Photoelectrochemical Water Splitting

Name: Sibimol Luke

Roll No: 164114002
Course: PhD (MEMS)
Date:

1. Introduction
Photocatalytic or photoelectrochemical water splitting generates much interest on scientific
community in recent years for energy storage in the form of hydrogen. Since hydrogen does not
exist naturally on earth, hydrogen has to be produced from its abundant source like water.
Photoelectrochemical water splitting promises both sustainable energy generation and energy
storage in the form of hydrogen. This is a combination of a light harvesting system and water
splitting system. In this artificaial photosynthesis process, input solar energy is converted into
chemical energy stored in the bonds of hydrogen molecule [1].

The advancements in material science concerning photoabsorbers [2], photocatalysts [3] and
device optimizations in multijunction solar cells [4] have brought considerable progress in this
field. A photoelectrochemical cell consists of a photoactive semiconductor working electrode
(either n- or p-type) illuminated by solar light and a counter electrode made of either metal (e.g.
Pt) or semiconductors, both immersed in the electrolyte containing suitable redox couples.

2. Water splitting process

Any light driven water splitting process can be written as H2O + 2γ H2 (g) + ½ O2 (g) with
Standard Gibbs free energy, ΔG = +237. 18kJ / mol which is equivalent to thermodynamic energy,
o

ΔEo = 1.23 eV needed for splitting water into its constituent gases at standard conditions of 25°C
and 1bar. A photoelectrochemical water splitting cell consist of a photovoltaic cell (PV) that
converts photons into electrons and holes and a electrochemical cell (EC) with two half reactions:
H2O + 2h+ 2H+ + ½ O2 (g), the oxygen evolution reaction (OER) and 2H+ + 2e- H2 (g),
the hydrogen evolution reaction (HER). This process must generate two electron-hole pairs per
molecule of H2 (2 × 1.23 eV = 2.46 eV) or four electron-hole pairs per molecule of O2 (4 × 1.23
eV = 4.92 eV) [5].

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2.1 Criteria for water splitting

For direct, efficient photoelectrochemical decomposition of water, there are certain criteria that
need to be fulfilled in the system: the semiconductor system must output the required voltage to
split water upon irradiation which includes the energy needed to overcome the energy barrier of
water oxidation, the overpotential losses at anode and cathode and ohmic losses in the device. So
the energy required for photoelectrolysis is 1.6 – 2.4 eV as reported [6].

Also, the bandgap should be sufficiently small to absorb a major portion of the incident solar
irradiation, the bandedge potentials of the semiconductors must straddle the hydrogen and oxygen
redox potentials, the system must be stable in aqueous electrolytes, and finally, the charge transfer
from the surface of the semiconductor to the solution must be facile to minimize energy losses due
to overpotentials associated with HER and OER. To date, no cost-effective materials system
satisfies all of the technical requirements listed above for practical hydrogen production [7].

2.2 Efficiency Calculation

The solar conversion efficiency of individual photoelectrode to drive either the HER or OER used
in a photoelectrolysis cell can be calculated from current-voltage data obtained using a potentiostat
in an illuminated three-electrode cell. It is useful to calculate efficiencies of a photoanode or
photocathode separately from the other half of the water splitting reaction, to allow for
optimization of the materials independently. Since potentiostat is operated in three-electrode mode,
polarization losses associated with driving the reaction at the counter electrode are not considered
in this calculation. Overall water splitting efficiencies (STH) for photoelectrolysis cells can be
calculated by overlapping the individually tested J-V data for each photocathode/anode as shown
in figure 1. The intersection of the two curves indicates the maximum operating current density
(Jop) for the complete cell [5].

Figure 1: Overlaid current density-potential behavior for a p-type photocathode

and an n-type photoanode

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2.3 Electrodes in a photoelectrochemical cell

Different electrodes in a photoelectrochemical cell are photoanodes, photocathodes, reference

electrodes and counter electrodes [8].

2.3.1 Photocathodes

Photocathodes are generally p – type semiconductors where HER takes place. Photocathodes are
likely to be more stable than photoanodes since they are cathodically protected from photo
oxidation which prevent photocorossion. The commonly used photocathode materials are metal
oxides, III–V group materials, Si, copper-based chalcogenides, and II–VI group materials. Cu2O
with 18% solar to fuel conversion efficiency is one of the most attractive photocathode which has
its bandedge potential straddle between water oxidation and reduction potentials [9]. p – GaP, p –
InP, p – GaInP2, p – Si are the other photocathodes being studied. CIGS is one from copper – based
chalcogenides. CdS is an II–VI material with direct band gap of 2.4 eV and appropriate
valence/conduction band edges for water oxidation/reduction, is one of the most promising
candidate for water splitting without external bias [8].

2.3.2 Photoanodes

Generally, a photoanode is an n-type semiconductor where electric field generated by band

bending drives holes toward the surface and facilitates OER to takes place. Most of the photoanode
materials that have been investigated are metal oxides or metal oxide anions (oxometalates), in
pure, mixed, or doped forms due to stability issues under oxidizing conditions. TiO2, WO2,
Hematite (α -Fe2O3), BiVO4 are some of the commonly used photoanodes [8].

2.3.3 Counter electrodes

The choice of the counter electrode (CE) is based on the type of working electrode (WE) and can
be made much larger than the WE. For n-type semiconductors, large surface area Pt foils (e.g., Pt
black) or meshes can make good CEs. For a p-type WE, oxides such as RuO2 and IrO2 are better
candidates and can reduce overpotentials compared to the noble metals [9].

2.3.4 Reference Electrodes

Reference Electrodes (RE) are required in PEC testing in order to measure the potential of the WE
with respect to the normal hydrogen electrode (NHE). Eventhough, several RE available, saturated
calomel electrodes (SCE, E0SCE = +0.241 V vs. NHE at 25oC) is used in acidic solutions and
Hg/HgO reference electrodes (E0Hg/HgO, KOH 20% = +0.097 V vs. NHE at 25oC) are preferred in basic
solutions [10].

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3. PEC multijunction device schemes

The high voltages required for water splitting can be generated by single-junction solar cells with
high band gap energy or by the use of multiple junctions connected in series. Since the optimal
band gap for single junction solar cells under AM1.5G illumination is 1.34 eV, the use of high
band gap solar cells leads to high optical transmission losses and thus less efficient solar cells.
Also, there is no single material satisfying all the criteria for water splitting is not found. So the
utilization of multijunction solar cells or spatially neighbouring interconnected solar cells, or a
combination of both is a better option for more photon absorption and also more voltage. The
commonly used multijunction schemes are PEC – PEC and PV – PEC [1,11].

In PEC – PEC configuration, separate photoanodes and photocathodes that are optically stacked
in series and electrically interconnected using external wires. A device level schematic of the
photoelectrodes is shown in Figure 2 (a). There are a number of significant design challenges in
this approach like the need of stable PEC semiconductors with optical compatibility for current
matching, and band alignment compatibility for production of sufficient photovoltage. Due to
these challenges, efficient PEC/PEC tandem systems have not been demonstrated to date [12].

Figure 2: (a) PEC – PEC device schematic (b) PV – PEC device schematic

In PV – PEC configuration, a PEC top cell is monolithically stacked with a solid-state single-
junction PV back cell. A device level schematic of this configuration is shown in Figure 2 (b). This
configuration reduces the need for transparent substrates as well as ohmic losses by monolithic
integration. But, this limit the processing temperature of the device and this can be avoided by
mechanical stacking. Stability of the PEC interface is the main issue in this system. High efficiency
photoelectrochemical water splitting cells in this configuration are reported [12].

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4. Summary

The need for hydrogen generation, water splitting process, criteria for a PEC cell, various
electrodes and multijunction device configurations of a PEC cell are discussed in this report. PEC
water splitting cells are facing numerous challenges that need to overcome for highly efficient
water splitting and hydrogen generation. Earth abundant materials are essential for the
development of electrodes and to reduce the cost of the device. Stability of the materials and
scalability of the techniques are certain concerns to be addressed. Photovoltaic cells with better
efficiency, transmittance and tunable voltage in multijunction device schemes can definitely boost
the efficiency of the PEC cells in the future.

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