Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 117 (2014) 702–706

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Spectrochimica Acta Part A: Molecular and

Biomolecular Spectroscopy
journal homepage: www.elsevier.com/locate/saa

Brown seaweed pigment as a dye source for photoelectrochemical solar

cells
Giuseppe Calogero a,⇑, Ilaria Citro a, Gaetano Di Marco a, Simona Armeli Minicante b,⇑, Marina Morabito c,
Giuseppa Genovese c
a
CNR-IPCF, Istituto per i Processi Chimico-Fisici, via F. Stagno D’Alcontres 37, I-98158 Messina, Italy
b
Department of Environmental Sciences, Informatics and Statistics, University Ca’ Foscari Venezia, Dorsoduro 2137, Venezia, Italy
c
Department of Department of of Biological and Environmental Sciences – Botany, University of Messina, Salita Sperone 31, Messina, Italy

h i g h l i g h t s g r a p h i c a l a b s t r a c t

 The UV–Vis spectra showed that

Chl-a is less absorbed onto
photoanode than Chl-c.
 Higher sensitization performance of
brown algae towards green ones was
demonstrated.
 High fill factor was obtained with
Undaria pinnatifida dye-sensitizer
solar cell.
 The use of algal pigments in DSSC
cells is a viable and attractive cheap
solution.
 The use of frozen brown algae as
sensitizer was successful
demonstrated.

a r t i c l e i n f o a b s t r a c t

Article history: Chlorophylls based-dyes obtained from seaweeds represent attractive alternatives to the expensive and
Received 6 July 2013 polluting pyridil based Ru complexes because of their abundance in nature. Another important character-
Received in revised form 25 August 2013 istic is that the algae do not subtract either cropland or agricultural water, therefore do not conflict with
Accepted 2 September 2013
agro-food sector. This pigment shows a typical intense absorption in the UV/blue (Soret band) and a less
Available online 13 September 2013
intense band in the red/near IR (Q band) spectral regions and for these reasons appear very promising as
sensitizer dyes for DSSC. In the present study, we utilized chlorophylls from samples of the brown alga
Keywords:
Undaria pinnatifida as sensitizer in DSSCs. The dye, extracted by frozen seaweeds and used without any
Seaweeds
Dye-sensitized solar cells
chemical purification, showed a very good fill factor (0.69). Even the photelectrochemical parameters
Solar energy if compared with the existent literature are very interesting.
Natural dyes Ó 2013 Elsevier B.V. All rights reserved.
Undaria pinnatifida
Venice Lagoon

Introduction experimented many advances in efficiency, cost and robustness.

One of the main target of contemporary scientific research is
finding a solution to the urgent need for a clean and cheap energy
source. In recent years, the photovoltaic (PV) technologies have
⇑ Corresponding authors. Tel.: +39 9039762247 (G. Calogero).
E-mail addresses: calogero@me.cnr.it (G. Calogero), simona.armeli@gmail.com
(S. Armeli Minicante).
There are three main types of PV systems: the p–n semiconductor
junction cells, the dye sensitized solar cells (DSSCs) and the organic
photovoltaic cells (OPVCs). Since their appearance in the 1991 [1],
DSSCs have drawn a lot of attention from the scientific community
due to their ease of fabrication, low cost and competitiveness with
different photovoltaic systems based on p–n junctions.
A typical DSSC, as shown in Fig. 1, is assembled placing in
succession a transparent photoanode, an electrolyte solution

1386-1425/$ - see front matter Ó 2013 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.saa.2013.09.019
 G. Calogero et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 117 (2014) 702–706
Fig. 1. Schematic performance of a dye-sensitized solar cells reaction (cross-section view).
containing a redox system and a counter-electrode (CE). Usually
the photoanode consists of a film of titanium dioxide (TiO2) semi-
conductor nanoparticles deposited onto a transparent conductive
oxide (TCO) glass support, sensitized with dye (D) molecules. The
electrolyte system, placed between the two electrodes, is usually
based on the iodide/iodine redox couple ðI =I
3 Þ, although other re-
dox mediators have been successfully tested.
When illuminated, the dye molecules capture the incident pho-
tons generating electron/holes pairs. The resulting electrons, at ex-
cited states, are immediately injected (within 100 fs) into the
conduction band of the TiO2 and transported to the electron-col-
lecting counter electrode, the cathode.
The main processes, of a DSSC are listed below:
D þ hv ! D 
D þ TiO2 ! Dþ þ ecb ðTiO2 Þ
D ! D
2Dþ þ 3I ! 2D þ I3
Dþ þ ecb ðTiO2 Þ ! þTiO2
I3 þ 2e ðcatalystÞ ! 3I
I3 þ 2e ðTiO2 Þ ! þ3I þ TiO2
The dye, upon absorption of a photon (hm), goes to an electronically
excited state D* (Eq. (1)) which lies energetically above the conduc-
tion band (CB) edge of the semiconductor nanoparticles and injects
an electron into the TiO2 conduction band (Eq. (2a)). The deactiva-
tion reaction (Eq. (2b)) is a relaxation of the excited states, which
occurs in competition with the electron injection into the TiO2.
The collection efficiency of the photo-injected electrons at the
anode back contact is hindered by two major recombination pro-
cesses, which are shown in Eq. (3b)(back electron transfer) and in
Eq. (4b)(the TiO2 conduction band electron capture by the oxidized
redox couple). These two processes are in competition with the oxi-
dation of iodide (Eq. (3a)) and tend to reduce the current production
of the cell. In the external circuit, the injected electrons give a
703
current flow and provide for the reduction of iodine at the CE (Eq.
(4a)). One of the most important components of the DSSC is the dye.
The mechanism of DSSCs reminds the natural photosynthesis
involving light-energy absorption and charge separation (Fig. 2).
So it is a good idea to employ the photosynthetic pigments for fab-
ricating DSSCs [2]. Due to its crucial role in such systems, in the
present research, considerable effort will be directed towards the
development and improvement of photosynthetic dyes. Among
these, natural dyes provide a viable alternative to expensive organ-
ic based DSSCs. Various components of terrestrial plant has been
tested over the last two decades as suitable sensitizers [3–8], and
many reports have showed that chlorophylls (Chl), which acts as
an effective photosensitizer in photosynthesis, have the potential
to be an environment friendly dye source [9–11]. However, Chl-a
ð1Þ
does not adsorb efficiently on TiO2 due to the weak interaction of
its ester and ketocarbonyl groups with the hydrophilic oxide sur-
ð2aÞ face [2], while Chl-c, including Chl-c1 and Chl-c2 (Fig. 3), have the
terminal carboxyl group, which is connected to the porphyrin mac-
ð2bÞ rocycle through a conjugated double bond. These dyes must bind
strongly to TiO2 by means of the carboxylic anchoring group, to en-
ð3aÞ sure efficient electron injection into the TiO2 conducting band and
to prevent gradual leaching by the electrolyte. The Chl-c1 and Chl-
ð3bÞ c2 absorb solar radiation strongly with absorption bands in the UV–
visible region, covering a broad range of wavelengths. Therefore,
ð4aÞ they have the potential to efficiently inject electron from the por-
phyrin macrocycle to TiO2.
ð4bÞ The most abundant photosynthetic species containing Chl-c,
generally a mixture of Chl-c1 and Chl-c2, belong to seaweeds and
marine plankton.
Actually, macroalgae show a broad range of applications and
their importance in several sectors is steadily increasing world-
wide. Aquaculture produces 15.8 million tonnes of aquatic plants,
with a total estimated value of US$ 7.4 billion [12]. About 47% of
the total production is used for human consumption, 43% in the
extraction of colloids, 7% in the production of maërl and the
remaining 3% in the fields of pharmacology, cosmetics, agriculture
and waste water treatments from aquaculture, sewage, agricul-
tural and industrial run-off. Algal biomass are also employed in
the field of renewable energies for the production of biogas.
However, macroalgae are an underexploited resource in the
photovoltaic technologies [10,13].
704 G. Calogero et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 117 (2014) 702–706
Fig. 2. Comparison between Photosynthesis and Dye-sensitized semiconductor system, the dye act as P680, the iodide as water, the anode behavior is similar to charge
transport to P700 from P680, the cathode work as P700 and NADP+.
Fig. 3. Molecular formula of chlorophyllins-c1 and c2.
In this research we concentrated our investigation on the brown
macroalga Undaria pinnatifida (Harvey) Suringar to extract the pho-
tosynthetic pigments and to prepare colored solution using appro-
priate solvent; to fabricate a titania-based dye-sensitized solar cell
(DSSC); to test the photovoltaic performance of the chlorophyll
based devices measuring current_voltage curves and the incident
photocurrent efficiency (IPCE). Algal species were collected in Ven-
ice Lagoon where they are highly invasive species, forming huge
biomass disturbing human activities, and presently removed as a
waste.
Experimental
Materials and dyes
All the solvents and the other chemicals employed for the
experiments were reagent or spectrophotometric grade and were
used as received without any further purification. The conductive
glass plate (FTO glass, Fluorine-doped SnO2, sheet resistance 7 X/
cm2), the Ti-nanoxide (T/SP) paste and the Surlyn foils 25 lm thick
were purchased from Solaronix SA and used as supplied.
Preparation of pigment solution
Samples of U. pinnatifida were collected in Venice Lagoon
(45°260 N; 12°200 E). A portion of each sample was dried in the
sun and subsequently minced, the remaining part was stored at
20 °C. The extraction of chlorophylls has been carried out both
on dry and frozen material, and was based on the protocol reported
by Wang et al. [13] and modified for this study. A quantity of the
brown seaweed was soaked in a solution of 90% acetone: 10%
deionized water. The dye solution used for the absorption spec-
trum was prepared by dissolving the extracted raw chlorophylls
in pure ethanol.
Preparation of TiO2 anodes, platinum counter-electrodes and DSSC
assembly
To prepare the transparent electrodes, the FTO-glass used was
first cleaned in a detergent and then washed with water and etha-
nol. The FTO-glass plates (15 cm  4 cm) were immersed in 100 ml
of TiCl4 water solution (40 mM) at 70 °C for 30 min, washed with
water and ethanol and dried in oven at 80 °C. The TiO2 layer were
deposited on the FTO conducting glass plates by screen printing
(43.80 mesh/cm, polyester fibers, snap off 0.8 mm) This screen
printing procedure (coating, storing in ethanol and drying at
125 °C) was repeated two times. The TiO2 coated plates were grad-
ually heated at 325 °C, then after 5 min reach the 375 °C and finally
were sintered at 450 °C for 30 min [14]. After sintering the result-
ing mesoscopic oxide film was transparent, with a thickness of
 G. Calogero et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 117 (2014) 702–706 705

10 lm (measured by a BRUKER, Detakk profilometer) and a surface
area of each spot of 0.196 cm2. After the size measurement, the
TiO2 film was treated with 40 mM TiCl4 solution as described
above, rinsed with water and ethanol and sinterized at 500 °C.
The cooled screen printed plates were seized in small rectangular
forms (2 cm  2 cm) and soaked overnight in the dye solution at
room temperature in the dark. The excess dye was removed by
rinsing with ethanol and then the photoanode was dried in oven
(at 80 °C for short time).
The photoanodes employed for the UV–Vis absorption measure-
ment were made using a screen printer with a mesh size of 77.48
in polyester fibers in order to obtain a transparent ultrathin TiO2
film with an estimated thickness, after sintering process, of about
3 lm and an active area of 1 cm2.
To prepare the Counter-electrodes a hole was drilled (1.5 mm
diameter) in each FTO-glass plate (2 cm  2 cm). The perforated
substrates were washed and cleaned with water and ethanol in or-
der to remove any residual of glass powder or organic contami-
nants. The Pt catalyst was deposited on the conductive face of
the FTO glass by dropping H2PtCl6 solution (5 mM in isopropanol)
and by heating at 500 °C for 30 min. The photoanode and the Pt
counter-electrode were assembled into a sandwich type cell and
sealed using a thermopress with a hot melt gasket of 25 lm thick-
ness made of the Surlyn ionomer (Solaronix). The aperture of the
surlyn frame was larger than the TiO2 area. A drop of electrolyte
solution was put on the hole in the back of the cathode. The elec-
trolyte (LiI 0.8 M, I2 0.05 M, in acetonitrile) was introduced into the
cell via vacuum backfilling. The cell was placed in a small vacuum
chamber to remove air inside. Exposing it again to ambient pres-
sure causes the electrolyte to be driven into the cell. Finally, the
hole was sealed and closed heating another Surlyn film and putting
a thin cover glass onto the hole.
the TiO2. Thermal and photochemistry stability are other essential
characteristics of dyes used in DSSCs. Fig. 4 shows the electronic
absorption spectra of U. pinnatifida solution. By increasing the
wavelength three main peaks are clearly observed. The wavelength
and the intensity of each absorption peak generally reflect the
transition energies and the transition–dipole moments in transi-
tions from the ground state to the Soret, Qx and Qy singlet-excited
states.
Fig. 5 shows the electronic-absorption spectra of U. pinnatifida
deposited on the TiO2 layer from the solution. Upon binding to
TiO2, substantial red shifts of all the absorption bands take place.
This is to be ascribed to the polarization of each macrocycle due
to the flow of electron toward TiO2 instead of the aggregation of
the Chls through the stacking of the porphyrin macrocycles [13].
Concerning the IPCE measurement (see Fig. 6) we found very low
values (2% in the Soret peak region and 1% in the Q band red re-
gion). The presence of other species which absorbs in the red re-
gion around 700 nm.
Photovoltaic performance of DSSCs
The experimental data obtained by our photoelectrochemical
studies are reported in Fig. 7 where it is showed the acquired I_V
curve characterized by the following parameters: Voc of 0.36 V, Jsc
of 0.8 mA/cm2 and efficiency of 0.178%. More importantly, for the
raw U. pinnatifida based DSSC, we found a very good fill factor of
0.20 U. Pinnatifida in solution
Absorbance (u.a.)

0.15
Apparatus and measurements

The absorption spectra of the photo-electrodes were recorded 0.10

by a Perkin Elmer L20 spectrophotometer UV–Vis (range 180–
1100 nm). Current–voltage curves were recorded by a digital
Keithley 236 multimeter connected to a PC and controlled by a 0.05
homemade program. Simulated sunlight irradiation was provided
by a LOT-Oriel solar simulator (Model LS0100-1000, 300 W Xe
Arc lamp powered by LSN251 power supply equipped with AM 0.00
1.5 filter, 100 mW/cm2). Incident irradiance was measured with a 400 500 600 700 800
Si-based pyranometer. Incident photon-to-current conversion effi- λ (nm)
ciency (IPCE) and relative photoaction spectra of sealed DSSCs
Fig. 4. Absorption spectra of U. pinnatifida in solution.
were measured by a IPCE station. The IPCE station was composed
by a 150 Xenon Light Source (model ASB-XE, Spectral Products),
a Monochromator (model CM110, Spectral Products) equipped
with a slit set, a Si calibrated detector (model 818-UV, Newport),
a Picoamperometer (model 6487, Keithley) and a IPCE Solarena
Software. The photoanodes thickness was measured by using a 0.5
DektakXT profilometer (Bruker) equipped with a diamond-tipped
Absorbance (a.u.)

stylus (radius of 2 lm) and selecting a vertical scan range of

65 lm with 8.0 nm resolution, a programmed scan length of
6000 lm, and a stylus force of 1 mg. Each measure was verified
by acquiring different runs with different start positions, by rotat-
0.3
ing or translating the sample.

Results and discussion

UV–Vis absorption spectra and IPCE

0.0
400 500 600 700 800
An efficient sensitizer should absorb light over a broad range λ (nm)
from the visible to the near-infrared and, the energy of its elec-
tronic excited state should lie energetically above the CB edge of Fig. 5. Absorption spectra of U. pinnatifida onto TiO2 transparent anode.
706 G. Calogero et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 117 (2014) 702–706

The UV–Vis measurements and our studies indicated that Chl-a

in the extract of algae shows less adsorbing property than that of
Chl-c. Works are in progress to isolate the chlorophyll-c, using sim-
ple purification method avoiding the complicated procedures used
by Wang et al. [13]. However, the use of algal pigments such as dye
for DSSC cells could represent a viable and attractive alternative
solution for the production of cells at a cheap cost. Also, the use
of chlorophylls extracted from these species would have a further
advantage in terms of ecological sustainability. U. pinnatifida is
highly invasive, classified among the top 100 global invasive spe-
cies, and has caused concern all over the world as it invaded the
coastal environments in parts of Europe, Australia, New Zealand,
Argentina and the USA, has the potential to displace native sea-
weed species and significantly alter habitat for associated fauna
including commercial species [16–18].
Fig. 6. IPCE curve photoaction spectra on DSSC of U. pinnatifida.
At present, in Venice Lagoon, U. pinnatifida is removed and pro-
cessed as a waste, stocked in dumps and incinerated. According to
a recent law (decree-law 217/2009), its employment as a fertilizer
in agriculture is allowed, but it is actually not practiced. The erad-
ication of U. pinnatifida in Venice Lagoon does not appear easy to be
implemented mainly because the colonization is established over
several years and also due to the complexity of the sites, which
are strongly related to anthropic activities and economic structures
or public utilities (docks, piers, pipes and cables buried under piles
of wood or concrete, etc.) [19].
In conclusion, in future, the exploitation of these brown sea-
weeds would result in the conversion of a waste into a valuable
biomass for energy applications.

Acknowledgement

We gratefully acknowledge PON – Industrial 2007–2013: Prog-

etto FotoRiduCO2 (Prot. PON01_02257) and ENERGETIC (Prot.
Fig. 7. Comparison of current_voltage curve for U. pinnatifida and green algae curve
from Taya et al. [15]. PON02_00665). Furthermore this research was financial supported
by ‘‘EFOR’’ Project financed by CNR.
0.69. It’s worth to note that this value is higher than that reported
by Wang et al. [13], obtained by using purified U. pinnatifida as sen- References
sitizer dye. Furthermore, taking into account the increasing photo-
[1]
electrochemical values obtained by these authors with increasing [2]
dye concentration [13], improved performances (in terms of cur- [3]
rent density and efficiency) are expected also for a DSSC based [4]
[5]
on a higher raw U. pinnatifida dye content. Finally, comparing our
result to literature data, we found that in the case of the green al- [6]
gae [15] the best values reported by other researcher are 0.397 mA/
[7]
cm2, 0.559 V, 0.44 and 0.1% for Jsc, Voc, fill factor and solar efficiency
[8]
respectively, which are lower than our results.
[9]
Conclusions [10]
The extracts obtained from the U. pinnatifida were used as sen- [11]
sitizers in DSSCs and gave a significantly higher fill factor and rea- [12]
sonable current density if compared to existing literature. The [13]
DSSC fabricated with the extract of U. pinnatifida exhibited the effi-
[14]
ciency of around 0.178% whereas for the cell based green algae the
best values reported by other researcher are 0.397 mA/cm2, [15]
0.559 V, 0.44 and 0.1% for Jsc, Voc, fill factor and solar efficiency
[16]
respectively, which are lower than our results. The improved effi-
ciency of the cell based on the U. pinnatifida extract is due to the
optimized procedures used for DSSC assembly and to the better
sensitization properties of the Chl-c versus other chlorophylls type [17]
[18]
[15], as shown in Fig. 7. Moreover U. pinnatifida was frozen when [19]
collected and this protects the pigment from the degradation and
could be important for the dye storage.
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