International Journal of Hydrogen Energy 31 (2006) 129 – 139

www.elsevier.com/locate/ijhydene

Electrocatalytic production of hydrogen boosted by organic

pollutants and visible light
Lluís Solera , Jorge Macanása , Maria Muñoza,∗ , Juan Casadob
a Centre Grup de Tècniques de Separació en Química (GTS), Unitat de Química Analítica, Departament de Química, Universitat
Autònoma de Barcelona, Campus UAB s/n, 08193 Bellaterra, Barcelona, Catalonia (Spain)
b MATGAS R&D Centre, Universitat Autònoma de Barcelona, Pl. Cívica, P12, 08193 Bellaterra, Barcelona, Catalonia (Spain)

Received 13 September 2004; received in revised form 19 October 2004

Available online 19 December 2004

Abstract
A new method to produce high-purity hydrogen using photoelectrocatalytic reactions is studied. This integrated process
uses solar energy and the Gibbs free energy of oxidation of organic wastes to help reducing the energy consumption of water
electrolysis. The method diminishes the thermodynamic potential to 0.77 V and practical voltages to ca. 1.2 V, due to an
electrocatalytic reaction in the presence of iron ions. The anolyte is illuminated, and separated from the catholyte by a proton
exchange membrane. The process oxidizes water pollutants and avoids the anodic corrosion of a stainless steel anode, but not
every sacrificial substance has a positive effect on it.
䉷 2004 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.

Keywords: Hydrogen production; Alternative technologies; Organic wastes; Photo-Fenton; Water electrolysis

1. Introduction
Steam methane reforming process, the most common pro-
cess of hydrogen production, has some disadvantages like
the generation of large quantities of by-products (carbon ox-
ides) that pollute the atmosphere and make difficult obtain-
ing high purity hydrogen in high yields [1,2].
Among of the various technologies for hydrogen produc-
tion not based on fossil fuels, electrolysis is the only one
of practical importance, but it is only economically feasible
where electricity is cheap enough. The hydrogen produced
by electrolysis is very pure, but the high cost associated with
electrolytic processes implies the need of improving differ-
ent aspects of the technology (temperature control, coupled
redox reactions, catalysts or solar energy use, among others)
∗ Corresponding author. Tel.: +34 93 581 2123;
fax: +34 93 581 2379.
E-mail address: maria.munoz@uab.es (M. Muñoz).
for decreasing the expenses and making this process more
competitive. Some emerging methods for producing H2 are
those based on photocatalytic or electrochemical processes
[3–10].
Actually, some studies reveal that the theoretical conver-
sion efficiencies for these production technologies could be
promising for industrial applications [3,10]. Among other
research lines, there is photoelectrolysis, which uses light to
provide some of the energy for the water splitting. A recent
patent [11] describes irradiation with a high-pressure mer-
cury lamp of an electrolytic solution containing ferric ions
and a semiconductor photocatalyst in suspension based on
solid particles of WO3 , in order to reduce the ferric ions to
ferrous ions. In a subsequent stage, the resulting solution is
electrolyzed by conventional means to produce hydrogen in
very low yield.
Another protected process [12] discloses an application
generating hydrogen by electrolysis of an aqueous solution
of an organic fuel, such as methanol. Anodic oxidation of

0360-3199/$30.00 䉷 2004 International Association for Hydrogen Energy. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2004.11.001
130 L. Soler et al. / International Journal of Hydrogen Energy 31 (2006) 129 – 139
methanol calls for lower potential than that of water, but
produces CO2 as a residue and since most methanol is pro-
duced nowadays from oil, this invention, if industrially fea-
sible, would not be a way out from fossil fuel sources. So
far, no method exists for producing high purity hydrogen
that is industrially profitable unless those based on the use
of fossil fuels.
A new method for the electrocatalytic production of hy-
drogen using waste products and light is described in this
paper. First results show that this technology might be useful
for reducing the threshold potential of hydrogen generation
by water electrolysis and combine, at the same time, waste
removal with clean fuel generation.
1.1. Process concept
The objective of this research is to develop a process us-
ing solar energy and the Gibbs free energy of oxidation of
waste compounds to reduce the energy consumption of hy-
drogen production from water electrolysis. For the electrol-
ysis of water, a standard thermodynamic potential of 1.24 V
is needed, and the actual operating voltages are around 2 V.
The aim of this work is to decrease the operating voltage
to ca. 1.2 V by using the combination of water electrolysis
and photo-Fenton like process by a photoelectrochemical
process based in the following electrode reactions:
Hydrogen is produced at the cathode
Cathode : H+ + e− → 21 H2 E 0 = 0.00 V. (1)
Fe (II) is oxidized at the anode
Anode : Fe2+ → Fe3+ + e− E 0 = −0.77 V. (2)
So, by using the method we present, the threshold poten-
tial for hydrogen production can be diminished until 0.77 V,
with an important saving in the energy consumption. Fe (III)
is photoreduced in a photo-Fenton like process in the ab-
sence of added hydrogen peroxide [13], closing the cycle of
iron in the anolyte solution. In the absence of organics, the
main reactions [14,15] are:
Fe(OH)2+ + h
→ Fe2+ + OH· (3)
Fe2+ + HO· → Fe(OH)2+ (4)
Fe(OH)2+ + HO·
2+
 Fe + H2 O2 (5)
Fe3+ + H2 O2 → Fe.OOH2+ + H+ (6)
Fe.OOH2+ → Fe2+ + HO2 · (7)
Fe3+ + HO2 · → Fe2+ + O2 + H+ (8)
Among the Fe (III) aquacomplexes, Fe(OH)2+ , which
refers to (Fe(OH)(H2 O)5 )2+ , is photolysed with the highest
quantum yield (Fe(II) = 0.14 at 313 nm) [16,17] according
to reaction (3). Oxidizing species from the above scheme
could react with oxidizable organic compounds. Particularly,
the hydroxyl radical is expected to oxidize most organic
species, minimizing the back reaction (4).
The anolyte should be illuminated, and separated from
the catholyte by a proton exchange membrane in order to
keep the reaction products isolated and allow the neces-
sary exchange of charges. When the membrane is placed in
an electrolyte solution and an electrical voltage is applied,
the mobile cations pass through it. To do this properly, the
membrane should have several characteristics: high proton
permeability below 100 ◦ C, high selectivity in order to per-
meate neither iron ions nor sacrificial compounds [18] and
high chemical and mechanical stability. Most common com-
mercial membranes, such as Nafion, that attends the require-
ments of high chemical stability and high proton conductiv-
ity, are not suitable in the studied system due to the draw-
back of high permeability to some organic compounds and
cations other than H+ [19]. So, a more selective membrane
has been used.
2. Experimental section
2.1. Chemicals
Ferrous sulfate 7-hydrate, ferric sulfate 9-hydrate, ox-
alic acid 2-hydrate, aniline, urea, nitrobenzene, ethanol and
Cobalt (II) sulfate 7-hydrate were supplied by PANREAC
and were used as received. Sulfuric acid was supplied by
J.T. Baker. Diethylamine was supplied by Carlo Erba. 1,3-
Phenylenediamine was supplied by Aldrich. Deionized wa-
ter was used to prepare all the aqueous solutions.
2.2. Apparatus, materials and measurements
The equipment for the experiments was the following
(Fig. 1):
1. A Pyrex glass cell of two compartments, which capacity
was about 300 ml, each containing 275 ml of anolyte and
catholyte solutions.
2. A light source. Anolyte solution was under artificial light
illumination: (lamp #1) incandescent lamp Ultra-Vitalux,
E27, 300 W from OSRAM, in order to simulate sun-
light [20]; or (lamp #2) halogen lamp model K4 Q1000
T3/CL, 1000 W, supplied by General Electric [21]. Un-
less otherwise noted, these lamps were separated 3 and
60 cm, respectively, from the anodic compartment. The
measured luminous flux densities under these conditions
were 1 W/cm2 for lamp #1 and 0.4 W/cm2 for lamp #2.
Flux densities were measured using a light power meter
(Laser Power Meter TPM-300 GENTEC; detector model
PSV-3103 GENTEC).
3. Two magnetic stirrers, in order to achieve a good mixing
of solutions.
4. An ion exchange membrane. Both compartments were
separated by a cation exchange membrane permselective
 L. Soler et al. / International Journal of Hydrogen Energy 31 (2006) 129 – 139
(9) N2(g) (7)
(2)
(6)
(8)
(4)
(1)
(5) (5)
(3) (3)
Fig. 1. Scheme of the experimental setup. A detailed description
of the different components is given in Section 2.2.
to monovalent cations. Neosepta CMX-S (supplied by
Eurodia Industrie S.A.) was selected for this study be-
cause of its appropriated chemical characteristics [22]
that were checked in previous assays. The membrane
was stored in 0.5 M sodium chloride solution to preserve
its performance. The chemical pre-treatment in order to
remove sodium chloride was a sequential rinsing and
stirring with H2 SO4 0.01 M (24 h) and deionized water
(24 h). Each membrane was re-used at least 5 times.
5. Two electrodes, which were placed in contact to both
membrane sides. The geometric section of the electrode-
membrane assembly framed by Teflon rings was 5.3 cm2 .
The anode used was a stainless-steel mesh (circular
shape; 3.5 cm diameter, nominal aperture 1.5 mm, wire
diameter 0.4 mm, supplied by Servei Estació Barcelona),
which was used as working electrode. The cathode was
either a stainless-steel mesh identical to the anode or a
nickel mesh (circular shape, 3.5 cm diameter, nominal
aperture 0.73 mm, wire diameter 0.25 mm, supplied by
Goodfellow Cambridge Limited). The selected cathode
was used both as auxiliary and reference electrode.
6. A power supply. The electrodes were connected to a
software-controlled Potentiostat/Galvanostat PAR model
263A.
7. A nitrogen gas flow through catholyte was applied along
the experiments in order to prevent dissolved oxygen
reduction as cathodic side-reaction.
8. A pH-meter (CRISON model micropH 2001) was used
to measure pH in anolyte and catholyte.
9. Each temperature compartment was continuously mon-
itored by a logging thermometer (Hanna Instruments
model HI 98840).
An ICP-OES (Iris Intrepid II XSP from Thermo) was used
to perform ion analysis.
131
Preliminary tests showed that in potentiostatic operation
hydrogen production grows, as expected, when pH becomes
lower in the catholyte solution. Therefore, we chose H2 SO4
1 M as catholyte solution. The usual operation mode was
a potentiostatic chronoamperometry with 1.20 V fixed be-
tween anode and cathode. Linear sweep voltametries were
performed under stirring of anodic and cathodic solutions.
Experiments were performed under the conditions above de-
scribed unless otherwise noted.
3. Results and discussion
3.1. Anolyte composition
The photo-Fenton like reaction is expected to take place in
the anolyte and the optimum reported anodic pH to achieve
this reaction is 2–3 [13]. Nevertheless, at pH < 2 the pre-
cipitation of ferric hydroxides is mostly prevented. Thus,
the chosen background anolyte was an aqueous solution of
H2 SO4 0.01 M.
Variation of ferrous and ferric ion concentrations allowed
increasing the rate of the anodic reaction and of the over-
all process. Several chronoamperometries were performed
at different concentrations. Illumination of the anolyte com-
partment produced the increasing currents, which can be as-
cribed to the photoreduction (3) and subsequent reactions
(5)–(8) leading to the recovery of Fe (II), which is reoxidized
at the anode. The higher currents were achieved with Fe (II)
0.3 M and Fe (III) 0.2 M. Similar currents where obtained
with Fe (II) 0.2 M and Fe (III) 0.3 M, but further increasing
of the Fe (III) concentration to 0.4 M, maintaining Fe (II)
concentration at 0.2 M, produced the precipitation of ferric
hydroxide. Due to this solubility limitation, we decided to
set up a total iron concentration of 0.5 M.
3.2. Effect of organic compounds addition
In this section, the results obtained for some electrolyses
where organic compounds were added to the anodic solution
are reported. These experiments present different effects on
the hydrogen production that help to understand the global
process.
3.2.1. Oxalic acid
For these experiments, the stainless-steel cathode and
lamp #2 were used. Initial anolyte composition was: 0.4 M
Fe (II), 0.1 M Fe (III), at pH 1.6.
Since the lamp heated the illuminated solution, anolyte
and catholyte temperature increased at the beginning of each
run (Fig. 2). After ca. 2.5 h of illumination, temperature
reached a practically constant value. The same general be-
havior was observed in all the experiments done, unless oth-
erwise noted.
In this case, the anolyte and catholyte steady-state temper-
atures were 75 and 65 ◦ C, respectively. This supplementary
132 L. Soler et al. / International Journal of Hydrogen Energy 31 (2006) 129 – 139

100 300
(a)
90
250
80
70 200
i (mA) 60

T (°C)
50 150
40
(b) 100
30
20 50
(c)
10
0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0
t (h)

Fig. 2. Chronoamperometry and temperature evolution plotted for oxalic acid experiment. Stainless-steel cathode, lamp #2, anolyte 0.4 M
Fe(II), 0.1 M Fe(III),
Ecat.an = 1.20 V: (a) current intensity, (b) anodic temperature, and (c) cathodic temperature.

energy input to the anolyte allowed to get higher currents
at constant voltage and, consequently, higher hydrogen pro-
duction during the experiments.
After 2.4 h, 46 mmols of oxalic acid were added to
anolyte. Fig. 2 shows that due to oxalic acid addition cur-
rent grew quickly and maintained a value > 80 mA, up to
4.6 h. At the end of the experiment, the anodic pH was 0.8.
This important effect can be explained by a mechanism
already described [15,23,24]. In the presence of ligands such
as carboxylic acids, Fe (III) forms stable complexes that,
however, can be photolyzed through a ligand to metal charge
transfer reaction as follows:
Fe(O2 CR)2+ + h
→ Fe2+ + CO2 + R·
In particular, oxalic acid and Fe (III) form complexes
which absorb light in the UV-vis range, from 250 to 500 nm,
with molar absorption coefficient higher than 103 /M/cm,
producing Fe (II) with a quantum yield 1.0–1.2 [17]:
[Fe(C2 O4 )3 ]3− + h
→ [Fe(C2 O4 )2 ]2− + C2 O•−
4 (10)
C2 O•−
4 + [Fe(C2 O4 )3 ]
3− → [Fe(C O ) ]2−
2 4 2
+ C2 O2−
4 + 2CO2
C2 O•− •−
4 + O2 → O2 + 2CO2
C2 O•− •−
4 → CO2 + CO2
Two further experiments were carried out in order to dis-
entangle the light effect from the temperature effect in hy-
drogen production using oxalic acid as sacrificial compound.
The anodic compartment of the first experiment was illu-
minated with lamp #1. In order to avoid anolyte heating,
a 5L Pyrex glass beaker filled with deionized water was
placed between the lamp and the anodic compartment. As
a result, anolyte and catholyte steady temperatures were 29
and 28 ◦ C, respectively. The rest of conditions were as in
the previous chronoamperometry. The results under illumi-
nation showed an initial intensity increase attributed to the
photoreduction reaction (3). At 3.0 h 24 mmols of oxalic acid
were added to the anolyte, causing an intensity increase of
(9) 2.3 mA (Fig. 3). The second experiment was performed in
darkness. In this case, anolyte and catholyte steady temper-
atures were of 26 ◦ C. An intensity increase of 1.6 mA was
observed after 24 mmols oxalic acid addition. This increase
could be due to an effect of pH and, consequently, it is rea-
sonable to think that in the illuminated experiment there are
two contributions to the intensity rising: pH decrease and
light effect. In the experiment under light, current continued
growing after oxalic acid addition. This behavior was not
(11) observed when the chronoamperometry was performed in
darkness conditions. Thus, such gradual current increase can
(12) also be ascribed to the photoxidation reactions (10)–(16).
(13)

CO•− •−
2 + O2 → O2 + CO2 (14) 3.2.1.1. Current efficiency In order to verify that practically
all the current can be ascribed to hydrogen production, the
CO•−
2 + [Fe(C2 O4 )3 ]
3− → [Fe(C O ) ]2−
2 4 2
faradaic efficiency of the overall process was determined us-
ing the equipment described in Section 2.2, with a few mod-
+ C2 O2−
4 + CO2 (15)
ifications in order to quantify the evolved gas. A nickel mesh
Fe3+ + O•−
2 → Fe
2+ + O
2 (16) cathode was coiled and introduced into a burette for hydro-
gen measurement. This burette was submerged in catholyte
Note that the Fe (II) product of ferrioxalate photoxidation and filled with H2 SO4 1 M. Catholyte solution was not
(reactions (10)–(16)) also contributes to hydrogen produc- stirred in order to avoid errors due to the eventual capture
tion through reaction (2). of any bubble from the nitrogen gas flow. Anolyte solution
 L. Soler et al. / International Journal of Hydrogen Energy 31 (2006) 129 – 139
12
10
i (mA) 8 (a)
4 (b)
0
0.0 1.0 2.0
t (h)
Fig. 3. Effect of light on chronoamperometries for oxalic acid addition. Stainless-steel cathode, anolyte 0.4 M Fe(II), 0.1 M Fe(III),

Ecat.an = 1.20 V: (a) illuminated with lamp #1, anolyte at 29 ◦ C, catholyte at 28 ◦ C and (b) in darkness, anolyte and catholyte at 26 ◦ C.
was illuminated with lamp #1. The electrolysis mode was
galvanostatic, applying a 80 mA current between anode and
cathode during 30 min. The rest of experimental conditions
were the same as in the first experiment using oxalic acid.
The measured hydrogen was compared with the theoretical
hydrogen produced using Faraday law. Current efficiencies
of 95% were obtained in six different runs. The remaining
5% can be ascribed to residual oxygen reduction.
3.2.2. Nitrobenzene
In this case, the stainless steel cathode and lamp #2 were
used. Anolyte initial composition was 0.4 M Fe (II), 0.1 M
Fe (III), and pH was 1.5.
In Fig. 4, it can be observed that at 3.3 h, after an addi-
tion of 24 mmols of nitrobenzene to anolyte, the current de-
creased quickly. At the same time, a significant decrease in
anolyte temperature was observed (Fig. 4). This effect can be
attributed to the endothermic enthalpy of solution in water
of nitrobenzene: 4.0 kJ/mol [25]. Moreover, nitrobenzene is
only slightly soluble in water and the formation of micelles
due to its excess was observed. At 5.3 h 9.7 mmols nitroben-
zene were further added to anodic compartment with a very
small effect.
Nitrobenzene was selected as a sacrificial compound be-
cause it is degradable by Fenton-like reaction [26] but, from
their negative effect, it is obvious that the envisaged process
is not as general as expected.
3.2.3. Urea
Stainless-steel cathode and lamp #1 (separated 8 cm from
the anodic compartment) were employed in this experiment.
Anolyte composition was 0.4 M Fe (II) and 0.1 M Fe (III)
and the initial pH was 1.4. The anolyte and catholyte steady-
state temperatures were 62 and 47 ◦ C, respectively.
133
3.0 4.0 5.0
Two additions of solid urea were performed: 18 mmols
at 3.8 h and 57 mmols at 4.0 h. No significant effects upon
these additions were observed, as shown in Fig. 5, so the
presence of urea in the anolyte had no effect on the hydrogen
production, in spite of its basic character. The anodic pH at
the end of the experiment was 1.6.
In Fig. 5, it is also observed that current had a slight
reduction during the trial. In fact, the limiting currents
observed with the stainless-steel cathode in the ab-
sence of organics were lower in consecutive runs. This
effect is due to instability of stainless-steel cathode,
which became black and lost 1.9% of its weight during
the experiment, whereas the cathodic solution became
bluish.
The analysis of catholyte showed the presence at low con-
centrations of several common metallic cations in stainless
steel, such as Fe, Ni, Mn and Cr, confirming that the cathode
was degraded.
In fact, ferritic stainless steel undergoes embrittlement
when subjected to cathodic hydrogen evolution in aqueous
solutions [27], yielding a slight but noticeable corrosion in
our working conditions. Further experiments showed that
this effect is not observed when a nickel mesh cathode is
used. Thus, this metal is more suitable for our system and
was used in the rest of the experiments.
3.2.4. Aniline
The cathode was the nickel mesh one and the selected
lamp was #1. Anolyte composition was 0.2 M Fe (II) and
0.3 M Fe (III), with an initial pH of 1.0. The anolyte and
catholyte steady temperatures were 85 and 55 ◦ C, respec-
tively.
At different moments, 2–3 ml of distilled water were
added into the anolyte to compensate the evaporation caused
by the light source, up to a total of 7 ml.
134 L. Soler et al. / International Journal of Hydrogen Energy 31 (2006) 129 – 139

80 80
70 70
60 (a) 60
50 50

T (°C)
i (mA)
40 (b) 40
30 30
20 20
(c)
10 10
0 0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 5.5 6.0 6.5 7.0
t (h)

Fig. 4. Chronoamperometry and temperature evolution for nitrobenzene assay. Stainless-steel cathode, lamp #2, anolyte 0.4 M Fe(II), 0.1 M
Fe(III),
Ecat.an = 1.20 V: (a) anodic temperature, (b) cathodic temperature, and (c) current intensity.

25

20

15
i (mA)

10

0
0.0 1.0 2.0 3.0 4.0 5.0
t (h)

Fig. 5. Chronoamperometry for urea experiment. Stainless-steel cathode, lamp #1, catholyte at 47 ◦ C, anolyte at 62 ◦ C, 0.4 M Fe(II), 0.1 M
Fe(III),
Ecat.an = 1.20 V.

In Fig. 6, it can be observed that current grew quickly after
an addition of 22 mmols of aniline to anolyte at 3 h. After this
addition, the anodic pH became higher, getting a value of
1.4. Current intensity had a broad peak of 37 mA. From this
increment, it can be concluded that the presence of aniline
in the anolyte has a positive, although transient, effect on
the hydrogen production. Formation of a dark polymer was
also observed in the anodic surface that can be accounted
as polyaniline accumulation.
At different times, sulfuric acid was added up to a total of
29 mmols into the anolyte in order to counter aniline basic
character and to keep pH low enough to avoid iron hydroxide
precipitation. The anodic pH at the end of this experiment
was 0.9.
Afterwards, another chronoamperometry was started us-
ing the final solutions of the previous run, in order to eval-
uate the system stability. Initially, the lamp was separated
15 cm from the anodic compartment and 60 ml of distilled
water were added into the anolyte in order to compensate
for overnight evaporation. After 14.5 h, the lamp was placed
at 3 cm from the anodic compartment. In the first part of
the stability test, the current intensity started at 80 mA and
achieved a stable value around 7 mA after 4 h (Fig. 7). When
the lamp was moved again towards the anodic compartment
current intensity grew up to 24 mA and maintained this value
during 6 h.
With the purpose of studying the reproducibility of ani-
line addition effect, a new experiment was performed, us-
ing the same conditions of the first aniline test. After ani-
line addition (22 mmols), the usual rise of current inten-
sity was observed. Then the potentiostatic chronoamperom-
etry (1.20 V) was stopped and three new ones were per-
formed during 1000 s. The reproducible behavior of the
experimental system is observed in Fig. 8, where every
chronoamperometry recovered the initial values of current
intensity, around 80 mA. Current decays found should be
ascribed to transient polarization phenomena, which can
be tentatively attributed to the formation of an insulating
layer on polyaniline surface that disappeared when circuit
is open.
 L. Soler et al. / International Journal of Hydrogen Energy 31 (2006) 129 – 139 135

Fig. 6. Chronoamperometric plot for aniline experiment. Nickel cathode, lamp #1, catholyte at 55 ◦ C, anolyte at 85 ◦ C, 0.2 M Fe(II), 0.3 M
Fe(III),
Ecat.an = 1.20 V.

100 100
90 (c) 90
80 80
70 70
60 60
(b)

T (°C)
i (mA)

50 50
40 40
(a)
30 30
20 20
10 10
0 0
0.0 2.0 4.0 6.0 8.0 10.0 12.0 14.0 16.0 18.0 20.0 22.0
t (h)

Fig. 7. Aniline system stability evaluation. Nickel cathode, lamp #1, anolyte 0.2 M Fe(II), 0.3 M Fe(III),
Ecat.an = 1.20 V: (a) current vs.
time, (b) cathodic temperature, and (c) anodic temperature. See text for further details.

100
90
80
70
60
i (mA)

50
40
30
20
10
0
0 200 400 600 800 1000
t (s)

Fig. 8. Reproducibility of aniline chronoamperometries. Three consecutive plots are presented under the same conditions of Fig. 7.
136 L. Soler et al. / International Journal of Hydrogen Energy 31 (2006) 129 – 139

(a) (b)
25

20

i (mA) 15

10

0
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
t (h)

Fig. 9. Chronoamperometry for experiment with wood chips and cobalt. Nickel cathode, lamp #1, catholyte at 58 ◦ C, anolyte at 89 ◦ C,
0.2 M Fe(II), 0.3 M Fe(III),
Ecat.an = 1.20 V: (a) additions of wood chips suspension filtrate, and (b) addition of Co(II).

Table 1
Comparison of the effects for different substances

Sacrificial substance Lamp # Cathode Anodic Final anodic mmol added Addition Final I (mA)
[Fe(II)] (M)a T ( ◦ C) effectb

Urea + 1 S.S. c 0.4 62e 74 + ↓ 2.7

1,3-phenylenediamineg 9.9
Benzaldehide 2 S.S. 0.4 61 49 ↓ 8.5
Diethylamineg 1 S.S. 0.4 60e 24 ↓ 17
Nitrobenzeneg 2 S.S. 0.4 51 34 ↓ 20
Urea 1 S.S. 0.4 62e 74 0 16
Wood chips + CoSO4 1 Nid 0.2 89 — 0 18
Blankg 1 Ni 0.2 85 0 — 13
Aniline 1 Ni 0.2 34f 22 ↑ 13
Anilineg 1 Ni 0.2 85 22 ↑ 15
Aniline None Ni 0.2 22 22 ↑ 18
Ethanol 2 S.S. 0.4 75 713 ↑ 21
Oxalicacidg 2 S.S. 0.4 75 46 ↑ 86
a In each case the [Fe (III)] was 0.5 M-[Fe (II)].
b ↑ was used when positive effect was observed, ↓ for negative effect case and 0 when the addition had no significant effect.
c S.S.: Stainless-steel cathode.
d Ni: Nickel cathode.
e Lamp #1 separated 8 cm from the anodic compartment.
f 5L Pyrex glass beaker filled with deionized water was placed between the lamp and the anodic compartment.
g Linear sweep voltametry shown in Fig. 10.

Both electrochemical and chemical oxidative syntheses
of polyaniline have been studied [28,29]. In particular, Fe
(III) has been shown to be an oxidant of aniline, capable
of both polymerize and degrade the polyaniline depending
mainly on temperature [30]. At 30 ◦ C, low molecular weight
polymers are known to be formed, which appear to be sol-
uble in our experimental conditions. On the other hand,
at 85 ◦ C the proposed mechanism yielding polyaniline is
anodic oxidation, either direct or mediated by Fe (III)/Fe
(II) couple [29]. Note that the Fe (II) product of aniline
oxidation also contribute to hydrogen production through
reaction (2).
Two additional experiments were carried out to evaluate
the light effect in hydrogen production and in aniline oxi-
dation. The anodic compartment of the first experiment was
illuminated with lamp #1. In order to avoid anolyte heat-
ing, a 5L Pyrex glass beaker filled with deionized water was
placed between the lamp and the anodic compartment. As
a result, anolyte and catholyte steady temperatures were of
34 and 29 ◦ C, respectively. The rest of conditions were as
in the first aniline chronoamperometry. At 3.4 h 22 mmols
aniline were added to anolyte, causing an intensity increase
of 10 mA. The second experiment was performed in dark-
ness. In this case, anolyte and catholyte steady temperatures
 L. Soler et al. / International Journal of Hydrogen Energy 31 (2006) 129 – 139
200.0
180.0
160.0
140.0
i (mA) 120.0
100.0
80.0
60.0
40.0
20.0
0.0
0.500 0.700
Fig. 10. Linear sweep voltametries. See experimental conditions in Table 1: (a) aniline, (b) oxalic acid, (c) nitrobenzene, (d) blank, (e)
diethylamine, and (f) urea + 1,3-phenylenediamine.
were of 22 ◦ C. After 22 mmols aniline addition, an intensity
increase of 11 mA was observed.
Experiments demonstrate that degradation of aniline can
be performed in absence of light, pointing to a case of an-
odic aniline oxidation mediated by Fe(III)/Fe(II) couple. On
the other hand, although the intensity increases are similar
on both experiments the increase slope is higher under light
irradiation (15 mA/h) than in darkness (12 mA/h). This sug-
gests a possible contribution of light in the aniline degrada-
tion.
3.3. Effect of woodchips and CoSO4 addition
To perform this experiment, the used cathode was the
nickel mesh and the selected lamp was #1. The anolyte com-
position was 0.2 M Fe (II) and 0.3 M Fe (III), with an initial
pH of 1.0. The anolyte and catholyte steady temperatures
were 89 and 58 ◦ C, respectively.
A total amount of 0.52 g of pine wood chips were
mixed with 10 ml of sulfuric acid 6 M. This suspension
was prepared 24 h before the experiment. During the usual
chronoamperometry, when current intensity achieved the
steady state, 1–2 ml aliquots of the suspension filtrate were
added into the anolyte at different times, up to a total of 6 ml
(Fig. 9). After these additions, diluted CoSO4 · 7H2 O was
added to anolyte, in order to achieve a Co (II) concentration
of 0.01 M as well as a final sulfuric acid concentration of
0.13 M in the anodic solution (pH = 0.4). As shown, the
different additions had no effects in intensity values.
In contrast with the results claimed by Dhooge [4,8,31]
the utilization of Co (II) as cocatalyst in sulfuric acid me-
dia 0.13 M did not afford any significant improvement in
hydrogen production. This may be explained by taking into
137
(a)
(b) (c)
(d)
(e)
(f)
0.900 1.100 1.300 1.500
E (V)
account that the anodic pH was 0.4, which is not appropri-
ate for the reaction depicted in (3), because at this pH the
formation of Fe(OH)2+ is minimum [14,32]. Thus, using
wood chips as sacrificial matter has no apparent effect in
this hydrogen production system, even in the presence of
Co (II).
3.4. Comparison of the effects for different substances
Several other sacrificial substances were tested for our
process with mixed results. Table 1 shows the apparent ef-
fect of organic compounds addition in hydrogen production.
It also shows the final current intensity, measured at the
end of each experiment, for the ensemble of experiments
performed. The negative results obtained in several cases
demonstrate that the envisaged process is not operative for
every organic substrate. Cooling of the anolyte (see entries
for benzaldehide and nitrobenzene in Table 1), anode poi-
soning or pH increase out of the optimum working limits
are possible reasons for this unwanted effects and cannot be
disregarded in the development of this process.
Fig. 10 shows several linear sweep voltametries per-
formed at the end of the chronoamperometries. It can be
observed that current raising of all the experiments started
around 0.77 V, which is the thermodynamic oxidation po-
tential of ferrous iron, supporting our assumed electrode
reactions. Depending on the added organic substance and
on the experimental conditions, the slope of the linear zone
reached a different value.
4. Conclusions
From the experiments reported in here, the technical fea-
sibility of the present process has been demonstrated. It has
138 L. Soler et al. / International Journal of Hydrogen Energy 31 (2006) 129 – 139
three main advantages. The first one refers to the ability
of producing hydrogen from water, wastes and solar light
at a reduced cost vs. conventional electrolysis. The second
one is to combine different environmentally friendly pro-
cesses in one, resulting in a more effective method due
to the synergies found. Finally, the oxidation of pollutants
in the water is achieved and this represents an additional
benefit.
The process also avoids the anodic corrosion of a
stainless-steel anode. The use of cheap metals as nickel
or stainless-steel mesh electrodes represents an additional
advantage because of the low price of this metals compared
with usual precious metal based anodes.
However, we have shown that not every sacrificial sub-
stance has a positive effect, understood as an increasing
in the obtained current. Consequently, further research is
needed in order to ascertain which wastes or wastewaters
have the physico-chemical properties required to be used in
the present process.
Acknowledgements
The authors express their gratitude to APCI for fi-
nancial support and to Eurodia Industrie S.A. for kindly
supply of Neosepta cation exchange membranes. Special
thanks to Francesc Ramon for his helpful comments, to
Mar Tristany for kindly supply of several reagent samples
and to José Luis Bourdelande for flux densities measure-
ments.
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