpose, the HPLC apparatus (Liquid
Chromatograph Agilent 1100) has been equipped with a diode
array UV/Vis detector (λ = 210 and 230 nm) and a Synergy 4μ
Hydro-RP 80A column, using a mobile phase of 50% buffer,
25% H2O and 25% CH3CN, flowing at 1.0 ml min−1 at 190 bar.
One litre of buffer has been made by 10 ml of phosphoric acid
solution (5.05 M) and 50 ml of methyl alcohol taking the
volume to 1000 ml by water for HPLC.
The concentrations of ferric and ferrous ions have been
measured by means of a colorimetric method using an analyti-
cal NANOCOLOR Eisen Test 1-36 kit purchased from
Macherey-Nagel. A UV/Vis spectrometer (Unicam) has been
used for the measurements at a wavelength of 492 nm. The
total organic carbon (TOC) was monitored by a Shimadzu
Total Organic Carbon analyser, model TOC-5000A.
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Photochemical & Photobiological Sciences
Materials
Fe(III) ions have been introduced into the system as ferric
sulfate nonahydrate (Fe2(SO4)3·9H2O). Perchloric acid, ferric
sulfate nonahydrate, benzyl and (2-, 3- and 4-)hydroxybenzyl
alcohols have been purchased from Sigma Aldrich as well as
the corresponding aryl aldehydes and carboxylic acids and
used as received.
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Results and discussion
Benzyl alcohol
The formation of benzaldehyde through benzyl alcohol Fe(III)-
assisted photocatalytic oxidation has been reported in the
past27,28 without a complete investigation of the effect of
different operative variables, such as pH, Fe(III) initial concen-
tration and the presence of oxygen, on the efficiency of the
process. An investigation of this type has been carried out in
the present work.
In aqueous solutions, iron(III) has a strong tendency to
hydrolyze to form Fe(III)-aquo/hydroxy complexes;29 some of
them are well characterized:30
Fe3þ þ 6H2 O Ð FeðH2 OÞ6 3þ
FeðH2 OÞ6 3þ Ð FeðH2 OÞ5 ðOHÞ2þ þ 2Hþ
FeðH2 OÞ6 3þ Ð FeðH2 OÞ4 ðOHÞ2 þ þ Hþ
2FeðH2 OÞ6 3þ Ð Fe2 ðH2 OÞ8 ðOHÞ2 4þ þ 2Hþ þ 2H2 O
Among these ferric complexes, Fe(H2O)63+ and Fe(H2O)5-
(OH)2+, under UV-light irradiation, are well known for under-
going photochemical reduction to Fe(II) that generates hydroxyl
radicals:31,32
hv
FeðH2 OÞ6 3þ þ H2 O ! FeðH2 OÞ6 2þ þ HO• þ Hþ
hv
FeðH2 OÞ5 ðOHÞ2þ ! FeðH2 OÞ5 2þ þ HO•
which attack promptly and unselectively the organic sub-
strates, in some cases, driving the system to complete
mineralization.33
However, in the wavelength range 305–366 nm, the
quantum yields of HO• radicals, produced from the photolysis
of Fe(H2O)5(OH)2+ (0.14–0.017 mol E−1),31 are much higher
than those for Fe(H2O)63+ direct photolysis (∼0.007 mol E−1,
2.25 M HClO4).34
Moreover, hexaaquoiron(III) species absorbs very weakly
when compared to the hydroxo-monomer Fe(H2O)5(OH)2+ at
the investigated wavelengths.31,35
Since the speciation of Fe(III) aquo/hydroxy complexes is
strongly influenced by the pH of the aqueous media,36 it is
evident that for an optimization of the partial oxidation of
benzyl alcohol to benzaldehyde, the right pH value has to be
chosen where the intervention of Fe(H2O)5(OH)2+ species can
be experimentally assumed to be negligible.
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Fig. 2 Effect of pH. ● Average selectivities; ▲ yields (after a reaction time of
300 min); ○ hydroxylated byproducts (after a reaction time of 300 min). [BA]o =
1.5 mM, [Fe(III)]o = 1.0 mM.
Effect of pH
Photocatalytic runs, devoted to assess the effect of pH on the
system efficiency in terms of selectivity and yield of benz-
ð1Þ aldehyde, have been carried out. The results, reported in
Fig. 2, indicate a marked decrease of the selectivities from
ð2Þ 86% to 54% with increasing the pH values of the solution
from 0.5 to 4.0, whereas the corresponding yield of the desired
ð3Þ
product remains almost constant at a value close to 30% for a
ð4Þ reaction time of 300 minutes.
Moreover, an increase of the hydroxylated intermediate con-
centration (2-, 3- and 4-hydroxy benzyl alcohols, 2- and 4-
hydroxybenzaldehydes, and 3-hydroxybenzoic acid), reported
in the figure as HO–S, has been recorded with raising the pH.
These results found are in agreement with the findings
reported elsewhere by others.36 At very low pH ( pH < 2),
ð5Þ
Fe(H2O)63+ is the prevalent species which, in spite of its low
quantum yield, can photolyze generating HO• species (reaction
ð6Þ
5), thus resulting in the formation of hydroxylated intermedi-
ates, detected in the solution at trace levels. With increasing
the pH ( pH > 2), its contribution to HO• photoproduction
decreases, whereas it becomes dominant in the Fe(H2O)5-
(OH)2+ species which photolyzes giving rise again to the
formation of hydroxyl radicals (reaction 6).
Although the selectivity achieved during the oxidation
experiments does not change significantly in the pH range of
0.0–1.0, with the aim of minimizing the contribution of
the hydroxylation reactions (undesired), a pH of 0.5 has been
chosen, for the experimental investigation, as one of the
values at which the system achieves the highest selectivity.
As shown in Fig. 3, BHA is produced through the partial
Fe(III) homogeneous photocatalytic oxidation of BA with a
maximum yield of 26.5%. Benzoic acid (BAC) is formed as the
primary byproduct (1.0%). Some hydroxylated aromatic deriva-
tives (3- and 4-hydroxy-benzyl alcohols, 3-hydroxy-benzoic acid)
have been also detected at trace levels (data not shown).
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Fig. 3 Production of benzaldehyde by Fe(III) homogeneous photocatalytic

partial oxidation of benzyl alcohol. [BA]o = 1.86 mM, [Fe(III)]o = 1.50 mM, pH = Fig. 4 Effect of oxygen in presence of light. [BA]o = 1.5 mM, [Fe(III)]o = 0.1 mM.
0.5. (●) BA, (■) BHA, (▲) BAC (×10), ○ TOC/TOCo. pH = 0.5. Without air: ■ [BA]/[BA]o, ● [BHA]/[BA]o, ▲ [BAC]/[BA]o. With air: □
[BA]/[BA]o, ○ [BHA]/[BA]o, △ [BAC]/[BA]o.

Mineralization is negligible as indicated by the total organic
carbon profile (empty circles).
Effect of radiation, air and Fe(III)
Since it has been reported that benzyl alcohol may undergo a
direct photo-oxidation for wavelengths higher than 285 nm,37
some tests have been carried out in the presence of both radi-
ation and air without ferric ions in order to assess an eventual
benzaldehyde production. The experimental results, under the
conditions adopted, evidenced a small photo-reactivity also for
prolonged reaction times (Table 1, entry 1).
No reactivity has been detected starting from Fe(III) and
benzyl alcohol containing solutions in the presence of air in
the dark (data not shown).
Moreover, the effect of air on the system photoreactivity is
shown in Fig. 4. It is evident that the presence of oxygen in the
solution containing Fe(III), in an unstoichiometric ratio with
benzyl alcohol, when compared with the anoxic system,
increases the benzyl alcohol conversion from 9.50% (Table 1,
entry 2) to 25.9% (Table 1, entry 3) to both benzaldehyde
(from 5.46% to 21.2%) and the benzoic acid (from 5.90 ×
10−2% to 0.55%).
Operating with initial concentrations of Fe(III) ions in large
stoichiometric excess with respect to the BA starting concen-
tration, a higher conversion degree is achieved in the presence
of air (63.4%, Table 1, entry 6) when compared to the system
in the absence of oxygen (53.7%, Table 1, entry 7), with a lower
selectivity value (69.4% versus 83.2%). The decreased selectivity
with the use of air can be ascribed to a higher HO• con-
centration and, therefore, to a more relevant formation of
hydroxylated by-products (1.8% versus 7.2 × 10−2%) when
oxygen is present in the solution.
Moreover, the comparison of Fe(III)/Fe(II) concentration data
collected for both systems, reported in Fig. 5, using benzyl
alcohol in high stoichiometric excess with respect to Fe(III),
suggests an efficient photoreoxidation of Fe(II), with the cycle
Fe(III)/Fe(II) supporting a real photocatalytic process, reported
in Scheme 1.38
These conclusions are supported by the results shown in
Fig. 6 and 7, obtained by comparing oxidation runs on solu-
tions originally containing ferrous (circles) or ferric (squares)
ions.
In Fig. 6 it can be observed that, when ferrous ions are
used, an initial period of induction appears in the profiles of
both benzyl alcohol (full circles) and the benzaldehyde (empty
circles). This lag-phase can be attributed to the need to form

Table 1 Results of the photocatalytic partial oxidation of benzyl alcohol under different experimental conditions for a reaction time of 5 h

No. [Fe(III)]o (mM) [BA]o (mM) Air pH Conv. (%) Yield(BHA) (%) Select (%) Yield(BAC) (%) Yield(HO–S) (%)

1 0 1.5 Yes 0.5 7.65 7.70 100 0.33 —

2 0.1 1.5 No 0.5 9.50 5.46 57.4 0.1 —
3 0.1 1.5 Yes 0.5 25.9 21.2 82.0 0.55 0.62
4 1.0 1.5 Yes 0.5 34.6 26.6 76.9 1.71 1.1
5 2.0 1.5 Yes 0.5 47.0 34.3 72.9 2.84 1.6
6 3.0 1.5 Yes 0.5 63.4 44.0 69.4 4.45 1.8
7 3.0 1.5 No 0.5 53.7 44.7 83.2 3.05 0.072

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Fig. 5 Effect of oxygen in presence of light. [BA]o = 1.5 mM, [Fe(III)]o = 0.1 mM.
pH = 0.5. Without air: ■ [Fe(II)]/[Fe(III)]o, ● [Fe(III)]/[Fe(III)]o. With air: □ [Fe(II)]/
[Fe(III)]o, ○ [Fe(III)]/[Fe(III)]o.
Scheme 1
the active Fe(III) species, not initially present in the solution
and generated through a photo-oxidation of Fe(II) species:
hv
FeðH2 OÞ6 2þ þ O2 ! FeðH2 OÞ6 3þ þ O2•
Instead, if ferric ions are present in the aqueous solution at
the starting reaction time, higher conversion degrees (full
squares) and yields (empty squares) are achieved than when
ferrous ions are used (circles).
Moreover, the results reported in Fig. 7 show that the Fe(II)
and Fe(III) concentrations (full and empty circles respectively)
starting from Fe(II) species containing solutions, after an
initial transient time due to reaction (7), reach almost constant
values due to the catalytic cycle previously reported. This result
indicates that for each species, Fe(II) and Fe(III), the rate of for-
mation and that of disappearance after a short transient time
are balanced. When benzyl alcohol and Fe(III) are present at
the beginning of the reaction, the latter starts to oxidize the
alcohol giving rise to the formation of Fe(II) which is also re-
oxidized to Fe(III) by oxygen (reaction 7). It is clear that for the
first 300 minutes of reaction, the rate of formation of Fe(II) is
higher than that of its reoxidation to Fe(III) thus causing the
concentration trends reported in the figure (squares).
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Fig. 6 Effect of initial Fe species on BA conversion and BHA yield, in presence
of air. [Fe(II)]o = 2.08 mM; [BA]o = 1.00 mM: (●) [BA]/[BA]o, (○) [BHA]/[BA]o.
[Fe(III)]o = 1.80 mM; [BA]o = 0.84 mM: (■) [BA]/[BA]o, (□) [BHA]/[BA]o.
ð7Þ
Fig. 7 Profile concentration for Fe(III) and Fe(II), starting from ferrous or ferric
salts, in presence of air. [Fe(II)]o = 2.08 mM ([Fetot]); [BA]o = 1.00 mM: (●) [Fe(II)]/
[Fetot], (○) [Fe(III)]/[Fetot]. [Fe(III)]o = 1.80 mM ([Fetot]); [BA]o = 0.84 mM: (■)
[Fe(III)]/[Fetot], (□) [Fe(II)]/[Fetot].
Effect of Fe(III) concentration
Fig. 8 reports the results on the benzaldehyde yield by the
partial photo-oxidation of benzyl alcohol at different ferric ion
concentrations. The system reactivity increases with increasing
initial iron(III) concentration. Moreover, a progressive decrease
of the selectivities has been detected with the increase of Fe(III)
initial load (Table 1, entries 3–6).
For example, for Fe(III) concentration increasing from
0.1 mM to 3.0 mM the benzaldehyde yield increases from
21.2% to 44.0% but the selectivity decreases from 82.0% to
69.4% for a reaction time of 5 h.
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Fig. 8 Effect of initial Fe(III) concentration on BHA yield, in presence of light
and air. [BA]o = 1.5 mM, pH = 0.5. [Fe(III)]o: (○) no; (●) 0.1 mM; (■) 1.0 mM; (◆)
2.0 mM; (▲) 3.0 mM.
To better investigate the role of Fe(III) species in the system
reactivity, further runs have been carried out at varying initial
Fe(III) and substrate concentrations.
Fig. 9 and 10 show the results on the conversions to Fe(II) at
different and fixed [Fe(III)]/[BA] feed ratios (R) respectively.
It can be stated that, with increasing the R ratio, the Fe(II)
production rate increases (Fig. 9) and that, at a fixed R value
(Fig. 10), an increase of the initial Fe(III) concentration causes
an evident decrease of the delay time for the appearance of
Fe(II) in the reacting solution.
Fig. 9 Conversions to Fe(II) at varying reaction times for different [Fe(III)]o/[BA]o
ratios (R). pH = 0.5. ▲ [Fe(III)]o = 1.85 mM; [BA]o = 0.55 mM (R = 3.36); ● [Fe(III)]o
= 2.82 mM; [BA]o = 1.35 mM (R = 2.09); ◆ [Fe(III)]o = 1.70 mM; [BA]o = 1.49 mM
(R = 1.14); ■ [Fe(III)]o = 0.85 mM; [BA]o = 1.35 mM (R = 0.63).
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Fig. 10 Conversions to Fe(II) at varying reaction times for the same [Fe(III)]o/
[BA]o ratio (R ≈ 0.6). pH = 0.5. + [Fe(III)]o = 2.82 mM, [BA]o = 4.26 mM; ◆ [Fe(III)]o
= 2.18 mM, [BA]o = 3.39 mM; ▲ [Fe(III)]o = 1.71 mM, [BA]o = 2.62 mM; ■ [Fe(III)]o
= 0.85 mM, [BA]o = 1.35 mM; ● [Fe(III)]o = 0.52 mM, [BA]o = 0.85 mM.
Previous studies indicated that only primary and secondary
alcohols form secondary solvation spheres (or second coordi-
nation spheres) of hexa-aquoiron(III).39 On the basis of these
suggestions in the literature, the following structure can be
postulated in the case where benzyl alcohol is used as alcohol:
in which different interactions occur between the hydroxyl
groups39 or the aromatic rings40 of the benzyl alcohol and the
water molecules. In this case, it has been proposed that the
alcohol molecules act as scavengers in the photoreduction of
Fe(H2O)63+ leading to the formation of Fe(II)-aquocomplex and
organic radical species.34,41
On the basis of the results collected and the literature find-
ings, it can be proposed that the photolysis of hexa-aquoiron(III)
solutions containing benzyl alcohol proceeds through two
major pathways. Firstly, a charge transfer from a water orbital
to an iron(III) centered orbital produces OH radicals according
to reaction 5 (which reacts with the aromatic ring generating
hydroxylated species).
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Secondly, a direct reaction of charge transfer in the outer
solvation sphere of the excited state of the complex between
hexa-aquoiron(III) and benzyl alcohol can lead to the oxidation
of the aromatic alcohol forming benzylic radical and iron(II)
species:16
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Taking into account this scheme, the rate of generation of
hydrated ferrous ions is promoted, in any case, by increasing
the Fe(III) initial concentration. Indeed, working at increasing
Fe(III) concentrations – i.e. increasing the R value or keeping
R constant by increasing the BA initial concentration – the
photolysis of the Fe(III)-hexa-aquocomplex is favoured and, as
a result, hydrated ferrous ions are generated faster (Fig. 9
and 10).
Benzaldehyde
With the aim to better clarify the chemical behaviour of benz-
aldehyde in the investigated system, Fig. 11 shows the results
obtained carrying out investigations on a BHA containing solu-
tion, without BA, under the same experimental conditions pre-
viously adopted. Benzaldehyde is unreactive under aerated
conditions in the dark, whereas it undergoes a direct photo-
lysis (triangle), as reported by others.42–44 In particular, these
Fig. 11 Benzaldehyde concentration profile under different experimental con-
ditions. pH = 0.5. ● In the dark with air. [Fe(III)]o = 1.50 mM, [BHA]o = 1.20 mM.
▲ With a lamp and air, without Fe(III). [BHA]o = 1.30 mM. ◆ With a lamp in
absence of air. [Fe(III)]o = 1.7 mM, [BHA]o = 1.10 mM. ■ With a lamp and air. [Fe
(III)]o = 1.70 mM, [BHA]o = 1.20 mM.
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studies indicated that BHA photolysis mainly leads to a
complex mixture of benzoin (an α-hydroxyketone), benzil (an
α-diketone) and some other oligomeric molecules. Among
them, benzoin can be easily oxidized by oxygen in the presence
of aldehyde and Fe(III) species.45
A marked enhancement of the reactivity is recorded under
irradiation in the presence of Fe(III) species, under aerated
(square) or deaerated (diamond) conditions.
On the basis of all the results collected, the results pre-
viously described, and the literature findings, a mechanism of
partial photo-oxidation of benzyl alcohol to benzaldehyde, in
aerated aqueous solution in the presence of Fe(III) species, is
depicted in Scheme 2. The Fe(III)-aquo-complex, under the
experimental conditions adopted, undergoes photoreduction
to hydrated Fe(II) species generating HO• radicals (reaction 5),
which attack mainly the organic molecules, such as BA, BHA
and BAC (reactions 8–10 in Scheme 2), producing hydroxyl aro-
matic byproducts (HO-S). BA forms a solvation complex with
hexa-aquoiron(III),39 which photolyzes thereby generating
hydroxy-benzyl radical (reactions 11 and 12)16 that is promptly
converted to benzaldehyde through the reduction of ferric ions
to ferrous ions (reaction 13).16 BHA, in turn, is photoconverted
to benzoic acid by the intervention of oxygen and Fe(III) species
(reactions 14–17).37,46 A simultaneous photo-reoxidation of
Fe(II) species to Fe(III) by oxygen also occurs (reaction 7).38
Scheme 2
Photochem. Photobiol. Sci.

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Scheme 3
Moreover BHA undergoes direct photolysis generating
α-hydroxyketones, α-diketones, peroxy acids and oligo-
mers,42,43 which can react with hydroxy radicals and/or Fe(III)
species (Scheme 3).45
Conclusion
The partial photocatalytic oxidation of benzyl alcohol to benz-
aldehyde in aqueous solution in the presence of Fe(III) ions,
oxygen and UV-solar simulated radiation has been studied in
the present work.
Due to the capability of Fe(III) hexa-aquo- and hydroxy-com-
plexes to photolyze giving rise to the formation of OH radicals,
after a preliminary set of runs, an optimal pH range
0.0–1.0 has been identified as one capable of achieving the
highest values of selectivity to benzaldehyde. After obtaining
these results, a pH equal to 0.5 has been chosen to carry out
all the investigations reducing the occurrence of unwanted
hydroxylation reactions. The results collected during the
experimental investigation have indicated that benzyl alcohol
can be partially converted into benzaldehyde with yield and
selectivity values higher than 40% and 80% respectively for the
conditions adopted, with a minor occurrence of benzoic acid
formation. The benzaldehyde produced can undergo a direct
photolysis with generation of a complex mixture of byproducts.
A minimal formation of hydroxylated derivatives of benzyl
alcohol, benzaldehyde and benzoic acid is in any case
observed, due to the presence of hydroxyl radicals generated
by the photolysis of the Fe(III)-hexa-aquocomplex at the wave-
lengths investigated.
Analytical determinations have shown that ferric ions
reduce to ferrous ones during the runs and that the latter are
simultaneously photoreoxidized. In this way a photocatalytic
oxidation process of the organic species is made possible
under ambient conditions.
The results collected in the present work allow us to con-
clude that non-toxic, cheap and easily available iron(III) salts
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can be really used as homogeneous photocatalysts to convert
benzyl alcohol into benzaldehyde, although a pH of the solu-
tion as low as at least 1.0 is required.
To minimize the disadvantages of the adoption of
low pHs, appropriate operating procedures are necessary
aiming, after the organic separation and recovery, at a com-
plete recycling of the acid aqueous effluent containing the
catalyst.
Acknowledgements
The authors are grateful to Ing. Carolina Macchiarelli and Ing.
Felicia Rugari for their assistance during the experimental
work.
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