Available online at www.sciencedirect.

com

Solar Energy 86 (2012) 15631575

www.elsevier.com/locate/solener

Anthocyanins and betalains as light-harvesting pigments

for dye-sensitized solar cells
Giuseppe Calogero a,, Jun-Ho Yum b, Alessandro Sinopoli a, Gaetano Di Marco a,
Michael Gratzel b, Mohammad Khaja Nazeeruddin b,
a

CNR-IPCF, Istituto per i Processi Chimico-Fisici, Viale F. Stagno DAlcontres 37, I-98158 Messina, Italy
b
Laboratory of Photonics and Interfaces, EPFL SB ISIC LPI, CH-1015 Lausanne, Switzerland
Received 10 November 2011; received in revised form 24 January 2012; accepted 17 February 2012
Available online 19 March 2012
Communicated by: Associate Editor Frank Nuesch

Abstract
We present the photoelectrochemical properties of dye-sensitized solar cells using natural pigments containing betalains and anthocyanins as sensitizers. The dyes extracted from grape, mulberry, blackberry, red Sicilian orange, Sicilian prickly pear, eggplant and radicchio have shown a monochromatic incident photon to current eciency (IPCE) ranging from 40% to 69%. Short circuit photocurrent
densities (Jsc) up to 8.8 mA/cm2, and open circuit voltage (Voc) ranging from 316 to 419 mV, were obtained from these natural dyes
under 100 mW/cm2 (AM 1.5) simulated sunlight. The best solar conversion eciency of 2.06% was achieved with Sicilian prickly pear
fruits extract. The inuence of pH and co-absorbers on natural sensitizers, were investigated and discussed.
2012 Elsevier Ltd. All rights reserved.
Keywords: Dye-sensitized solar cells; Natural dyes; Anthocyanins; Betalains; Solar energy; Titanium oxide

1. Introduction
Dye-sensitized solar cells (DSSCs) are devices for the
conversion of visible light into electricity, based on sensitization of wide band-gap semiconductors (ORegan and
Gratzel, 1991). The rst high ecient nanocrystalline
DSSC was pioneered by Gratzel in the early nineties with
eciency (g) exceeding 10% (Nazeeruddin et al., 1993). A
typical DSSC, as shown in Fig. 1, is assembled placing in
succession a transparent photoanode, an electrolyte solution containing a redox system and a counter-electrode
(CE) (Calogero et al., 2010a; Bonaccorso, 2010; Calogero
et al., 2011). Usually the photoanode consists of a lm of
titanium dioxide (TiO2) nanoparticles deposited onto a

Corresponding authors. Fax: +41 21 693 4311 (M.K. Nazeeruddin).

E-mail addresses: calogero@me.cnr.it (G. Calogero), mdkhaja.nazeer

uddin@ep.ch (M.K. Nazeeruddin).
0038-092X/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.solener.2012.02.018

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 (I =I
3 ), although other redox mediators have been successfully tested. The main processes, of
a DSSC are listed below:
D hv ! D
1
D TiO2 ! D e
cb TiO2

2a

D ! D

2b

2D 3I

! 2D

I
3

! D TiO2

2e
cb TiO2

2e catalyst ! 3I

3a

e
cb TiO2


D
I
3
I
3

! 3 I TiO2

3b
4a
4b

The dye, upon absorption of a photon (hv), goes to an electronically excited state D (Eq. (1)) which lies energetically
above the conduction band (CB) edge of the semiconductor

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G. Calogero et al. / Solar Energy 86 (2012) 15631575

Fig. 1. Scheme of a natural dyes sensitized solar cell.

nanoparticles (Eq. (2a)) and injects an electron into the

TiO2 conduction band. The deactivation reaction (Eq.
(2b)) is a relaxation of the excited states, which occurs in
competition with the electron injection into the TiO2. The
collection eciency of the photo-injected electrons at the
anode back contact is hindered by two major recombination processes, 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 oxidation of iodide (Eq.
(3a)) and tend to reduce the current production of the cell.
In the external circuit, the injected electrons give a current
ow and provide for the reduction of iodine at the CE (Eq.
(4a)). One of the most important components of the DSSC
is the dye. An ecient sensitizer should absorb light over a
broad range from the visible to the near-infrared and, the
energy of its electronic excited state should lie energetically
above the CB edge of the TiO2. Thermal and photochemistry stability are other essential characteristics of dyes used
in DSSCs. Commonly, transition metal coordination compounds such as ruthenium (Nazeeruddin et al., 1993, 2001)
and osmium (Kuciauskas et al., 2001; Argazzi et al., 2004;
Altobello et al., 2005) polypyridil complexes and synthetic
organic dyes (Yum et al., 2007; Campbell et al., 2007), are
used as eective sensitizers in DSSCs. Over the last two
decades ruthenium complexes, equipped with appropriate
ligands and anchoring groups, have been the most widely
used choice of charge transfer sensitizers for mesoscopic

solar cells (Nazeeruddin et al., 1993; Polo et al., 2004).

However, the preparation routes for metal complexes are
based on multi step procedures involving tedious and
expensive chromatographic purication procedures
(Nazeeruddin et al., 1993). Recently the interest in organic
dyes is raised. Their solar to electric power conversion eciencies (g), have been sharply increased reaching 9.5% for
the indoline dye D205 developed by Uchida (Ito et al.,
2008) and 9.8% for the dye C217 developed by Zhang
et al., 2009, which are promising if compared to 11.1% obtained with DSSCs based on ruthenium complexes (Nazeeruddin et al., 2005). Other ruthenium-free sensitizers, based
on pushpull substituted porphyrins, with high solar-toelectric power conversion eciency have been reported
(Bessho et al., 2010). Recently some of the authors of this
work has improved the eciency of the famous Gratzel solar cells to 12.3% (Yella et al., 2011).
A DSSC with a ruthenium-based sensitizer has a dye
uptake (C of ca. 107 mol cm2 (layer thickness d =
10 lm), which corresponds to 1 g of dye per m2. The price
of the dye per Wp (Watt peak) can be calculated using the
following equation:
P total

C  M dye  P mass
I AM1:5  g

where Ptotal is the price per Wp ( W1), C is the surface

coverage above described, Mdye is molecular mass of the
dye (g mol1), Pmass is the price per mass ( g1) while

G. Calogero et al. / Solar Energy 86 (2012) 15631575

IAM1.5 is the light intensity of AM 1.5 (W m2) with g being

the eciency of the DSSC. For ruthenium based compound, the Pmass is strictly dependent on the production
scale. Actually its commercial price is estimated to be
300 g1 but, large scale production, could reduce it, in
the future it to 30 g1 resulting in a Ptotal of 0.8 per
Wp. So the cost of the dye for a DSSC based panel of
3 kWp will be 2400 . Even, for organic dyes, the production costs and the Ptotal are estimated similar to ruthenium
dyes. Moreover, the actual production is still far to satisfy
large scale demand. Apart from cost related issues (aforementioned dyes aect for the 1015% the total expense of
DSSCs) (Smestad et al., 1994; Kalowekamo and Baker,
2009), indirect environmental charges, due to the chemical
byproducts disposal, need to be considered. Unlike synthetic dye-sensitizers, natural ones are easy to prepare,
cheap, non-toxic, environmentally friendly and fully biodegradable. Among natural pigments, three main families of
compounds have been exploited as sensitizer in DSSCs:
chlorophylls (Kay and Gratzel, 1993; Chang et al., 2010),
anthocyanins (Cherepy et al., 1997; Polo and Murakami
Iha, 2006) and betalains (Calogero et al., 2010b). Raw
chlorophylls are not ecient sensitizers for DSSC, thus different strategies to enhance their eciency have been tested
such as chemical reactions, selective purication by column
chromatography (Wang et al., 2007) and the mixing with
other natural dyes (Kumara et al., 2006; Chang et al.,
2010). In this context the possibility to obtain interesting
photoconversion eciencies, using natural dyes, was performed (Calogero et al., 2009).
In this article we focused our attention only on anthocyanins and betalains. Anthocyanins are a very large group of
redblue plant pigments, which naturally occurs in all higher
plants. They are responsible for the coloration of owers,
fruits, fruit juice, wines, leaves, stems, bulbs, roots, etc. (Timberlake and Bridle, 1975). The main sources of anthocyanins
are some vegetables such as blackberries, grapes, blueberries,
eggplant (aubergine), red cabbage, red radicchio, red
oranges, elderberry, red onion, black rice, mango and purple
corn. The production of anthocyanins in nature is estimated
to be 109 tonnes/year (Takeoka and Dao, 2002; Timberlake and Henry, 1988). Over 500 dierent types of anthocyanins have been isolated from plants and all are derivatives of
the single basic core structure of 2-phenylbenzopyrylium
(avylium) ion, shown in Fig. 2. Betalains are a class of red
and yellow indole-derived pigments (see Fig. 3), which are
found in plants of the order Caryophyllales. To date, the betalains comprise a quite modest number of about 55 structures. The most promising source of betalains is the prickly
pear fruit, a member of the family Cactaceae, which originates from Mexico and spread widely throughout Latin
America, South Africa and Mediterranean area. Sicily ranks
second among all countries in the world for producing and
exporting prickly pear fruits. Like the anthocyanins, the betalains show light absorption in the visible region and are
antioxidant compounds (Stintzing and Carle, 2007; Azeredo, 2009); conversely to the anthocyanins, that present

1565

functional groups (AOH), betalains have the requisite functional groups (ACOOH) to bind better to the TiO2 nanoparticles (Calogero et al., 2010b; Quin and Clark, 2007; Zhang
et al., 2008), than the functional groups (AOH) presents in
the formers. Indeed the interaction between TiO2 lm and
carboxylic functions should bring to a stronger electronic
coupling and rapid forward and reverse electron transfer
reactions. In this work we present the results obtained using
natural photosensitizers such as wild Sicilian prickly pear,
blackberry, red Sicilian orange, mulberry, radicchio, eggplant and giacche` grape (see Fig. 4). Their sensitization activities are fully described and the results compared with that
obtained with other natural pigments. Results on stability
tests, essential for the successfully use of natural dyes in
DSSCs, are also presented.
2. Experimental
2.1. Preparation of dye-sensitizers
The synthetic dye di-tetrabutylammonium cis-bis(isothiocyanato)bis(2,20 -bipyridyl-4,40 -dicarboxylato)
ruthenium(II), called N719, was prepared following the
procedure described elsewhere (Nazeeruddin et al., 1999).
Briey, a solution of 5.5  104 M of N719 was prepared
in ethanol and serves as standard reference. All the natural
dyes except for the eggplant, radicchio and red Sicilian
orange, were prepared by the following steps: fresh fruits
were crushed using a mortar, then solid residues were ltrated out. Eggplant and radicchio dyes were extracted
from the peels and the leaves, respectively, according the
following procedures: rst the vegetable materials were
immersed in ethanol solution to remove the chlorophyll
and successively in a dilute solution of HCl (0.1 M)
(Todaro et al., 2009). The resulting solutions, according
to a patent reported elsewhere (Calogero and Di Marco,
2010), were ltered with the addition of some natural
organic co-absorbers and then stored at pH < 2.0 at 5 C
with the exception of the Sicilian Prickly pear juice that
was stored at pH 5.5 (Castellar et al., 2003). The process
for obtaining extracts of the sensitizing dye compounds
from vegetal products, was made with the aim of maximizing the amount of extracted dye and to preserve their
chemical properties. The use of acids and co-adsorbers,
such as HCl or carboxylic acids, considerably increases
the sensitizing activities of the studied natural dyes. Usually we added tartaric acid, in powder form to the juice
solution until the pH of the nal solution is less than 2.
Alternatively to the method previously described, only to
extract the sensitizing dye compounds from the aubergine
skins, we used the technique named Calorio bis that
has been developed by Calogero and Di Marco, as a
home-made ecologic method (Calogero and Di Marco,
2010). According to this new procedure, the aubergine
skins (20 g) were putted in a metallic container, with
250 g of distilled water; to the mixture, the juice of a lemon
for each 20 g of skins and about 5 g of sodium bicarbonate

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G. Calogero et al. / Solar Energy 86 (2012) 15631575

Fig. 2. The avylium ion, the basic structure of some anthocyanins.

Fig. 3. General structure of betalain (A) and indixanthin (B).

(NaHCO3) is added. Then, it is heated at a temperature

ranging between 40 C and 60 C, for a period of time
ranging between 30 and 120 min, preferably 60 min, until
the appearance of a violet coloration. For the case of red
Sicilian orange juice we used the fresh solution by squeezing the fruit, although for some experiments we used acidied and/or concentrated extracted. In the following of the
paper, the acid juice solution is indicated with the symbol
H+ added to the name. All the investigated dyes were protected from direct sunlight exposition and resulted to be
stable for more than 1 year.

2.2. Preparation of electrodes

Fluorine-doped tin oxide (FTO) deposited on glass is
usually used both at the photoanode, as support for the
dye-sensitized oxide and at the CE. Indeed, it allows light
transmission while providing suitable conductivity for current collection. Photoelectrodes, used in this work, consisted of a multi-layer TiO2 lm deposited onto the FTO
glass. FTO glass plates (Nippon Sheet Glass, Solar, 4 mm
thick) were cleaned in a detergent solution using an ultrasonic bath for 15 min, rinsed with water and ethanol. The

G. Calogero et al. / Solar Energy 86 (2012) 15631575

1567

400 C. This method produces optically transparent electrodes (Papageorgiou et al., 1997). The nal DSSC (see
Fig. 5) was assembled sealing the photoanode with the
CE having a pinhole through the glass, needed for the
injection of the liquid electrolyte. The sealing polymer used
is called Surlyn, a plastic foil of 25 lm cut as an O-ring.
The electrolyte was then injected through the small hole
of the CE with a pump that created a vacuum in the cell.
This technique permits to the electrolyte to ll completely
the gap, created by Surlyn, between the two electrodes.
Finally, the pinhole was sealed with another full round
piece of Surlyn, covered by a small piece of glass to
enhance the mechanical strength.
Fig. 4. Picture of the investigated natural dyes sources.

FTO glass plates were immersed in aqueous 40 mM TiCl4

at 70 C for 30 min and washed with water and ethanol.
A paste (paste A) was prepared as described in literature
(Wang et al., 2003), for the transparent nanocrystallineTiO2 layer, a FTO glass plates was coated by screen printing and then dried for 6 min. at 125 C. This coatingdrying procedure was repeated to increase the thickness from
2.6 (one time) to 9.3 lm (four times), as required. The
thickness of the nanocrystalline TiO2 layer was separately
measured, after sintering without scattering layers, by
using a surface proler. After drying a nanocrystalline
TiO2 layer at 125 C, a paste for the scattering layer containing 400 nm sized anatase particles (CCIC, HPW-400,
paste B) (Wang et al., 2003), was deposited by screen printing. One printing application resulted in a 4 lm thick layer
of paste B. The electrodes coated with the TiO2 pastes were
gradually heated under an air ow at 325 C for 5 min., at
375 C for 5 min, at 450 C for 15 min., and at 500 C for
15 min. The TiO2 lms were treated again with aqueous
TiCl4 and sintered at 500 C for 30 min. All the photoanodes were obtained for adsorption of TiO2 lms in sensitizer solutions, 28 h for natural dyes and 18 h for the
articial one. The CE was prepared depositing nanosized
platinum metal clusters onto FTO glass using a precursor
composed of 5 mM solution of hexachloroplatinic (IV)
acid hexahydrate in anhydrous isopropanol. About 5
10 lL/cm2 of the precursor solution was spread onto
FTO glass and then left to dry in air for 15 min at

2.3. Preparation of electrolytes

Electrolytes were prepared by dissolving/mixing dierent
components (see Table 1 for detailed composition) in solvents such as acetonitrile (AN), valeronitrile (VN), 3-methoxyproprionitrile (MPN). Based on the volatility of the
solvent, electrolytes were classied as volatile (AN:VN solvent) or nonvolatile (MPN solvent). Generally, apart from
the redox couples, Guanidinium thiocyanate (GuNCS)
and/or 4-tert-butyl-pyridine (TBP) or pyridine (PY) was
added with the aim to increase the Voc of the cell.
2.4. Measurements
For photovoltaic measurements of the DSSCs, the irradiation source was a 450 W xenon light source (Osram XBO
450, USA) equipped with a lter (Schott 113) to eliminate
UV radiation and to provide a good transmittance in the visible range. The lamp power was regulated to the AM 1.5G
solar standard by using a reference Si photodiode equipped
with a color matched lter (KG-3, Schott) in order to reduce
the mismatch, in the region of 350750 nm, between the simulated light and AM 1.5G to less than 4%. The incident photon-to-current conversion eciency (IPCE) was plotted as a
function of excitation wavelength by using the incident light
from a 300 W xenon lamp (ILC Technology, USA), which
was focused through a Gemini-180 double monochromator
(Jobin Yvon Ltd.). The measurement delay time of photo J
V characteristics of DSSCs was xed to 40 ms. In order to
reduce the scattered light from the edge of the dyed TiO2
layer, a light shading mask was used onto the DSSC. Unless
otherwise specied A6979 was used as electrolyte for the IV
and IPCE experiments. The active area of the DSSC was
xed to 0.2 cm2.
3. Results and discussion
3.1. Absorption spectra of the natural photosensitizers

Fig. 5. Scheme of a closed dye-sensitized solar cell.

As mentioned sensitizers for DSSCs, need to full most

stringent requirements such as absorb in the visible and
near-infrared regions of the solar spectrum, and strongly
bind to the semiconductor oxide surface (Cherepy et al.,

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G. Calogero et al. / Solar Energy 86 (2012) 15631575

Table 1
Electrolyte composition.a
Electrolyte

Solvent

Composition

Additive

A6979
A6141

AN:VN (85:15)
AN:VN (85:15)

BMII 0.6 M, LiI 0.1 M, I2 0.05 M

BMII 0.6 M, I2 0.05 M,

G1
G2

MPN
MPN

LiI 0.7 M, I2 0.07 M

LiI 0.7 M, I2 0.07 M

TBP 0.5 M
GuNCS 0.1 M

PY 0.25 M

Where AN is acetonitrile, VN is valeronitrile, MPN 3-methoxyproprionitrile, BMII is methyl_benzimidazolium iodide, TBP is 4-tert-butylpyridine, PY
is pyridine.

Fig. 6. Absorption spectra of anthocyanins dyes onto TiO2 lm: red mulberry (purple dashed dot line), eggplant (blue dot line), red orange extract (red
dashed line), radicchio (black dashed line), blackberry (orange dashed dot line), giacche` (green line).

1997). Moreover, the lowest unoccupied molecular orbital

(LUMO) of the dye should lay at higher energy level than
the semiconductor so that, upon excitation, the dye should
inject electrons into the conduction band of the TiO2 with
high quantum yield. The highest occupied molecular orbital (HOMO) energy level of the dye needs to be more positive than the redox potential of the couple (I =I
3 ), indeed,
if the dierence between HOMO of the dye and redox
potential of the electrolyte mediator is small, a weak driving force lead to a shorter eective electron-diusion and to
a slow dye reduction rate, resulting in a low current density
produced by the DSSC (Ardo and Meyer, 2009). In nature
it is not easy found a pigment which posses all the above
cited photophysical and photochemical properties. Generally, anthocyanins show a broad absorption band in the
visible region due to charge transfer transitions from
HOMO to LUMO (Cherepy et al., 1997; Liu, 2008). As
reported in the literature (Cherepy et al., 1997; Wongcharee et al., 2007; Dai and Rabani, 2001; Dai and Rabani,
2002a,b) the absorption band of the anthocyanin is sensitive to pH and solvent, showing the red avylium form in
acidic solution and the purple deprotonated quinonodial

form as increasing the pH. The visible absorption band

also shifts to lower energy upon complexation with metal
ions. Adsorption of anthocyanidins onto the TiO2 surface
forms strong complexes showing prevalently the quinonodial form, which arises from AOH (or @O) groups and
Ti(IV) sites on the semiconductor nanocrystalline layer
(Kay and Gratzel, 1993; Cherepy et al., 1997; Smestad,
1998; Tennakone et al., 1997). The strong chelation on
TiO2 photoanode lms is evidenced by shift in the absorption maxima from 510 nm in solution to 530550 nm (see
Fig. 6). The betalains, that are water soluble nitrogenbased pigments, absorb in the range 450600 nm and are
divided in betanins (Bn) and bethaxantins (Bx). Fig. 7
shows the absorption spectrum of raw Sicilian prickly
pears fruits juice, adsorbed onto TiO2 monolayer structured lm. The absorption maximum peak is at about
450 nm with a tail in the longer wavelength range. The
spectrum has three contributions due to betalamic acid
(430 nm), yellow indicaxanthin (470 nm) and red purple
betacyanins (536 nm), respectively. This suggests that, the
yellow betaxanthin compounds (such as indicaxanthin)
and the betalamic acid, are more adsorbed onto TiO2 lm

G. Calogero et al. / Solar Energy 86 (2012) 15631575

1569

Fig. 7. Absorption spectra of Sicilian prickly pear dyes onto TiO2.

than betanin or betanidin. Using the following formulas

(where A is the absorbance at the specied wavelength):
Bx 23:8 A482  7:7A536

Table 2
IPCE% maximum values, measured at kmax for some selected dyes
adsorbed on TiO2 multilayer structures (13.3 lm thick, including a
scattering layer).

Bn 15:38 A536

Dye

It is possible to estimate, from the absorption spectrum, the

betaxanthin (Bx) and betanin (Bn) concentration in molarity. In the case of Sicilian prickly pear fruits the concentration of [Bx] and of [Bn] are 18.7 lM and 6.9 lM
respectively; which are higher if compared to literature
(Zhang et al., 2008) data of similar class of sensitizer.
3.2. Incident photon-to-electron eciencies (IPCEs), and
current voltage characterization of natural dyes
The IPCE corresponds to the number of electrons, measured as photocurrent in the external circuit, divided by the
monochromatic photon ux that strikes on the cell. Other
names for IPCE include calibrated spectral response and
external quantum eciency (EQE). Commonly the IPCE
is obtained from the following formula:
IPCE

12:4V  nmphotocurrent densitylA=cm2

wavelenghtnm photon fluxW=m2

The IPCE can also be expressed as a function of light harvesting (LHE(k)) and absorbed photon to current conversion eciency (APCE), by:
IPCEk LHEk  APCE

Here LHE(k) represents the fraction of photons of wavelength (k) absorbed by the dyes and is given by:

Electrolyte kmax (nm) IPCE (%)

N719
A6979
N719
A6141
Sicilian prickly pear (H+)
A6979
Blackberry (H+)
G1
Blackberry (H+)
A6979
Red Sicilian orange concentrated juice A6979
Red Sicilian orange concentrated juice G1

LHE 110OD

550
550
450
550
550
550
550

89
86
69
46
44
42
40

10

where OD is the optical density or absorbance. The LHE

depend on extinction coecient of the sensitizers, concentration of the adsorbed dyes and thickness of TiO2
photoanode.
The APCE or internal quantum eciency (IQE), can be
simply calculated by dividing the IPCE by LHE(k at each
k. The APCE is also the product of the quantum yield
for electron injection /inj), and the electron collection eciency /c) as reported below:
APCEk /inj  /c

11

Concerning the anthocyanins, /inj was calculated as 0.98 in

a previous work (Cherepy et al., 1997), while for the betalains no data are available in literature. IPCE values, for
some selected dyes, have been measured at a xed wavelength, (Table 2). The best IPCE value for natural dyes

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G. Calogero et al. / Solar Energy 86 (2012) 15631575

Table 3
LHE, IPCE, APCE and Uc values at the (kmax for some selected natural pigments adsorbed on transparent TiO2 lm (2.6 lm thick).
Dye
+

Blackberry (H )
Red Sicilian orange concentrated juice
Red mulberry (H+)
Blackberry

kmax (nm)

LHE

IPCE

APCE

Uc

543
538
538
532

0.42
0.74
0.21
0.85

0.32
0.29
0.20
0.19

0.76
0.39
0.96
0.22

0.77
0.40
0.97
0.23

was obtained from Sicilian prickly pear (69%). Data reported from Table 2 demonstrated that the nature of the
dye and its preparation, seems to be the key factor for
the IPCE values. IPCE, LHE, APCE and /c have been calculated applying the Eqs. (8)(11) to the experimental data
measured for the natural dyes, as reported in Table 3. The
employment of a thinner single layer TiO2 nanocrystalline
lm (2.6 lm) as photoanode as been necessary. In fact to
respect the limit of LambertBeer law, avoid absorbance
values out of the reasonable range it is required. As can
been observed comparing the data reported in Table 3
the red Sicilian orange concentrated juice shows low /c (despite high value of LHE), when compared to blackberry
(H+) or red mulberry (H+). The /c is very high conrming
that the process reported in the patent (Calogero and Di
Marco, 2008), which contemporary employ co-adsorbates
and acid, it is important to block surface trap sites limiting
triiodide contact with the semiconductor surface as well as
inhibiting dye aggregation. Table 4 summarizes the photoelectrochemical parameters for the natural dyes, adsorbed
onto multi layer TiO2 lm (9.3 lm). The analysis of these
data permits us to select the best four sensitizers, in terms
of eciency. Photoanodes with TiO2 multi layer structure
(13.3 lm) with on the top a scattering layer, employing
some selected dyes (Sicilian prickly pear, blackberry, red
Sicilian orange and red mulberry), have been prepared.
The corresponding IV curves, for the selected sensitizers,
are shown in Fig. 8. The best g was obtained by Sicilian
prickly pear dyes, showing a Voc and Jsc values of
0.389 V and 8.82 mA/cm2 respectively. In Fig. 9 are shown
the photoaction spectra of the best selected natural dyes.
The IPCE spectra (from the blue region of the spectrum
to 630 nm) of the Sicilian prickly pear dye showed clearly
a higher IPCE value on the ordinate axis when compared
to the other dyes (based on anthocyanins). On the other
hand, in the red part of the spectrum (>630 nm), the

Fig. 8. Currentvoltage characteristics curves of DSSCs sensitized with

red mulberry natural pigments (black line), red Sicilian orange concentrated juice (blue line), blackberry (green line) and Sicilian prickly pear
(red line). The photoanode, characterized by multilayer TiO2 structures, is
13.3 lm thick. The CE is Pt/FTO optically transparent. A6979 as electron
transfer mediator and power intensity of 100 mW/cm2 of a Xe lamp as
simulated solar source, are used.

anthocyanins show slightly better IPCE value on the ordinate axis in comparison with Sicilian prickly pear. This
could be ascribed mainly to their red shifted absorption
properties. The higher IPCE value, obtained with the Sicilian prickly pear sensitization, is also reected in an overall
increase in Jsc compared to the other dyes. In the following
sections the results obtained with the selected sensitizers
will be discussed in greater detail, as well as how the addition of pyridine and 4-tert-butylpyridine, to the liquid electrolyte, will aect the nal photo-electrochemical
parameters of the DSSCs.

Table 4
Photoelectrochemical parameters of DSSCs based on natural dye sensitizers, adsorbed on TiO2 multilayer structures (9.3 lm thick).
Dye
+

Sicilian prickly pear (H )

Blackberry (H+)
Red Sicilian orange extract
Red mulberry (H+)
Radicchio (H+)
Red Sicilian orange (H+)
Eggplant (H+)
Giacche` grapes (H+)

Jsc (mA/cm2)

Jmax (mA/cm2)

Vmax (mV)

Voc (mV)

FF

g (%)

7.85
5.85
5.13
4.45
5.05
4.98
3.48
3.06

7.0
9
4.5
4.0
4.3
3.8
2.9
2.4

267
216
224
243
212
207
221
240

382
320
329
340
322
325
346
333

0.62
0.57
0.59
0.64
0.55
0.48
0.53
0.56

1.87
1.07
1.01
0.99
0.90
0.78
0.64
0.57

G. Calogero et al. / Solar Energy 86 (2012) 15631575

Fig. 9. IPCE spectra of DSSCs using A6979, nanorized Pt/FTO as CE

and TiO2 lm sensitized with blackberry extract (green line), red Sicilian
orange concentrated juice (blue line) and Sicilian prickly pear (red line).

3.2.1. Blackberry dye

The ultrafast charge injection processes from blackberry
anthocyanins into the conduction band of the TiO2 semiconductor, has been demonstrated (Cherepy et al., 1997).
This behavior is consistent with the strong electronic coupling occurring through catechol moiety, which results in
a charge transfer interaction between the cyanin and the
Ti(IV). Despite very fast charge injection, from blackberry
anthocyanins the IPCE and the power conversion eciency
is quite low (19% and 0.5% respectively), due to dye aggregation. Table 5 reports the IV parameters of DSSCs based
on photoanode prepared using the methods reported in
Section 2.2. In particular the IV parameters, obtained
by DSSCs equipped with photoanodes of two dierent
thicknesses, were compared with that reported in literature
(Cherepy et al., 1997). Clearly, as the photoanode thickness
increase, a higher Jsc is obtained. Comparing the data of
this work, obtained using a multilayer photoanode
13.3 lm thick with a similar of 12 lm prepared in a recent
previous patent application (Calogero and Di Marco,
2010), we found that the presence of the scattering layer
and of the blocking layer increase g of 28% For the dye
preparation we used the same procedure developed and
patented (Calogero and Di Marco, 2010). From the data

1571

reported in Table 5 it is clear how the combination of optimized natural sensitizers, and high performance nanostructured photoanode, prepared at EPFL, permitted us to
surpass the state of the art performances, both in term of
Jsc and g. The obtained results have been ascribed to the
combination of three important factors: (i) the decrease
of the pH dye-solutions increases the stability of the avylium ion present in the anthocyanin (Calogero et al., 2009;
Calogero and Di Marco, 2008; Liu, 2008; Dai and Rabani,
2002a,b; Wongcharee et al., 2007), (ii) the introduction of
co-adsorbents in the non-puried sensitizer solutions that
prevents dye aggregation on the nanocrystalline lm (Calogero and Di Marco, 2010), (iii) the use of a compact thin
TiO2 underlayer minimize dark current eect. Concerning
the IPCE measurements, the best value (46%) was reached
for the blackberry dye (see Fig. 9). Its good to point out
how obtained value is approaching the theoretical limit
of 69% using the following equation and considering
/c = 1
IPCE LHE  K inj =K inj K r K nr K b

12

where Kinj  1013 s1 is the injection constant,

Kr = 3.85  107 s1 is the radiative recombination constant, Knr = 3.85  1011 s1 is the non-radiative recombination constant and Kb = 1.9  1012 s1 is the back-electrontransfer constant reported in literature (Cherepy et al.,
1997).
3.2.2. Red Sicilian orange dye
Although red Sicilian orange juice was already investigated (Calogero and Di Marco, 2008) as sensitizer for
DSSCs, here we examined the pH eect and concentration
of the dye for the performance of the DSSC. As for the case
of many natural dyes, the acid treatment (pH = 1.0)
induces a red shift in the absorption of the anthocyanins
on the order of tens of nanometers. Moreover, the acid
treatment stabilizes the avylium form and increases the
molar extinction coecient e (Fossen et al., 1998). Furthermore, the acidied solution containing the dye aect the
conduction band edge of the titanium dioxide according
Eq. (14). So the anthocyanins contained in the red Sicilian
orange juice when at pH < 2.0 absorb more light and
because of this the LHE increase, furthermore because of
the lowering of the band edge (Ecb) of TiO2 the electron
injection (Eq. (2a)), depending from the gap between the
Ecb of TiO2 and the LUMO level of the dye, become more

Table 5
Performance of DSSCs based on blackberry sensitizers presenting dierent anode thickness.
Dye
+

Raw Blackberry (H )
Raw Blackberry (H+)
Raw Blackberry (H+)
Raw Blackberry
Puried Blackberry
a

Jsc (mA/cm2)

Voc (mV)

FF

g (%)

Anode thickness (lm)

Reference

6.52
5.85
4.68
1.57
2.20

316
320
350
400
400

0.55
0.57
0.54
0.67
0.63

1.13
1.07
0.88
0.42
0.55

13.3a
9.3
12
12
12

This work
This work
Calogero and Di Marco (2010)
Calogero and Di Marco (2010)
Cherepy et al. (1997)

A scattering layer (4 lm thick) was employed.

1572

G. Calogero et al. / Solar Energy 86 (2012) 15631575

ecient and faster and the sum of all these eects increase
the Jsc of the DSSC. The use of concentrated red Sicilian
orange extract instead of red Sicilian orange acidied juice
increase the g from 0.78% to 1.01% (see Table 6) probably
because the DSSCs equipped with photoanodes sensitized
with concentrated juice contain an high quantity of anthocyanins (1.38% of cyanin, at is natural pH). On the other
hand, the Voc values remain almost the same (see Table 6).
We obtained an improvement of the Jsc (12%), by assembling DSSCs which make use of scattering layers. However, this improvement is not reected in a consequent
increase of g. This is essentially due to the reduction in
the ll factor value.
3.2.3. Eggplant dye
The investigation of the eggplant is a crucial point
towards a future successful use of natural dyes in DSSCs.
As previous reported in a recent work (Calogero and Di
Marco, 2008), eggplant skin extract containing mainly nasunin could be potentially employed as sensitizer in DSSCs.
In fact, the eggplant skin extract has shown high absorption
properties in the visible region (kmax 545 nm). Consequently,
the DSSCs based on eggplant skin extract dye have a high
IPCE maximum value (65%) at 540 nm. Furthermore, the
presence of three OH groups in the nasunin promote the chelating eect towards TiO2, while the presence of glycoside
groups in 3 and 5 resulted in a strong steric hindrance which
reduced the probability to link the nasunin with TiO2 using
OH groups dierent from 30 , 40 and 50 . Despite of a maximum
IPCE value of 65%, the DSSCs equipped with eggplant
extract show a g of 0.7% and Jsc of 3.4 mA/cm2, as reported
in Table 4. Similar values, in terms of g and Jsc have been
achieved in literature (Calogero et al., 2009). All the cyanin-based DSSCs with exception of the Giacche` grape have
shown IV parameter higher than the corresponding ones
based on nasunin. This can be explained taking into accounts
the dye regenerations kinetic (Eq. (3a)) which, depending on
the dierence between redox potential of iodide and dye,
occurs more quickly for cyanin than for nasunin due to a
more ecient antioxidant activity of the latter (Noda et al.,
2000).
In general the anthocyanins and in particular the nasunin, due to the slow kinetic regeneration process (Eq. (3a))
under intense irradiation, led to an accumulation of the
dye oxidized form (D+) onto TiO2 surface, which accelerates the recombination process (Eq. (3b)), increasing the
recombination current (Jrec). The latter is expressed by
the following formula:

J rec K 1 nI
3  K 2 nD 

13

with K1 and K2 being the kinetic constant of Eqs. (4b) and

(3b), respectively, while n is the electron concentration in
TiO2 and m is the reaction order. An elevated Jrec value,
usually determines a corresponding decrease in Jsc and
Voc (Koelsch et al., 2004; Lee et al., 2009). Furthermore,
the absorption process rate (Eq. (1)) is decreased because
most of D are in the D+ form and not absorb the light
and this also decreases Jsc. This fully explains the high
IPCE results, which are performed with a monochromatic
light at low intensity.
3.2.4. Purple wild Sicilian prickly pear dye
Wild Sicilian prickly pear fruits dyes have shown interesting g, when employed as sensitizers in DSSCs. The presence of carboxylic groups and an oxidation potential,
similar to that of ruthenium polypyridyl complexes, presents mainly two advantages: a better anchoring between
the dye and the TiO2 surface and an ecient dye regeneration by iodine/iodide redox couple. For this study have
been selected a typical wild specie that spontaneously grow
in Sicily (opuntia vulgaris). This specie contains a high concentration of betaxanthin (Fernandez-Lopez et al., 2010).
Since the betaxantin sensitized activity is higher than betacyanin (Zhang et al., 2008), a g over 2% (see Table 7) has
been obtained using the wild Sicilian prickly pear specie.
To our knowledge, this is the highest value ever achieved
with natural dye sensitizers used without any purication
process. Indeed, our result improves the state of art with
a corresponding IPCE value of 69% (see Table 2). Preliminary tests demonstrated that our natural dyes are stable for
long period (Calogero et al., 2010b; Calogero and Di
Marco, 2010). In particular stability tests performed on
sealed cells (active area 1 cm2) have shown no decrease in
eciency under 20 h of illumination at 1 sun. Unfortunately, the most important problem was the sealant longevity due to solvent evaporation. However these results seem
to indicate the wild Sicilian prickly pear as the most promising natural dyes for DSSCs.
3.2.5. Pyridine and 4-tert-butylpyridine case
It is well known that a signicant improvement of solar
cell performance can be obtained, by the addition of certain pyridine-based compounds to the electrolyte. For
example, the addition of TBP to a DSSC results in
increases of the Voc on the order of 100260 mV (Boschloo
et al., 2006). This eect is principally due to the shift of the
conduction band edge of TiO2 to the negative direction, as

Table 6
Performance of DSSCs based on red Sicilian orange sensitizers with dierent anode thickness.
Dye
Red
Red
Red
Red
a

Sicilian
Sicilian
Sicilian
Sicilian

orange extract
orange extract
orange (H+)
orange

Jsc (mA/cm2)

Voc (mV)

FF

g (%)

Anode thickness (lm)

Reference

5.75
5.13
4.98
3.84

337
329
325
340

0.51
0.59
0.48
0.50

1.00
1.01
0.78
0.66

13.3a
9.3
9.3
12

This work
This work
This work
Calogero and Di Marco (2008)

A scattering layer (4 lm thick) was employed.

G. Calogero et al. / Solar Energy 86 (2012) 15631575

1573

Table 7
Performance of DSSCs based on Sicilian prickly pear sensitizers dierent anode thickness were employed.
Jsc (mA/cm2)

Dye
+

Sicilian prickly pear (H )

Sicilian prickly pear (H+)
Sicilian prickly pear (H+)
a

8.80
7.85
7.32

Voc (mV)

FF

389
382
400

g (%)

0.60
0.62
0.41

2.06
1.87
1.21

Anode Thickness (lm)

a

13.3
9.3
12

Reference
This work
This work
Calogero et al. (2010b)

A scattering layer (4 lm thick) was employed.

Table 8
TBP eect on photoelectrochemical parameters related to DSSCs sensitized with articial dye (N719).
Dye

Jsc (mA/cm2)

Voc (mV)

FF

g (%)

Anode thickness (lm)

Electrolyte

N719
N719

16.2
17.8

776
590

0.73
0.61

9.12
6.37

13.3a
13.3a

A6141
A6979

A scattering layer (4 lm thick) was employed.

consequence of TBP addition. Furthermore, the adsorption

of TBP onto TiO2 determines a dark current suppression,
due to covering nanoparticles free space. The dark current
is originated by the reduction of I
3 at the photoanode, giving rise an electrons ow opposite to the photocurrent
direction. This photovoltaic eect can take place both,
due to porosity of TiO2, on the semiconductor surface or
on the FTO-glass one.
The dependence of conduction band edge from the pH
ts the equation:
Ecb pH Ecb pH 0  0:059pH

14

The value of Ecb (pH = 0) for TiO2 anatase (vs SCE) is

0.4 V. The CB we estimated in presence of tert-pyridine
0.50.6 eV V vs NHE. (Kalyasundaran and Gratzel,
1998)Furthermore, according the following equation:

I
3 TBP TBP  I2 I

15



the TBP in I
3 =I electrolyte solution react with I3 decreasing the concentration of iodine of one order of magnitude
(Boschloo et al., 2006). This is proved experimentally in
DSSCs sensitized by ruthenium compounds (see Table 8).
However, the addition of such compounds fails to have
an impact on the DSSCs performance when natural dyes
are used as sensitizer. Here is demonstrated that the use
of PY (0.25 M) as additive to the electrolyte from one hand
results in an increase in Voc and Vmax, but on the other one
decreases drastically the Jsc value of 70%. Taking to a low
solar energy conversion eciency (see Table 9). This occurs
because the PY, as well as the TBP, is a basic compound;
while on the other hand, anthocyanins and betalains
are pH sensitive. The addition of basic compounds to

anthocyanin dyes electrodes determines: (i) a partial desorption of the dyes from the TiO2, (ii) a changes of the cation from stable avilyium form in partially stable quinonodial form (iii) a shift of the absorption spectra towards the
red region, with a consequently decreasing of the molar
extinction coecient e. The eect is very important, when
PY (0.25 M) is added to the electrolyte, the resulting pH
on the DSSC is 9.3, inducing a red shift of the cyanin
maximum wavelength peak and reducing more than 50%
the molar extinction coecient e. Consequently, the optical
absorption cross section r is reduced as well as the LHE,
IPCE and Jsc. Concerning the betalains, the use of TBP
was already investigated and to a modest gain in photovoltage and in ll factor it corresponded to a dramatic drop
in photocurrent. This phenomenon is probably determined
by a reducing activity of the indicaxanthin under basic conditions. This eect was not documented by Zhang et al.
(2008) because they used betanin puried and they remove
the bethaxanthin; indeed, betanin it is more robust and
does not readily decompose following pH changes (Pedreno and Escribano, 2001).

4. Conclusion
We have considered the use of anthocyanins and betalains extracts as sensitizers for DSSCs application. In particular, the use of raw betalains, having high concentration
of betaxantins, gives a promising result converting 2.06%
of 1 sun of light power into electricity. The presence of carboxylic groups in the betalains presents, together with the
higher oxidation potential, an advantage for anchoring

Table 9
Pyridine eect on photoelectrochemical parameters related to DSSCs sensitized with blackberry and red Sicilian orange dyes.
Dye

Jsc (mA/cm2)

Jmax (mA/cm2)

Vmax (mV)

Voc (mV)

FF

g (%)

Electrolyte

Blackberry (H+)
Blackberry (H+)
Red Sicilian orange extract
Red Sicilian orange extract

7.68
1.91
5.90
1.83

5.5
1.8
4.4
1.6

208
315
220
296

348
419
367
408

0.43
0.69
0.45
0.65

1. 15
0.55
0.97
0.49

(G1)
(G2)
(G1)
(G2)

1574

G. Calogero et al. / Solar Energy 86 (2012) 15631575

the dye to the semiconductor and to interact better with the

iodine/iodide redox couple. The addition of organic coabsorbers and the pH variation improved the current density value, produced by DSSCs sensitized by natural dyes.
The use of pyridine improved the Voc of the DSSCs sensitized by antocyanins but, at the same time, resulted in a
decrease of Jsc. Future work will be addressed towards
the increase in concentration of bethaxantin in betalains;
new additives need to be investigated with the aim to
improve the Voc, but avoiding the drastic reduction of
Jsc. We stress that the achievement of these results derives,
also, from the optimization of the photoanodes, realized
employing TiO2 multilayer structures. Finally, preliminary
stability tests demonstrated that DSSCs based on betalains
are stable for 20 h. Successful test over longer time period
will require a more severe sealing process and the development of less volatile solvent.
Acknowledgements
We acknowledge Dr. Francesco Bonaccorso for useful
discussion. We thank Dr. P. Rapisarda from CRA-Centro
di Ricerca per lAgrumicoltura e le Colture Mediterranee,
Acireale, Italy for generously supply of red orange extract. Technical assistance for realization of electrical connection for the prototypes was furnished by G. Lupo` and
G. Spinella (IPCF_CNR). This research was supported
by the CNR Short Term Mobility Program 2009, by PRIN
2008 (2008ALLB79) and Dyecells (cod. 121) project nanced by Ministero dellAmbiente del Territorio e della
Tutela del Mare.
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