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Review

An overview of photocells and photoreactors for photoelectrochemical water splitting

Lorna Jeffery Minggu a,*, Wan Ramli Wan Daud a,b, Mohammad B. Kassim a,c
Fuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor, Malaysia Department of Chemical & Process Engineering, Faculty of Engineering & Built Environment, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor, Malaysia c School of Chemical Sciences & Food Technology, Faculty of Science & Technology, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor, Malaysia
b a

article info
Article history: Received 5 November 2009 Received in revised form 18 February 2010 Accepted 27 February 2010 Available online 8 April 2010 Keywords: Photocell Photoreactor Photoelectrochemical Water splitting Hydrogen

abstract
Solar hydrogen production from direct photoelectrochemical (PEC) water splitting is the ultimate goal for a sustainable, renewable and clean hydrogen economy. While there are numerous studies on solving the two main photoelectrode (PE) material issues i.e. efciency and stability, there is no standard photocell or photoreactor used in the study. The main requirement for the photocell or photoreactor is to allow maximum light to reach the PE. This paper presents an overview of the PE congurations and the possible photocell and photoreactor design for hydrogen production by PEC water splitting. 2010 Published by Elsevier Ltd on behalf of Professor T. Nejat Veziroglu.

1.

Introduction

Generation: H2O energy (solar) / H2 O2 (PEC reactor) Consumption: H2 O2 / H2O energy (Fuel cell) Photoelectrochemical (PEC) water splitting has the potential to be an efcient and cost effective way to produce hydrogen where the PE in PEC system absorb sunlight and split water directly into hydrogen and oxygen. The main work in PEC water splitting still concern increasing the efciency and stability of the photoactive materials [3,4] to achieve the required efciency target of 10% that will be viable for commercialization [5]. At the moment stable PE materials

The interest in extracting hydrogen from water is fueled by the need to nd a renewable, sustainable and environmentally safe alternative energy source. Hydrogen is considered as a viable option to todays fossil fuel based energy source especially when it is produced from water and only sunlight as the energy input [1]. Hydrogen is an energy carrier, when used in fuel cell which combines it electrochemically with oxygen from air thus producing water and energy in the process [2]. This completes the consumption and regeneration cycle of hydrogen.

* Corresponding author. Tel.: 603 89216050; fax: 603 89216024. E-mail address: lorna_jm@yahoo.com (L.J. Minggu). 0360-3199/$ e see front matter 2010 Published by Elsevier Ltd on behalf of Professor T. Nejat Veziroglu. doi:10.1016/j.ijhydene.2010.02.133

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based on metal oxide have rather low efciency of several percent [6e8] while high efciency materials based on multijunction conventional semiconductor can achieve slightly above 10% [9e11] but degraded within a short time. There are various types of photocell or photoreactor used for testing the photoactive materials that forms the PE. Apparatus for PEC water splitting is essentially a heterogeneous photoreactor as the photoactive material is immobilized on a substrate forming the PE. As electrodes are involved, the apparatus are also known as cell or photocell as commonly referred to in electrochemistry. Photocell or photoreactor geometry should allow for good exposure to light such that maximum photons can reach the PE. The irradiation from the light source is usually normal to the photoreactor surface [12]. Photoconversion efciency measurement for PEC water splitting has been described by [13e15]. Although a standard photoreactor for studying particulate system especially with UV light such as in environmental application is commercially available, photoreactor for heterogeneous lm type PEC water splitting is not readily available. This paper presents an overview of the commonly used photocell or photoreactor in PEC water splitting study.

Table 1 e Main PEC water splitting requirements Conditions

PEC water splitting Minimum potential required Practical potential (overpotential & losses) For efcient utilization of sunlight Band edges requirement

Main requirements
H2O(liquid) 2hy / O2(gas) H2(gas) E H2O(25  C)min 1.229 eV E H2O(25  C)prac 1.6e2.0 eV Ebandgap > E H2O UV > hy (Vis) > IR hy  Ebandgap Cbandedge < E H2/H Vbandedge > E O2/H2O

1.1.

Basic PEC water splitting set up

The basic PEC set up (Fig. 1) consists of two electrodes immersed in an aqueous electrolyte contained within a vessel, where one or both of the electrodes is photoactive [1]. The vessel containing the aqueous electrolyte is transparent to light or tted with an optical window that allow light to reach the photoactive electrode or also known as photoelectrode (PE). Water splitting will occur when the energetic requirements are met as shown in Table 1 [3,9,16] where the practical potential will be much higher than the minimum required to overcome overpotential and other system losses. In a lab test situation for solar/photon to current conversion efciency measurement, a reference electrode is also used and this method is commonly referred to as the three electrodes cell. In practical application and also for measurement of true solar to hydrogen conversion efciency, a two electrodes system is used [17].

p-type (Fig. 2b) or coupling of n-type and p-type (Fig. 2c). This can be a single photosystem as in the n-type (TiO2) [8] or p-type (InP) [18], but for the coupled n- & p-types involve two photosystems (n-GaAs/p-InP) [19e21]. Several n-types can be layered together so their band gaps cover most part of the usable solar spectrum or several p-types can also be done the same way (Fig. 2d). Another way is to combine different layers of n- and p-types as discussed in the later section under internal biased. When involving more than one photosystem, it is important to match the currents generated by the different layers to obtain better efciency and this is achieved by aligning complimentary band gaps and controlling the thickness or active area [22]. In PEC water splitting, metal oxide and conventional PV material or their combination are used. The anode and cathode are usually physically separated, but can be combined into a monolithic structure [23] either using a metal substrate by depositing the anode on one side and cathode on the other and sealing the edges (Fig. 2e) or stacking the anode on its own substrate with the cathode on its own substrate and providing an electrical connection between the two (Fig. 2f).

1.3. 1.3.1.

Biased and non-biased systems Zero bias

1.2.

Photoelectrode congurations

Semiconductor is the main photoactive material used for the PE. The semiconductors for PEC water splitting can be generally classied as metal oxide and conventional photovoltaic (PV) material. The semiconductor PE can be n-type (Fig. 2a),

The ideal PEC hydrogen production from water is the direct water splitting without any other external energy supply but the light energy itself where the semiconductor has the right band gap and band edges to split water (Fig. 1). Therefore no additional potential is required. However, so far no single junction (single band gap) semiconductor is able to achieve this in a satisfactory manner where the efciency remains very low.

1.3.2.

Biased systems

Fig. 1 e Schematic of PEC water splitting.

The single photosystem conguration (n-type or p-type) is a single junction or single band gap arrangement and is normally not efcient due to the inappropriate band gap or nonmatching band edges. Additional voltage or bias, is required to either increase the rate by reducing electron-hole recombination in the bulk semiconductor when using wide band gap semiconductor or if it is not energetic enough when the band edges do not overlap water splitting potential. The bias can be external or internal as discussed in the following sections. The external bias will make the system performs better but not

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Fig. 2 e Types of PE for PEC water splitting (SC-semiconductor; M-metal).

necessarily increase its solar energy conversion efciency. However, internal biasing with properly matched current and potential will contribute to the solar energy conversion efciency as they utilized the same solar radiation.

1.3.2.1. Electrical bias (grid) e fossil based. Using electricity from the grid to bias the PEC water splitting is not an attractive option because fossil based energy source is commonly used to generate the electricity (Fig. 3a). Some may come from sources such as thermal, hydro, wind, nuclear or solar, but this is usually a very small percentage. 1.3.2.2. Chemical bias e pH. Chemical bias is basically using electrolyte with different pH in the anode and cathode chambers separated by ion exchange membrane (Fig. 3b). Each unit pH difference between the electrolytes chambers provides 0.06 V [24]. Normally acid electrolyte is used on one side of the chamber and alkaline electrolyte on the other [25e27]. However, the energy source used to manufacture the acid or alkali is normally fossil based and raw materials are required to produce the acid or alkali. The bias will decrease with progress of the PEC reaction as H (acid) and OH (alkali) will be consumed and the pH on both sides tend towards equilibrium. Hence, the acid and alkali have to be constantly supplied to maintain the sufcient bias. This method of providing the additional voltage is not favorable because the system requires additional input of chemicals besides sunlight. 1.3.2.3. PV cell bias. The solar PV cell is connected directly to
the PEC water splitting device without going to the grid rst

(Fig. 3c). The other conventional solar hydrogen is using a solar PV panel converting sunlight into electricity and transferring this electricity to an electrolyzer to perform water electrolysis. However, for PV cell biased PEC water splitting, instead of going to an electrolyzer, the PV panel generated current goes to the PEC cell. The PV cell normally consists of multi-junction semiconductor layers of various n- and p-combinations. When the PV cell is illuminated by sunlight, current is generated by the creation, separation and movement of the electron-hole pairs (compare to DSSC below). The PEC cell can potentially have lower cost than an electrolyzer [13,28]. The PV and PEC cells can be integrated into a single unit as described in later section under internal biased.

1.3.2.4. Dye sensitized solar cell (DSSC) bias. This is a new generation of solar cell based on a cheap material TiO2. The principle is similar to the PV cell biased system (Fig. 3c). Instead of the conventional solar cell, a DSSC is used to capture sunlight and convert it to current which then ow to the PEC cell where water splitting occurs [6]. The DSSC itself is a PEC system because it also involves electrolyte which in this case can be regenerated. The conventional solar PV cell on the other hand is a solid state device. In DSSC, TiO2 which forms the photoanode is sensitized by incorporation of dye that acts as antenna to capture visible light and a Pt coated substrate forms the cathode. The electrolyte consists of I2/KI redox couple. Upon irradiation of the DSSC, the dye molecule (D) becomes excited (D*) and injects electron into TiO2 conduction band. The reduced dye (D) is regenerated by oxidizing the I2/ KI electrolyte. The electron from TiO2 conduction band then

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Fig. 3 e The different methods of biasing for PEC water splitting.

ows out to do work and connected to the counter electrode where the I2/KI electrolyte is reduced. The DSSC is capable of generating current continuously with light irradiation [29]. The DSSC and PEC cells can also be integrated into a single unit as described below.

improved efciency as this is based on the total active area of solar collection. Since these systems are capable of splitting water directly, therefore internally biased structure is essentially a zero bias system.

1.4. 1.3.2.5. Internal bias. The internal bias refers to the biasing
potential produced on the PE itself (Fig. 3d). This is normally known by its structure as layered or stacked or hybrid which involves arranging several different semiconductors lms on top of each other such that the total band gap is large enough for water splitting but also small enough to absorb visible portion of the light spectrum which has high photons concentration. This also allows the arrangement of the resultant band edges to overlap water splitting redox potential. The internal biased PE structure can be of several type such as PV/PEC (PVwa-SiGe, PECwWO3) [30], PV/PV (PV1wGaInP, PV2wGaAs) [10] and PEC/PEC (PEC1wDSSC, PEC2wWO3) [31]. These are the general arrangements used for the PE in the later section under photoreactor. There are numerous possibilities of combinations to achieve the appropriate band gap and band edges for direct water splitting by internal biasing but the drawback is this system can become rather complex [22]. As mentioned in previous section it is critical to match the potential and current for each layer of the PV/PEC, PV/PV or PEC/PEC structure in order to achieve

Photoelectrode assembly

In the more basic apparatus, the PE is usually made by depositing a thin layer of the semiconductor on top of the conductive side of the substrate. The substrate is normally

Fig. 4 e Preparation of PE.

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a transparent conductive glass or metal foil. A small area usually a strip at the top or side of the conductive substrate is left uncoated to allow for electrical connection. The ohmic contact is normally made by attaching copper wire to the exposed part with silver conductive glue and covering the connection with epoxy resin to provide insulation and also to strengthen the connection (Fig. 4). If the substrate is metal, then the ohmic contact is usually made on the back side. The copper wire can be further protected by inserting it into a glass tube which also functions as a handle for the PE. All the four edges and the back of the PE are then covered with epoxy resin for insulation [32,33]. A transparent epoxy can be used for back side illumination with glass substrate provided the epoxy layer is very thin or only the sides are covered by epoxy leaving exposed area on the front and back. The area of the exposed PE which will be in contact with the electrolyte produced in this way is non-dened. The area can be estimated using the method by Kelly & Gibson [34], where a piece of paper with known area and weight is used as a standard. The surface of the PE is photocopied and the exposed area is carefully cut along the outline. The weight of the cutout of the exposed PE area is compared with the weight of a standard piece of paper (1 cm 1 cm) and using the weight/area ratio to get the required area. Where unknown PE area weight of standard paper (known standard paper area w1 cm2)/(weight of PE cutout). Other method to estimate the area is by tracing the image of the exposed PE area onto a predened grid and then estimates the area by counting the squares in the grid. The PE produced in this method is completely immersed in the electrolyte in PEC water splitting study.

where the curved surface of the beaker provides light focusing (Fig. 5c). As light is concentrated, more photons will reach the PE surface for the required reaction. The light focusing effect can also be achieved by using round or semi-round transparent container [37]. To simulate higher light concentration in lab setting, a higher powered light source was used to provide the higher intensity.

2.1.2.

With ports

Other vessels have separate ports for the PE, counter electrode and reference electrode (Fig. 5d and e). The advantage of having separate ports is to ensure consistence distance between the electrodes for each measurement. One example is a circular disc made from quartz with ports at the top and on both sides [38,39] and a rectangular vessel [40] which also allow illumination from front and back surfaces.

2.1.3.

With optical window

2.

Photocell and photoreactor types

The photoreactors reported for PEC water splitting have various shapes and congurations. The apparatus used range from simple vessel to more complicated assembly. There are numerous variations to the PEC water splitting set up reported in the literature and some of the designs have been patented. Some articles show just the schematic and others show the apparatus 3D drawing or actual picture. The actual pictures are normally only available through their websites. Some of the more sophisticated apparatus show the arrangement of the PE and the gases separation system which usually require electrolyte separation.

Quartz vessels are very expensive and therefore normally used in a very small size and thickness, hence it tends to be more fragile. An alternative to this is to have an opening where a at quartz piece can be attached. For glass material, the design is easier using a horizontal cylindrical vessel, with ports at the top, where both or one end is open to attach the quartz piece for the optical window. The open end of the glass vessel can be melted around the edge to fuse it with the quartz piece to form sealing so that the electrolyte does not leak out [14] (Fig. 6a), or the opening is in the form of screw type where the quartz piece can be screw on, usually with o-ring to form a leak proof seal. It is known that quartz and glass does not fused easily. The vessel can also be made from other inert and more robust material such as Perspex and Teon or other plastic material instead of glass. This allows both cylindrical and rectangular shapes to be made easily. Optical window is provided by making an opening on the vessel at the illuminated side. The at quartz piece can be tted to the side of the vessel with the opening by sandwiching it with a holder plate that holds the quartz with o-ring or silicone gasket to form a tight seal (Fig. 6b) using nuts and bolts. The top of the

2.1. 2.1.1.

Single chamber vessel Open vessel

The most basic set up of a photocell for PEC water splitting is an open vessel that is transparent which allows light to reach the PE and sufcient to immerse all the electrodes (working electrode-WE/PE, reference electrode-RE, counter electrodeCE) (Fig. 5b). The simplest is a square quartz vessel [34] with a at surface area as optical window to allow most of the light spectrum including UV to pass through (Fig. 5a). A at surface is important during measurement to avoid distortion of the impinging light. A simple beaker has also been used to demonstrate PEC water splitting using a monolithic PE [35,36],

Fig. 5 e (a) Simple square transparent open vessel, (b) Schematic of PEC water splitting set up, (c) Simple open beaker, (d) Single chamber circular vessel (adapted from [39]), (e) Single chamber rectangular vessel (adapted from [40]).

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Fig. 6 e Vessel with optical window. (a) Cylindrical (adapted from [14]), (b) Cubic (adapted from [41]).

cathode. Since the proton is consumed equimolarly with electrons at the cathode, this will increase the pH at the cathode [44]. The membrane divider also allows different electrolytes to be used for the anode and cathode chambers. Besides naon membrane, glass frit and diaphragm can also be used as the electrolyte separator (Fig. 7b). The photoreactor can also be made into a single vessel where glass frit is used as a divider to separate the two liquids but still allow ion movement [14]. As pointed out previously, if the electrolytes in the two compartments have different pH then this will lead to potential difference which can contribute to additional voltage to the system.

Perspex [41,42] or Teon vessel can have various ports drilled easily into the vessel for the electrodes and other requirements. The PE can be inserted through the port and immersed in the electrolyte. The vessel can be sealed completely and have additional outlets for collecting the evolved gases. However, as the efciency of most PE material for water splitting is low, the gas produced is in the order of several ml/h for a few cm2 test area.

2.2.2.

H-type

2.2. 2.2.1.

Vessel with gas separation With electrolyte separation

The H-type vessel allows gas separation without a membrane separator. The construction of the vessel is quite simple in which two or more vertical glass tubes are connected by smaller horizontal tube [45e48] (Fig. 8). The connection allows for ion movement and as the electrodes are placed above the connection, and since the gases evolved will ow upward, therefore the gases will be separated naturally. Ion permeable divider such as glass frit can be placed in the connection tube to allow different electrolytes to be used in the compartments. However, it is quite difcult to get a at surface for the optical window on a tube or attaching a at quartz piece to the tube.

In PEC water splitting system, it is important to separate H2 and O2 as a mixture of the two gases are potentially explosive. In a small scale lab photocell this does not pose a signicant concern. However for large scale practical hydrogen production, it is essential to separate the gases. Traditionally, for an electrochemical reaction study with two different electrolytes, two separate vessels containing the electrolytes are connected by a salt bridge. In a PEC water splitting photoreactor, this can be made from two separate vessels held together by nuts and bolts with a membrane acting as a separator for the electrolytes. Proton exchange membrane (Naon) commonly used in fuel cell is also used in PEC water splitting study to separate the anode and cathode compartments [43] (Fig. 7a). The naon membrane does not allow H2 or O2 gas to crossover but only allow H to pass through. In PEC water splitting reaction in acidic medium, ion conduction is achieved by H movement, therefore it is quite well suited to use this type of membrane. However, the naon membrane is not suitable to be used in electrolyte that contains cation (eg. Na) as this will replace the H in the membrane and therefore limit the movement of H across. Hence, less H ions are available to be reduced to H2 at

2.3.

Photocell with xed area photoelectrode

Instead of immersing the PE in the vessel, it can also be placed outside the vessel where it is xed to an opening that allows a certain area of the PE to be in contact with the electrolyte [49,50]. In a front attachment conguration, the PE can then be glued to a holder plate that has an opening with a predened area (Fig. 9a). The PE can also be sandwiched between the holder plate and the vessel (Fig. 9b) with o-ring to provide sealing. The PE active area for both front attachment and sandwich assemblies is xed or dened by the opening of the holder plate, the o-ring or gasket. The holder plate can be attached using screws and bolts to the vessel which has an opening that allow the electrolyte to reach the PE. Care must be taken when assembling the PE to the vessel to ensure no electrolyte leak outside the predened area, as the leak will increase the actual test area and this leads to higher current density. The PE on glass substrate functions as the optical window if illuminated from the back side. On the other hand,

Fig. 7 e Vessel with electrolyte/gas separation. (a) Separate vessels (adapted from [43]), (b) Single vessel (adapted from [14]).

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chambers to reduce ohmic losses when the current collection area becomes large.

3.2.

Photoreactor e PV-biased monolithic photoelectrode

Fig. 8 e H-type vessels. (a) With three compartments (adapted from [46]), (b) With two compartments (adapted from [45]).

illumination from the front side through the electrolyte requires a piece of glass or quartz used as the optical window. Comparison of the results from the back side and front side illumination has to be done by considering the distance between the PE, in both cases, from the electrolyte and the light source since the front side illumination can produce a different result due to interference by electrolyte and also changes in the light intensity.

3.

Potential for large scale application

In another design [53,54], the PV-based semiconductor PE is totally separated from the aqueous electrolyte. The photoreactor is also a rectangular shaped plate-type conguration (Fig. 10b). Stainless steel is used as the substrate and PV semiconductor material (triple-junction Si) is deposited on one side and hydrogen evolving catalyst is deposited on the other (CoMo). The electrons generated from the PV-based PE move through the stainless steel substrate to reach the electrolyte to reduce H to H2 and the holes are collected on the surface of the PV by interconnect and joined to the other substrate deposited with oxygen evolving catalyst (Fe:NiOx) where H2O is oxidized to O2. The membrane for the gas separation is placed in the middle on a porous support between H2 evolution chamber and the O2 evolution chamber. In the same publication, the hydrogen and oxygen evolving substrates (anode and cathode) are placed side by side and the membrane is placed perpendicular to the electrodes thus separating the two compartments which are similar to Section 3.4 under bi-photoelectrodes. This design also allows interconnected chambers and other similar PE assembly suitable for this set up is by [55].

The shape and geometry of PEC water splitting photoreactor depend much on the PE assembly. The PE is always at to ensure maximum exposure to light therefore the simplest photoreactor design is based on plate-type conguration. For PE that does not require bias, metal substrate will make a simpler PE because the counter electrode can be deposited on the opposite side and form a monolithic device as mentioned in earlier section. Hence, wiring is not required and the monolithic device can be completely enclosed.

3.3. Photoreactor e DSSC-biased monolithic photoelectrode

This tandem photosystem enables the use of the wide band gap but stable and cheap metal oxide coupled to a relatively cheap DSSC also based on metal oxide alternative to the PV solar cell. However, water splitting only occurs on one of the cell termed photolysis cell. The other cell, DSSC, only generate electricity to provide bias potential for the photolysis cell. The function of the DSSC is similar to a conventional solar cell. However, the DSSC is based on PEC reaction to generate electricity as described previously in Section 1.3.2 under DSSC-biased. The DSSC used for biasing the photolysis cell can be placed separately or combined into a monolithic unit as shown by Gratzel [56]. It is important to match the current and voltage generated by the DSSC and the photolysis cell to obtain better efciency and this is achieved by controlling the active area [57]. More than one DSSC connected in series may be required to supply enough voltage for water splitting as the voltage for one DSSC is about 0.7 V [58]. The apparatus is made from glass container where the front compartment is the photolysis cell and the glass based DSSC is placed directly behind it. In another layout, still made from glass container, the photolysis cell is separated into two compartments so that the evolved gases are separated [31]. The front compartment is the oxygen evolution chamber followed by the DSSC and the back compartment is the hydrogen evolution chamber (Fig. 11a). The hydrogen evolution compartment is placed on the back so that it does not interfere with light reaching the PE of the photolysis and PE of the DSSC. The electrolyte in the front compartment is connected with the back compartment by a membrane to allow ion

3.1. Photoreactor e non-biased monolithic photoelectrode

The photoreactor is a plate-type rectangular container enclosing the monolithic PE forming two separate compartments lled with aqueous electrolyte (acid or alkaline) as demonstrated by Deng and Xu [51] (Fig. 10a). For the PE, on one side of the metal substrate, multi layers of PV-based semiconductor material (double or triple-junction Si) is deposited and the outer layer that is in contact with the aqueous electrolyte is covered by a protective material which is transparent, conductive and corrosion-resistant (doped-metal oxide or doped-polymer). As mentioned earlier it is important to match the current and potential of each photoactive layer in order to achieve higher solar energy conversion efciency. On the other side of the metal substrate, hydrogen evolution catalyst is deposited (carbon-Pt). Other group has developed monolithic PE that is suitable for use in this set up [22,52]. The top compartment has an optical window for light to reach the PE. Here, the placement of the ion exchange membrane is such that the area that is exposed to sunlight is utilized for the photon reaction and not for non-photon related function such as the membrane. This design allows interconnected

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Fig. 9 e Dened area PEs. (a) Front attachment, (b) Sandwich assembly.

movement. The tandem DSSC design has been licensed to Hydrogen Solar [59]. As both photolysis cell and the DSSC have PEs that absorbs different part of solar spectrum, to achieve higher efciency, they can be placed in front of each other and ensuring the current and potential are properly matched. Therefore the effective area is reduced by half compared to when they are placed side by side instead of stacked together, as the efciency calculation involves dividing by the effective area. Hence the rst PE absorbs the shorter wavelength and the second PE will absorb the longer wavelength. The arrangement will require a transparent PE and substrate so that light can reach the second PE placed behind the rst. To connect these two systems electrically wire is used as in Gratzel [57] system. To eliminate wiring, a bi-polar system using metal substrate can be used as shown by Park and Bard [56]. The PE of the photolysis cell is sharing the substrate with the CE of the DSSC and the PE of DSSC is sharing the substrate with the photolysis cell CE (Fig. 11b). Therefore, the electron can pass through the metal substrate directly from one photosystem to the other. However, the advantage of eliminating the wiring might be outweighed by the disadvantage of less active area as the PE is slanted to allow both PEs to receive light. This DSSC also has less efciency due to the bigger electrodes distance and also lower redox electrolyte concentration is used so that light can pass through the colored electrolyte to reach the second PE.

3.4.

Photoreactor with bi-photoelectrodes

This PEC water splitting apparatus where both electrodes are photoactive have two PEs arranged side by side where both PEs can face the light. One PE is the photoanode based on n-type semiconductor and the other is the photocathode based on p-type semiconductor. To eliminate wiring, metal substrate can be used and both the PEs semiconductor materials can be deposited on the surface of the metal substrate side by side. To separate the gases evolved, an arrangement to separate the compartment is required and ion exchange route is provided as shown by Aroutiounian et al. [60] (Fig. 12). In this design, n-type PE (n-doped TiO2 or n-Fe2O3) and p-type PE (p-doped TiO2 or p-Cu2O) [60,61] are placed towards the top of the reactor, therefore they are only submerged slightly in the electrolyte. The underlying metal substrate back side has to be covered with insulating material so the current doesnt leak to the electrolyte. The two PEs are separated by placing a divider along the length of the middle of the two PEs separating them into their own compartment, hence separating the evolved gases. Along the divider, a membrane is placed to allow ion movement. Light concentrator parabola and focusing optical window are also placed on top of the photoreactor. For n-type and p-type system, water splitting occurs spontaneously without bias if the right conditions are fullled

Fig. 10 e Monolithic photoreactors. (a) Non-biased (adapted from [51]), (b) PV-biased (adapted from [53]).

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Fig. 11 e DSSC-biased photoreactor. (a) Tandem DSSC PEC (adapted from [31]), (b) Bi-polar (adapted from [57]).

[3]. However, the PEs used by Aroutiounian et al. [60,61] are based on metal oxides that are not very efcient in utilizing the solar spectrum. Hence, the system has very low efciency. To increase the rate, they biased their system by using electrolyte with different pH for the two compartments. This difference in pH provides the additional potential however, as described in earlier section pH biasing needs chemical input as well as sunlight and therefore is not a suitable method for practical hydrogen production. They have also biased their system with external PV cell (Si) but as discussed in Section 3.2 the n- and p-type PEs can also be coupled internally with the PV-biased system. In term of efciency calculation, the side by side conguration has lower efciency because the solar collection area is larger instead of reduced by half as in the stacked arrangement.

However, the number of photons required is also more per unit of H2 produced. This system has the drawback of difculty in ensuring cyclic operation of the donor/acceptor and need further development of the redox mediator [67].

3.6.

Photoreactor with electrolyte containment

3.5.

Dual bed photoreactor

Another system using two PEs is the dual bed system [62e65] (Fig. 13) which is basically a two photosystem where two PEC cells are linked together and each cell has half the electrochemical potential for water splitting. The apparatus consist of two shallow, at sealed containers where photocatalytic particles are immobilized on the bed at the bottom of the container or grids. An aqueous solution (alkaline) containing the redox mediator (M IO 3 /I ) is pumped between the two chambers. In large scale application, to eliminate the need to pump large volume of solution between the two chambers, an alternative is to use some form of membrane between the two beds that allow the ions of the mediator and electrolyte to crossover. Since the two beds are now isolated, particles can be suspended in the solution instead of immobilized on the bed [66]. In this system, both oxidation and reduction reactions occur on each PE, compared with only the oxidation half reaction on one PE and reduction on the other PE in the previously described system. For water oxidation, acceptor (M) is used to accept the electron from PE1 (TiO2 or Ir-TiO2) while the hole created by PE1 is used to oxidize water to O2. The acceptor (M) is then reduced (M) and becomes the donor for the H reduction on the second PE2 (InP or TiO2-Pt). H is reduced by electron produced by PE2 and the donor will donate electron (M) to the hole on PE1. As such, the electron is moved through the donor/ acceptor. As the potential for each cell is smaller (smaller band gap), it can absorb broader range of the solar spectrum.

A design that protects the PE from direct exposure to aqueous environment is shown by Fan et al. [68] (Fig. 14). The photoreactor shown by this group is based on plate-type. The hydrogen and oxygen evolving electrodes are put side by side. They used conventional solar cells in series and also a metal oxide layer which they termed as light sensitive catalytic layer. The structure of the hydrogen evolving electrode (n-type) is comprised of Naon membrane, porous metal substrate layer, porous PV solar cell layers and an outermost layer of metal oxide semiconductor (n-doped TiO2-C with eg. Pt, Ni, Fe or dye) formed by mixing with Naon solution and deposited on the porous solar cell layer. The porous nature of the layers allows water to permeate. Similar structure is also constructed for the oxygen evolving electrode (p-doped TiO2-C with eg. Pt, Ni, Fe or dye). The metallic layer serves as support for the electrode and also as current collector. When put side by side with the photoactive sides facing up, the electrolyte (acidic) is contained behind the electrodes by the membrane that is the bottom layer in the electrodes assembly. Water will permeate through the membrane and

Fig. 12 e Bi-photoelectrodes reactor (adapted from [60]).

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report the model shows that particulate system is more cost effective. Nonetheless, the concept used for the particulate system in the report has a lot of uncertainties. The report also indicated that the photoelectrode system based on PV/PV or PV/ PEC system has the most mature concept with several examples have been fabricated. The PV/PEC system has advantage over the PV/PV system because the PEC face (layer) can replace the face conductor grids which partially obscure the PV layer. Fig. 13 e Dual bed photoreactor (adapted from [63]).

5.
throughout the electrode through its porous nature to reach the surface layer. Therefore, only thin layer of water is in the three-phase zone. Since no electrolyte at the surface resulting in surface tension that hinder the release of the formed gas from the surface, the gas can escape easily. And also, since there is no thick layer of electrolyte, sunlight can reach the PEs surface without absorption by the electrolyte. However, water normally only absorb IR radiation from light therefore it does not affect much of the other light wavelength (UV and visible) but it will reects and disperse the light.

Conclusion

4.

Other considerations

Direct PEC water splitting is still a very challenging task in term of nding material that can match the energetic and stability requirements. In some PEC studies, organic additives had been included in the aqueous electrolyte to enhance the H2 production. The study by [69e73] using various organic additives (ethanol, methanol, formic acid and formaldehyde) all indicated that the photocurrent improved with addition of the organic substance. The organic addictive acts as sacricial donor and is preferentially oxidized then water. However, the organic additives will decompose to form CO2 along side H2. This is only attractive when used in conjunction with a rather transparent liquid waste clean up application which provides the source of the organic additives. Otherwise, the issue will be similar to the pH biased system as discussed in earlier section. Recently a report has been produced on the initial technoeconomic analysis of several possible version of PEC reactor for hydrogen production which considered particulate system and also photoelectrode (photocell) system [66]. The particulate system is not considered in our review because it has been identied early on that it is not favorable for large scale hydrogen production. However, based on the technoeconomic

There are not many reports on photoreactor for PEC water splitting as there is much work still needed to improve on the efciency and stability of the PE. Generally, the shape and geometry of photocell and photoreactor for PEC water splitting depends very much on the PE assembly. PE based on multijunction PV with PEC layer seems promising however, the cost prediction indicates that using this arrangement is still not commercially viable. Discovery of new PE material has the greatest potential in driving the PEC water splitting to achieve the set target. In the mean time improvement of current semiconductor efciency and stability will help this move forward. The ideal design of the photocell and photoreactor is such that the PE has a maximum exposure to light. The requirement for product gases management and ion movement also affect the design consideration. In most case for bench scale testing, a vessel with optical window that can t all the electrodes and electrolyte is sufcient. In practical applications, there are various conguration options to explore and the plate-type design seems to be the simplest.

Acknowledgement
The authors gratefully acknowledge Universiti Kebangsaan Malaysia for the nancial support of this project under the grant UKM-GUP-BTT-07-30-189.

references

Fig. 14 e Electrolyte containment photoreactor (adapted from [68]).

[1] Bak T, Nowotny J, Rekas M, Sorrell CC. Photo-electrochemical hydrogen generation from water using solar energy. Materials-related aspects. International Journal of Hydrogen Energy 2002;27:991e1002. [2] Stambouli AB, Traversa E. Fuel cells, an alternative to standard sources of energy. Renewable and Sustainable Energy Reviews 2001;6(3):297e306. [3] Meng N, Michael M, Leung KH, Leung DYC, Sumathy K. A review and recent developments in photocatalytic water-splitting using TiO2 for hydrogen production. Renewable and Sustainable Energy Reviews 2007;11: 401e25. [4] Nowotny J, Sorrell CC, Sheppard LR, Bak T. Solar-hydrogen: environmentally safe fuel for the future. International Journal of Hydrogen Energy 2005;30:521e44. [5] U.S. Department of Energy. Hydrogen, fuel cells & infrastructure technologies program. Hydrogen production. DOE/GO-102007-2430. p. 3.1e20. Available from: http://www. eere.energy.gov/hydrogenandfuelcells/mypp; 2009.

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 5 ( 2 0 1 0 ) 5 2 3 3 e5 2 4 4

5243

[6] Gratzel M. Photoelectrochemical cells. Nature 2001;414: 338e44. [7] Cesar I, Kay A, Martinez JAG, Gratzel M. Translucent thin lm Fe2O3 photoanodes for efcient water splitting by sunlight: nanostructure-directing effect of Si-doping. Journal of the American Chemical Society 2006;128:4582e3. [8] Fujishima AK, Honda K. Electrochemical photolysis of water at a semiconductor electrode. Nature 1972;238:37e8. [9] Kocha SS, Montgomery D, Peterson MW, Turner JA. Photoelectrochemical decomposition of water utilizing monolithic tandem cells. Solar Energy Materials and Solar Cells 1998;52:389e97. [10] Khaselev O, Bansal A, Turner JA. High-efciency integrated multijunction photovoltaic/electrolysis systems for hydrogen production. International Journal of Hydrogen Energy 2001;26:127e32. [11] Licht S, Wang B, Mukerji S, Soga T, Umeno M, Tributsch H. Over 18% solar energy conversion to generation of hydrogen fuel; theory and experiment for efcient solar water splitting. International Journal of Hydrogen Energy 2001;26: 653e9. [12] Ampelli C, Passalacqua R, Perathoner S, Centi G. Nanoengineered materials for H2 production by water photoelectrolysis. Proceeding of The ninth International Conference on Chemical & Process Engineering. Available from: http://www.aidic.it/icheap9/webpapers/392Ampelli. pdf; 2009. [13] Bolton JR. Solar photoproduction of hydrogen: a review. Solar Energy 1996;57(1):37e50. [14] Murphy AB, Barnes PRF, Randeniya LK, Plumb IC, Grey IE, Horne MD, et al. Efciency of solar water splitting using semiconductor electrodes. International Journal of Hydrogen Energy 2006;31:1999e2017. [15] Varghese OK, Grimes CA. Appropriate strategies for determining the photoconversion efciency of water photoelectrolysis cells: a review with examples using titania nanotube array photoanodes. Solar Energy Materials and Solar Cells 2008;92:374e84. [16] Butler MA, Ginley DS. Review: principles of photoelectrochemical solar energy conversion. Journal of Materials Science 1980;15:1e19. [17] Chen Zhebo, Jaramillo Thomas F, Deutsch Todd G, KleimanShwarsctein Alan, Forman Arnold J, Gaillard Nicolas, et al. Review: accelerating materials development for photoelectrochemical hydrogen production: standards for methods, denitions, and reporting protocols. Journal of Materials Research 2010;25(1):3e16. [18] Chandra N, Wheeler BL, Bard AJ. Semiconductor electrodes. 59. Photocurrent efciencies at p-indium phosphide electrodes in aqueous solutions. Journal of Physical Chemistry 1985;89:5037e40. [19] Kainthla RC, Khan SUM, Bockris JOM. The theory of electrode matching in photoelectrochemical cells for the production of hydrogen. International Journal of Hydrogen Energy 1987;12: 381e92. [20] Nozik AJ. PeN photoelectrolysis cell. Applied Physics Letters 1976;29:150. [21] Nozik AJ. Photochemical diodes. Applied Physics Letters 1977;30:567e9. [22] Miller EL, Rocheleau RE, Deng XM. Design considerations for a hybrid amorphous silicon/photoelectrochemical multijunction cell for hydrogen production. International Journal of Hydrogen Energy 2003;28:615e23. [23] Grimes CA, Varghese OK, Ranian S. Light, water, hydrogen e the solar generation of hydrogen by water photoelectrolysis. New York, US: Springer; 2008 (Section 3.3, p. 123). [24] Bard AJ, Faulkner LR. Electrochemical methods: fundamentals and applications. New York, US: Wiley; 2001.

[25] Bak T, Nowotny J, Rekas M, Sorrell CC. Photoelectrochemical properties of TiO2-Pt system in aqueous solutions. International Journal of Hydrogen Energy 2002;27:19e26. [26] Currao A, Reddy VR, Veen MKV, Schropp REI, Calzaferria G. Water splitting with silver chloride photoanodes and amorphous silicon solar cells. Photochemical & Photobiological Sciences 2004;3:1017e25. [27] Selli E, Chiarello GL, Quartarone E, Mustarelli P, Rossetti I, Forni L. A photocatalytic water splitting device for separate hydrogen and oxygen evolution. Chemical Communications; 2007:5022e4. [28] Bansal A, Khaselev O, Turner JA. Photoelectrochemical system studies. Proceedings of the 2000 hydrogen program review. NREL/CP-570e28890. US: Department of Energy National Renewable Energy Laboratory. Available from:, http://www1.eere.energy.gov/hydrogenandfuelcells/pdfs/ 28890b.pdf; 2000. [29] Oregan B, Gratzel M. A low-cost, high-efciency solar cell based on dye-sensitized colloidal TiO2 lms. Nature 1991;353: 737e40. [30] Miller EL, Paluselli D, Marsen B, Rocheleau RE. Development of reactively sputtered metal oxide lms for hydrogenproducing hybrid multijunction photoelectrodes. Solar Energy Materials and Solar Cells 2005;88:131e44. [31] Gratzel, M. and Augustynski, J. 2005. Tandem cell for water cleavage by visible light. Patent no. US 6936143. [32] Madan A. Photoelectrochemical hydrogen production: MVSystems Incorporated. US DOE Hydrogen Program.2008 Annual Progress Report. II.E.9. Available from: http://www. hydrogen.energy.gov/pdfs/progress08/ii_e_9_madan.pdf; 2008. [33] Varner K, Warren S, Turner JA. Photoelectrochemical systems for hydrogen production. In: Proceedings of the 2002 hydrogen program review. NREL/CP-610e32405. US: Department of Energy National Renewable Energy Laboratory. p. 125e129. Available from: http://www1.eere. energy.gov/hydrogenandfuelcells/pdfs/33098_sec2-3.pdf; 2002. [34] Kelly NA, Gibson TL. Design and characterization of a robust photoelectrochemical device to generate hydrogen using solar water splitting. International Journal of Hydrogen Energy 2006;31:1658e73. [35] Miller EL, Rocheleau RE. Photoelectrochemical hydrogen production. Proceedings of the 2001 DOE Hydrogen Program Review. NREL/CP-570-30535. Available from: http://www. hnei.hawaii.edu/docs/PEC/HNEI_PEC_01.pdf; 2001. [36] Miller EL, Rocheleau RE. Photoelectrochemical production of hydrogen. Proceedings of the 2002 U.S. DOE Hydrogen Program Review. NREL/CP-610-32405. Available from: http:// www.hnei.hawaii.edu/docs/PEC/HNEI_PEC_02.pdf; 2002. [37] Kelly NA, Gibson TL. Solar energy concentrating reactors for hydrogen production by photoelectrochemical water splitting. International Journal of Hydrogen Energy 2008;33:6420e31. [38] Dresselhaus MS, Thomas IL. Alternative energy technologies. Nature 2001;414:332e7. [39] Cook Gary, editor. New horizons for hydrogen. US NREL 2003 research review. p. 5e7. Available from: http://www.nrel. gov/research_review/pdfs/2003/36178.pdf; 2004. [40] Kamat PV. Meeting the clean energy demand: nanostructure architectures for solar energy conversion. The Journal of Physical Chemistry C 2007;111(7):2834e60. [41] Mishra PR, Shukla PK, Singh AK, Srivastava ON. Investigation and optimization of nanostructured TiO2 photoelectrode in regard to hydrogen production through photoelectrochemical process. International Journal of Hydrogen Energy 2003;28:1089e94. [42] Mishra PR, Shukla PK, Srivastava ON. Study of modular PEC solar cells for photoelectrochemical splitting of water

5244

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 5 ( 2 0 1 0 ) 5 2 3 3 e5 2 4 4

[43]

[44]

[45]

[46]

[47]

[48]

[49]

[50] [51] [52]

[53] [54]

[55]

[56] [57]

[58]

[59] [60]

employing nanostructured TiO2 photoelectrodes. International Journal of Hydrogen Energy 2007;32:1680e5. Bae S, Kang J, Shim E, Yoon J, Joo H. Correlation of electrical and physical properties of photoanode with hydrogen evolution in enzymatic photo-electrochemical cell. Journal of Power Sources 2008;179:863e9. Rozendal RA, Hamelers HVM, Molenkamp RJ, Buisman CJN. Performance of single chamber biocatalyzed electrolysis with different types of ion exchange membranes. Water Research 2007;41:1984e94. Allam NK, Shankar K, Grimes CA. Photoelectrochemical and water photoelectrolysis properties of ordered TiO2 nanotubes fabricated by Ti anodization in uoride-free HCl electrolytes. Journal of Materials Chemistry:2341e8. Available from: http:// www.rsc.org/ejga/JM/2008/b718580d-ga.gif, 2008;18. Grimes CA, Varghese OK, Ranian S. Light, water, hydrogen e the solar generation of hydrogen by water photoelectrolysis. New York, US: Springer; 2008 (Section 5.7, p. 323). Honda K. Dawn of the evolution of photoelectrochemistry. Journal of Photochemistry and Photobiology A: Chemistry 2004;166:63e8. Yae Shinji. Water splitting to produce solar hydrogen using silicon thin lm. SPIE Newsroom. Solar & Alternative Energy;. doi:10.1117/2.1200702.0641. Available from:, http://spie.org/ x8413.xml?highlightx2358&ArticleIDx8413; 2007. Miller EL. A study of the electrochemical behavior and optical properties of reactively-sputtered nickel oxide and nickel-iron oxide. PhD thesis. University of Hawaii; 1996. p. 35e257. Sawyer DT, Roberts JJL. Experimental electrochemistry for chemists. New York, US: John Wiley; 1974. p. 160. Deng X, Xu L. Integrated Photoelectrochemical cell and system having a liquid electrolyte. Patent no. WO 2004/050961 A1; 2004. Miller EL, Marsen B, Paluselli D, Rocheleau RE. Optimization of hybrid photoelectrodes for solar water-splitting. Electrochemical and Solid-State Letters 2005;8(5):A247e9. Deng X, Xu L. Interconnected Photoelectrochemical Cell. Patent no. WO 2005/081326 A1; 2005. Xu L. Critical research for cost-effective photoelectrochemical production of hydrogen. US DOE Hydrogen Program. 2006 Annual Progress Report. II.F.6 p. 149e153. Available from: http://www.hydrogen.energy.gov/ pdfs/progress06/ii_f_6_xu.pdf; 2006. Jahagirdara AH, Dhere NG. Photoelectrochemical water splitting using CuIn1xGaxS2/CdS thin-lm solar cells for hydrogen generation. Solar Energy Materials and Solar Cells 2007;91(15e16):1488e91. Gratzel M. Mesoscopic solar cells for electricity and hydrogen production from sunlight. Chemistry Letters 2005;34:8e13. Park JH, Bard AJ. Photoelectrochemical tandem cell with bipolar dye-sensitized electrodes for vectorial electron transfer for water splitting. Electrochemical and Solid-State Letters 2006;9(2):E5e8. Longo C, De Paoli MA. Dye-sensitized solar cells: a successful combination of materials. Journal of the Brazilian Chemical Society 2003;14(6):889e901. Available from: http://www.hydrogensolar.com/; 2009. Aroutiounian VM, Arakelyan VM, Shahnazaryan GE. Metal oxide photoelectrodes for hydrogen generation using solar

[61]

[62]

[63]

[64]

[65]

[66]

[67]

[68] [69]

[70]

[71]

[72]

[73]

radiation-driven water splitting. Solar Energy Materials and Solar Cells 2005;78:581e92. Aroutiounian VM, Arakelyan VM, Shahnazaryan GE, Stepanyan GM, Turner JA, Khaselev O. Investigation of ceramic Fe2O3-Ta photoelectrodes for solar energy photoelectrochemical converters. International Journal of Hydrogen Energy 2002;27:33e8. Linkous CA, Slattery DK. Solar photocatalytic hydrogen production from water using a dual bed photosystem. Proceedings of the 2000 Hydrogen Program Review. NREL/CP570e28890. US. Department of Energy National Renewable Energy Laboratory. Available from: www1.eere.energy.gov/ hydrogenandfuelcells/pdfs/28890v.pdf. Linkous CA, Slattery DK. Solar photocatalytic H2 production from water using a dual bed photosystem. Proceedings of the 2001 DOE Hydrogen Program Review. NREL/CP-570e30535. US. Department of Energy National Renewable Energy Laboratory. Available from: www1.eere.energy.gov/ hydrogenandfuelcells/pdfs/30535v.pdf. Lee K, Seok-Nam W, Young-Han G. Photocatalytic watersplitting in alkaline solution using redox mediator. 1: parameter study. International Journal of Hydrogen Energy 2004;29:1343e7. Seok-Nam W, Eun-Young K, Young-Han G. Photocatalytic production of oxygen in a dual bed system using a reversible redox mediator on Ir-TiO2 catalyst. Korean Journal of Chemical Engineering 2008;25(6):1355e7. Directed Technologies Inc. (DTI). Technoeconomic Analysis of Photoelectrochemical (PEC) Hydrogen Production. US DOE Report; 2009. Linkous CA, Slattery DK, Fowler JR. Solar photocatalytic hydrogen production from water using a dual bed photosystem. US DOE report no. DE-FC36-99G010449. Available from: http://www.osti.gov/bridge/servlets/purl/ 828249-9qMWfP/webviewable/828249.pdf; 2003. Fan Q, Onischak M, Liss WE. Solar cell electrolysis of water to make hydrogen and oxygen. Patent no. US 7,241,950 B2; 2007. Antoniadou M, Lianos P. Photoelectrochemical oxidation of organic substances over nanocrystalline titania: optimization of the photoelectrochemical cell. Catalysis Today 2009;144:166e71. Antoniadou M, Lianos P. Near ultraviolet and visible light photoelectrochemical degradation of organic substances producing electricity and hydrogen. Journal of Photochemistry and Photobiology A: Chemistry 2009;204:69e74. Antoniadou M, Bouras P, Strataki N, Lianos P. Hydrogen and electricity generation by photoelectrochemical decomposition of ethanol over nanocrystalline titania. International Journal of Hydrogen Energy 2008;33:5045e51. Solarska R, Santato C, Jorand-Sartoretti C, Ulmann M, Augustynski J. Photoelectrolytic oxidation of organic species at mesoporous tungsten trioxide lm electrodes under visible light illumination. Journal of Applied Electrochemistry 2005;35:715e21. Yang B, Barnes PRF, Zhang Y, Luca V. Tungsten trioxide lms with controlled morphology and strong photocatalytic activity via a simple solegel route. Catalysis Letters 2007;118: 280e4.