Spectrochimica Acta Part A: Molecular and Biomolecular Spectros
Spectrochimica Acta Part A: Molecular and Biomolecular Spectros
Spectrochimica Acta Part A: Molecular and Biomolecular Spectros
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
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
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) 702–706 703
containing a redox system and a counter-electrode (CE). Usually current flow and provide for the reduction of iodine at the CE (Eq.
the photoanode consists of a film of titanium dioxide (TiO2) semi- (4a)). One of the most important components of the DSSC is the dye.
conductor nanoparticles deposited onto a transparent conductive The mechanism of DSSCs reminds the natural photosynthesis
oxide (TCO) glass support, sensitized with dye (D) molecules. The involving light-energy absorption and charge separation (Fig. 2).
electrolyte system, placed between the two electrodes, is usually So it is a good idea to employ the photosynthetic pigments for fab-
based on the iodide/iodine redox couple ðI =I
3 Þ, although other re- ricating DSSCs [2]. Due to its crucial role in such systems, in the
dox mediators have been successfully tested. present research, considerable effort will be directed towards the
When illuminated, the dye molecules capture the incident pho- development and improvement of photosynthetic dyes. Among
tons generating electron/holes pairs. The resulting electrons, at ex- these, natural dyes provide a viable alternative to expensive organ-
cited states, are immediately injected (within 100 fs) into the ic based DSSCs. Various components of terrestrial plant has been
conduction band of the TiO2 and transported to the electron-col- tested over the last two decades as suitable sensitizers [3–8], and
lecting counter electrode, the cathode. many reports have showed that chlorophylls (Chl), which acts as
The main processes, of a DSSC are listed below: an effective photosensitizer in photosynthesis, have the potential
to be an environment friendly dye source [9–11]. However, Chl-a
D þ hv ! D ð1Þ
does not adsorb efficiently on TiO2 due to the weak interaction of
its ester and ketocarbonyl groups with the hydrophilic oxide sur-
D þ TiO2 ! Dþ þ ecb ðTiO2 Þ 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-
D ! D ð2bÞ rocycle through a conjugated double bond. These dyes must bind
strongly to TiO2 by means of the carboxylic anchoring group, to en-
2Dþ þ 3I ! 2D þ I3 ð3aÞ sure efficient electron injection into the TiO2 conducting band and
to prevent gradual leaching by the electrolyte. The Chl-c1 and Chl-
Dþ þ ecb ðTiO2 Þ ! þTiO2 ð3bÞ c2 absorb solar radiation strongly with absorption bands in the UV–
visible region, covering a broad range of wavelengths. Therefore,
I3 þ 2e ðcatalystÞ ! 3I ð4aÞ they have the potential to efficiently inject electron from the por-
phyrin macrocycle to TiO2.
I3 þ 2e ðTiO2 Þ ! þ3I þ TiO2 ð4bÞ The most abundant photosynthetic species containing Chl-c,
generally a mixture of Chl-c1 and Chl-c2, belong to seaweeds and
The dye, upon absorption of a photon (hm), goes to an electronically marine plankton.
excited state D* (Eq. (1)) which lies energetically above the conduc- Actually, macroalgae show a broad range of applications and
tion band (CB) edge of the semiconductor nanoparticles and injects their importance in several sectors is steadily increasing world-
an electron into the TiO2 conduction band (Eq. (2a)). The deactiva- wide. Aquaculture produces 15.8 million tonnes of aquatic plants,
tion reaction (Eq. (2b)) is a relaxation of the excited states, which with a total estimated value of US$ 7.4 billion [12]. About 47% of
occurs in competition with the electron injection into the TiO2. the total production is used for human consumption, 43% in the
The collection efficiency of the photo-injected electrons at the extraction of colloids, 7% in the production of maërl and the
anode back contact is hindered by two major recombination pro- remaining 3% in the fields of pharmacology, cosmetics, agriculture
cesses, which are shown in Eq. (3b)(back electron transfer) and in and waste water treatments from aquaculture, sewage, agricul-
Eq. (4b)(the TiO2 conduction band electron capture by the oxidized tural and industrial run-off. Algal biomass are also employed in
redox couple). These two processes are in competition with the oxi- the field of renewable energies for the production of biogas.
dation of iodide (Eq. (3a)) and tend to reduce the current production However, macroalgae are an underexploited resource in the
of the cell. In the external circuit, the injected electrons give a 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+.
10 lm (measured by a BRUKER, Detakk profilometer) and a surface the TiO2. Thermal and photochemistry stability are other essential
area of each spot of 0.196 cm2. After the size measurement, the characteristics of dyes used in DSSCs. Fig. 4 shows the electronic
TiO2 film was treated with 40 mM TiCl4 solution as described absorption spectra of U. pinnatifida solution. By increasing the
above, rinsed with water and ethanol and sinterized at 500 °C. wavelength three main peaks are clearly observed. The wavelength
The cooled screen printed plates were seized in small rectangular and the intensity of each absorption peak generally reflect the
forms (2 cm 2 cm) and soaked overnight in the dye solution at transition energies and the transition–dipole moments in transi-
room temperature in the dark. The excess dye was removed by tions from the ground state to the Soret, Qx and Qy singlet-excited
rinsing with ethanol and then the photoanode was dried in oven states.
(at 80 °C for short time). Fig. 5 shows the electronic-absorption spectra of U. pinnatifida
The photoanodes employed for the UV–Vis absorption measure- deposited on the TiO2 layer from the solution. Upon binding to
ment were made using a screen printer with a mesh size of 77.48 TiO2, substantial red shifts of all the absorption bands take place.
in polyester fibers in order to obtain a transparent ultrathin TiO2 This is to be ascribed to the polarization of each macrocycle due
film with an estimated thickness, after sintering process, of about to the flow of electron toward TiO2 instead of the aggregation of
3 lm and an active area of 1 cm2. the Chls through the stacking of the porphyrin macrocycles [13].
To prepare the Counter-electrodes a hole was drilled (1.5 mm Concerning the IPCE measurement (see Fig. 6) we found very low
diameter) in each FTO-glass plate (2 cm 2 cm). The perforated values (2% in the Soret peak region and 1% in the Q band red re-
substrates were washed and cleaned with water and ethanol in or- gion). The presence of other species which absorbs in the red re-
der to remove any residual of glass powder or organic contami- gion around 700 nm.
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 Photovoltaic performance of DSSCs
counter-electrode were assembled into a sandwich type cell and
sealed using a thermopress with a hot melt gasket of 25 lm thick- The experimental data obtained by our photoelectrochemical
ness made of the Surlyn ionomer (Solaronix). The aperture of the studies are reported in Fig. 7 where it is showed the acquired I_V
surlyn frame was larger than the TiO2 area. A drop of electrolyte curve characterized by the following parameters: Voc of 0.36 V, Jsc
solution was put on the hole in the back of the cathode. The elec- of 0.8 mA/cm2 and efficiency of 0.178%. More importantly, for the
trolyte (LiI 0.8 M, I2 0.05 M, in acetonitrile) was introduced into the raw U. pinnatifida based DSSC, we found a very good fill factor of
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
0.20 U. Pinnatifida in solution
hole was sealed and closed heating another Surlyn film and putting
a thin cover glass onto the hole.
Absorbance (u.a.)
0.15
Apparatus and measurements
Acknowledgement