i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 1 2 7 3 e1 1 2 8 1

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Analysis of a photochemical water splitting reactor with

supramolecular catalysts and a proton exchange membrane

C. Zamfirescu*, I. Dincer, G.F. Naterer

Faculty of Engineering and Applied Science, University of Ontario Institute of Technology (UOIT), 2000 Simcoe Street North,
Oshawa, ON L1H 74K, Canada

article info abstract

Article history: In this paper, a new type of photochemical water splitting system is proposed and analyzed.
Received 29 November 2010 The system comprises two reactors in which photocatalytic half-reactions of water reduc-
Received in revised form tion and water oxidation are conducted. The two reactors are divided by a proton conducting
24 December 2010 membrane. Complex molecular devices based on ruthenium-(bipyridine)2þ
3 photosensi-
Accepted 28 December 2010 tizers are dissolved in both reactors, which generate electrons or holes when exposed to high
Available online 11 March 2011 energy photonic radiation, and act as catalysts for water splitting. The selected molecular
devices for water reduction have a unique property to enhance the existence time of
Keywords: photoelectrons, such that the likelihood of generated electron pairs to produce a molecule of
Hydrogen production hydrogen is increased. In this study, the physicalechemical processes are analyzed and the
Solar light main design parameters of the reactor are determined. The engineering design consists of
Photocatalytic method a photochemical reactor, a mass flow controller to supply the fresh water, and two fans that
Reactors extract the products of water splitting.
Copyright ª 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights
reserved.

1. Introduction thermochemical water splitting, photo-electrochemical cells,

The most abundant source of energy on earth comes from
solar irradiation. The majority of physical and chemical
reactions encountered on earth, including photosynthesis and
water and air circulation in the atmosphere, are a direct or
indirect result of solar radiation. Fossil fuels (oil, coal, natural
gas, etc.) were originally produced by photosynthesis and
solar heating. Solar radiation, although fluctuating over short
periods of time, is a constant source of energy over long-term
periods. Moreover, unlike conventional power generation
stations, gradual expansion of solar power generating
systems is relatively inexpensive [1].
Several ways of harvesting and storing solar energy have
been developed over the past century. They include water
heating, steam generation with solar concentrators, solar
driven heat engines, solar ponds, photovoltaic panels,
and photocatalytic water splitting. In recent years, research
on the conversion of solar energy into chemical energy of
a fuel has gained momentum. Hydrogen fuel is viewed as
a promising means for storing solar energy because of its
beneficial energetic and ecologic qualities. Moreover, the
feedstock for solar hydrogen production is only water.
Water decomposition is a multi-electron chemical process.
For a complete reaction cycle, it needs two molecules of water
to generate one molecule of oxygen and two molecules of
hydrogen. The energy needed to drive the reaction at standard
conditions is 4.915 eV. This energy can be generated from one
photon of ultraviolet light with a wavelength shorter than
252.3 nm, or by two photons in the visible spectrum with
a wavelength shorter than 504.5 nm, or four infrared photons
of 1.23 eV. For a full reaction cycle to occur, 4 valence electrons
of two water molecules must be dislocated. This is normally

* Corresponding author.
E-mail addresses: calin.zamfirescu@uoit.ca, calinzam@gmail.com (C. Zamfirescu), ibrahim.dincer@uoit.ca (I. Dincer), greg.naterer@
uoit.ca (G.F. Naterer).
0360-3199/$ e see front matter Copyright ª 2011, Hydrogen Energy Publications, LLC. Published by Elsevier Ltd. All rights reserved.
doi:10.1016/j.ijhydene.2010.12.126
11274 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 1 2 7 3 e1 1 2 8 1
not achieved with a single photon, even at high energy,
because one photon can dislocate a single electron only on
a higher energy band. Thus, at least two photons are needed
for driving a half cycle and the other two in a subsequent
reaction to complete the water splitting process.
In nature, photosynthesis is the basic mechanism to split
the water molecule. It works through intermediate storage of
photoelectrons in complex catalytic cycles. The existing
commercial technology of splitting water is based on elec-
trolysis, which can be driven by solar-derived electricity. In an
electrolysis process, electrodes are used to “inject” electrons
into water for driving the oxygen and hydrogen half-reactions
for splitting of water. As mentioned above, the energy to drive
the reaction is 1.23 eV in standard conditions, for 4 electrons.
Thus, the difference of potential between the electrodes must
be at least 1.23 V. The electricity required to drive electrolysis
can be obtained from a photovoltaic panel or a solar heat
engine, thereby assembling in this way a solar hydrogen
generation device.
One of the barriers of solar hydrogen generation is related to
its high investment cost, as compared to hydrogen produced
from fossil fuels (e.g., natural gas). In electrolysis driven by
solar energy, the high cost is caused by two factors. Firstly, the
electrodes for electrolysis must be plated with platinum group
materials (PGM), which act as heterogeneous catalysts. It is
difficult to transfer electrons to water otherwise, since water is
not a conductive media. Secondly, photovoltaic cells and solar
heat engines are costly technologies with rather low efficiency
(8e25% maximum). Recent studies focused on the develop-
ment of supramolecular homogeneous catalysts dissolved in
a solution capable to transport electrons from the electrode’s
surface to the water molecule or the other way around
with high turnover rates. Geleti et al. [2] demonstrated
tetraruthenium homogeneous catalysts embedded in a bipyr-
idine molecular chain, capable of effectively oxidizing the
water molecule. Karunadasa et al. [3] discovered very active
homogeneous catalysts that evolve hydrogen from water with
turnover frequencies of 2.4 mol H2 per mol catalyst and per
second. When using such homogeneous catalysts, the need of
coating electrodes with PGM is eliminated and thus the cost of
the overall system may be more economically attractive.
Another approach, which potentially eliminates the need
of PV-panels and is believed to be one of the ways of producing
inexpensive and sustainable hydrogen fuel and oxygen is
photochemical water splitting through supramolecular
devices, capable of capturing incident solar radiation, gener-
ating electrons or holes at the active centre where water can
be reduced or oxidized, respectively. Such systems, currently
in development throughout the world, consist of supramo-
lecular complexes of organic molecules which possess active
metallic centers and mimic (partially) the natural photosyn-
thesis. The water photo-oxidizing reaction is according to
hv
2H2 OðlÞ/4Hþ þ 4e þ O2 ðgÞ; Vox ¼ þ0:82 V; NHE:
Here the active centre absorbs two electrons from one water
molecule under the influence of photonic radiation and for
a complete cycle two water molecules are required. The water
reduction reaction needs also two molecules of water
according to
hv
2H2 O þ 2e /H2 þ 2OH ; Vred ¼ 0:41 V; NHE: (2)
It is a major technological challenge to maintain photo-
electrons for a sufficiently long duration at the active centre.
A recently declassified proprietary technology of Phoenix
Canada Oil Ltd., developed by Brewer and Elvington [4]
demonstrated at a laboratory scale the water photo-reduc-
tion reaction, with supramolecular devices capable of gener-
ating multiple electrons and maintaining them at the active
center for a long enough duration. In this process, water is
exposed to an electrically charged supramolecular complex
that reduces water to hydrogen at the active centre. Simulta-
neously, the supramolecular complex is exposed to solar
radiation, during which the incident photons dislocate
multiple electrons. Electrons propagate along a molecular
chain within nanoseconds and “recharge” the supramolecular
complex with electrons. The supramolecular complex can be
placed on a support, or dissolved in water.
This paper extends the analysis of a new photochemical
water splitting device proposed previously by the same
authors [5], by considering new paths for improved efficiency.
The reactor comprises a photocatalytic water reduction
reactor, and a photocatalytic water oxidation reactor sepa-
rated by a proton exchange membrane of nafion. The water
oxidation reactor generates, according to Eq. (1), protons and
oxygen gas. It is continuously supplied with fresh water, while
all other chemicals remain in solution, which keeps an acidic
pH. The oxygen rises up and it is continuously removed from
the solution with a fan (vacuum pump or compressor). The
protons migrate through the membrane, due to a concentra-
tion differential. Cheap electrodes and an external wire are
used to transfer electrons from the oxygen production to the
hydrogen production reactor. On the photo-reduction reactor,
special chemical complexes are dissolved in water to reduce
protons according to reaction (2). In the same reactor, the
following reactions arise in competition with reaction (2),
hv
2Hþ þ 2e /H2 ðgÞ (3)
and
OH þ Hþ /H2 O: (4)
The role of an engineer consists of finding the best surface
areas exposed to solar radiation and best catalyst concentra-
tions that split the water molecule effectively and steadily.
The paper examines the system design, and its performance
and improvement recommendations. In the design, the
supramolecular complexes, as mentioned above, are not
consumed during the process.
2. System description
(1) The conceptual design of the system is shown in Fig. 1, which
illustrates a vessel comprising two photochemical reactors
separated by a proton exchange membrane (PEM). Both reac-
tors are exposed to solar radiation. On the left side, the water
photo-oxidation reactor is located, in which selected supra-
molecular photo-catalysts are dissolved in a proper quantity
to generate electrical charges at reaction sites to oxidize water
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 1 2 7 3 e1 1 2 8 1 11275

Separation
O 2 out wall H 2 out
solar radiation

solar radiation
Exposure to

Exposure to
Water oxidation reactor Water reduction reactor
(dissolved supramolecular (dissolved supramolecular
complexes for water complexes for water
oxidation ) reduction)
2H 2O+2e-→H2 (g)+2OH -
2H 2O→O2 (g)+4H ++4e-
2OH-+2H +→2H2 O
+ Electrode 2H ++2e-→ H 2(g)
H+ - Electrode

Fresh Proton exchange

water in membrane
Electrons flow

Fig. 1 e Conceptual design of the photochemical water splitting reactor.

and produce oxygen gas and protons, according to Eq. (1). The
electrons are “donated” by supramolecular complexes to
a positively charged electrode. Fresh water is continuously
supplied to this reactor, while all other chemicals remain in
solution. The flow rate of fresh water is adjusted such that the
water level in the vessel remains constant. The protons
released by the photochemical oxidation reaction are driven
by a concentration gradient and they cross the proton
exchange membrane. In the water reduction reactor, selected
supramolecular complexes for photocatalytic reduction of
water to hydrogen are dissolved in proper concentration.
These catalysts generate photoelectrons which facilitate
reactions (2)e(3) to occur. Electrons, which are transferred
from the oxygen-evolving reactor are donated at the electrode
surface to the supramolecular devices, which under the
influence of photonic radiation transmit negative charges to
the reaction sites. Water is not consumed in a steady-state
operation; the only overall reaction in this reactor is that of
proton reduction to form hydrogen gas. Above the liquid level,
the product gases (oxygen and hydrogen, respectively) are
continuously extracted with the use of external fans, which
maintain low pressure in the system. In order to avoid effec-
tive water migration through the proton exchange membrane,
the pressure is maintained at about the same level on both
sides. In a practical implementation, the photochemical
reactor can be constructed with a flat plate type geometry.
Some part of this incident radiation (UV and V spectra) is used
for the photochemical reaction. The remaining portion
(mostly IR) can be used to heat water by a flat panel below the
photochemical reactor. A combined hydrogen and heating
system can be devised in this way.
3. System analysis and photochemical
process selection
The photochemical system has four main components: the
oxidation and reduction reactors, the proton exchange
membrane and the electrodes. In this section, the main char-
acteristics and modeling aspects of all four components are
analysed, in view of rational selection of the materials and for
improving the design of the complete system. In the subse-
quent section, results are presented based on these models.
3.1. Water oxidation reactor
There are many catalysts based on complex organic mole-
cules and rare metals (especially PGMs) that are capable of
11276 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 1 2 7 3 e1 1 2 8 1

oxidizing water to evolve oxygen photocatalytically. Past
results were summarized by several authors, e.g., Amouyal [6],
MacDonnell [7]. Ruthenium based complexes based on
4-picoline and 2,20 -bipyridine were synthesized and charac-
terized by Duan et al. [8]. They promote photochemical water
oxidation. Bipyridine is a key chemical compound which can
be linked to a ruthenium metal active center to have the role
of photosensitizer. The photosensitizer “dislocates” electrons
each time when the active center is hit by photons of appro-
priate energy. Bipyridine is derived from pyridine C5H5N,
which is an aromatic heterocyclic organic compound. Bipyr-
idine, with chemical formula (C5H4N)2, comprises two pyri-
dine rings. A typical photosensitizer embeds a ruthenium
atom in three bipyridine molecules and it is known as
[Ru(bpy)3]2þ. This molecule is both a good reductant and
oxidant.
The characteristics of the rutheniumebipyridine
[Ru(bpy)3]2þ complex are discussed here in view of selecting
an appropriate molecular device for water oxidation as part of
the oxygen production reactor design. Fig. 2a shows the
molecular structure of [Ru(bpy)3]2þ. The molecule has the
ability to store electronic energy in an excited orbital around
the Ru atom. It absorbs photons at 450 nm (2.75 eV) and
evolves [7] to an excited single molecule [Ru(bpy)3]2þ**, which
rapidly loses energy (0.65 eV) to become the more stable triplet
structure [Ru(bpy)3]2þ* that remains stable for 860 ns, enough
time for one quarter of the water oxidation reaction to be
catalyzed, according to Fig. 2b. The [Ru(bpy)3]2þ* donates 1
electron to an electron acceptor and loses 0.57 eV, while
transforming itself in [Ru(bpy)3]3þ. In this state, it becomes
catalytically active to assist one quarter of the water oxidation
reaction by delivering 1.53 eV and receiving 1 electron from
water, while returning at the ground state [Ru(bpy)3]2þ. Four
successive catalytic cycles are needed to complete one water
oxidation cycle. The energy efficiency of this process can be
defined as the useful energy (transmitted to the water oxida-
tion reaction) divided by the photonic energy. From Fig. 2b, the
efficiency of the catalytic cycle for water photochemical
oxidation through the rutheniumebipyridine complex at
450 nm is 55.5%.
One crucial issue with the operation of this oxidation
mechanism regards the nature of the electron acceptor. The
electron acceptors consume in the reaction; therefore for
a continuous process one must supply the process with fresh
electron acceptors and remove the consumed acceptors.
Many types of electron acceptors are known, i.e., [Co(NH3)5Cl]
Cl2, Na2S2O8 (Duan et al. [9]), K2S2O8 (Mori et al. [10]), AgNO3
(Tessier et al. [11]), S2O8 or [Co(NH3)5Cl]2þ (Christensen et al.
[12]). For example, if the persulfate S2O2
8 is used as an electron
acceptor, the photo-excitation yields

2þ hv
3þ
2 RuðbpyÞ3 þS2 O2
8 /2 RuðbpyÞ3 þ2SO2
4 : (5)
The peroxodisulfate (S2 O2
8 )
is consumed as it transforms in
sulphate (SO2 4 ). Once the photosensitizer is excited, it is able
to react with the water molecule at the active centre. Chris-
tensen et al. [12] used colloidal RuO2 as catalyst which receives
electrons from the exited [Ru(bpy)3]3þ. The compete catalytic
cycle reads:

3þ RuO2
2þ
4 RuðbpyÞ3 þ2H2 O / 4 RuðbpyÞ3 þO2 þ 4Hþ : (6)
In reaction (6), the photosensitizer steals one electron from
the catalyst (RuO2) at each photocatalytic cycle; then, during 4
catalytic cycles it charges with þ4e “holes” and becomes able
to split 2 water molecules.
An electron acceptor mentioned in the literature is meth-
ylviologen (MV2þ), a chemical molecule based on the bipyr-
idine structure (Lyris et al. [13]; Autrey et al. [14]). However,
coupling rutheniumebipyridine systems with methylviologen
as electron acceptor, in order to oxidize water is improbable e
as reported by Christensen et al. [12] e because the oxidation
process is slower than the electrical charge lifetime in the
system. Another recyclable (non-sacrificial) electron acceptor
has been identified by Hauenstein et al. [15], namely mercury-
II. The oxygen generation with mercury-II as an electron
acceptor has also been investigated by Christensen et al. [12],
who show that upon irradiation of water containing
[Ru(bpy)3]2þ at pH 3 and 0.01 mol/dm3 Hg(NO3)2 and colloidal
RuO2 of 3.2  105 mol/dm3, the rate of oxygen production was
about (1.3  0.3)  108 mol/dm3min. However, the quantum
efficiency of oxygen production was rather low, i.e., 0.25%.

2+**
Charge 2+ [RuBpy]
0.65 eV

2+*
[RuBpy] EA

0.57 eV
+
EA
hν@ 450 nm [RuBpy]
3+
2.75 eV
+ -
0.5H 2O+hν→0.25O 2(g)+H (aq)+EA
η=1.53eV/2.75eV=55.5% 0.5H 2O

ΔH=1.53 eV
ΔG=-0.71 eV
Ruthenium atom ΔS=7.5 meV
2+
[RuBpy]
+
0.25O 2(g)+H (aq)
Pyridine ring

a 2+
Molecular structure of [RuBpy] b Water oxidation cycle at 450 nm

Fig. 2 e Photo-oxidation of water molecule with [RuBpy]2D complex [Discovery Studio 3.0 has been used to generate the
molecule].
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 1 2 7 3 e1 1 2 8 1 11277

In previous work [5], the photo-oxidation system in Ref. [12]
has been selected for the oxidation reactor of the photochemical
water splitting device from Fig. 1. However, the oxygen
production rate of the system reported in Ref. [12] is relatively
low as compared with more recent studies. The authors found
the results of Duan et al. [8] to be more suitable as a basis for
developing the newly proposed system, which reported
a generation rate of 80 mdm3/h of oxygen at a turnover rate of
0.23 s1 and a turnover number (TON) of 550. The system
operates in pH 7 solution and uses the following complex as
photosensitizer: [Ru(bpy)2(dcb)]2þ, where dcb ¼ 4,40 -dicarbox-
ylethyl. The photosensitizer functions similarly as the
[Ru(bpy)3]2þ analyzed above. Once excited by the photonic
radiation, the photosensitizer releases electrons to the electron
acceptor, which in this case was S2O2 8 . Once it donates elec-
trons, the electron acceptor transforms irreversibly according to
S2O2 2
8 / 2SO4 and it remains in the solution. The activated
photosensitizer delivers electrons to the catalyst [RuL(pic)3]
(pic ¼ 4-picoline, H2L ¼ 2,6-pyridine-carboxylic acid). When
activated, this generates one oxygen molecule per four catalytic
cycles. The preparation and performance characteristics of the
system [8] are indicated in Table 1.
The proton production rate is four times higher than the
oxygen yield rate. Based on the data reported in Table 1, this is
8 mmol (Hþ)/dm3s. The rate of fresh water to be added to the
system is double than the moles of produced oxygen, namely
it is 4 mmol (H2O)/dm3s.
We attempt to design and control the reactor such that it
operates at (or as close as possible to) design conditions
reported in Table 1, which are demonstrated by real measure-
ments. In order to accomplish this, the products (oxygen and
protons) must be continuously drained out of the system, and
fresh water must be added to the system in the appropriate
rate. Extraction of oxygen is relatively easy. With reference to
Fig. 1, this can be performed by a fan (or a vacuum pump) to
slightly de-pressurize the space above the liquid level in the
reactor. Extraction of the protons can be made via a proton
exchange membrane, which is discussed in the next section.
3.2. Proton exchange membrane
Nafion is used as the proton exchange membrane, with the role
to extract protons produced in the oxidation reactor, and
deliver them to the water reduction reactor e see Fig. 1. Nafion
is a sulfonated tetrafluoroethylene based fluoropolymerecopol-
ymer. The membrane is impermeable to oxygen and hydrogen.
Therefore, these gases do not have any chance to mix together as
they are collected from two separate compartments. The
membrane is also permeable to water, but water migration can
be minimized through the adjustment of the osmotic pressure.
Proton exchange membranes (PEMs) are extensively used in fuel
cells and water electrolysers. In a water electrolyser, a gradient of
proton concentration across the membrane is continuously
maintained by application of an electric voltage between the
cathode and anode. In our case, the gradient of proton concen-
tration is assured by creating a proton source in the water
oxidation reactor, and a proton sink in the water reduction
reactor. Therefore, the externally applied electrical current
which makes a PEM electrolyser work is replaced in the case of
our photocatalytic system with the flux of externally applied
photonic radiation.
Fig. 3 illustrates the differences between a typical PEM
electrolysis cell and our system, both of which utilize Nafion
membranes for proton transport. The electrolysis cell is
characterized by a complex flow system:
 the transport of protons is mainly due to electro-osmotic
forces applied at the two porous electrodes (the anode acts
as proton source and the cathode as a proton sink);
 transport of protons by Fick’s diffusion is in general
neglected;
 convective transport of protons occurs and it is accounted
for, if there is a significant pressure difference between the
anode and cathode sides to create a Darcy flow;
 water is transported across the membrane by the Darcy flow
under pressure differences;
 water is also transported by diffusion due to concentration
differences;
 water is also transported by electro-osmosis drag (protons
pull some water molecules).
In our system, however, there is no external potential
applied on the two sides of the membrane. Therefore, the
main driving force of proton transport is caused by a concen-
tration gradient. The water oxidation reactor contains an acid
solution, characterized by a high concentration of protons,
and a low pH. The typical pH values e used in this study e are
indicated in the figure. In the oxidation reactor there is a pH of
7.2 (see previous section), while in the reduction reactor e
which contains a basic solution e the pH is 9.1 (see next
section). Therefore the concentration difference can be
approximated with

 
DCHþ ¼ 1= V0 10pHoxy  10pHred (8)
3
where V0 is the molar volume of 24.5 dm /mol, approximately
655 molHþ/m3.

Table 1 e Characteristics for photochemical water oxidation system by [8].

Parameter Characteristics Remarks

Photosesitizer Bi(2,2’-bipyridil)ruthenium-II(dcb); [Ru(bpy)2(dcb)] 2þ

5.0  104 mol/dm3
Catalyst Tris(4-picoline)ruthenium-L; [RuL(pic)3] 5.0  105 mo/dm3
Electron acceptor Dissolved Na2S2O8 9.0  103 mol/dm3
Illumination Filtered light with 400 nm < l < 780 nm at 0.3 W/cm2 w900 W/dm3
pH pH adjuster e phosphate/acetonitrile (10/1.1 per volume) 7.2
O2 yield rate At turnover number 550 and turnover frequency 0.23 s1 2 mmol/dm3s
11278 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 1 2 7 3 e1 1 2 8 1

O2 ,out H2 ,out O2 ,out H2 ,out

H2 O,out Anode Cathode H2 O,out

H+ High H+
H2 O,ΔP concentration
Low H+
Water concentration
H2O,diffusion oxidation Water
reactor H+ reduction
(pH=7.2) reactor
H2O,electro-
PEM osmosis PEM (pH=9.1)

H2O,in H2O,in

Electrons Electrons

a
out in
Flows in a PEM electrolyser cell b Proton transport in photochemical
(main driving force: electroosmotic) reactor (driving force: pH difference)

Fig. 3 e (a) Proton exchange and flow processes in a PEM electrolysis cell, and (b) the combined photochemical reactor.

Fick’s law for diffusion can be used to estimate the flow
rate of protons across the membrane.
 
dCHþ
J ¼ D
dx
where dx represents the coordinate along the membrane
thickness. The typical proton diffusion coefficient for the nafion
membrane, according to Haddad et al. [16], is D ¼ 4.5  109m2/
s, and a typical thickness of 0.3 mm. Therefore, the proton flux
is 0.01 mol/m2s, which corresponds to a proton current density
through the membrane of w0.95 A/cm2.
3.3. Water reduction reactor
For photocatalytic water reduction, we focus on the system by
Brewer and Elvington [4], also described in Brown et al. [17],
Arachchige et al. [18], and Rangan et al. [19]. In total, 7 molec-
ular complexes were investigated from which 4 have been
dissolved in water and 3 in a solution of acetonitrile (CH3CN).
The molecular compound that showed the maximum yield
was [{(bpy)2Ru(dpp)}2RhBr2](PF6)5 in a basic aqueous solution of
pH 9.1. This molecular complex has two 2,20 -bipyridine (bpy)
branches that embed one ruthenium (Ru) atom each. The
structure of the subunit [{(bpy)2Ru(dpp)}2RhBr2]5þ is presented
in Fig. 4. The Ru atom is the light absorber (LA) and it transfers
one electron each time it is hit by a photon. The compound acts
as a molecular device which generates two photoelectrons at
the active centre for each catalytic cycle. The electrons are
long-lived at the catalytic centre where the hydrogen-evolving
reaction occurs according to 2H2 O þ ED/H2 ðgÞ þ 2OH þ EDþ
(where ED stands for electron donor).
Bipyridine has the role of a terminal ligand (TL) that
possesses the quality of long-lived metal-to-ligand charge
transfer excited states. This facilitates the presence of elec-
trical charge in the system for enough time to react with the
water molecule (as mentioned also above). The complex (dpp)
represents 2,3-bis(2-pyridil)pyrazine, which has the role of
a bridging ligand that transfers the electrical charge to an
electron collector, which is a metal atom, in this case rhodium
(Rh). This molecular complex is unique and shows effectively
the water reduction to hydrogen. The two-branch complex
with Ru light absorbing atoms can collect up to 2 electrons and
convert trivalent Rh to monovalent Rh, which further reduces
(9) the water molecule. This feature is unprecedented and allows
for multi-electron photochemistry.
With a 5 W monochromatic LED array, the yield of hydrogen
was a maximum 10.9 mmol in 4 h for a wavelength of 470 nm
(blue light). The electric-to-photons efficiency of the illumi-
nation system has been found as 1.3%. At a wavelength of
520 nm, the hydrogen production rate diminishes substan-
tially. Brewer and Elvington [4] measured the produced
hydrogen, both in the gas phase (above the reactor) with
a chromatograph, and dissolved in liquid, which was calcu-
lated using Henry’s law, with the reported solubility of
hydrogen in various solvents.
3.4. Electron transport subsystem
The equivalent electrical circuit of the photochemical water
splitting device is presented in Fig. 5. The voltage generated by
the photo-sensitizers dissolved in the oxygen and hydrogen
production reactors are >0.82 V, NHE and 1.8 V, NHE [17],
respectively. The generated energy is used to drive the half
reactions, which consume 0.82 V and 0.41 V, respectively. The
remaining electric energy is dissipated through various losses,
Fig. 4 e The multi-electron molecular device
[{(bpy)2Ru(dpp)}2RhBr2]5D for water photochemical
reduction [Discovery Studio 3.0 has been used to generate
the molecule].
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 1 2 7 3 e1 1 2 8 1 11279

Protons flow Table 2 e Characteristics for photochemical water

reduction system [18].
Parameter Characteristics Remarks

Oxygen Hydrogen Molecular [{(bpy)2Ru(dpp)}2RhBr2](PF6)5 65 mmol/dm3

evolving evolving device dissolved in CH3CN
>0.82 V, 1.8 V, Electron N,N-dimethylaniline (DMA) 1.5 mol/dm3
NHE NHE donor
0.82 V, 0.41 V, Illumination Monochrome l ¼ 470 nm 15 W/dm3
NHE NHE and l ¼ 520 nm
pH pH adjuster CF3SO3H, 4.46 mL 9.1
total volume
H2 yield rate Maximum achieved during 1.15 mmol/dm3s
3 tests at l ¼ 470 nm
Electrons flow H2 yield rate Maximum achieved during 0.33 mmol/dm3s
3 tests at l ¼ 520 nm
Cumulated losses
H2 yield rate Averaged for solar 0.75 mmol/dm3s
< 1.39 V
radiation (TON w38)
Fig. 5 e Equivalent electrical circuit of the photochemical
water splitting device.

 the volume (and therefore the content of chemicals) of the

reactors must be adjusted such that the two reactors can be
coupled by the interface condition. The flow rate of protons
including ohmic, concentration and activation loses at the
produced in the oxidation reactor must be the same as the
electrodes. For the system to be self-sustaining, these must be
flow rate of protons crossing the membrane, and the same
lower than 1.39 V. Practical experience with PGM coated
as the number of reduced protons in the water reduction
electrodes in fuel cell and electrolysis cells shows that the
reactor;
over-potentials are about 0.4e0.6 V.
 the surfaces exposed to solar radiation of each reactor must
The ionic molecular devices attach to the electrode surface
be calculated such that the reaction conditions e regarding
where they exchange electrons (donate or accept) with high
the illumination e are met;
activity. Therefore, there is no need for expensive catalysts
 the parameters of two fans must be specified (flow rate per
(like PGM) to be coated on the electrode surface. Basic graphite
capacity of reactor) to assure that the oxygen and hydrogen
electrodes or lower cost titanium dioxide or iron-based elec-
are swept out at the rate corresponding to the reaction;
trodes, with relatively low activity, can be deposited on the
 a mass flow controller for dosing fresh water must be pro-
electrode surface. Hematite and titanium dioxide are
grammed to deliver the required water in the oxidation
preferred candidates because of lower cost and they have
reactor and thus maintain the desired pH.
photo-catalytic activity in the ultraviolet and visible spectra.
In a typical approach [20], titanium dioxide is deposited on
Based on the above remarks, the main parameters char-
glass as a transparent layer and it shows high activity when
acterizing the design geometry are determined and listed in
interacting with a [Ru(bpy)3]2þ photo-sensitizer.
Table 3. The assumed geometrical configuration of the system
consists of a compound flat plate panel having:

 glass exposed to incident radiation on tilt surface; the

4. Results and discussion
Assume that the photocatalytic water splitting device e based
on the concept introduced in Fig. 1 e maintains the reaction
conditions in its two reactors. The composition of chemicals
in the oxidation reactor is summarized in Table 1. Table 2
presents the chemical composition in the water reduction
reactor. The processes in both reactors were demonstrated in
the lab by the respective authors [8,17]. Both investigators
used batch reactors and artificial sunlight in their tests. This
paper shows a device which transforms the batch reactors in
flow reactors. As discussed above, oxygen and hydrogen gas
are continuously drawn out from the process, while protons
flow through the proton exchange membrane under the
driving force created by the pH difference between the two
reactors.
The following issues affect the design of the photocatalytic
water splitting device:
average incident radiation is assumed 250 W/m2day;
 a titanium dioxide transparent layer acting as photo-
electrode;
 a planar reaction room for water oxidation with thickness
dO2 where fresh water is supplied, from where oxygen
evolves and the solution is prepared according to Table 1;
 the oxidation reactor is assumed to absorb light in the UV
and highest range of visible spectrum, namely 300e420 nm;
 a transparent proton exchange membrane allowing protons
to pass;
 a planar reaction room for water reduction with thickness
dH2 from where hydrogen evolves; the reactor absorbs light
in the visible spectrum in the range 420e600 nm;
 a flat plate solar collector for water heating placed below the
hydrogen production reactor and separated by an IR trans-
parent filter which absorbs radiation in the lowest range of
the visible spectrum and in infrared, for wavelengths higher
than 600 nm.
11280 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 1 2 7 3 e1 1 2 8 1

Table 3 e Main geometric design parameters of the water splitting device.

Design parameter Equation Value Remarks
R l2 IO2 ¼ 20 W=m2
Absorbed radiation I¼ l1 Il dl Calculated based on reference irradiance
IH2 ¼ 70 W=m2
spectrum from [21]
Iheating ¼ 160 W=m2
000
VH2  IH2  n_ H2 2 VH2 000
Volume ratio of reactors 000 ¼ ¼ 1:5 n_ , mols produced per second and volume
VO2  IO2  n_ O2 1 VO2

dH2 VH2  A dH2

Thickness ratio of the ¼ ¼ 1:5 A is the panel surface
dO2 VO2  A dO2
plate reactors
n_ H2
Proton exchange ¼ 0:005 APEM ¼ 0:005n_ H2 Assumed 0.3 mm PEM thick n_ H2 ,
APEM
membrane area in mmol H2 per s

The design calculations show that the water reduction
reactor will have a higher volume than that of water oxidation
and that 8% for the oxygen-evolving reaction, 28% for the
hydrogen-evolving reaction and the rest of 64% is delivered to
the solar water-heating panel.
The efficiency of hydrogen production is low; for example if
only the hydrogen reactor is considered, with a 5 W mono-
chrome light source with 1.3% electricity-to-light efficiency at
470 nm during 2 h the hydrogen production is only 8 mmol.
Thus 468 J are consumed to produce hydrogen equivalent with
8 mmol  0.286 J/mmol ¼ 2.29 J; the efficiency is 0.48%. More
radiation energy is needed if one considers the combined
reactor for hydrogen and oxygen production; the efficiency
becomes 0.31%. A general definition for production efficiency
of the reactor proposed in Fig. 1 is:
00
n_  HHVH2
h¼
IO2 þ IH2
00
where n_ is the hydrogen production rate in mmol/m2s and I is
the intensity of incident solar radiation per unit of reactor
surface measured in W/m2.
Fig. 6 presents the efficiency of hydrogen production for
three cases. The only difference among the three cases regards
only the water reduction reactor, namely the molecular
complex has been changed. The considered molecular
complexes are those published in the paper by Arachchige et al.
[18]; note that the complex [{(bpy)2Ru(dpp)}2RhBr2](PF6)5 is the
one selected for the present reactor design (the selection has
been made based on the criterion of maximum hydrogen yield).
The low value of the efficiency justifies the practical
application of the system only on the basis of reduced
investment cost, which eventually can result in lower lifetime
cost for hydrogen production as compared to other systems.
However, at this early stage, the system is not enough efficient
to compete with other hydrogen production systems because
of its low efficiency. Heat delivered to the infrared solar panel
is a useful effect, and with such a case, the system efficiency
can be defined as:
n_ 00  HHVH2 þ 0:9  Iheating
hcog ¼ ; (11)
IO2 þ IH2 þ Iheating
where it has been assumed that there are 10% thermal losses
at the solar thermal panel, and the subscript “cog” refers to
(10)
cogeneration (of hydrogen and heating). The efficiency of the
cogeneration system becomes 58%, which is due to the heat-
ing component. The hydrogen generation contribution to the
efficiency is about 0.11%.
A simple system (which includes mainly a glass panel and
a nafion based porous media) can cost e considering the cost
of transparent glass e below 10$ per square meter. The lab
experiments are at an early stage of development. It is
believed that the system can be optimized to reach more than
1% efficiency e a fact that can lower the cost of produced
hydrogen below 1 $/kg.

0.32

5. Conclusions
Selected
0.31
This paper proposes a device for hydrogen production through
η, %

photocatalytic water splitting that uses two photo-reactors. In

0.30 the first reactor, water is photo-oxidized to oxygen gas, while
in the second, hydrogen is generated photocatalytically.
0.29 Several chemical reactions occur concurrently in the second
reactor: proton reduction, water reduction with hydroxide
formation, hydroxide and proton recombination to form
water. The overall result is hydrogen and oxygen generation,
without consumption of any chemicals. This result is
conjectural because in the original system by the authors
[8,17] electron donor and electron acceptors were consumed
in the reaction. The newly proposed system eliminates the
Fig. 6 e The production efficiency of photocatalytic water electron donors and acceptors by inserting an electron con-
splitting. ducting media between the two reactors (electrodes and
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 3 6 ( 2 0 1 1 ) 1 1 2 7 3 e1 1 2 8 1
external circuit). This hypothetical electron transfer process
remains to be proved experimentally.
In both reactors there are prepared solutions with complex
molecular devices which contain photo-sensitizers, electron
acceptors and donors, active catalytic centres and pH regula-
tors. The preparation of chemicals in both reactors was
adopted from previous work of others. This paper proposed
a means to couple the two reactions, with the help of a proton
selective porous transport membrane based on nafion, which
is typically used in proton membrane exchange fuel electrol-
ysis cells or fuel cells.
From this study, is feasible to couple the two reactions in
order to obtain a system which, overall, splits water, at the
expense of only solar energy and water. The chemicals used
are inexpensive and meant to be prepared only once. The
general geometric characteristics of the design are calculated
and reported. Although the efficiency is low (below 1% with
respect to hydrogen’s HHV) this can be compensated by the
fact that the system is inexpensive. Further investigation with
respect to transport phenomena through the membrane, and
regulation of the system under variable light conditions, must
be pursued in order to progress toward a working prototype.
Using photochemical hydrogen production in combination
with other generation e such as heating e can be a promising
path toward early commercialization of the technology.
Acknowledgements
Assistance and financial support of this research from
Phoenix Canada Oil Company Ltd. (particularly Mr. Donald
Moore) are gratefully acknowledged. The discussions with our
colleague Ron Roberts suggesting the insertion of the external
circuit are greatly appreciated.
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