Electrochimica Acta 240 (2017) 225–230

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Electrochimica Acta
journal homepage: www.elsevier.com/locate/electacta

A photoelectrochemical flow cell design for the efficient CO2

conversion to fuels
Erdem Irtema , María D. Hernández-Alonsob , Andrés Parraa , Cristian Fàbregaa ,
Germán Penelas-Pérezb , Joan R. Morantea,c, Teresa Andreua,c,*
a
Catalonia Institute for Energy Research (IREC), Jardins de les Dones de Negre 1, 08930 Sant Adrià de Besòs, Spain
b
Repsol Technology Center, Agustín de Betancourt, s/n, 28935 Móstoles, Madrid, Spain
c
Universitat de Barcelona (UB), Martí i Franquès, 1, 08028 Barcelona, Catalonia, Spain

A R T I C L E I N F O A B S T R A C T

Article history:
Received 28 January 2017 A solar driven photoelectrochemical flow cell consisting of TiO2 nanorods and an electrodeposited Sn on
Received in revised form 11 April 2017 gas diffusion electrode (GDE) has been studied for the reduction of CO2 (CO2R) and O2 evolution reaction
Accepted 14 April 2017 (OER) under visible light irradiation. Two strategies were proposed to enhance the overall product
Available online 17 April 2017 efficiency which are (i) adjustment of cathode dimensions and (ii) concentration of solar light on the
photoanode. With the TiO2 photoanode, at an applied bias potential of 1.2 V, faradaic efficiencies of 40–
Keywords: 65% for HCOO
production were obtained on the Sn cathode, reaching energy efficiencies up to 70%. The
CO2 electrochemical reduction Sn-GDE presented results prove that optimized system efficiency could be obtained with a stable photoanode
TiO2 photoanode
providing a large photovoltage for OER and a GDE cathode with improved CO2 mass transfer which paves
photoelectrochemical cell
the way towards efficient synthesis of industrial solar fuels.
formate
solar fuels © 2017 Elsevier Ltd. All rights reserved.

1. Introduction dioxide, however few attention was paid to the cell configuration
and cathode selectivity [4,5].
The efficient photoreduction of CO2 using solar energy is one of In an electrolytic cell, CO2 is reduced on the cathode while the
the current challenges in catalysis. Similarly to solar hydrogen, the oxygen evolution reaction takes place on the anode. Unlike water
photoelectrochemical (PEC) approach can lead to a more efficient reduction were the major product is hydrogen, carbon dioxide
fuel production than conventional photocatalysis due to the reduction requires a higher overvoltage for its activation and
effective charge-carrier separation. In the case of carbon dioxide, produces several products simultaneously. The product selectivity
this approach is of outmost importance since the PEC cells can is intrinsic to the electrocatalyst material, the experimental
physically separate both half-reactions avoiding energy efficiency conditions (pH, electrolyte, T) and the cathodic polarization [6].
loses from reoxidation of CO2 products (methanol, methane, The most common half-reactions at pH 7 at the cathode are the
carbon monoxide) at the photoanode [1–3]. Among several followings [7]:
configurations, photoanode driven PEC approach resembles
CO2 + H2O + 2e
! HCOO
+ OH
E0 =
0.61 VNHE (1)
artificial photosynthesis since it is a two-step process: (i) light
dependent reaction by means of water oxidation at the photo-
anode involving the photogenerated minority carriers (ii) CO2
CO2 + H2O + 2e
! CO + 2OH
E0 =
0.53 VNHE (2)
reduction (CO2R) into hydrocarbon fuels via a catalyst at the
cathode (dark reaction) using the photogenerated majority carriers `
from the anode that are injected in the cathode through the
external circuit. It is worth mentioning Lee et al. references the CO2 + 6H2O + 8e
! CH4 + 8OH
E0 =
0.24 VNHE (3)
feasibility of the photoanode-driven PEC reduction of carbon

2H2O + 2e
! 2OH
+ H2 E0 =
0.41 VNHE (4)

* Corresponding author at: Catalonia Institute for Energy Research (IREC), Jardins
de les Dones de Negre 1, 08930 Sant Adrià de Besòs, Spain.
E-mail addresses: tandreu@irec.cat, tandrear@gmail.com (T. Andreu).
Formic acid or formate (depending on the pH of the electrolyte)
is one of the relevant possible products in the electrolysis of
aqueous solutions of CO2, when a metal electrocatalyst with high

http://dx.doi.org/10.1016/j.electacta.2017.04.072
0013-4686/© 2017 Elsevier Ltd. All rights reserved.
226 E. Irtem et al. / Electrochimica Acta 240 (2017) 225–230

hydrogen overvoltage and negligible CO adsoption such as Sn, Pb or

In is used [8]. Nevertheless, the major drawback in the utilization
of CO2 in aqueous solution derives from its moderate solubility in
water at standard temperature and pressure, which limits the
operational current density due to mass transport limitations. To
circumvent this hurdle, higher pressures are necessary to increase
the CO2 concentration in the liquid phase, but electrode stability in
these conditions is limited. Solvents with high solubility for CO2
are used in the nonaqueous electrochemical reduction of CO2, but
low electrolytic conductivity leads to high ohmic losses. Another
problem is that high current densities are required to increase the
productivity maximizing the formation of hydrocarbons, but a fast
deactivation can occur in these conditions. [9,10] The use of porous
electrodes such as gas diffusion electrodes (GDEs) on the
electrochemical reduction of CO2 to formate using filter-press
type cells have been object of recent studies [11–15]. The GDEs
allows for operation at higher current densities and also permits
direct feed of gaseous CO2 to the cell. Following this strategy,
Alvarez-Guerra M. et al. described the influence of some key
variables on the performance of an experimental system under
dark conditions for continuous electroreduction of CO2 to formate
with a gas diffusion electrode (GDE) loaded with commercial Sn as
electrocatalyst whereas our group have reported tin catalyst
electrodeposition on GDE for low-energy formate production
[16,17].
In this work, a back-illuminated TiO2 photoanode has been
implemented in a filter-press photoelectrochemical flow cell using
a Sn-GDE as cathode [18]. This configuration enables electrolyzing
CO2 at relatively low cell potentials, with high faradaic efficiencies
and an improved energy balance, thus requiring less external
energy input. This innovative design maximizes selective CO2
conversion to the desired product under irradiation by adjusting
the area ratio between cathode and anode, so that the current
density at the cathode is optimal for the conversion towards a
certain product, while maintaining the photoanode in an effective Fig. 1. (a) ECf-Dark: Electrochemical flow cell scheme using DSA anode, (b)PECf-
Light: Photoelectrochemical flow cell scheme using TiO2 photoanode and (c)
point of its photoresponse. Furthermore, a cell voltage that favors photograph of the PECf cell setup.
the energy balance thanks to the contribution of the solar energy
harvesting is also preserved. Accordingly, it is possible to optimize
simultaneously the working points of photoanode and cathode, and two outputs (anolyte, catholyte + CO2). Anolyte (0.5 M NaOH)
maximizing the solar energy conversion to the product of interest and catholyte (0.5 M NaHCO3, pre-electrolysed at
2 V under
and reducing the consumption of external electrical bias. nitrogen bubbling to remove metal impurities) were kept in two
separated tanks and recirculated continuously to the cell by a dual
2. Experimental peristaltic pump (Major Science, MU-D02) to accumulate liquid
products. A mass flow controller (Bronkhorst F-201CV) was used to
The designed photoelectrochemical flow cell (PECf) was a control CO2 flow rate entering the system, measured downstream
home-made modification from a filter-press type electrochemical by a volumetric digital flowmeter Agilent ADM 2000. The flow of
cell (Micro Flow Cell, Electrocell A/S) to allocate a back-illuminated CO2 gas and electrolytes were kept at 10 mL min
1 (gas-to-liquid
photoanode (10 cm2) and customized cathode current collectors to ratio of 1), as optimized in our previous work. [17] The experiments
allocate Sn-GDE cathodes of variable size (10-5-2-1 cm2) in were carried out under potentiostatic conditions in two-electrode
separated compartments divided by a membrane. configuration, applying a voltage between (photo)anode and
In this work, TiO2 has been used as one of the well-known and cathode, using a potentiostat/galvanostat Biologic VMP3. A second
stable metal oxides suitable as photoanode material. TiO2 was potentiostat/galvanostat Biologic VMP3 was used to monitor, in
prepared by growing crystalline rutile nanorods layer, with around three-electrode configuration, the voltage of each electrode versus
200 nm average width and 3 microns length, on FTO substrates by the Ag/AgCl reference electrode.
hydrothermal method [19,20] while the Sn-GDE was synthetized The photoelectrochemical cell (PECf) was irradiated using a
by electrodeposition using a pyrophosphate bath (2.6 mgSn cm
2) solar simulator Solar Light 16S equipped with a 300W Xe-lamp and
on carbon paper (Toray carbon paper, TGP-H-60)[17,21]. SEM AM 1.5G filter. Irradiance was measured using a thermopile
images and photographs of both electrodes are shown in Fig. S1. In detector (Gentec-EO, XLPF12-3S-H2-DO) and adjusted from 1 to 10
the electrochemical reduction experiments (ECf), in the absence of suns (100–1000 mW cm
2), by controlling the distance between
irradiation, a Dimensionally Stable Anode plate (DSA/O2, Electro- the light source and the cell.
cell S/A) was used as anode (Fig. 1a). An ionic transport membrane The faradaic efficiency to formate is the percentage of the total
(Nafion 117) divided the cell in two separated anodic and cathodic charge supplied that is used to produce formate. For its
compartments. A leak-free Ag/AgCl 3.4 M KCl reference electrode quantification, a total charge of 4C/mL of catholyte (typical
(Warner Instuments) was assembled in a polytetrafluoroethylene 50 mL) was employed for the (photo)electrolysis to assure a
(PTFE) frame of the cell, placed very close to the cathode surface. As measurable quantity of formate at every potential. The product in
seen in Fig. 1, the cell had three inputs (catholyte, anolyte and CO2) the liquid phase was analyzed, after acidification, by High
 E. Irtem et al. / Electrochimica Acta 240 (2017) 225–230
Performance Liquid Chromatography system (HPLC, Perkin Elmer
Flexar SQ300MS) equipped with a Rezex ROA-Organic Acid H+ (8%)
column (300  7.8 mm, Phenomenex), with an isocratic pump
(2.5 mM H2SO4, 6 mL min
1) and a UV Detector set at 210 nm.
3. Results and discussion
3.1. Reaction at the cathode side: CO2 reduction reaction (CO2R)
First, the electrochemical process under dark conditions was
tested in a filter-press flow cell using the configuration shown in
Fig. 1a, working with a conventional anode (DSA) and the proposed
cathode to be implemented in the photoelectrochemical cell. In
this work, were a Sn-GDE electrode was used, the product of
interest was formic acid (produced as formate ion) from carbon
dioxide reduction. Besides, carbon monoxide and hydrogen were
also detected, that can be valorised as synthesis gas [17].
In Fig. 2a the faradaic efficiency to formate with a Sn cathode as
a function of the applied cell voltage is shown. No cathodic reaction
is obtained at Ecell  1.6 V. Cathode polarization is observed from
1.8 V, from which CO2 to HCOO
faradaic efficiency starts to rise
and after Ecell 2.4 V faradaic efficiencies to formate around to 60-
75% can be achieved.
If we consider just formate as the main product of interest, the
energy efficiency of the process describes the amount of the
electrical applied energy to the cell that is used in making the
product and is given by Eq.5.
   1.6 V.

1
Productivity mol s
1 Þ  DH0comb J mol
E:E:ð%Þ¼  100
Icell ðAÞ  Ecell ðVÞ
Etherm ðVÞ
¼ F:E:ð%Þ 
Ecell ðVÞ
Where the combustion energy under standard conditions associ-
ated to formic acid is 254.6 kJ mol
1 (70.7 W h mol
1), that
corresponds to a thermoneutral voltage of 1.32 V [22]. This
parameter is especially relevant for ensuring the economic
viability of the process, which requires a high faradaic efficiency
with a reduced cell voltage. Fig. 2b represents the energy efficiency
of the dark electroreduction, reaching the highest value at 35%
with and energy consumption of 200 W h mol
1.
Besides cell voltage (polarization between anode and cathode)
in two electrode configuration, in our setup it is also possible to
measure individually the potentials of anode and cathode against a
reference electrode with a second potentiostat. Fig. 3 shows the
evolution of current density and faradaic efficiency of the process
Fig. 2. Faradaic efficiency to formate (a) and energy efficiency (b) as a function of
cell voltage.
227
as a function of individual cathode potential, which increases in
absolute value with increasing cell voltage. It is important to note
that the faradaic efficiency to formate depends on the individual
cathode potential and that for reaching faradaic efficiencies above
40% cathode potentials of at least
1.35 VAg/AgCl are required.
Additionally, data show that to achieve these conversion values,
electrolysis must reach a cathodic current density higher than 2.5–
3 mA cm
2. Finally, to corroborate that CO2(g) is effectively reduced
at the gas diffusion electrode, a blank test was done under a
cathode polarization of
1.5 VAg/AgCl but flowing Ar, obtaining a
formate production rate of 3 mmol h
1 from bicarbonate reduction,
whereas when CO2 is introduced at the Sn-GDE, the production
rate increases to 400 mmol h
1.
3.2. Photoelectrochemical cell: carbon dioxide photoelectroreduction
The photoelectrochemical cell (Fig. 1b) was designed to
facilitate the irradiation of the photoanode, located in the anodic
compartment of the cell, in which the photoactive layer was grown
on a glass substrate that allows solar light enter from the back side
while the electrochemical reaction takes place on the side facing
the membrane. Using this approach it is possible to reduce the gap
between electrodes to minimize the ohmic drop of the electro-
chemical cell and full illumination of the thin film photocatalyst.
Considering that there is no electrochemical reaction in dark
conditions when the cell voltage is equal or lower than 1.6 V, the
operational range of our PECf cell was preferably between 0 and
Among the different metal oxide photoanodes, as seen in
Fig. S2, compared to DSA anodes working in dark-conditions, TiO2
photoanode could have the largest shift of the onset potential of
oxygen evolution reaction (OER) under illumination thanks to the
appropriate band edge positions of titania relative to water redox
potentials [23] which would enable a lower cell potential. Besides,
BiVO4 photoanodes can be a good alternative for having higher
conversion efficiencies than TiO2 but its chemical stability limits
the pH range of the electrolyte [24]. Thus, TiO2 was selected for this
study due to its robustness.
Once assembled, with the TiO2 photoanode in the anodic
compartment and Sn-GDE at the cathodic one, the cell was
polarized for 5 min at different cell potentials from 0.4 to 2.4 V. As
can be observed in Figs. 4 and S3, contrary to what occurs in the
process under dark conditions, under irradiation of the photo-
anode, cathode polarizes at applied cell voltages lower than 1.8 V.
When the cell voltage increases, then photoanode polarization
increases. Nevertheless, contrary to what is observed in the
process under dark conditions, wherein increasing the cell voltage,
Fig. 3. Current density (a) and faradaic efficiency to formate (b) at different cathode
potentials.
228 E. Irtem et al. / Electrochimica Acta 240 (2017) 225–230
Fig. 4. Photoanode and cathode potentials of the photoelectrochemical cell under
different cell voltage (Ecell), and 1 sun illumination.
then higher cathode polarization occurs, in the photoelectrochem-
ical process, it is observed that between 1.2 V and 1.6 V, the cell
voltage increase is invested in polarizing the photoanode while the
cathode polarization remains constant. As seen in Fig. S3A, at this
voltage range (1.2-1.6 V), the photogenerated current is limited by
the TiO2 to 5–6 mA, which results in a cathode potential of
-1.3 VAg/AgCl and consequently the expected faradaic efficiency
will be lower than 20%. Therefore, working with this photo-
electrode and the Sn cathode above 1.2 V (Ecell) will not be
translated into an improvement of the faradaic efficiency of the
photoelectrochemical process. Above 1.8 V (outside the working
range of the photoelectrochemical cell), the photoanode no longer
limits the process and again the cathode polarization increases
with increasing the cell voltage. A photoelectrolysis test was done
at an applied cell voltage of 1.2 V for quantification of formate by
HPLC and a faradaic efficiency to formate of around 16% was
obtained.
3.3. Photoelectroreduction of CO2 with different photoanode/cathode
area ratio
In photo-assisted electrochemical cells, the optimum energy
balance could be obtained by maintaining the optimum operation
Fig. 5. Photoanode (empty symbol) and cathode (filled symbol) potential of the photoelectrochemical cell under different cell bias applied (Ecell) and solar irradiances: 1 sun
(square symbol), 2 suns (triangle symbol), 5 suns (round symbol) and 10 suns (diamond symbol). Photoanode size: 10 cm2, and different cathode sizes: 10 cm2 (a), 5 cm2 (b),
2 cm2 (c) and 1 cm2 (d), resulting in the photanode-to-cathode ratio (ATiO2:ASn-C) indicated in the figure.
potentials of both electrodes. The previously described results
could provide guidelines for approaching the optimum operation
conditions. For OER, as seen in Fig. S4, the maximum photocurrent
efficiency using the TiO2 nanorods will be achieved between
0.5
and
0.3 VAg/AgCl providing 0.5 mA cm
2. This corresponds to an
intensity of ca. 5 mA respect to TiO2 for an electrode of 10 cm2. On
the other hand, the most suitable potential for CO2R over HER
would be between
1.4 and
1.6 VAg/AgCl providing from 3 to
5 mA cm
2. Thus, this potential range would provide 30–50 mA on
the 10 cm2 cathode (Sn-GDE10) in PECf assembly. These calcu-
lations indicate that net currents at both electrodes must be
balanced, which could be achieved with the selected electrodes by
two strategies, (i) decreasing the Sn-GDE geometrical area to
confine a higher energy density at the cathode or (ii) increasing
solar flux on TiO2 photoanode by solar concentrators to uplift the
photocurrent.
Therefore, the photoelectrochemical cell was adapted to
accommodate different cathode sizes (10, 5, 2, and 1 cm2) while
maintaining the photoanode size fixed at 10 cm2. Fig. 5 shows the
evolution of the individual cathode (filled symbols) and photo-
anode (empty symbols) potentials as a function of applied cell
voltage (ǀEǀcell) at different radiation fluxes, from 100 mW cm
2 to
1000 mW cm
2, and for a photoanode-to-cathode area ratio of 1:1
(Fig. 5a), 1:0.5 (Fig. 5b), 1:0.2 (Fig. 5c) and 1:0.1 (Fig. 5d). The
polarization curves of both electrodes are shown in Fig. S5. It is
observed that in all cases increasing the radiation flux increases the
photoanode polarization, as seen also for the current intensity
(photocurrent) and cathode polarization; besides cathode polari-
zation increases as cathode area decreases and thus higher cathode
potentials are obtained. Since the absolute value of applied voltage
is the difference of both electrode polarizations, Sn-GDE potential
can be shifted cathodically by either increasing the radiation flux or
adjusting the geometrical area of the cathode, to avoid the
drawback of reaching the limiting photocurrent of TiO2 where
further polarization lies just at the photoanode and not at the
cathode.
Considering the results of dark electrolysis, the correlation
between the cathode polarization values and the cathode current
intensity ranges required to obtain different faradaic efficiencies
allow us to estimate the faradaic efficiency range that could be
expected in each case. Thus, cathode potential below
1.3 VAg/AgCl
results in faradaic efficiencies below 20%; cathode potential
between
1.3 and
1.35 VAg/AgCl accompanied by current densities
 E. Irtem et al. / Electrochimica Acta 240 (2017) 225–230
Table 1
PECf cell conditions and system efficiencies of discrete electrolysis (charge accumulated 4C/mL).
Ecell (V) Area cathode (cm2) jcathode (mA cm
2)
1.2 10 0.5
1.2 5 2.9
1.2 2 3.4
1.2 1 4.0
0.95 1 4.5
a
Faradaic Efficiency.
b
Energy Efficiency.
c
Solar to Fuel Efficiency.
at the cathode between 1 and 2 mA cm
2 lead to faradaic
efficiencies between 20 and 40%; values between
1.35 and

1.4 VAg/AgCl and current densities below 2 mA cm
2 result in
faradaic efficiencies between 30 and 50%; cathode potential
between
1.4 and
1.7 VAg/AgCl and current densities above
2 mA cm
2 faradaic efficiencies between 40 and 65% will be
obtained; and finally, faradaic efficiencies between 60 and 75% can
be expected only at cathode potential above
1.7 VAg/AgCl with
current densities above 5–6 mA cm
2. Based on these values, the
energy and solar to fuel efficiencies were also estimated and they
are shown in Tables S1-S5.
In order to validate these estimations, some specific experi-
ments were performed with accumulation of enough formate for
its quantification by HPLC after the photoelectrocatalytic process,
which are summarized in Table 1. Using the proposed strategy of
optimizing both photoanode and cathode polarizations, it is
possible to reach energy efficiencies up to 70%. Besides, another
figure of merit in PEC cells is solar-to-fuel efficiency, STF,
here fuel
could be defined as formate
[25]. In our system, that requires an
external bias, a photo-assisted electrolysis system efficiency (STF*)
can be similarly defined as the ratio of output power (chemical
energy stored in terms of formate) to solar input power (AM 1.5G
solar light and applied bias) given by Eq. (6) [26].

1
Productivityðmol s
1 Þ  DH0comb ðJ mol Þ
STF ð%Þ ¼  100
½Psolarf lux þ Pbias;PV ðW m
2 Þ  Areaðm2 Þ
Where Psolarflux is the power generated by the solar light simulator
that irradiates the PEC cell and Pbias,PV is the equivalent solar
irradiance for a photovoltaic cell to generate the electrical bias
applied by the potentiostat, assuming a PV efficiency of 20%. It is
evident from the data in Table 1 that both strategies gave the
highest efficiency, 0.24%.
Most of the results in the literature are based on half-cell
reactions covering only CO2R or OER under light illumination.
Amongst a few study on full cell configuration, a photoelectro-
chemical flow cell is first of its kind so far, that minimizes the
electrolyte gap and optimizes solar to fuel conversion by adjusting
the operational working conditions of the photoelectrochemical
cell (irradiance and anode-to-cathode area ratio). Among the data,
coupling of Sn-GDE
TiO2 in PECf shows the highest faradaic
efficiency (45-64% HCOO
) for reduction of CO2 to HCOO
with the
lowest cell bias, compared to the use of BiVO4 coupled with Cu[4]
or WO3 coupled Sn/SnOx [5] where the faradaic efficiency was
limited to 44.3% (CO + HCOO
) since the cell was not rationally
optimized. Moreover, 0.24% solar conversion is one of the highest
efficiencies reported amongst the data obtained from full cell
configurations using metal oxides (e.g. 0.14% efficiency obtained
with SrTiO3 photoanodes [27]). A comparative table can be found
at Table S6, where the highest solar to fuel efficiencies were
obtained using photovoltaic light absborbers, such as silicon or III–
V semiconductors.
229
Irradiance (mW cm
2) F.E.a (%) E.E.b(%) STF* c(%)
100 17 19 0.11
500 64 70 0.24
200 53 58 0.24
100 42 46 0.22
500 46 64 0.05
4. Conclusions
A photoelectrochemical flow cell working under continuous
flow of gas and liquid was constructed for CO2 conversion to
HCOO
. Under external bias, Sn coated GDE carbon fibres exhibited
superior electrocatalytic activity for CO2R after PECf cell optimi-
zation, overcoming the intrinsic limitations of the photoanode, by
effective coupling of both electrodes changing two parameters:
photon flux and photoanode-to-cathode area ratio. Faradaic
efficiencies higher than 40% were obtained at applied potentials
as low as 0.95 V, and after optimization the achieved solar-to-fuel
efficiency is 0.24%. These results provide strategies for materials
scientists in order to modify cell designs to rationally optimize
solar to fuel conversion matching individual polarization curves.
We believe that this work will bring significant interest for further
developments of artificial photosynthesis devices.
Acknowledgements
This work was supported by Repsol, S.A. Authors from IREC and
UB thank Generalitat de Catalunya for financial support through
the CERCA Programme, M2E (2014SGR1638) and XaRMAE net-
work. IREC also acknowledges additional support by the European
Regional Development Funds (ERDF, FEDER) and by MINECO
projects ENE2012-3651 and MAT2014-59961-C2-1-R and
ENE2016-80788-C5-5-R. EI thanks to AGAUR for his PhD grant
(FI-2013-B-00769).
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.
electacta.2017.04.072.
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