Optical Materials 73 (2017) 172e178

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Optical Materials
journal homepage: www.elsevier.com/locate/optmat

Studies on the optical and photoelectric properties of anthocyanin and

chlorophyll as natural co-sensitizers in dye sensitized solar cell
Hui Nan a, He-Ping Shen b, *, Gang Wang c, Shou-Dong Xie b, Gui-Jun Yang b, Hong Lin a, d, *
a
State Key Laboratory of New Ceramics & Fine Processing, Department of Material Science and Engineering, Tsinghua University, Beijing, 100084, PR China
b
Centre for Sustainable Energy System, Research School of Engineering, The Australian National University, Canberra, 2601, Australia
c
Chemistry and Chemical Engineering, Qinghai University for Nationalities, Xining, Qinghai 810016, PR China
d
Collage of Chemical Engineering, Qinghai University, Xining, Qinghai 810016, PR China

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

Article history: Anthocyanin and Chlorophyll extracted from Troll flower and Cypress leaf respectively are used as
Received 9 May 2017 natural sensitizers in dye sensitized solar cells (DSCs), with their optical and electrochemical properties
Received in revised form investigated. UVeVis absorption measurement showed that the mixture of two dyes enabled an
16 July 2017
enhanced and wider absorption in the wavelength range of 300 nme700 nm compared to each single
Accepted 17 July 2017
Available online 17 August 2017
dye. FTIR results proved that anthocyanin is chemically adsorbed onto the TiO2 film, while it is physical
adsorption for chlorophyll. The energy level offsets on the TiO2/dye/electrolyte interface for each dye and
the dye mixture with different ratios were calculated from the electrochemical analysis, which affect the
Keywords:
Anthocyanin
electron injection and dye regeneration efficiencies. The optimized ratio of the two dyes in the mixture
Chlorophyll was found to be ~2:5, inducing both sufficient charge transfer driving force and minimal energy loss. By
Natural dyes incorporating this mixture into the solar cell as co-adsorbing sensitizer, the photovoltaic performance
Energy levels was prominently improved compared with the single dye sensitization system.
Co-sensitization © 2017 Elsevier B.V. All rights reserved.
Dye sensitized solar cell

1. Introduction synthesized molecules, which show high cost and complicate

The ever-decreasing fossil fuels, progressively expanding human
being's demand of energy, and more and more severe environ-
mental issues motivated researchers to explore clean, renewable
and abundant energy resources, of which solar energy is one of the
most promising. Photovoltaics technology has been a very suc-
cessful approach to utilize solar energy by directly generating
electricity. Dye-sensitized solar cells (DSCs) have attracted exten-
sive attention both scientifically and industrially due to their easy
fabrication, low cost and wide application possibilities such as
serving as flexible and colorful devices. Dye molecule, anchored on
the surface of TiO2 [1,2], is one of the key components in DSC since
it accomplishes the light absorption process thus primarily deter-
mining current yield. To obtain highly efficient device, the dyes
need to be stable under sunlight illumination, and possess chemical
groups (such as hydroxyl, carboxyl, and so on) in the molecules to
assist in their anchoring onto the TiO2 surface [3]. Currently, the
mostly used dye sensitizers are still restricted to the artificially
* Corresponding authors.
E-mail address: hong-lin@tsinghua.edu.cn (H. Lin).
preparation process leading to the limitation of their application.
The natural dyes, which could be obtained directly from flowers,
leaves and vegetables, are considered to be promising candidates,
ascribed to their easy availability, non-toxicity, and biodegradation
capability with no environmental issue [4,5]. At present, the main
natural dyes that have been widely explored include chlorophyll
[6e8], anthoxanthins [9e11], and carotenoids [12e14]. Wong-
charee et al. used dyes extracted from blue pea, rosella and the
mixture of these dyes to fabricate DSC, reporting power conversion
efficiency (PCE) of 0.37%, 0.05% and 0.15% respectively [15]. DSC
fabricated with dyes extracted from ivy gourd fruits and red fran-
gipani flowers reached an efficiency of 0.08% and 0.30%, respec-
tively [16]. Though vigorous efforts have been devoted to
developing highly efficient DSCs based on natural dyes, their effi-
ciencies are still significantly lagging behind those based on syn-
thesized ones. One main factor that limits the device performance
is the narrow sunlight absorption spectra of the single natural
sensitizer. Co-sensitization, by combining two or more dyes with
complementary absorption spectra, is an effective strategy to
extend the absorption spectra and correspondingly enhance the
solar cell performance. Wang and his colleagues used anthocyanin,

http://dx.doi.org/10.1016/j.optmat.2017.07.036
0925-3467/© 2017 Elsevier B.V. All rights reserved.
 H. Nan et al. / Optical Materials 73 (2017) 172e178
b-carotene and their mixture extracted from flowers to fabricate
DSC, reporting power conversion efficiency (PCE) of 0.17%, 0.04%
and 0.21% respectively [17]. In addition, challenges existing for
future improvement of natural dye sensitized solar cells also
involve issues like their fast degradation, instability and short life
span.
This work focuses on resolving these issues by exploring
anthocyanin and chlorophyll as natural sensitizers and making a
further step to use these sensitizers as co-adsorbents. Anthocyanin
containing massive flavonoids shows strong light absorption in the
visible light range (300e400 nm and 500e600 nm), and is
considered to be a promising sensitizer. Anthocyanin containing
carboxyl functional group in its molecule, enabling its strong
anchoring onto the TiO2 film chemically and being favorable for
efficient charge transfer on the dye/TiO2 interface [18]. Meanwhile,
chlorophyll, with porphyrin ring structure [19], shows prominent
absorption in the wavelength region of 600e700 nm. Therefore,
these two natural sensitizers with complementary absorption
spectra offer a good opportunity to implement co-sensitization
strategy to enhance the solar cell performance, with a wide light
absorption range anticipated. In this work, anthocyanin and chlo-
rophyll were firstly extracted from natural plants, with the process
optimized using solvent engineering to ultimately enhance the
purity of the extracted products. Consequently, their optical prop-
erties and the anchoring ways onto TiO2 surfaces were studied via
UVeVis absorption spectra and the Fourier-transformation infrared
spectrograph (FTIR) spectra, respectively. The two dyes were then
mixed to serve as co-adsorbents for solar cells with the optimiza-
tion for the concentration of each dye molecule, targeting for the
energy level engineering on the TiO2/dye/electrolyte interface by
the electrochemical analysis. The optimized ratio of these two dyes
in the mixed system was utilized into the cell and showed advanced
photovoltaic performance compared to the singe dye sensitized
solar cells.
2. Experimental
2.1. Materials
Trollflower and Cypress leaves used in this study were collected
from Xining city, P. R. CHINA. LiI, I2, 4-Tert butyl pyridine (4-TBP),
acetonitrile, pure ethyl alcohol, and ethyl acetate, petroleum ether
were purchased from Adrich (China). Platinum target material
(99.999%) was purchased from Yipin (China). Fluorine doped tin
oxide (FTO, sheet resistance 15U/,) was used as the substrate from
Asahi company in Japan. TiCl4 (99.9%, Allatin, Shanghai) was used
for both pre-treatment and post-treatment for the substrate. P25
TiO2 powder (Degussa, Germany) was used to prepare TiO2 film.
2.2. Extraction of anthocyanin from trollflower and chlorophyll
from Cypress leaves
Anthocyanin was extracted from trollflower with the following
procedure. Trollflower petals were cleaned with deionized water
and dried at 50
C for 15 min. They were then crushed and soaked
into ethanol-water (99.7%) solution (pH ¼ 3) by ultrasonic for
30 min at 30
C [17,18]. The resultant solution was then filtered and
centrifuged, with the centrifuged solution poured into a separated
ion column and extracted consecutively by ethanol and ethyl ace-
tate for three times. The preparation procedure of chlorophyll is the
same as that of anthocyanin with only some minor changes in the
solvents (petroleum ether and ethanol). The co-sensitized dye so-
lution was prepared using different proportions of anthocyanin and
chlorophyll with ultrasonic for 30 min at 30
C.
173
2.3. Assembly of DSC devices
TiO2 films were fabricated according to our previous reports
[20]. The TiO2 films were then immersed into the mixed solutions
of anthocyanins in ethanol and ethyl acetate (9:1, 7:5, 5:7, 1:1) and
chlorophyll in ethanol and petroleum ether (9:1, 6:4, 4:6, 1:9) for
24 h. They were used as photoanode directly. The counter-electrode
was prepared by sputtering Pt onto the FTO conductive glass (the Pt
sputtering time of 30s) [28]. The surface and cross-sectional SEM
images of Pt-coated FTO are shown in Fig. S1 (The particle size of Pt
is ~25 nm and the thickness of Pt is ~95 nm). The photoanode and
counter-electrode were then assembled into DSC devices by infil-
trating with I/I3 electrolyte solution, which was composed of
0.3 M LiI, 0.03 M I2, 0.5 M 4-Tert butyl pyridine in the acetonitrile
solution. In the process of testing, the active area of the DSCs was
0.16 cm2 without the mask.
2.4. Characterization
FTIR (NICOLET 560, Nicolet, USA) was used to analyze the
functional groups in the natural dye molecules. Their optical
properties were measured by UVeVis spectra (UV-4802, Shanghai
NILONGKE Company, China). The electrochemical workstation
(CHI650C, CH Instrument Company, USA) was employed to carry
out the Cyclic Voltammetry (C-V) measurements. The
photocurrent-voltage (J-V) characteristics of the DSC was measured
with a digital source meter (Keithley2400, USA) under AM 1.5G
illumination (100 mW cm2), supplied by a solar simulator (91192,
Oriel, USA). The incident monochromatic photon-to-current con-
version efficiency (IPCE) spectra were measured by IPCE measure-
ment system (PEC-S20, Peccell Technologies, Japan). The High-
Performance Liquid Chromatography (HPLC) instrument (LC-
20AT, Himadzu, Japan) was used to conduct the HPLC analysis un-
der the following conditions: chromatograph separation pillar was
PILLAR C18 (250 mm  4.6 mm, 5 mm); flowing plash was Water
(AeMethanol(B); flowing speed was 1.0 mL/min; supply volume
was 10 mL; DAD detector (pillar temperature 40
C). The pro-
grammers of 2-phase high-pressure elution gradient are shown in
Tables S1 and S2.
3. Results and discussion
3.1. Optical properties
The purity of the dyes extracted from the natural dyes affects the
photovoltaic performance of the as-prepared DSC markedly. It is
also well-known that the reagents used during the extraction
process are critical for the purity of the obtained dyes, which
therefore is the first factor we explored. Generally, ideal extraction
reagents possess the properties such as larger density than water,
insoluble in water and so on. Here, mixture solvents of ethanol and
ethyl acetate with different volume ratios (9:1, 7:5, 5:7, 1:1) were
used as the extraction reagent for anthocyanin. In parallel, we
adopted petroleum ether and ethanol mixture with different vol-
ume ratios (9:1, 6:4, 4:6, 1:9) as extraction reagent for chlorophyll.
The solubility of the two pigments was characterized by the ab-
sorption properties of the resultant dye solutions, which are shown
in Fig. 1. It is obviously observed that the strongest absorption for
anthocyanin is at the ratio of 7:5 (ethanol: ethyl acetate), while it is
9:1 (petroleum ether and ethanol) for chlorophyll, which is adopted
later for preparing co-adsorbing solution.
The High Performance Liquid Chromatography (HPLC) separa-
tion test is carried out with selected wavelength and elution
gradient to the purity of pigment. The standard curve shown in
Fig. 2 is drawn with the peak area A of analyzed materials (standard
174 H. Nan et al. / Optical Materials 73 (2017) 172e178

Fig. 1. UVeVis absorption spectra of pigments in different solutions: (a) anthocyanin in the mixture of ethanol and ethyl acetate, and (b) chlorophyll in the mixture of petroleum
ether and ethanol.

Fig. 2. Standard C-A curves of (a) anthocyanin, and (b) chlorophyll.

anthocyanin and chlorophyll) as Y-axis and the mass concentration
C (mg/L) as X-axis [21]. The regression equation of C (Y, the content
of the material)-A (X, the area of the material) of anthocyanin as
shown in Fig. 2 (a) is Y ¼ 3909.51Xþ2743.78, which shows a good
linear relationship between the concentration and peak area when
the mass concentration of anthocyanin varies from 0.1 mg/mL to
1.0 mg/mL. Meanwhile, the regression equation of C-A of chlorophyll
as shown in Fig. 2 (b) is Y ¼ 1224.23Xþ9403.61, with the mass
concentration of chlorophyll varying from 0.1 mg/mL to 1.0 mg/mL.
The chromatograph of each dye solution is shown in Fig. 3,
which demonstrates that the separation of the two dyes is
completed within 20 min. The purities of anthocyanin (86.9%,

Fig. 3. HPLC of (a) anthocyanin, and (b) chlorophyll.

 H. Nan et al. / Optical Materials 73 (2017) 172e178 175

Fig. 4. UVeVis absorption spectra evolution of anthocyanin (a) under intense ultraviolet ray illumination for different times and (b) preserved under different temperatures and
chlorophyll (c) under intense ultraviolet ray illumination for different times and (d) preserved under different temperatures.

shown in Fig. 3 (a)) and chlorophyll (80.1%, shown in Fig. 3 (b))
could be achieved by inserting the values of the absorption peak
area into regression equation for calculation.
3.2. Photo-thermal stability
Apart from the optical properties, photo-thermal stability of the
dyes is another important parameter for the devices [22], which
was investigated and shown in Fig. 4. The insets incorporated in
Fig. 4 illustrate the regions around the maximum absorption peak
of different natural dyes. These two dye solutions are illuminated
with intense ultraviolet ray for 1e10 h, with the evolution of the
UVeVis absorption spectra shown in Fig. 4 (a) for anthocyanin and
Fig. 4 (c) for chlorophyll respectively. The absorption peak in-
tensities of anthocyanin almost have not changed, while the ab-
sorption peak intensities of chlorophyll have been slightly changed
revealing the degradation of chlorophyll. The degradation is prob-
ably attributed to the formation of intermediate product C4 carboxy

Fig. 5. UVeVis absorption spectra of (a) the mixture solution of anthocyanin and chlorophyll and the sensitized TiO2 photoanode; and (b) the sensitized TiO2 photoanode under
intense ultraviolet ray illumination for different durations and under different temperatures.
176 H. Nan et al. / Optical Materials 73 (2017) 172e178
Fig. 6. FTIR spectra of bare TiO2 and the TiO2 photoanodes sensitized with each dye
pigment.
and chalcone, for which the chalcone can transfer to substitutive
benzoic acid and 2,4,6-three hydroxy phenyl formaldehyde and so
on [23e25]. In addition, the influence of the preservation temper-
ature (-10-40
C) for these dyes was also revealed by the UVeVis
Fig. 7. Cyclic-Voltammogram curves of (a) anthocyanin, (b) chlorophyll, and (c) their mixtures.
spectra in Fig. 4(b) and (d) for each dye molecule. The absorption
peak intensities almost have not changed for both dyes, indicating
no changes of molecular structure and thus good thermal
stabilities.
3.3. UVeVis
These two dyes were then mixed to serve as co-sensitizer of the
solar cell. UVeVis absorption spectra of the mixture (anthocyanin:
chlorophyll ¼ 2:5) in ethanol solution and the TiO2 films co-
sensitized with this mixture were shown in Fig. 5a. It is observed
that the absorption peak of dye sensitized TiO2 film was red-shifted
compared to that of the solution, as indicated by red circle in Fig. 5a.
This shift could be due to the surface chemical adsorption, for
which the surface of the narrow band between the mixture
pigment molecule and TiO2 so that the energy of the electron
transition is reduced and the absorption spectrum is extended to
the visible region [26]. The UVevis absorption spectra of the
sensitized TiO2 under intense ultraviolet ray illumination with
different durations and under different temperatures were inves-
tigated and shown in Fig. 5b. The absorption peak intensities of the
sensitized TiO2 have slightly changed under intense ultraviolet ray
illumination for different times and temperatures. However, it
should be noted that such tiny changes of the absorption spectra
impose negligible effect on the photovoltaic properties of the
resultant DSCs. Therefore, the relatively good stability of this co-
sensitized system under strong light and a wide range of temper-
ature, by employing the mixture of anthocyanin and chlorophyll,
enables itself as a suitable candidate for making stable DSCs.
 H. Nan et al. / Optical Materials 73 (2017) 172e178
Fig. 8. Energy level diagram for anthocyanin, chlorophyll, and their mixture.
3.4. FTIR
FTIR spectra of bare TiO2 and that sensitized with anthocyanin
or chlorophyll are shown in Fig. 6. The slightly different absorption
peak at 1450 cm1 was found for the TiO2 sensitized with chloro-
phyll compared with the bare TiO2, since chlorophyll contains a few
functional groups like eOH and eCOOH which can form chemical
bonds with TiO2 weakly. Hence, the connection between chloro-
phyll and TiO2 mainly relies on Van der Waals' force. In the
meantime, obvious differences can be observed for the TiO2 films
before and after anthocyanin sensitization from the insets incor-
porated in Fig. 6, among which the main difference lies in the
characteristic peak in the range of 1600e1400 cm1 corresponding
to the aromatic compounds. These characteristic absorption peaks
also confirm the successful chemical adsorption of anthocyanin
onto the surface of TiO2 [27].
3.5. Electrochemical performance
The C-V curves of anthocyanin, chlorophyll and their mixture in
ethanol solution were shown in Fig. 7. The C-V measurements were
utilized to estimate the energy level of Highest Occupied Molecular
Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO)
of natural dyes, where the HOMO and LUMO can be calculated from
the reduction potential (Ered) and oxidation potential (Eox),
respectively, according to Equations (1) and (2) [33]. The energy
levels properties of the natural dyes studied in this work is listed in
Table S3.
Fig. 9. J-V curves (a), IPCE curves and integrated current densities (b) of DSCs using natural dyes.
177
Table 1
Photovoltaic performance of DSCs sensitized with natural dyes.
System VOC [mV] JSC [mA* cm2] FF h[%]
A 493 0.341 0.725 0.122
A:C ¼ 2:5 521 0.589 0.711 0.220
C 525 0.157 0.744 0.062
*A:Anthocyanin; C:Chlorophyll.
HOMO ¼ (Eox þ 4.71) eV (1)
LUMO ¼ (Ered þ 4.71) eV (2)
Upon light illumination, the electrons are excited in dye mole-
cules and injected into TiO2, leading to photovoltaic effect [28]. The
energy level offset between the conduction band of TiO2 and the
LUMO of dye molecules serves as electron driving force, thus affects
the electron injection efficiency directly. Meanwhile, the ground
state energy level of the dye molecule determines the capability of
electron acquisition (regeneration) of dye molecules from I/I 3
electrolyte. Fig. 8 shows the energy levels of TiO2, electrolyte, and
the five types of dyes and their combination [29e33]. It is seen that
the injection driving forces of 0.19 eV and the regeneration force of
0.03 eV for anthocyanin: chlorophyll ¼ 2:5 as a result of chemical
reaction of impurities in the natural dyes to produce functional
groups make for electron transport, which means the effective
electron injection and regeneration can be realized. This is in turn
beneficial for improving the charge collection efficiency and ulti-
mately photoelectric conversion efficiency of the solar cells [34].
Therefore, we deployed the mixture using this ratio to incorporate
into solar cells.
3.6. Photovoltaic performance
Solar cells were then fabricated with single dye sensitization
and the mixture co-sensitization, with the J-V curves shown in
Fig. 9a and all the photovoltaic parameters listed in Table 1. The
IPCE curves of these devices are shown in Fig. 9b. Consistent with
the optical analysis above, the current density obtained for the
device based on the dye mixture was significantly enhanced
compared to those based on each single dye. Specifically, the short-
circuit current density (JSC) increases from 0.341 mA cm2 for
anthocyanin and 0.157 mA cm2 for chlorophyll to 0.589 mA cm2
for the mixture. The IPCE was correspondingly enhanced for the
device based on the co-sensitization system, and a more suitable
energy-level alignment with TiO2. Integrating the IPCE spectra
178 H. Nan et al. / Optical Materials 73 (2017) 172e178
yields photocurrent densities of 0.338, 0.152 and 0.537 mA cm2 for
DSCs based on anthocyanin, chlorophyll and the mixture, respec-
tively, which are in general in good agreement with the measured
photocurrent densities. Correspondingly, the power conversion
efficiency was increased by 80.3% as compared with the device
based on anthocyanin and by 254% as compared with that based on
chlorophyll. Eventually, an efficiency reaching up to 0.22% was
achieved for the device co-sensitized with anthocyanin and chlo-
rophyll, with an open-circuit voltage (Voc) of 521 mV and fill factor
(FF) of 0.711.
4. Conclusions
In summary, the extraction and separation process of anthocy-
anin and chlorophyll dyes from natural plants were optimized, both
of which showed reasonable absorption response in the visible
light region. More importantly, the photoanode sensitized with the
mixture of these two dyes enabled a better and wider absorption in
the range of 300 nme700 nm. The electrochemical characterization
showed that a proportion of 2:5 (anthocyanin: chlorophyll) renders
both an optimized electron injection driving force and sufficient
regeneration driving force of dye molecules. Finally, an overall ef-
ficiency of 0.22% was obtained for the device based on the co-
sensitization of the two dyes. The success of the device perfor-
mance enhancement by using the dye mixture proves that co-
sensitization could be a very promising and effective strategy for
further improvement for natural dye sensitized solar cells.
Although the photovoltaic performance of the devices based on the
natural dyes is generally inferior compared to that based on the
commercial dyes, they show superior economic and environmental
advantages. This constantly stimulates considerable interest from
the research community in keeping on exploiting efficient natural
dye molecules, targeting gradually improving the performance and
ultimately replacing the commercial synthetic dye.
Acknowledgments
We express gratitude to the National Natural Science Founda-
tion of China (NSFC No. 51362025) and the Ministry of Science &
Technology, P. R. China: Sino-Italy International Cooperation on
Innovation (2016YFE0104000) for their financial support.
Appendix A. Supplementary data
Supplementary data related to this article can be found at http://
dx.doi.org/10.1016/j.optmat.2017.07.036.
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