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Aqueous dye-sensitized solar cell based on

new ruthenium diphenyl carbazide complexes

Hashem Shahroosvand a,*, Leyla Heydari a, Sara Tarighi b,

Mohammadreza Riahi c, Babak Nemati Bideh a, Babak Pashaei a
a
Chemistry Department, University of Zanjan, Zanjan, Iran
b
Faculty of Petrochemicals, Iran Polymer and Petrochemical Institute, Tehran, Iran
c
Physics Department, K. N. Toosi University of Technology, Kavianst, Mojtabaeest, Shariatist, Tehran, Iran

article info abstract

Article history: The major challenge of the operation of every solar cell based on dye including water
Received 18 January 2017 splitting solar cell (WSSC) and dye sensitized solar cell (DSSC) is the using organic solvent
Received in revised form medium which causes to decompose the solar cell structure, resulting environmental
19 April 2017 impact. Here, we synthesized and characterized two new ruthenium complexes with ni-
Accepted 21 April 2017 trogen and oxygen donor ligands for DSSC application which show good stability on TiO2
Available online xxx surface in water solvent. Interestingly, the DSSC based on [Ru(dcbpy)2(DPC)]Cl, where
dcbpy ¼ 4,4-dicarboxilic acid 2,2-bipyridin and DPC ¼ diphenylcarbazide, was shown better
Keywords: efficiency in water than methanol dye loading as well as N3 as a benchmark sensitizer in
Dye-sensitized solar cell the same condition. The DPC-based exhibited open circuit voltage (Voc) of 0.63 V, short-
Rutenium circuit current density (Jsc) of 2.5 mA/cm2 and fill factor (FF) of 70%, resulting an overall
Diphenyl carbazide power efficiency of 1.12%. The incident-photon-to-current conversion efficiency (IPCE)
NO donor ligand value is also reached to 45% for [Ru(dcbpy)2(DPC)]Cl in the same condition It is proposed
that the ruthenium complex containing nitrogen and oxygen donor ligands is more sta-
bility on TiO2 and prevent the decomposition of TiO2 porous under water solvent condition.
© 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Nowadays, many renewable energy processes use sunlight as
the source of energy to produce the fuel, promising the
replacement of fossil fuel by affordable solar energy [1]. H2
molecule can also act as an effective source of energy which
molecule H2O splits to oxygen and hydrogen molecules [2].
Light-driven water oxidation or water splitting has been per-
formed by the direct electrolysis of water by photovoltaic cells
based on semiconductor electrodes [3,4]. The catalytic sys-
tems are usually based on transition-metal photosensitizers
and metal oxide water-oxidation catalysts [5]. In contrast,
light-driven water oxidation by molecular catalysts has rarely
been reported, mainly due to the lack of suitable catalysts
bearing a low overpotential for water oxidation. Ruthenium-
based complexes have shown promising catalytic properties
due to interesting photophysical and photochemical proper-
ties which facilities the efficient electron transfer process. One
of the first examples of a ruthenium-based catalyst capable of
water oxidation was the so-called “blue dimer”, prepared by
Meyer and co-workers in the early 1980s [6]. Moreover, it is
well known that [Ru(bpy)3]3þ and its derivatives are capable of
oxidizing water to O2 in the presence of colloidal and bulk
heterogeneous catalysts [7]. The mechanism of the light-
driven water oxidation by molecular catalysts is as follow:
the excitation of the sensitizer attached onto the TiO2 surface

* Corresponding author.
E-mail address: shahroos@znu.ac.ir (H. Shahroosvand).
http://dx.doi.org/10.1016/j.ijhydene.2017.04.222
0360-3199/© 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Please cite this article in press as: Shahroosvand H, et al., Aqueous dye-sensitized solar cell based on new ruthenium diphenyl car-
bazide complexes, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.04.222
2 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e7

by light absorption produces the excited sensitizer, then the
excited sensitizer injects an electron into the conduction band
of the TiO2 and is therefore oxidized which is subsequently
reduced by electron donation from colloidal and bulk het-
erogeneous catalysts. Finally, the oxidized catalysts oxidize
H2O to O2. In fact, the dye-catalyst colloid replaces the visible
light-absorbing sensitizer of a dye sensitized solar cell (DSSC),
and water replaces iodide as the electron donor [8].
Similarly, the operation of a water splitting solar cell
(WSSC) and DSSC is analogous, except catalyst in WSSC con-
verts H2O to O2, while in DSSC excited dye generates electricity
in circuit. The great challenge between DSSC and WSSCs is the
solvent medium which both devices work. For DSSC, the polar
solvent such as methanol or dimethylformamide (DMF) are
suitable while in WSSC an aqueous solution is necessary [9].
Interestingly, it must be noted that the first generation of
DSSC developed in the 1980e1990 decade were intended to
operate with fully aqueous electrolytes [10]. In the recent years,
the research is again focused on more deeply investigating the
influence of water in DSSCs, the final challenging aim being the
full replacement of the traditionally used organic solvents
which are dangerous for human and environment. O'Regan
and coworkers in 2010 progressed the fundamental contribu-
tion for the scientific community in this context [11]. However,
a large number of photoelectrochemical device with molecular
Ru polypyridyl catalyst assembled via different modified mol-
ecules on a dye-sensitized nanostructured semicounductor as
anode has been successfully investigated to split water into O2
and H2 driven by visible light [12].
However, DSSC based on aqueous electrolyte is more
explored than fabricated DSSC in aqueous dye loading condi-
tion [13]. Thanks to their broad absorption spectra and excel-
lent light harvesting ability, Ru complexes would represent the
sensitizer of choice for aqueous DSSCs. Nevertheless, in order
to obtain cells demonstrating sufficient durability, efforts
must be devoted to ameliorate the bonding between dye
molecules and TiO2 nanoparticles (NPs) [14].
There are other types of DSSC using water such as
Quantum-dot DSSC (QDSSC) which attracts great interest due
to their stability towards water and tunable bandgap. Because
of the limitation of CdS cell based on Fe(CN)3/4
6 [15], poly-
sulfide (S2/Sn2) is the only most commonly used electrolyte
for water QDSSCs [16].
Despite all these achievements and ongoing research,
however, stable and rapid molecular and homogeneous cat-
alysts for H2O oxidation and O2 generation have yet to be
achieved. Thus, the need to develop highly active and stable
H2O oxidation catalysts remains of considerable importance.
Here, for first one, as our knowledge, we synthesized and
characterized two new ruthenium complexes which DSSC
based on complexes were fabricated in water solution. Inter-
estingly, the power conversion efficiency of fabricated cell
based on new N^O donor (abbreviated as DPC) as ancillary
ligand is greater than N3 as benchmark sensitizer in aqueous
solution. Our findings can provide useful insight to design new
dyes which operate in WSSC to produce H2. Fig. 1 shows a
graphical comparison between the operation of DSSC and
WSSC.
Considering above advantages, two new ruthenium com-
plexes were synthesized according to sensitizer pattern in
DSSC which named [Ru(dcbpy)2(DPC)]Cl and [Ru(DPC)(dcb-
py)(NCS)2]NEt3, where dcbpy and DPC are 4,4ʹ dicarboxylic
acid 2,2 bipyridin and diphenylcarbazide, respectively (Fig. 2).
Full experimental procedure is explained in electronic
Supplementary Information (ESI. S1.1 and S1.2).
In the IR spectra of the complexes, a broad band at
~3500 cm1 related to antisymmetric and symmetric stretch-
ing of OeH as well as NeH bond at ~1630 cm1. The absorption

Fig. 1 e The graphical comparison of operation of water splitting solar cell (WSSC) and dye sensitized solar cell (DSSC).

Please cite this article in press as: Shahroosvand H, et al., Aqueous dye-sensitized solar cell based on new ruthenium diphenyl car-
bazide complexes, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.04.222
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e7
Fig. 2 e The molecule structure of two synthesized sensitizers.
bands in the region 390e500 cm1 assigned to stretching vi-
brations of RueO and RueN bonds were observed in the FTIR
spectra of these compounds. Stretching vibrations of carbonyl
groups of C]O and C]S bonds of NCS ligand are also
observable in ~1700 and 2108 cm1 frequencies, respectively
[17]. 1H NMR tool is a useful method to investigate the NeH
bond because of the significant signal at obvious region
(4e6 ppm) between aromatic and aliphatic regions. For both
two complexes, there is a signal around 5.6 ppm which was
assigned to the NeNHeC (phenyl) of DPC ligand which con-
firms the coordination of DPC to metal [18]. In addition, a
crystal structure of coordination of DPC ligand to Zn metal
was also accessible which shown the mode of coordination of
DPC to metal (details of results are also given in ESI. S2. 1).
The DPC ligand having four acidic protons is a pH depen-
dent ligand which creates interesting optical properties. Sur-
prisingly, DPC has a relatively intense broad band in visible
region (about 550 nm) which was rarely seen in aromatic
ligand because of its only intraligand charge transfer. Fig. 3
Fig. 3 e The UVevis of DPC ligand in pH of 8, 10.5 and 11.5.
Please cite this article in press as: Shahroosvand H, et al., Aqueous dye-sensitized solar cell based on new ruthenium diphenyl car-
bazide complexes, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.04.222
3
shows the pH dependency of DPC ligand. Notably, the molar
absorbance coefficient (ε) of absorption band in visible region
of DPC ligand (27,000 M1 cm1) in basic media (pH ¼ 11) is
higher than benchmark sensitizers such as N3 and N719
(>15,000 M1 cm1) [19]. Therefore, DPC ligand can be a very
good candidate for light harvesting device such as WSSC and
DSSC.
The electronic absorption spectra of [Ru(DPC)(dcbpy)(NCS)]
NEt3 and [Ru(DPC)(dcbpy)2]Cl recorded in methanol and water
respectively are shown in Fig. 2. Interestingly [Ru(DPC)(dcbpy)2]
Cl complex was soluble in all solvents even water. The high-
energy absorption band of the Ru(II)-bipyridyl complex is
contributed by two components including metal-to-ligand
charge transfer (MLCT) transition and pi-pi transitions of
the ancillary bipyridyl ligand [20]. The absorption spectra of
both sensitizers display the characteristic MLCT bands
appearing at 414 and 587 nm (ε ¼ 1.36  104 M1 cm1)
in [Ru(DPC)(dcbpy)(NCS)]NEt3 and 374 and 555 nm
(ε ¼ 7775 M1 cm1) in [Ru(DPC)(dcbpy)2]Cl (The progress of
reaction was monitored by UVevis, please see ESI. S2. 2 and S2.
3). The red shift of absorption band in visible region up about
580 nm and their good overlapping with solar radiation region
are remarkable properties of DPC complexes.
Cyclic voltammetry of complexes (CV) was measured in
DMF solution using dye concentrations of 103 M and 0.1 M
tetrabutylammonium perchlorate as a supporting electrolyte.
Complexes of [Ru(dcbpy)(DPC)(NCS)2] and [Ru(dcbpy)2(DPC)]
presented irreversible oxidation wave with potential about
0.8 V vs. g/AgCl, attributed to the RuII/RuIII oxidation. The
broad and structureless of waves in negative region can be
attributed to the redox behavior of polypyridyl ligand [21].
The results also indicated that the redox potential of I/I
3 is
favorable negative than the high occupied molecular orbital
(HOMO) indicating that the sensitizer can be easily regener-
ated by accepting electrons from the electrolyte [22]. The
location of the HOMOs and low unoccupied molecular orbitals
4 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e7
Fig. 4 e UVevis spectra of [Ru(dcbpy)(DPC)(NCS)2] in DMF
and [Ru(dcbpy)2(DPC)] in H2O at 10¡5 M. The spectrum of
solar radiation is also shown. The green box shows the
overlap of visible region of absorption band of complexes
and the spectrum of solar radiation. (For interpretation of
the references to colour in this figure legend, the reader is
referred to the web version of this article.)
(LUMOs) in these complexes were calculated using B3LYP-DFT
methods (ESI. S2.2 and S2.5). The delocalization of charge
density of HOMO on DPC as ancillary ligand and LUMO on
carboxylic acid moieties prepared the compatible condition
for convenient regeneration and prevent recombination
processes (Figs. 4 and 5).
In order to study the influence of substituent DPC on the
DSSC device performance of dyes, photovoltaic experiments
were conducted. The devices were fabricated using a layer of
TiO2 film sensitized with these dyes and in conjunction with
I/I
3 electrolyte. Fig. 6 shows the photocurrent densityevolt-
age curves of the devices using [Ru(dcbpy)(DPC)(NCS)2] and
[Ru(dcbpy)2(DPC)] under AM 1.5 G simulated sunlight.
Fig. 5 e Cyclic voltammetry of [Ru(dcbpy)(DPC)(NCS)2] and
[Ru(dcbpy)2(DPC)] in DMF solution. Insert:Survey of
diffusion current in [Ru(dcbpy)2(DPC)].
Please cite this article in press as: Shahroosvand H, et al., Aqueous dye-sensitized solar cell based on new ruthenium diphenyl car-
bazide complexes, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.04.222
Fig. 6 e I-V of DSSC based on [Ru(dcbpy)2(DPC)]Cl dye in
methanol (red line) and water (black line) immersion (15 h).
The mediator is I3/3I¡. (For interpretation of the references
to colour in this figure legend, the reader is referred to the
web version of this article.)
The short-circuit photocurrent density (JSC), open-circuit
voltage (VOC), fill factor (FF) and power conversion efficiency
(PCE) of devices are tabulated in Table 1 and were compared to
N3.
The value of 70% of FF for dye in water is among the best FF
in DSSC. To determine the coordination of dye into TiO2 in
during dye loading, the FT-IR of complexes after absorbing
on dye were recorded (ESI. S2.6 and S2.7). FT-IR results showed
that the complexes were posited on TiO2 surface and were not
decomposed during loading onto TiO2. To determine the
photoresponsibility of complexes, incident photon to current
efficiency (IPCE) of complexes were also recorded (Fig. 7).
Interestingly, as shown in Fig. 7 and given in Table 1, although
the PCE of [Ru(dcbpy)(DPC)(NCS)2] in DMF is higher than
[Ru(dcbpy)2(DPC)] in water, nevertheless the IPCE value is
reverse. This evidence also confirms the good conversion
properties of light to photon of which can be attributed to the
high molar absorbity of complexes in visible region.
For more discussion about above interesting results, we will
give more comparisons and literatures in following. Miyasaka
and coworkers assembled two DSSCs based on N719 and N3
sensitizer molecules in water electrolyte which adsorbed onto
the surface of the TiO2 layer [23]. As summarized in Table 1, in
the presence of a truly aqueous electrolyte (KI 0.50 M and I2
25 mM), efficiencies of 0.6% and 0.5% were obtained using N3
and N719 dyes, respectively. These obtained values are clearly
lower than dyes based on DPC ancillary ligand in our study.
Moreover, the left time which dyes and TiO2 in water is in
contact is more than DSSC based on water electrolyte solution.
This outstanding behavior can be attributed to adsorption
strength of the DPC dyes at the TiO2 surface; in fact, being more
hydrophilic than N3, N719. Moreover, the high solubility of
DPC in water can be responsible for high adsorption of dye
onto TiO2 through carboxylic acid anchoring groups. The
four eCOOH groups of the [Ru(dcbpy)2(DPC)]Cl dye molecule
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e7 5

Table 1 e Photovoltaic performances of DSSCs sensitized with [Ru(DPC)(dcbpy)2]þ[Ru(dcbpy)(DPC)(NCS)2], radiant power:

88 mW cm¡2 (AM 1.0 direct); redox electrolyte, LiI (0.1 M), I2 (0.05 M) and 4-tertbutylpyridine (0.5 M). Foe N3 and N719, PV
parameters (Pin ¼ 1 sun) of DSSCs assembled with electrolytes based on water and/or ethanolewater mixtures recovered
from industrial effluents.
Dye Solvent Jsc (mA/cm2) Voc (V) FF (%) h (%) (±0.1) IPCE (±1) Reference
þ
[Ru(DPC)(dcbpy)2] Methanol 1.5 0.58 0.61 0.53 42 Current work
[Ru(DPC)(dcbpy)2]þ H2O 2.5 0.63 0.71 1.12 45 Current work
[Ru(dcbpy)(DPC)(NCS)2] DMF 7.5 0.65 0.4 2.3 40 Current work
N3 H2O 2.7 0.37 0.6 0.6 e [19]
N719 H2O 2.0 0.40 0.63 0.5 e [19]

ensure a more efficient electronic interaction at the oxide
interface which, as a result, guarantees a much stronger
adsorption at the interface with the active material particles,
thus improved stability under water was achieved.
As another comparison, the first exotic redox couple for
aqueous DSSCs was a cerium based compound which was
proposed by Teoh and coworkers in 2008 [24]. Ce(NO3)3, 0.10 M
and Ce(NO3)4, 50 mM were dissolved in a 35:65 of EtOH:H2O
mixture. This electrolyte was coupled with a variety of com-
mercial and natural sensitizers. Although, the PCE is very low,
their simple preparation techniques, wide availability and low
cost, make them as the best option for an aqueous and truly
eco-friendly solar cell device.
The composition of ruthenium component in our study is
very similar to water splitting device to produce H2. Therefore,
a link between DSSC and WSSC can be occurred through using
cerium nitrate composition in water solution media. Recently,
Graetzel et al. unveiled aqueous dye sensitized solar cells
based on new composition of I/I 3 -based redox mediator,
which thoroughly investigated the speciation of ions, the ef-
fect of the concentration of the redox mediator and the type of
counter-ion. The most PCE was achieved about 0.81% when
the concentration of [I], [KI] and [I2] controlled at 5.5, 12 and
50 mM, respectively [25].
Of course, the procedure of electrolyte replacement is
much easier and safe when an aqueous system is envisaged
than an organic volatile one that carries around severe envi-
ronmental hazards. With the advent of DSSCs in 1990 decade
[8], organic solvents replaced water, and cells operating in an
aqueous environment were no longer investigated for the
following 10e15 years. Nevertheless, to the best of our
knowledge, no scientific group has undertaken dye loading
onto TiO2 in water path so far.
The attractive dye stability on TiO scientists to follow such
N^O dyes to other water based applications such as WSSC for
H2 production.
In conclusion, we have demonstrated a water soluble Ru
sensitizer based on diphenylcarbized (DPC) which can convert
sun light to electricity more efficient than N3 and N719 in
water electrolyte medium. The easiness of DPC synthesis high
light harvesting in visible region due to remarkable ε value
(23000 mol1 L1 cm1) as well as high solubility in both protic
and aprotic solvent makes it as attractive ligand for antenna
effect. Therefore, the power conversion efficiency of 1.12%
was achieved in water dye loading condition, which is among
the highest values which are reported for water DSSCs. The
stability of this complex containing N^O donor ancillary ligand
in water onto TiO2 during dye loading process (16 h) also
promises to new good water soluble candidate for other water
based solar cell devices such as water splitting solar cell.

Acknowledgments

Authors thank the University of Zanajn, Iran Polymer and

Petrochemical Institute and K. N. Toosi University. Authors
also wish to thank professor Mohammad Mahdi Najafpour for
proof reading of water splitting section and his useful
comments.

Appendix A. Supplementary data

Supplementary data related to this article can be found at

http://dx.doi.org/10.1016/j.ijhydene.2017.04.222.

references

Fig. 7 e IPCE of DSSC based on [Ru(dcbpy)2(DPC)]Cl in water

and methanol immersion, and, [Ru(dcbpy)(DPC)(NCS)2] in [1] Voloshin RA, Rodionova MV, Zharmukhamedov SK,
DMF immersion. The mediator is I3/3I¡. Veziroglu TN, Allakhverdiev SI. Review: biofuel production

Please cite this article in press as: Shahroosvand H, et al., Aqueous dye-sensitized solar cell based on new ruthenium diphenyl car-
bazide complexes, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.04.222
6 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e7
from plant and algal biomass. Int J Hydrogen Energy
2016;41(39):17257e73.
[2] (a)Schlapbach L, Züttel A. Hydrogen-storage materials for
mobile applications. Nature 2001;414(6861):353e8.
(b)Agrafiotis CC, Pagkoura C, Zygogianni A, Karagiannakis G,
Kostoglou M, Konstandopoulos AG. Hydrogen production via
solar-aided water splitting thermochemical cycles:
combustion synthesis and preliminary evaluation of spinel
redox-pair materials. Int J Hydrogen Energy
2012;37(11):8964e80.
(c)Rodionova MV, Poudyal RS, Tiwari I, Voloshin RA,
Zharmukhamedov SK, Nam HG, et al. Biofuel production:
challenges and opportunities. Int J Hydrogen Energy 2016.
http://dx.doi.org/10.1016/j.ijhydene.2016.11.125 [in press].
[3] Khaselev O, Turner JA. A monolithic photovoltaic-
photoelectrochemical device for hydrogen production via
water splitting. Science 1998;280:425e7.
(b)Xiao J, Hou X, Zhao L, Li Y. A conductive ZnO: Ga/ZnO core-
shell nanorod photoanode for photoelectrochemical water
splitting. Int J Hydrogen Energy 2016;41:14596e604.
(c)Najafpour MM, Allakhverdiev SI. Manganese compounds
as water oxidizing catalysts for hydrogen production via
water splitting: from manganese complexes to nano-sized
manganese oxides. Int J Hydrogen Energy
2012;37(10):8753e64.
[4] Zhong DK, Sun J, Inumaru H, Gamelin DR. Solar water
oxidation by composite catalyst/a-Fe2O3 photoanodes. J Am
Chem Soc 2009;131:6086e7.
(b)Najafpour MM, Abasi M, Hołyn  ska M, Pashaei B.
Manganese oxides as water-oxidizing catalysts for artificial
photosynthetic systems: the effect of support. Int J Hydrogen
Energy 2016;41(12):5475e83.
(c)Najafpour MM, Salimi S, Safdari R. Nanosized manganese
oxide supported on carbon black: a new, cheap and green
composite for water oxidation. Int J Hydrogen Energy 2016 [in
press].
(d)Najafpour MM, Zarei Ghobadi M, Sarvi B, Madadkhani S,
Jafarian Sedigh D, Rafighi P, et al. Polypeptide and MneCa
oxide: toward a biomimetic catalyst for water-splitting
systems. Int J Hydrogen Energy 2016;41(12):5504e12.
[5] Youngblood WJ, Lee SA, Kobayashi Y, Hernandez-Pagan EA,
Hoertz PG, Moore TA, et al. Photoassisted overall water
splitting in a visible light-absorbing dye-sensitized
photoelectrochemical cell. J Am Chem Soc 2009;131:926e7.
(b)Visible light active Ce/Ce2O/CeO2/TiO2 nanotube arrays for
efficient hydrogen production by photoelectrochemical
water splitting. Int J Hydrogen Energy 2016;41(12):5437e44.
(c)Tan Y, Zhang S, Shi R, Wang W, Liang K. Effect of proton
intercalation on photo-activity of WO3 anodes for water
splitting. Int J Hydrogen Energy 2016;41(9):4922e30.
(d)Najafpour MM, Hosseini SM, Hołyn  ska M, Tomo T,
Allakhverdiev SI. Platinum/manganese oxide
nanocomposites as water-oxidizing catalysts: new findings
and current controversies. Int J Hydrogen Energy
2015;40(34):10825e32.
[6] (a)Gersten SW, Samuels GJ, Meyer TJ. Catalytic oxidation of
water by an oxo-bridged ruthenium dimer. J Am Chem Soc
1982;104:4029e30.
(b)Gilbert JA, Eggleston DS, Murphy WR, Geselowitz DA,
Gersten SW, Hodgson DJ, et al. Structure and redox
properties of the water-oxidation catalyst [(bpy)2(OH 2)
RuORu(OH2)(bpy)2]4þ. J Am Chem Soc 1985;107:3855e64.
[7] Bekir H, Buket Bezgin CY, Sonmezoglu S, Karaman M,
Toppare L. A photoelectrochemical device for water splitting
using oligoaniline-crosslinked [Ru(bpy)2(bpyCONHArNH2)]þ2
dye/IrO2 nanoparticle array on TiO2 photonic crystal
modified electrode. Int J Hydrogen Energy
2016;41(33):14615e29.
Please cite this article in press as: Shahroosvand H, et al., Aqueous dye-sensitized solar cell based on new ruthenium diphenyl car-
bazide complexes, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.04.222
[8] O'Regan B, Gra € tzel M. A low-cost, high-efficiency solar cell
based on dye-sensitized colloidal TiO2 films. Nature
1991;353:737e40.
[9] Pashaei B, Shahroosvand H, Gratzel M, Nazeeruddin M k.
Influence of ancillary ligand in dye-sensitized solar cells.
Chem Rev 2016;16:9485e564.
(b)Molinari R, Marino T, Argurio P. Photocatalytic membrane
reactors for hydrogen production from water. Int J Hydrogen
Energy 2014;39(14):7247e61.
[10] (a)Desilvestro J, Graetzel M, Kavan L, Moser J, Augustynski J.
Highly efficient sensitization of titanium dioxide. J Am Chem
Soc 1985;107:2988e90.
(b)Matsumura M, Matsudaira S, Tsubomura H, Takata M,
Yanagida H. Dye sensitization and surface structures of
semiconductor electrodes. Ind Eng Chem Prod Res Dev
1980;19:415e21.
[11] Law CH, Pathirana SC, Li X, Anderson AY, Barnes RF,
Listorti A, et al. Water based electrolytes for dye-sensitized
solar cells. Adv Mater 2010;22:4505e9.
[12] (a)Li L, Duan L, Xu Y, Gorlov M, Hagfeldt A, Sun L. A
photoelectrochemical device for visible light driven water
splitting by a molecular ruthenium catalyst assembled on
dye-sensitized, nanostructured TiO2. Chem Commun
2010;46:7307e9.
(b)Gao Y, Ding X, Liu J, Wang L, Lu Z, Li L, et al. Visible light
driven water splitting in a molecular device with
unprecedentedly high photocurrent density. J Am Chem Soc
2013;135:4219e22.
(c)Peng T, Dai K, Yi H, Ke D, Cai P, Zan L. Photosensitization
of different ruthenium(II) complex dyes on TiO2 for
photocatalytic H2 evolution under visible-light. Chem Phys
Lett 2008;460:216e9.
(d)Odrobina J, Scholz J, Pannwitz A, Franca  s L, Dechert S,
Llobet A, et al. Backbone immobilization of the bis(bipyridyl)
pyrazolate diruthenium catalyst for electrochemical water
oxidation. ACS Catal 2017;7(3):2116e25.
(e)Sherman BD, Xie Y, Sheridan MV, Wang D, Shaffer DW,
Meyer TJ, et al. Light-driven water splitting by a covalently
linked ruthenium-based chromophoreecatalyst assembly.
ACS Energy Lett 2017;2(1):124e8.
(f)Sherman BD, Sheridan MV, Wee KR, Marquard SL, Wang D,
Alibabaei L, et al. A dye-sensitized photoelectrochemical
tandem cell for light driven hydrogen production from water.
J Am Chem Soc 2016;138(51):16745e53.
[13] Bella F, Gerbaldi C, Barolo C, Graetzel M. Aqueous dye-
sensitized solar cells. Chem Soc Rev 2015;44:3431e73.
[14] Vlachopoulos N, Liska P, McEvoy AJ, Graetzel M. Efficient
spectral sensitisation of polycrystalline titanium dioxide
photoelectrodes. Surf Sci 1987;189e190:823e31.
[15] (a)Li CT, Lin RY-Y, Lin JT. Sensitizers for aqueous-based solar
cells. Chem Asian J 2017;12:486e96.
(b)Tachibana Y, Umiketa K, Otsuka Y, Kuwabata S.
Performance improvement of CdS quantum dots sensitized
TiO2 solar cells by introducing a dense TiO2 blocking layer.
J Phys D 2008;41:102002,.
(c)Evangelista RM, Makuta S, Yonezu S, Andrews J,
Tachibana Y. Semiconductor quantum dot sensitized solar
cells based on ferricyanide/ferrocyanide redox electrolyte
reaching an open circuit photovoltage of 0.8 V. ACS Appl
Mater Interfaces 2016;8:13957e65.
[16] (a)Lee Y-L, Chang CH. Efficient polysulfide electrolyte for CdS
quantum dot-sensitized solar cells. J Power Sources
2008;185(1):584e8.
(b)Tian J, Shen T, Liu X, Fei C, Lv L, Cao G. Enhanced
performance of PbS-quantum-dot-sensitized solar cells via
optimizing precursor solution and electrolytes. Sci Rep
2016;6:23094.
(c)Jun HK, Careem MA, Arof AK. A suitable polysulfide
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e7
electrolyte for CdSe quantum dot-sensitized solar cells. Int J
Photoenergy 2013:10. Article ID 942139.
(d)Jovanovski V, Gonzalez-Pedro V, Gimenez S. A sulfide/
polysulfide-based ionic liquid electrolyte for quantum dot-
sensitized solar cells. J Amer Chem Soc 2011;133(50):20156e9.
[17] Nakamoto K. Infrared and Raman spectra of inorganic and
coordination compounds, Part B, applications in
coordination, organometallic, and bioinorganic chemistry.
6th ed. Wiley publication; 2009.
[18] (a)Chen Y, Bin Xu B, ShixiongShe S, Hu B, Li Y. Bis(1,5-
diphenylcarbazonato)dimethanol cobalt(II). Acta Crystallogr
Sect E Struct Rep Online 2010:66. m114.
(b)Liu S, Zubieta J. Chemical and X-ray structural
characterization of diphenylcarbazone and
diphenylthiocarbazone complexes of molybdenum(VI), (n-
Bu4N)[MoO2(C6H5NNC(X)NNC6H5)(C6H5N NC(X)NN(H)
C6H5)](X ¼ O or S) and (n-Bu4N)[MoOCl3(C6H5NNC(O)NNC6H5)];
isolation of 2,3-diphenyltetrazolium-5-thiolate, C6H5NNC(S)
NNC6H5, from the reaction of diphenylthiocarbazone with
molybdate. Polyhedron 1989;8:677e88.
[19] Johansson EJ, Hedlund M, Siegbahn H, Rensmo H. Electronic
and molecular surface structure of Ru(tcterpy)(NCS)3 and
Ru(dcbpy)2(NCS)2 adsorbed from solution onto
nanostructured TiO2: a photoelectron spectroscopy study.
J Phys Chem B 2005;109:22256e63.
(b)Nazeeruddin MK, Humphry-Baker R, Liska P, Gra € tzel M.
Investigation of sensitizer adsorption and the influence of
Please cite this article in press as: Shahroosvand H, et al., Aqueous dye-sensitized solar cell based on new ruthenium diphenyl car-
bazide complexes, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.04.222
7
protons on current and voltage of a dye-sensitized
nanocrystalline TiO2 solar cell. J Phys Chem B
2003;107:8981e7.
[20] Shahroosvand H, Najafi L, Sousaraei A, Mohajerani E,
Janghouri M, Bonaccorso F. Ruthenium tetrazole-based
electroluminescent device: the key role of counter-ions for
the light emission properties. J Phys Chem C
2016;120(43):24965e72.
[21] Fattoria A, Petera LM, Beldingb SR, Compton RG, Marken F.
Cis-bis(isothiocyanato)-bis(2,20-bipyridyl-4,4dicarboxylato)-
Ru(II) (N719) dark-reactivity when bound to fluorine-doped
tin oxide (FTO) or titanium dioxide (TiO2) surfaces.
J Electroanal Chem 2010;640:61e7.
[22] Pashaei B, Shahroosvand H, Abbasi P. Transition metal
complex redox shuttles for dye-sensitized solar cells. RSC
Adv 2015;5:94814e48.
[23] Saito H, Uegusa S, Murakami TN, Kawashima N, Miyasaka T.
Fabrication and efficiency enhancement of water-based
dye-sensitized solar cells by interfacial activation of TiO2
mesoporous. Electrochemistry 2004;72:310e6.
[24] Lai WH, Su LH, Teoh LG, Hon MH. Commercial and natural
dyes as photosensitizers for a water-based dye sensitized
solar cell loaded with gold nanoparticles. J Photochem
Photobiol A 2008;195:307e13.
[25] Bella F, Galliano S, Falco M, Viscardi G, Barolo C, Gratzel M,
et al. Unveiling iodine-based electrolytes chemistry in
aqueous dye-sensitized solar cells. Chem Sci 2016;7:4880e90.