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Deep eutectic solvents (DESs) as low-cost and
green electrolytes for electrochromic devices†
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Cite this: Green Chem., 2017, 19,
1653
Hugo Cruz,* Noémi Jordão and Luís C. Branco*
Received 31st January 2017,
Accepted 10th February 2017
DOI: 10.1039/c7gc00347a
rsc.li/greenchem
The application of deep eutectic solvents based on choline
chloride or lithium chloride with ethylene glycol and glycerol as
low-cost, recyclable and green electrolytes for electrochromic
devices is reported. Reversible electrochromic devices incorporat-
ing DESs as alternative electrolytes and bipyridinium electrochromic
probes have been tested and compared to conventional systems.
Nowadays, the choice of the suitable solvent is essential, since
it constitutes around 80% of the total volume of chemicals
used in a specific process. It is recognized that solvents have
several environmental, health and safety challenges including
safety hazard, waste management as well as human and eco-
toxicity issues.1 Following the principles of green chemistry,
most of the common organic solvents do not achieve the
requirements for their use in green technological applications
due to their inherent toxicity and higher volatility.2 In this
context, the search for green and alternative solvents to replace
the classical organic solvents is a great challenge for academic
and industrial communities.
Different options have been explored, including water;
supercritical fluids, fluorous solvents, and polyethylene glycol
(PEG) derivatives.3–5 Each of these alternative solvents have its
own strengths, as well as significant limitations including reac-
tivity to highly basic or nucleophilic reagents, limited solubi-
lity for reagents and catalysts as well as reduced recyclability.6
In the last few decades, the discovery of room temperature
ionic liquids (RTILs) has attracted much attention mainly
because of their ability to tune properties according to cation/
anion combinations.7 The cost of RTIL production compared
to conventional solvents is a real limitation in order to enlarge
its applications for industry.8 Recently, Deep Eutectic Solvents
(DESs) have been described as a new class of RTIL ana-
LAQV, REQUIMTE, Departamento de Quíımica, Faculdade de Ciências e Tecnologia,
Universidade Nova de Lisboa, 2829-516 Monte de Caparica, Portugal.
E-mail: hg.cruz@fct.unl.pt, l.branco@fct.unl.pt; Fax: +351212948550;
Tel: +351 212948300
† Electronic supplementary information (ESI) available. See DOI: 10.1039/
c7gc00347a
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logues.9,10 DESs are prepared by the complexation between
suitable hydrogen bond acceptors and hydrogen bond donors.
It is known that all HBA and HBD combinations will not give
DESs (they are called “deep” in the case of low melting point).
They can comprise a variety of anionic and/or cationic species
and have a large depression in melting point compared to the
pure substances.11 Contrarily to RTILs, the specific cost, bio-
degradability and biocompatibility of DESs are solely dependent
on the components used. The most typical DES, such as
choline chloride/urea or choline chloride/glycerol, are compar-
able in cost to typical organic solvents such as acetonitrile or
N,N-dimethylformamide, thus eliminating much of the
concern with their use. There are four types of DESs based on
the combination of quaternary ammonium salts with metal
chloride (type I); metal chloride hydrate (type II) and a hydro-
gen bond donor (type III) or metal chloride hydrate with a
hydrogen bond donor (type IV).
The main applications of DESs are concerned with metal
deposition processes and alternative reaction media in organic
synthesis.12 In particular, some specific DESs have been
employed as alternative media for metals that are traditionally
difficult to plate or process; or involve environmentally hazar-
dous processes.9 Also, the application of DESs for the prepa-
ration and stabilization of nanoparticles, metal–organic frame-
works, colloidal assemblies, thermochromic composite films,
nanostructure metal films, hierarchically porous carbons,
DNA/RNA architectures, DNA concentration and dissolution
have been reported.13–21 Some studies about the application of
DESs for selective extraction processes (e.g. bioactives or biopo-
lymers) as well as the solubility of biomaterials (e.g. chitin or
cellulose) are recently described.22–25 In addition, relevant
reports about the application of DESs for the preparation of
electrocatalysts; bioinspired functional materials as well as in
supercapacitors have been published.26–28
It is difficult to predict the whole range of possibilities,
since the number of compounds suitable for the preparation
of DESs including natural compounds is enormous. Although
there is a large pool of substances and several DESs have been
presented, the mechanism of their formation is not well
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value (8.9 mS cm−1) while LiCl : 3Gly gives a denser liquid

(1.31 g cm−3).
In particular, the conductivity values of the ChCl based DES
are at least six times higher than a similar LiCl based DES.
Complementary calorimetric studies (DSC analysis) can prove
the efficient preparation of the desired DES.
The electrochemical window is one of the most important
parameters, once it allowed the determination of the anodic
and cathodic limit, where it is possible to work without the
degradation of the DES. For the prepared DES, the largest EW
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Fig. 1 Type of the prepared DES as well as electrochemical and
electrochromic compounds.
clarified. The depression of the melting point is considered to
arise from a combination of hydrogen bond interactions,
lattice energy, and entropy change.22
Herein, we report the application of DESs (type III and IV)
in particular based on the suitable combination of HBA
choline chloride with ethylene glycol and glycerol (1 : 2) or
lithium chloride with the same hydrogen bond donors (1 : 3),
as alternative green electrolytes for electrochromic devices as
indicated in Fig. 1.
Results and discussion
In order to elucidate the potential of the prepared DES
in electrochemical applications, different properties such as
density, conductivity and electrochemical window (EW) have
been studied and compared to conventional ChCl : 2urea as
indicated in Table 1.
The DESs containing glycerol (Gly) showed higher densities
but lower conductivity values compared to the ethylene
glycol (EG) series. ChCl : 2EG presents the highest conductivity
is observed for the cases of LiCl : 3EG (3.8 V) and LiCl : 3Gly
(3.7 V). For the same hydrogen bond donors (HBD), EG
promotes an increase of almost 500 mV from the replacement
of ChCl to LiCl. One possible reason for this observation is
related to the lithium cation which could stabilize the DES,
when compared with ChCl, (300 mV higher in the anodic and
200 mV in the cathodic limit). An even higher increase is
observed for the case of Gly (700 mV) both in the anodic and
the cathodic limitation, 200 mV and 500 mV respectively.
The electrochemical measurements were performed in a
three electrode configuration system as indicated in Fig. 2a.
For cyclic voltammetry experiments, a glassy carbon disk as a
working electrode and Pt wire as a counter-electrode were
used. The potential was measured versus an Ag/AgCl leakless
electrode for the first set of trials. Then, for the second series
of trials PET-ITO as the working and counter electrode, in
order to understand the process inside the electrochromic
device (see Fig. 2a) were used. The electrochromic studies were
performed using a similar electrochromic device configur-
ation, which consisted of two PET-ITO layers separated by a
spacer. This type of electrochromic device presents a sym-
metric behaviour, once the potential applied to one face
corresponds to a symmetric potential applied to the other as
indicated in Fig. 2b.
Previous studies about the electrochemical window of the
prepared DES electrolytes were performed using ferrocene (Fc)
and methyl viologen (MVCl2) in order to calculate the presence
of water and then by direct comparison of the water content in
each DES. From these analyses, it is possible to conclude that
ChCl : 2EG contains approximately 8% of water ChCl : 2Gly and
LiCl : 3Gly approximately contains 5% of water.

Electrochemical and electrochromic studies

Table 1 Deep eutectic solvent characterization
Two electrochromic probes based on methyl viologen
DESs (eq.) (1,1′-(dimethyl)-4,4′-bipyridinium di-chloride [(CH3)2bpy]Cl2)
Density Conductivity and previously prepared 1,1′-[di-(methoxyethoxyethane)]-4,4′-
HBA HBDa (g cm−3) (mS cm−1) EWb [Epc/Epa]
bipyridinium di-iodide [(C5O2)2bpy]I2 were selected.29
ChCl 2Ureac 1.25 0.75 1.8 The electrochemical behaviour of [(CH3)2bpy]Cl2 is well-
ChCl 2EG 1.14 8.85 3.3 [−2.2/1.1]
ChCl 2Gly 1.21 2.08 3.0 [−1.9/1.1] known30 and it presents two successive electron-transfer (ET)
LiCl 3EG 1.14 1.45 3.8 [−2.4/1.4] processes. The first one corresponds to the dication reduction
LiCl 3Gly 1.34 0.29 3.7 [−2.4/1.3] to a radical cation, and the second from the radical cation to a
a
Hydrogen bond donor: EG-ethylene glycol; Gly-glycerol. neutral compound (di-reduced species). For all DESs studied
b
Electrochemical window (EW) is defined by the anodic or cathodic in this work, a similar behaviour is observed, where the same
limit (where the oxidation or reduction processes for the DES begin). cathodic peaks are detected. The first monoelectronic revers-
The EW can be calculated by the difference between the reduction
potential and the oxidation potential of the DES. c Values from the ible ET at −0.50 V vs. the Ag/AgCl leakless electrode for
literature.9 ChCl : 2EG, −0.53 V vs. the Ag/AgCl leakless electrode for

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Fig. 2 General scheme for: (A) the electrochemical device used as the three electrode configuration system and (B) the electrochromic device.

ChCl : 2Gly, −0.52 V vs. the Ag/AgCl leakless electrode for
LiCl : 3EG and −0.57 V vs. the Ag/AgCl leakless electrode for
LiCl : 3Gly that leads to the radical cation electrogenerated, is
presented in Table 2. The second electron-transfer process was
also studied, one electron reversible ET for all the DESs
studied (−0.85 V for ChCl : 2EG, −0.88 V for ChCl : 2Gly, −0.95 V
for LiCl : 3EG and −0.88 V for LiCl : 3Gly).
These two successive one-electron reversible ET is not
affected by these media; it means that the process generates a
stable radical cation in all DESs as electrolytes. These experi-
ments reveal slight differences in the standard potential (E°) :
the radical cation is 30 to 20 mV negatively shifted when
it used ChCl : 2Gly or LiCl : 3EG respectively instead of
ChCl : 2EG and 70 mV shifted, also negatively shifted to lower
potentials, when it used LiCl : 3Gly. Thus the direct compari-
son of both glycerol based DESs reveals that the difference is
the 40 mV negative shift for the LiCl : 3Gly containing DES.
In the case of the previously prepared [(C5O2)2bpy]I2, a
similar behaviour compared to [(CH3)2bpy]Cl2 is observed, in
particular with those two successive one electron-transfer (ET)
processes. When compared with those two bipyridinium salts,
a positive shift of redox potentials of [(C5O2)2bpy]I2 can be
observed as described in previous papers31,32 due to the inser-
tion of oxygen in the alkyl side-chain that makes its reduction
easier. When it is compared with the media effect in the first
one electron reversible ET process, the shift occurs in the
same direction while the current intensity decreases 10 or
2.5 fold for the cases of LiCl : 3Gly or ChCl : 2Gly, respectively,
compared to ChCl : 2EG. Fig. 3 illustrates the cyclic voltammetry
of [(C5O2)2bpy]I2 in an electrochromic device using LiCl : 3Gly
as the electrolyte (Fig. 3a) as well as [(CH3)2bpy]Cl2 in an
electrochromic device using DES ChCl : 2EG as the electrolyte
(Fig. 3c). Two successive ET processes are observed in the
direct cathodic scan (from 0 V to −2 V) at 20 mV s−1, for
the case of [(C5O2)2bpy]I2. The first wave (ca. −1.53 V) corres-
ponds to the reduction of the dication and the formation of

Table 2 Redox potentials of deep eutectic solvents

DES HBA : HBD

(solvent + supporting Epc (V vs. E° (V vs. ΔEb
Compounds electrolyte) Ag/AgCl) Ag/AgCl)a (mV)

[(CH3)2bpy]Cl2 ACNc — −0.41 —

ChCl : 2EG −0.53 −0.50 70
ChCl : 2Gly −0.56 −0.53 70
LiCl : 3EG −0.57 −0.52 70 Fig. 3 Cyclic voltammetry of 15 mM [(C5O2)2bpy]I2 (a) in an electro-
LiCl : 3Gly −0.60 −0.57 70 chromic device using the LiCl : 3Gly DES as the electrolyte between
[(C5O2)2bpy]I2 ACN + 0.1 M TBAP — −0.38d — 0/−2/2/0 at a scan rate of 20 mV s−1 with the respective colour tran-
ChCl : 2EG −0.48 −0.45 70
sition; (b) at a 3 electrode device using the 3 DES as the electrolyte at a
ChCl : 2Gly −0.50 −0.47 70
LiCl : 3Gly −0.54 −0.49 100 scan rate of 20 mV s−1; and of 15 mM [(CH3)2bpy]Cl2 (c) in an electro-
chromic device using the ChCl : 2EG DES as the electrolyte between
a
Standard potential, calculated as E° = (Epc + Epa)/2 measured versus 0/−2/2/0 at a scan rate of 20 mV s−1 with the respective colour tran-
Ag/AgCl. b ΔE = (|Epc| − |Epa|) in mV (vs. Ag/AgCl). c Ref. 33. d Ref. 29. sition; (d) at a 3 electrode cell using the same conditions as before.

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the radical cation, which in this specific medium (DES
LiCl : 3Gly) presents a pinkish coloration. The second wave
could be attributed to the reduction of the radical cation
electrogenerated to give the neutral species (ca. −1.92 V).
This observation can be attributed to the oxidation of
iodide in one electrode and the reduction of the radical,
usually pale coloured or uncoloured species, at the other
electrode (the cell presents a brownish coloration). The device
becomes pinkish again at a potential of ca. −1.7 V at the
anodic back scan and reaches the bleach state at ca. 1 V prob-
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ably due to a slow diffusion process.
In general, the process is symmetric for this electrochromic
device using LiCl : 3Gly as the new electrolyte. In the case of
ChCl : 2Gly as the electrolyte, a similar electrochemical window
(0/−2/2/0 at 20 mV s−1) is observed and on tracking the direct
cathodic scan from 0 to −2 V only one wave is observed
(ca. −1.68 V) possessing a more violet/pinkish coloration. In
this electrochemical window the second ET process wasn’t
observed. At the anodic back scan a peak at ca. −0.14 V and
the starting of the bleaching process are also observed. Finally,
for the DES based on ChCl : 2EG a similar behaviour was
observed for the same conditions described before, and a
unique wave was observed in the direct cathodic scan
(ca. −1.86 V) associated with the violet coloration. All studies
using DESs as electrolytes indicated us no dimerization
process, in contrast to previous observations in other electro-
lyte media.31
The most relevant point is the first observation of the
second electron-transfer using DESs as the electrolytes in this
electrochemical setup (electrochemical window 0/−2/2/0 and
at 20 mV s−1 scan rate).
Fig. 3c presents the cyclic voltammetry for methyl viologen
[(CH3)2bpy]Cl2; the reduction process of the compound to the
radical cation at extreme potentials, almost at −3 V with the
corresponding blue coloration is required. For example, when
the applied potential of −2 V to the electrochromic device for
about one hour is used, a blue colour appears (ChCl : 2EG) and
a more violet coloration for ChCl : 2Gly and LiCl : 3Gly but for
LiCl : 3EG the electrochromic device showed colour after just
Fig. 4 Electrolysis at a controlled potential in an electrochromic device and the colour coordinate for 15 mM [(CH3)2bpy]Cl2 and 15 mM
[(C5O2)2bpy]I2.
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15 seconds, a pale blue colour appears, then becomes darker
and more violet after 600 s due to the generation of the
coloured species, the radical cation. To obtain a stable colour-
ation it was necessary to apply a potential of −2.5 V to each
electrochromic device. A similar behaviour was observed and
the first electrochromic device to gain colour was LiCl : 3EG,
which after 120 s presents a blue/violet coloration and then
becomes darker (600 s). After 4 hours in an open circuit the
electrochromic device recovered its original coloration. Thus
in the case of other 3 DES (ChCl : 2Gly, ChCl : 2EG and
LiCl : 3Gly) based electrochromic devices a larger time was
required to observe a similar bleach on the device. The electro-
chemical process in the device works in a way that when
one electrode gains colour, the other stays bleached or
slightly yellow (Fig. S1 ESI†). When the potential is reversed,
one electrode bleaches and the coloration diffuses through
the solution and the other electrode becomes coloured,
as presented in Fig. S1 ESI.† They can also be successfully
used as alternative electrolytes in electrochromic devices once
they acquire a lower voltage to enhance the electrochemical
and electrochromic process, in the same electrochemical
window.
The time for the coloration and bleach processes is depen-
dent on the electrochromic as well as the electrolyte systems.
The first series of experiments using commercially available
MVCl2 as an electrochromic compound and the well-known
DES (ChCl : 2urea) showed longer transition times and the
need for higher potentials in order to achieve an efficient elec-
trochromic stability. Compared to DESs based on LiCl the time
can be reduced according to a predictable higher mobility of
the species and lower viscosity media. In our opinion, the
improvement of coloration/blench efficiency is related to the
type of electrolyte, and the possibility to reduce the intrinsic
viscosity of the system can improve the ECD performance sig-
nificantly. Looking for the low toxicity of the prepared DES
compared to the conventional electrolytes based on toxic and
volatile organic solvents, this work can contribute to a green
advance in order to create low-cost, greener and efficient ECDs
with potential applications in industry (Fig. 4).
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Green Chemistry
Experimental
Chemicals
Anhydrous lithium chloride (LiCl) and glycerol (Gly) were
purchased from Sigma-Aldrich (ReagentPlus ≥99% GC),
choline chloride (ChCl) and ethylene glycol (EG) from
Alfa Aesar (99%), and N,N′-(methyl)-4,4′-bipyridinium chloride
[(CH3)2bpy]Cl2 from Fluka (98%). All the commercially avail-
able reactants were of high purity and used without further
purification (stored under inert conditions).
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The eutectic mixtures were prepared under vigorous stirring
of the two components (1 : 2 for the DESs based on ChCl and
1 : 3 for the DESs based on the LiCl salt) at 60 to 70 °C,
adapted from ref. 22. After 4 to 6 hours of mixing, a homo-
geneous colourless viscous liquid is formed.
The bipyridine derivative [(C5O2)2bpy]I2 was prepared
according to the previously reported work.29,31
Cyclic voltammetry and electrochromic experiments
All electrochemical studies including cyclic voltammetry (CV)
and electrolysis at a controlled potential were performed on an
Autolab PGSTAT 12 potentiostat/galvanostat, controlled with
GPES software version 4.9 (Eco-Chemie, B.V. Software Utrecht,
The Netherlands), using a three-electrode cell of 3 ml. A glassy
carbon electrode (ET074 eDAQ) was used as the working
electrode and a Pt wire as the counter or auxiliary electrode. All
potentials refer to an Ag/AgCl leakless (3.5 M KCl) reference
electrode (ET072 eDAQ). Prior to use, the working electrode
was polished in aqueous suspensions of 1.0 and 0.3 μm
alumina (Buehler) over 2–7/8″ micro-cloth (Buehler) polishing
pads, then rinsed with water and methanol. This cleaning pro-
cedure was applied always before any electrochemical measure-
ment. Cyclic voltammetry (CV) at 20–100 mV s−1 scan rate was
used to characterize the electrochemical responses in the
desired electrochemical window.
The electrochromic device is manufactured using two
PET-ITO layers as electrodes with the electrochrome dissolved
in the chosen electrolyte, and CV measurements and electro-
lysis at a controlled potential with an applied potential (Eapp)
of 100 mV higher than the peak potential (Ep) determined by
CV (Eapp = Ep + 100 mV) were performed to assess the electro-
chromic material.
Density measurements were determined by using a micro-
picnometer and conductivity measurements were performed
using a conductimeter Basic 30 Crison.
Conclusions
Novel DESs based on choline or lithium chloride with ethylene
glycol and glycerol as low-cost and green electrolytes were pre-
pared and successfully applied in electrochromic devices.
Reversible electrochromic devices incorporating these DESs as
alternative electrolytes and two bipyridinium electrochromic
probes have been efficiently tested. The development of green
electrolyte based DESs can open excellent alternatives to con-
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ventional electrolytes in future device applications such as
smart windows.
Acknowledgements
This work was performed under the project “SunStorage –
Harvesting and storage of solar energy”, with reference
POCI-01-0145-FEDER-016387, funded by the European
Regional Development Fund (ERDF), through the COMPETE
2020 – Operational Programme for Competitiveness and
Internationalisation (OPCI), and by national funds (PTDC/
QEQ-QFI/1971/2014), through FCT – Fundação para a Ciência
e a Tecnologia. H. Cruz and L. C. Branco thank for the finan-
cial support of FCT/MCTES (Post-Doc grant SFRH/BPD/102705/
2014 and IF/0041/2013/CP1161/CT00). The NMR spectrometers
are part of The National NMR Facility, supported by FCT/
MCTES (RECI/BBB-BQB/0230/2012).
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