Subscriber access provided by READING UNIV

Article
Deep Eutectic Solvents as suitable electrolytes for Electrochromic Devices
Hugo Cruz, Noémi Jordão, Patricia Amorim, Madalena Dionísio, and Luis Branco
ACS Sustainable Chem. Eng., Just Accepted Manuscript • DOI: 10.1021/
acssuschemeng.7b03684 • Publication Date (Web): 12 Dec 2017
Downloaded from http://pubs.acs.org on December 13, 2017

Just Accepted

“Just Accepted” manuscripts have been peer-reviewed and accepted for publication. They are posted
online prior to technical editing, formatting for publication and author proofing. The American Chemical
Society provides “Just Accepted” as a free service to the research community to expedite the
dissemination of scientific material as soon as possible after acceptance. “Just Accepted” manuscripts
appear in full in PDF format accompanied by an HTML abstract. “Just Accepted” manuscripts have been
fully peer reviewed, but should not be considered the official version of record. They are accessible to all
readers and citable by the Digital Object Identifier (DOI®). “Just Accepted” is an optional service offered
to authors. Therefore, the “Just Accepted” Web site may not include all articles that will be published
in the journal. After a manuscript is technically edited and formatted, it will be removed from the “Just
Accepted” Web site and published as an ASAP article. Note that technical editing may introduce minor
changes to the manuscript text and/or graphics which could affect content, and all legal disclaimers
and ethical guidelines that apply to the journal pertain. ACS cannot be held responsible for errors
or consequences arising from the use of information contained in these “Just Accepted” manuscripts.

ACS Sustainable Chemistry & Engineering is published by the American Chemical

Society. 1155 Sixteenth Street N.W., Washington, DC 20036
Published by American Chemical Society. Copyright © American Chemical Society.
However, no copyright claim is made to original U.S. Government works, or works
produced by employees of any Commonwealth realm Crown government in the course
of their duties.
Page 1 of 10 ACS Sustainable Chemistry & Engineering

1
2
3
4
5
6
7 Deep Eutectic Solvents as suitable electrolytes for Electrochromic
8 Devices
9
10 Hugo Cruz*, Noémi Jordão, Patrícia Amorim, Madalena Dionísio, Luís C. Branco*
11
12 E-mail: l.branco@fct.unl.pt; hg.cruz@fct.unl.pt; Fax: +351 212948550; Tel.: +351 212948300.
13 LAQV-REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, 2829-
14 516 Caparica, Portugal.
15
ABSTRACT: The development of chloride free Deep Eutectic Solvents (DES) based on lithium acetate, triflate, bistriflimide and sodium
16
triflate combined with glycerol, ethylene glycol and polyethylene glycol (PEG400) as suitable electrolytes were developed and successful-
17 ly applied in electrochromic devices (ECD). Reversible ECD incorporating selected DES as electrolyte and bipyridinium as electrochromic
18 probes display a comparable performance than conventional systems, with slower transition times (2.5 times), improving the coloration
19 contrast and efficiency (147.1 cm2.C-1 at 520 nm) and is stable for at least 1250 redox cycles.
20
21 KEYWORDS: deep eutectic solvents, electrochromic materials, electrolytes; coloration efficiency; electrochemical redox
22 probes.
23
24 INTRODUCTION between transparent (bleached state) and colored state, or between
25 at the least two distinct coloration states.25, 26
Recently, Deep Eutectic Solvents (DES) as Room Temperature
Several applications such as electrochromic windows,27 electro-
26 Ionic Liquid (RTIL) analogues have attracted much attention due
chromic displays,28, 29 anti-glare car mirrors,30, 31 eye-glasses,32
27 to the possibility to use as greener alternative solvents. Abbott and
solar attenuated windows,33, 34 and flexible electrochromic devic-
co-workers defined eutectic mixtures as "deep" when a large
28 es,35 have been reported.
depression in melting point occurs comparing to the pure compo-
29 nents.1 DES can be formed from eutectic mixture between Lewis
The most important classes of electrochromic materials include
30 and Brønsted acids and bases and it can be comprised by a variety
viologen derivatives, transition metal/lanthanide coordination
31 complexes, metal phthalocyanines, transition metal oxides, metal-
of anionic and/or cationic species. In this way, they are prepared
lopolymers, Prussian blue systems, and conducting polymers,
32 by the complexation between hydrogen bond acceptors (HBA)
among others.36-42
33 and hydrogen bond donors (HBD).1-3
Two-electrode configuration cell for an electrochromic system
34 Generally, DES showed several properties similar to RTIL, such
comprises a conductive surface (electrode) such as ITO (indium
as high solvation ability and wide electrochemical windows.
35 Contrarily to RTIL, DES can be synthesized by simple mixing of
tin oxide) or FTO (fluorine-doped tin oxide) coated in a PET or
36 the low-cost and environmental friendly starting materials just
glass surface combined with another conductive surface (elec-
37 trode) separated by a thickness lower than one millimeter using a
heat up most of the times and without further purifications.1,2
double sided adhesive tape. One possible approach corresponds to
38 The main applications of DES include: a) chemical synthesis as
the possibility of the electrochromic material to be dissolved in
39 alternative reaction media in organic synthesis4 b) electrochemical
the electrolyte and the mixture placed between those two conduc-
40 applications, where it has been used for the determination of its
tive layers. Thus, the choice of a suitable solvent/electrolyte is
physical-chemical properties,5-6 electroplating and electrodeposi-
41 tion,7-8 or involve environmentally hazardous processes,2,7,8 as
essential, and it can be considered one of the most important
42 well as in electrocatalysis and for supercapacitors and batteries.9-12
parameters in electrochemical or chemical processes. Recently,
43 Also, it was reported the use of DES for the preparation and stabi-
greener and safer solvents/electrolytes with peculiar properties
(e.g. negligible vapor pressure at room temperature) gained much
44 lization of nanoparticles, metal-organic frameworks, colloidal
attention in academia, since it can be an alternative to replace the
45 assemblies, thermochromic composite films, nanostructures metal
classical organic solvents, which could present several environ-
46 films, hierarchal porous carbons, bioinspired functional materi-
mental, health and safety challenges, including safety hazard,
als,9-11 application for selective extraction processes (e.g. bioac-
47 waste management as well as human and eco-toxicity issues.
tive or biopolymers) as DNA/RNA architectures, DNA concentra-
48 tion and dissolution have been reported13-20 as well as solubility of
Herein, we reported the application of DES based on the suitable
49 biomaterials (e.g. chitin or cellulose).1, 21-23 Previously, we report-
combination of several HBD such as ethylene glycol (EG), glyc-
50 erol (Gly) and PEG 400 and HBA such as lithium triflate (LiOTf),
ed the preparation and characterization of DES based on choline
lithium bistriflimide (LiNTf2), lithium acetate (LiAcO) and sodi-
51 chloride or lithium chloride with ethylene glycol and glycerol as
um triflate (NaOTf) as alternative greener electrolyte for electro-
52 low-cost, recyclable and green electrolytes for electrochromic
chemical studies as well as electrochromic devices as indicated in
devices.24
53 Figure 1.
Nowadays, electrochromic materials for academic and industrial
54 applications have been explored due to their interesting properties.
55 Electrochromic materials exhibit a distinct visible color switch
56 1
57
58
59
60 ACS Paragon Plus Environment
 ACS Sustainable Chemistry & Engineering Page 2 of 10

of 1.0 and 0.3 µm alumina (Buehler) over 2-7/8” micro-cloth

Hydrogen Bond Aceptor (HBA) Hydrogen Bond Donor (HBD)
1 (Buehler) polishing pads, then rinsed with water and methanol or
Anion
2
Cation OH Acetonitrile. This cleaning procedure was applied always before
F O HO OH
3 F S O Glycerol (Gly)
any electrochemical measurement. CV measurements were per-
F O formed at 20-100 mV.s-1 scan rate and it was used to characterize
4 Trifluoromethanesulfonate (OTf) Na
Sodium the electrochemical responses (I-E curves) in the desired electro-
5 F
F O O F
S N S F
HO
OH
chemical window.
6 F O O F
Ethylene Glycol (EG)
Bis((trifluoromethyl)sulfonyl)amide (NTf2)
7 HO O
H
2-electrode configuration Cyclic Voltammetry and Electro-
Li
8
n
CH3COO Lithium Poly(Ethylene Glycol) 400 (PEG 400) chromic Experiments: In the 2-electrode configuration cell
9
Acetate (AcO) (area of electroactive surface is 2 x 1.5 cm2) the conductive
layers were rinsed with ethanol. CV measurements and elec-
10 Electrochemical Redox
trolysis at a controlled potential at applied potential (Eapp)
11 Co PF6 S S 100 mV higher then peak potential (Ep) predetermined by
Fe
12 Cobaltocinium S S CV (Eapp=Ep+100 mV) were performed to characterize the
13 Hexafluorophosphate (Cc) Ferrocene (Fc) Tetrathiafulvalene (TTF)
electrochromic material.
14 Cl I I
Cl
15 O O
Conductivity measurements: The conductivity of the different
N N O N N O DES was performed by dielectric relaxation spectroscopy (DRS).
16
N,N'-[di(methoxyethoxy)ethane-[4,4'-bipyridinium] For the DRS measurements, samples were placed between two
17
N,N'-dimethyl-[4,4'-bipyridinium]
dichloride (MVCl2) di-iodide
stainless steel electrodes (10 mm diameter) in a BDS 1200 paral-
18 Figure 1. Chemical structures of the Hydrogen Bond Acceptors and lel plate capacitor, using two 50 µm silicon spacers to maintain
19 Donors selected to prepare Deep Eutectic Solvents (DES); and the tested sample thickness and the sample cell was mounted on a BDS
20 electrochemical redox probes. 1100 cryostat. All measurements were carried out using an Alpha-
21 A combination of electrochemical techniques like cyclic voltam- N analyser from Novocontrol, covering a frequency range from
22 metry (CV) and electrolysis at a controlled potential as well as 10−1 Hz to 1 MHz at 22ºC.
23 thermal and conductivity studies allowed us a more detailed char-
Spectroelectrochemical and cycling measurements: Spectroelec-
24 acterization of the prepared DES. The incorporation of the pre-
pared DES in efficient and reversible electrochromic devices have trochemistry studies were performed using UV-Vis- NIR spectro-
25 been performed. photometer Varian Cary 5000. The potential was controlled with a
26 device potentiostat/galvanostat Model 20 Autolab. The device
27 EXPERIMENTAL SECTION
was placed in the spectrophotometer compartment perpendicular-
28 ly to the light beam. Cycling stability tests were also performed in
Chemicals: All the commercial available reactants were pur- the same setup.
29 chased in high purity level without further purification. Anhy-
30 drous triflate compounds (LiOTf, NaOTf, KOTf) and lithium Water measurements by Karl-Fischer: The water content was
31 bistriflimide (LiNTf2) from Solchemar (99%). Glycerol (Gly) and measured using an 831 KF Coulometer, 230 Metrohm with gener-
32 Polyethylene glycol (PEG400) were purchased from Sigma- ator electrode and without diaphragm. The water content is pre-
Aldrich (ReagentPlus 99% GC). Ethylene Glycol (EG), Tetrathia-
33 sented as average values of at least three independent measure-
fulvalene (TTF, 97%) from Alfa-Aaeser (99%), Ferrocene (Fc)
34 from BDH, Cobaltocinium hexafluorophosphate from Aldrich and
ments.
35 N,N’-(methyl)-4,4’-bipyridinium dichloride [(CH3)2bpy]Cl2 from DSC measurements: DSC analysis is carried out using a TA
36 Fluka (98%). 1,1’-[di-(methoxyethoxyethane)]-4,4’-bipyridinium Instruments Q-series TM Q2000 DSC with a refrigerated cooling
37 di-iodide [(C5O2)2bpy)]I2 was prepared according to the synthetic system. The sample is continuously purged with 50 ml.min-1
38 route reported in previous work.43 nitrogen. About 2-15 mg of salt was crimped in an aluminum
39 standard sample pan with lid. Glass transition temperature analy-
Synthesis of DES: The Eutectic mixture were prepared under sis using a heating/cooling rate of 10ºC.min-1 was determined in
40 vigorous stirring of the both components (HBA and HBD) in the
41 the 2nd heating after a thermal treatment up to 150ºC. Crystalliza-
different proportions at a temperature between 60 to 70ºC. After 6 tion (Tc) were determined by DSC analysis using a heat-
42 hours of mixing the compound a colorless viscous liquid is ob- ing/cooling rate of 10ºC min-1 at 2nd cycle.
43 tained, adapted from literature. 1,24
44 Viscosity measurements: The viscosity of DES was measured
45 Electrochemical measurements: All the electrochemical studies using a Brookfield DV-II+ Pro Viscometer with a cone spindle
were performed on an Autolab PGSTAT 12 potenti-
46 ostat/galvanostat, controlled with GPES software version 4.9
CPE-40, at 25ºC.
47 (Eco-Chemie, B.V. Software Utrecht, The Netherlands).
48 RESULTS AND DISCUSSION
49 3-electrode configuration Cyclic Voltammetry and Electro- Our previous work reported the preparation of five DES as well as
its first application as greener electrolytes for electrochromic
50 chromic Experiments: All the electrochemical Cyclic Voltamme-
try (CV) and Electrolysis at a controlled potential, using a 3- devices.24
51 In this work, we develop a series of DES based on lithium and
electrode configuration cell (3 mL). A glassy carbon electrode
52 (ET074 eDAQ) was used as working electrode and a Pt wire as sodium salts for application as efficient electrolytes tested in
53 counter or auxiliary electrode. All potentials refer to a Ag/AgCl different electrochemical redox probes (see Figure 1).
54 leakless (3.5 M KCl) reference electrode (ET072 eDAQ). Prior to The preparation and characterization of new DES and their ther-
55 use, the working electrode was polished in aqueous suspensions mal, physical and electrochemical properties are presented and
56 2
57
58
59
60 ACS Paragon Plus Environment
Page 3 of 10 ACS Sustainable Chemistry & Engineering

discussed. Finally, the stability of electrochromic devices (ECD) extended plateau, a decrease is observed (see ESI).51 This arises
1 using the most promissory DES were evaluated. from ions accumulation in the sample/electrode interface without
2 discharging, blocking ionic conduction.51 To compare the electri-
3 Thermal analysis: All prepared DES were studied by differential cal behavior of the different systems studied, five frequencies
scanning calorimetry (DSC). The glass transition temperature (Tg) were selected (as indicated in Table 2).
4
as well as melting and crystallization temperatures are summa-
5 rized in Table 1. Additionally, the water content (determined by Table 1. Physical-Chemical properties of prepared DES as electrolytes.
6 Karl Fischer titration) and viscosity are also presented. As ex- DSChydrated [a] DSCafter 150ºC [b]
7 pected, the water content contributes to change both thermal (e.g. DES H2O EW
8 glass transition due to plasticizing effect) and physical-chemical (HBA: Tc
Visco
Tg-mid Tc/Tm Tg-mid sity
9 properties such as viscosity and conductivity. HBD)
(oC) (oC) (oC)
/Tm
o
/wt% [c]
(Pa.s)[d]
(V) [e]
In the case of Gly (see Figure 2), under the experimental condi- ( C)
10
tions tested in this work, neither crystallization nor melting are
11 detected, the only observed thermal event is the glass transition Gly -79.6 - /- -76.8 - /- 0.5 0.725 n.a.
12 indicated by the discontinuity in the heat flow occurring below -
13 70ºC. LiOTf: -70.7 - /- -62.8 - /- 3.5 0.683
1.8 /
14 This general behavior is followed by the Gly based DES with a -2.0
3Gly
15 shift to higher temperatures according the following order:
1.6 /
16 Tg(LiAcO:3Gly) > Tg(LiOTf:3Gly) > Tg(Gly). This observation LiAcO: -67.1 -/- -51.3 - /- 5.1 1.713
-2.5
can be related to the strength of the hydrogen bonding interac- 3Gly
17 tions. In fact, acetate anion can establish stronger hydrogen bonds -42.1
18 with the OH groups of Gly as already described for biopolymers EG -
-53.3 /
- / 0.2 0.016 n.a.
19 such as cellulose derivatives.44, 45 -15.3
-12.3
20 The DES containing EG did not showed any melting and crystal-
21 lization in the selected experimental conditions contrarily to pure LiNTf2: - -/- - - /- 1.0 0.055
2.5 /
EG; it seems reasonable to assume, at least in the temperature -2.3
22 4EG
range explored, that the addition of the LiOTf, NaOTf or LiNTf2
23 salts originates the suppression of both crystallization and melt- 1.9 /
LiOTf: - -/- - -/ - 5.0 0.060
24 ing. This observation can be explained by an anti-freeze behavior. 4EG
-2.0
25 The thermal behavior of the PEG solvent is highly cooling rate 1.9 /
26 dependent. While vitrification process is avoided upon cooling at LiOTf: - -/- - - /- 3.7 0.036
-2.1
27 10 ºC.min-1, it emerges in the hydrated state when the cooling rate 6EG
28 increases to 20ºC.min-1 (close to -70ºC); crystallization and melt- 1.9 /
ing are always observed occurring in reasonable agreement with LiOTf: - -/- - - /- 7.2 0.025
-2.1
29 10EG
the values reported in the literature.46
30 Concerning the LiOTf:6PEG, the most striking effect is the de- -16.8
PEG400 - -12.6/ - 0.5 0.077 n.a.
31 pression of the crystallization temperature, whereas the melting /5.7
4.0
32 temperature undergoes almost no changes (2ºC decrease). The
PEG400 -20.1
33 glass transition shifts towards higher temperatures by 5ºC.
(20ºC/min)
-70.9 -49.1[f]/ -
/5.3
34 -7.1
Viscosity: In general, the viscosity of DES (at 25ºC) is higher than
35 -
the reported for classical ILs41 and it is strongly influenced by the
36 nature of the solvent and salt, once its determine the nature of -28.5;
31.3;
2.2 /
LiOTf: -65.4 -66.2 -48.1
37 intermolecular interactions between the molecules and ions pre- 6PEG
-41.5[f] [f]
/
1.4 0.163 -2.5
38 sent in solution.47-49
/ -1.13
3.2
39 In the case of DES based on EG, it was observed a decrease on
1.9 /
40 the viscosity value with an increase of EG content. Comparing NaOTf: - - /- - - /- 3.1 0.025
-2.3
41 LiOTf:6EG and LiOTf:6PEG, higher viscosity values are ob- 6EG
served due to polymeric nature of PEG.
42 [a]
Glass transition (Tg-mid), melting and crystallization temperatures were deter-
43 Conductivity: Ionic conductivity is another property that is
mined in the 1st cycle scanned at 10ºC. min-1 (hydrated). [b] Glass transition (Tg-
nd
mid), melting and crystallization temperatures were determined in the 2 cycle
44 strongly affected by the nature of the components to form eutectic scanned at 10oC. min-1 (after thermal treatment up to 150oC). [c] Measurement by
45 mixture. For all prepared DES, the dependence of ionic conduc- Karl Fischer titration at 25oC. [d] Measurement by microviscometer at 25oC. [e]
46 tivity with frequency from 10-1 to 106 Hz was measured at 22ºC. Electrochemical window (EW) is defined by the anodic or cathodic limited
47 Usually in these disordered systems, the profile of the real com- (onset of DES oxidation or reduction processes). The EW can be calculated by
ponent (
′ (f)) from the complex conductivity obeys to a universal the difference between reduction potential and the oxidation potential of the
48 DES. [f] Cold crystallization was detected upon the heating run.
behavior with a frequency dependent conductivity at high fre-
49 quencies, exhibiting a plateau at low frequencies; the latter corre-
50 sponds to the direct current (dc) conductivity (
′dc), i.e. transla- It was previously observed a correlation between the emerging of
51 tional motion of charge carriers.50 This is not obeyed by the pre- the plateau region and the surpassing of the glass transition,52, 53
52 pared DES, at room temperature. being interpreted as a conductivity mechanism enabled by struc-
tural motion, i.e. a dynamic glass transition assisted hopping
53 In general, for the systems here investigated, the conductivity
response shows a similar frequency dependence being mainly mechanism of charge transport.52-54
54 Therefore, it is important to note that for all the DES studied,
dominated by electrode polarization; therefore, instead of an
55 conductivity measurements were carried out above Tg, which for
56 3
57
58
59
60 ACS Paragon Plus Environment
 ACS Sustainable Chemistry & Engineering Page 4 of 10

all the DES occurs below -50ºC (in some cases, possibly below -
1 90ºC). The experiments were performed at least 70ºC above Tg, in
2 a temperature region where electrode polarization strongly dis-
3 plays highly masking the dc plateau. It should be mentioned that
stainless steel electrodes were tested (even though originating a
4
higher electrode polarization), since redox reaction was observed
5 in gold plated electrodes.55
6
7 Table 2. Real part of complex conductivity at plateau region of the pre-
pared DES.
8
σ' (mS/cm) at 22ºC
9
10 DES
102 103
Figure 3. (Left) General scheme of sample preparation for conductivity
104 Hz 105Hz 9.08x105Hz measurements; (Right) Real part of complex conductivity in function of
11 Hz Hz the frequency for LiAcO:3Gly and LiOTf:3Gly.
12
13 LiAcO:3Gly 0.034 0.081 0.157[a] 0.175[a] 0.175[a] Usually, for electrolytes a correlation between conductivity and
14 [a] [a] [a]
viscosity is reported 56. This is investigated through a Walden’s
LiOTf:3Gly 0.018 0.104 0.248 0.291 0.294
15 plot, where the molar or molal conductivity () and fluidity (the
inverse of viscosity) are plotted on log−log scales. This plot for
16 LiNTf2:4EG 0.015 0.069 0.394 2.702[a] 2.614[a]
the prepared DES is presented in figure 4, in which the conductiv-
17 ity was normalized by molality (ratio between the number of
LiOTf:4EG 0.018 0.077 0.403 2.540[a] 2.600[a]
18 moles of solute and 1000 g of solvent); the ideal conductivity
19 LiOTf:6EG 0.016 0.071 0.354 1.920[a] 2.297[a] behavior of a non-interacting ionic material is given as a dashed
20 line with slope equal to 1 obtained for high diluted (0.01 M) of
21 LiOTf:10EG 0.015 0.053 0.126[a] 0.169[a] 0.165[a] KCl aqueous solution.1,2,56
22 LiOTf:6PEG 0.029 0.086 0.199[a] 0.228[a] 0.226[a]
23
24 NaOTf:6EG 0.025 0.096 0.632 3.417[a] 2.430[a]
25
[a]
26
′ values taken from the plateau (see ESI)
27
28 For all investigated systems, the plateau always falls in the high
frequency range (see sigma at ~105 – 106 Hz in Table 2 and Fig-
29 ure 3).
30
31
32
33
34
35 Figure 4. Walden plot for prepared DES. dashed line corresponds to ideal
36 behavior using a diluted (0.01 M) of KCl aqueous solution.
37
Indeed, the expected correlation is obeyed in general for the stud-
38
ied DES, with LiOTf:6PEG, LiOTf:3Gly, LiAcO:3Gly falling in
39 the ideal line. The other DES, fall close but under the ideal line
40 which can be rationalized as result of ion-ion interaction. The
Figure 2. (Left) General schematic of the DSC. (Right) Heat flow ther-
41 mogram for Gly (full line), LiOTf:3Gly (dot line) and LiAcO:3Gly (dash
applicability of Walden’s rule to DES it is validated by Abbott
42 dot line) obtained at 10 oC.min-1 (heating/cooling rate) after a thermal and co-workers using the hole theory, which assumes that the
43 treatment up to 150ºC. predicted relationship occurs due to an almost infinite dilution of
suitable sized empty spaces/voids in a material, determining ion
44
mobility. 2
45 It is possible to conclude that the EG based DES exhibit higher
46
dc values, by a factor of approximately 20. DES based Li-
OTf:nEG (n=4, 6, 10) allowed to infer about the influence of salt Electrochemical Measurements: The solubility of electrochemi-
47 concentration and it seems that an increase of LiOTf salt origi- cal compound in the presence of specific electrolyte is a key
48 nates an increase
dc. parameter. In our case, the prepared DES were firstly tested in the
49 presence of four different electrochemical redox probes: N,N’-di-
methyl-4,4’-bipyridinium di-chloride ([(CH3)2bpy]Cl2) or
50
MVCl2), ferrocene (Fc), tetrathiafulvalene (TTF) and cobaltocini-
51 um hexafluorophosphate (Cc). Cyclic voltammetry and electroly-
52 sis at a controlled potential were used to study the electrochemical
53 and electrochromic behavior of the probes. Those probes present-
54 ed a well-known electrochemical behavior in the reduction
55 (MVCl2 and Cc) or oxidation (Fc and TTF) processes.57, 58 The
56 4
57
58
59
60 ACS Paragon Plus Environment
Page 5 of 10 ACS Sustainable Chemistry & Engineering

standard (Eo) and peak (Ep) potentials are summarized in Table 3. Table 3. Standard (Eº) and peak (Ep) potentials of selected redox electro-
1 The shapes of the cyclic voltammogram of the electrogenerated chemical probes dissolved in different Deep Eutectic Solvents in a 3-
electrode cell.
2 species in aprotic solvents containing bulky organic counter-
3 cations and in RTILs57 are comparable to the DES. Figure 5 illus- DES Ep E0 a ∆Eb
trates the respective response I-E curves at a 3-electrode configu- Compounds
4 HBA:HBD (VvsAg/AgCl) (VvsAg/AgCl) (mV)
ration cell using MVCl2 and Fc as probes.
5 The electrochemical behavior of MVCl2 is a well-defined two
ChCl:2EG -0.53 -0.50 70
6 successive mono-electronic electron-transfer (ET) with a standard ChCl:2Gly -0.56 -0.53 70
7 potential of -0.651 and -1.085 V vs Ag/AgCl leak less obtained in LiCl:3EG -0.56 -0.53 69
8 aqueous media (in a phosphate buffer solution).58 In our case, the LiCl:3Gly -0.60 -0.57 70
9 electrogenerated species (radical-cation and neutral species) were LiAcO:3Gly -0.62 -0.54 153
stable during the time of the experiment and our focus is centered
10 LiOTf:3Gly -0.67 -0.62 82
in the first mono-electronic ET due to color switch process (high- MVCl2
11 er electrochromic behavior; see Figure 5 and ESI Figure S1). LiNTf2:4EG -0.70 -0.65 109
12 In the case of the DES using Gly (a viscous liquid) as HBD and LiOTf:4EG -0.62 -0.59 72
13 lithium salt, such as LiCl, LiAcO and/or LiOTf as HBA, a cathod- LiOTf:6EG -0.61 -0.57 85
14 ic peak potential for the first mono-electronic ET decreases in the
LiOTf:10EG -0.58 -0.55 71
15 sequence: -0.60 V vs. Ag/AgCl leak less (Cl), -0.62 V vs.
Ag/AgCl leak less ([AcO]) and -0.67 V vs. Ag/AgCl leak less LiOTf:6PEG -0.55 -0.47 160
16
([OTf]). This observation can be explained by the size of each NaOTf:6EG -0.59 -0.56 59
17 anion as well as their stronger hydrogen bond acceptor. For the LiOTf:3Gly 0.27 0.22 96
18 case of EG as HBD combined with LiCl, LiOTf and/or LiNTf2 as
LiNTf2:4EG 0.23 0.18 106
19 HBA, a similar electrochemical behavior, i.e. two successive Fc
LiOTf:6PEG 0.49 0.42 144
20 monoelectronic ET are observed. The study of the first electron
21 transfer presents a standard potential of -0.53 V vs. Ag/AgCl leak NaOTf:6EG 0.53 0.49 81
22 less (Cl), -0.59 V vs. Ag/AgCl leak less ([OTf]) and -0.65 V vs. TTF LiOTf:6PEG 0.43 0.36 144
Ag/AgCl leak less ([NTf2]) respectively, see ESI Figure S2.
23 The anion effect also affected the standard potentials in the fol-
Cc LiOTf:6PEG -0.96 -0.91 110
a
24 Standard potential, calculated as E0 = (Epc +Epa)/2 measured vs. Ag/AgCl
lowing order: E0 (Cl) > E0 ([OTf]) > E0 ([NTf2]). leak less; b∆E = (|Epc| – |Epa|) in mV, with Epa (anodic peak potential) and
25 In the case of the DES composed by LiOTf:nEG (n= 4, 6 and 10), Epc (cathodic peak potential).
26 a dilution effect leads to a decrease in the viscosity and conductiv-
27 ity profile, is affecting the electron transfer process, which is
28 displaced for higher potentials E0(LiOTf:4EG) < E0(LiOTf:6EG) For Fc, the [Ep] and [E0] are well-known for several electrochemi-
< E0(LiOTf:10EG) as can be seen in Table 1, Figure 5 left upper cal solvents and electrolytes, including ILs and polar aprotic
29
and ESI Figure S2. solvents.57 In the selected DES, a well-defined one mono-
30 In the case of the DES LiOTf:6PEG [E0 (LiOTf:6PEG) = - 0.47 V electronic ET is observed, the electrogenerated radical cation is
31 vs. Ag/AgCl leak less] vs. LiOTf:6EG [E0(LiOTf:6EG) = - 0.57 V formed than LiOTf:Gly and LiOTf:PEG. It is also observed that
32 vs. Ag/AgCl leak less], the shape of the I-E curve for the two- the LiNTf2:4EG easily form the electrogenerated radical contrari-
33 successive ET are similar. However, the polymeric nature of PEG ly to NaOTf:6EG see Table 1 and Figure 5 left down and ESI
34 leads to an increase of the standard potential to higher values and Figure S5.
the reduction of MVCl2 became easier (100 mV) see Table 1 and
35 To evaluate the potential application of DES as electrolyte for
ESI Figure S2.
36 Finally, ET became easier around 10 mV in the case of sodium
ECDs (two-electrode system), an additional test was performed as
37 control, using the same conditions of the redox probes, i.e. CV in
based DES [LiOTf:6EG vs NaOTf:6EG], and about 20 mV for the an electrochemical window of 0/-3/3/0 in a scan rate of 20 mV.s-1
38 first cathodic peak as can be seen in Table 1and ESI Figure S2. is performed and ET processes are detected in those conditions
39 For the case of Cc as another reduction probe, the DES Li- (see Figure 6).
40 OTf:6PEG was selected because it is one that presents a lower In general, for two-electrode system containing MVCl2 dissolved
41 standard potential, see Table 1 and ESI Figure S3. A similar in DES, a characteristic electrochemical response in the cathodic
behavior was reported in the literature for other ILs and polar
42 aprotic solvents (E0 in DPA and ILs and comparing to DES; E0= -
direct scan (0/-3/3/0) is observed. However, no ET is detected for
43 the reduction of the probe in this electrochemical window. It is
0.91 V and Ep= -0.96 V vs. Ag/AgCl leak less).18 required the application of higher potentials, almost -3 V to obtain
44 In the case of oxidation probes TTF, LiOTf:6PEG is suitable to the corresponding blue coloration, i.e. radical cation formation
45 solubilize the TTF and it is the one that presents two successive (see Figures S7-S10 from ESI).
46 mono-electronic ET, see Table 1 and ESI Figure S4. Other exam-
47 ples of electrochemical solvents and ILs reported a similar behav- In the cases of LiAcO:3Gly, LiOTf:6PEG and NaOTf:6EG, a
ior: E0 = 0.316 V (Ep1 = 0.358 V) and E0 = 0.602 V (Ep2= 0.568
48 well-defined ET and blue coloration characteristic for the radical
V) in the presence of DMF + 0.1M [TBA][BF4]; E0 = 0.175 V cation are detected at lower peak potentials [Ep (LiAcO:3Gly) = -
49 (Ep1 = 0.203 V) and E0 = 0.495 V (Ep2 = 0.529 V) in 2.57 V, Ep (LiOTf:6PEG) = -2.87 V and Ep (NaOTf:6EG) = -2.52
50 [BMIM][BF4] and E0 = 0.184 V (Ep1 = 0.129 V) and E0 = 0.572 V V] in the cathodic reverse scan (see Figures S11-S13 from ESI).
51 (Ep2 = 0.649 V) in [BMIM][PF6] (all the potentials are presented Following the cyclic voltammetry at the higher potential (+3 V),
52 V vs. Ag/AgCl leak less). 56 In the selected DES, TTF presents E0 the MVCl2 increases the blue coloration. The same DES presented
53 = 0.36 V (Ep1 = 0.43) and E0 = 0.62 V (Ep2 = 0.70 V). a well-defined ET with Ep (LiAcO:3Gly) = 2.46 V, Ep (Li-
54 OTf:6PEG) = 2.85 V and Ep (NaOTf:6EG) = 2.42 V also fol-
55
56 5
57
58
59
60 ACS Paragon Plus Environment
 ACS Sustainable Chemistry & Engineering Page 6 of 10

lowed by an increase in the blue coloration intensity at lower

1 potentials but don´t return the initial coloration.
2
3
4
5
6
7
8
9
10
11
12
13
14 Figure 7. RGB coordinates for the ECD containing MVCl2 as redox
probe.
15
16 To obtain a stable and darker coloration, it is required -2.5 V of
17 potential and a transition time between minutes to hours for each
18 ECD [NaOTf:6EG, LiOTf:10EG, LiNTf2:4EG and LiOTf:6PEG].
19 For the LiOTf:EG, ECDs gained color slower depending on the
20 Figure 5. (Right) Schematic 3-electrode configuration cell for the study of amount of HBD used, the higher amount of EG allowed a signifi-
cant reduction of viscosity and perhaps also increasing the diffu-
21 the DES as electrolyte at a scan rate 50 mV/s, [(CH3)2bpy]Cl2, Fc, Cc and
sion coefficient of the species. No color change was observed in
TTF in concentration of 15 mM and (Left) the respective response I-E
22 curves at a 3-electrode configuration cell for the [(CH3)2bpy]Cl2 and Fc in the case of cobaltocinium as an electrochromic cathodic probe
23 the same conditions as before. Legend: A-DES and Electrochromic; B- using these experimental conditions.
24 Ref. Electrode (Ag/AgCl leak less); C- Counter Electrode CE (Pt wire); The study of ferrocene as electrochromic anodic probe was tested
D-Inert gas flow (N2); E- Working Electrodes WE (Glassy Carbon, CV &
25 PET-ITO electrolysis).
in five DES, the most promising ones, LiOTf:6PEG, LiNTf2:4EG,
26 NaOTf:6EG, and LiOTf:3Gly. For the case of ECD using Li-
OTf:6PEG, the color change at 1.8V for a gray green coloration
27 Figure 7 illustrates the coloration gradient for the ECD of the
and after four days in open circuit the ECD was permanently gray.
28 MVCl2 between pale brown to five different pallet colors: pale
LiNTf2:4EG at 2V for 1h, the ECD showed a light blue greenish
29 blue (LiOTf:6PEG); blue green (LiOTf:10EG); blue
coloration that increases to a blue gray coloration and returns to
(NaOTf:6EG); dark blue (LiAcO:3Gly); violet (LiCl:3Gly).
30 It is possible to conclude that in the case of DES containing EG,
gray after one day in open circuit. NaOTf:6EG at -2V showed a
31 the electrogenerated radical cation becomes blue and in the case
light green brown coloration that increases at -3V to dark brown-
32 ish coloration and after five days in open circuit the coloration
of the glycerol becomes more violet.24
remains brown. The ECD using LiOTf:3Gly at 2V for 30 to 60
33
minutes changed between gray to a blue greenish gray coloration.
34 ne-
TTF as an electrochromic probe was tested in the ECD using
35 ne-
LiOTf:6PEG at 2V for 1h, it changed between pale brown to a
36 Electrode
surface
To the
Surface
Add drop
DESs and
Close the
cell with brownish green coloration and after 24h at open circuit almost
37
add electrochromic another
spacer mixture electrode recover its original color.
38 For all the DES successfully used as electrolyte for the viologen
derivatives a well-defined electron transfer at approximately 0V is
39
observed, in both cathodic and anodic back scans, this could be
40 related to an oxidation process that don’t lead to a color change or
41 an adsorption process at the electrode surface, it’s not clear at this
42 time in this study.59,63
43 Preliminary studies for the determination of stabilities of the ECD
44 were performed using three of the most promising DES as electro-
45 lytes (LiOTf:10EG, LiOTf:6PEG and NaOTf:6EG) and N,N’-[di-
(methoxyethoxyethane)]-4,4’-bipyridinium di-iodide
46 [(C5O2)2bpy]I2 as an alternative electrochromic probe. In the case
47 of the NaOTf:6EG applying a potential of -/+2V for 600 s ECD
48 gained a purple coloration in the first seconds and it required a
49 Figure 6. (Top) General schematic for construction of the 2-electrode cell longer time than MVCl2 to return to original coloration (see ESI
50 and (Bottom) Overlapping CV in a 2-electrode configuration cell, electro- Figure S18 -S19). For the case of LiOTf:6PEG, the transition
chromic device, using as electrolyte the DES LiOTf:10EG between 0/- times are shorter to obtain a green-gray coloration (15 minutes)
51 3/3/0 at a scan rate of 20 mV/s, green line and using as probe the MVCl2 and to recover its original coloration (7 minutes). It is particularly
52 in 15 mM, blue line 1st cycle and red line 2nd cycle.
interest the case of LiOTf:10EG as electrolyte in the presence of
53 [(C5O2)2bpy]I2 as probe, only 60 seconds is required to gain pur-
54 ple coloration and to recover its original coloration longer time is
55 necessary (at least 200s).
56 6
57
58
59
60 ACS Paragon Plus Environment
Page 7 of 10 ACS Sustainable Chemistry & Engineering

ECD Stability Studies for ECD stability studies, the These novel class of DES can open outstanding alternatives to
1 [(C5O2)2bpy]I2 as alternative electrochromic redox probe dis- conventional electrolytes for application in potential industrial
2 solved in LiOTf:10EG as electrolyte was selected as the model device applications.
3 system. The electrochromic parameters such as chromatic contrast
4
(∆T, %), transition times (t90 or t70) and coloration efficiency (CE) ASSOCIATED CONTENT
of this ECD was evaluated. Chromatic contrast (∆T, %) increases
5 Supporting Information
until 96.2%. The transition times, t90 or t70 (to reach 90% or 70%
6 The Supporting Information is available free of charge on the
of its maximum colour (or bleach state)) increases using the se-
7 lected DES as electrolyte comparing to previous work using ACS Publications website.
8 bipyridinium based ILs in a gel electrolyte (t90 9.7s to 21.4s and
9 t70 4.9s to 12.4s).64 Cyclic voltammetry in 3- and 2- electrode configuration, RGB
coordinates, DSC/DRS measurements (file type, i.e., PDF)
10 The coloration efficiency (CE that corresponds to the amount of
11 colour reached (or bleached) by charge consumed per cm2 of the
ECD at a specific wavelength) is higher (147.1 cm2.C-1 at 520
12 ACKNOWLEDGMENT
nm).
13 Figure 8 illustrates a preliminary cycling stability study of the This work was performed under the project “SunStorage - Har-
14 ECD using [(C5O2)2bpy]I2 with LiOTf:10EG as electrolyte. The vesting and storage of solar energy”, with reference POCI-01-
15 following experimental conditions: coloration time (15 s) and/or 0145-FEDER- 016387, funded by European Regional Develop-
16 bleaching time (90 s) by applying +/-2V and 0Vof potential, ment Fund (ERDF), through COMPETE 2020 - Operational
17 respectively were used. Programme for Competitiveness and Internationalisation (OPCI),
18 and by national funds (PTDC/QEQ-QFI/1971/2014), through FCT
- Fundação para a Ciência e a Tecnologia. H. Cruz and L. C.
19 Branco thanks to financial support of FCT/MCTES (Post-Doc
20 grant SFRH/BPD/102705/2014 and IF/0041/2013/CP1161/CT00).
21 The NMR spectrometers are part of The National NMR Facility,
22 supported by FCT/MCTES (RECI/BBB-BQB/0230/2012).
23
24 REFERENCES
25 (1) Abbott P.; Boothby D.; Capper G.; Davies D. L.; Rasheed R.
26 K. Deep eutectic solvents formed between choline chloride and
carboxylic acids: versatile alternatives to ionic liquids. J. Am.
27 Chem. Soc. 2004, 126, 9142-9147. DOI: 10.1021/ja048266j
28 (2) Smith E. L.; Abbott A. P.; Ryder K. S. Deep Eutectic Solvents
29 (DESs) and Their Applications. Chem. Rev. 2014, 114, 11060-
30 11082. DOI: 10.1021/cr300162p
31 (3) Florindo C.; Oliveira F. S.; Rebelo L. P. N.; Fernandes A. M.;
32 Marrucho I. M. Insights into the Synthesis and Properties of Deep
Eutectic Solvents Based on Cholinium Chloride and Carboxylic
33
Figure 8. Switching cycles of [(C5O2)2bpy]I2 ECDs fabricated with Li- Acids. ACS Sustainable Chem. Eng. 2014, 2, 2416-2425. DOI:
34 OTf:10EG as electrolyte. Cycles 1–14 and 1236–1250 are illustrated for 10.1021/sc500439w
35 ECD switched at 15s and 90s cycles between -2 and 0 V respectively at (4) Liu P.; Hao J.-W.; Mo L.-P.; Zhang Z.-H. Recent advances in
36 520 nm. the application of deep eutectic solvents as sustainable media as
37 well as catalysts in organic reactions. RSC Adv. 2015, 5, 48675-
38 CONCLUSIONS and PERSPECTIVES 48704. DOI: 10.1039/C5RA05746A
(5) Bahadori L.; Manan N. S. A.; Chakrabarti M. H.; Hashim M.
39 Different DES based on lithium and sodium salts with glycerol,
ethylene glycol and polyethylene glycol as sustainable and suita- A.; Mjalli F. S.; AlNashef I. M. The electrochemical behaviour of
40 ferrocene in deep eutectic solvents based on quaternary ammoni-
ble electrolytes were developed and successfully applied in elec-
41 trochromic devices (ECD). Some of the prepared DES could um and phosphonium salts. Phys. Chem. Chem. Phys. 2013, 15,
42 completely solubilize and stabilize different electrochemical 1707-1714. DOI: 10.1039/C2CP43077K
43 probes requiring a lower voltage to enhance the electrochemical (6) Bahadori L.; Chakrabarti M. H.; F. Mjalli S.; AlNashef I. M.;
44 and electrochromic processes at the same electrochemical win- Manan N. S. A.; Hashim M. A. Physicochemical properties of
45 dow. The most promising DES are NaOTf:6EG and LiOTf:10EG ammonium-based deep eutectic solvents and their electrochemical
requiring a lower potential to enhance the blue coloration for the evaluation using organometallic reference redox systems. On the
46 cobalt and cobalt oxide electrodeposition from a glyceline deep
MVCl2 as electrochemical redox probe as well as LiOTf:6PEG
47 which presented the lower standard and peak potentials for the eutectic solvent. Electrochim. Acta 2013, 11, 205-211. DOI:
48 first electron transfer in the case of MVCl2 and Fc probes. 10.1016/j.electacta.2013.09.102
49 Comparing to previous work using conventional gel electrolytes, (7) Sakita A. M. P.; Noce R. D.; Fugivaraa C. S.; Benedetti A. V.
50 LiOTf:10EG as DES showed a significant increase in the chro- On the cobalt and cobalt oxide electrodeposition from a glyceline
51 matic contrast as well as coloration efficiency. However, longer deep eutectic solvent. Phys. Chem. Chem. Phys. 2016, 18, 25048-
transition times are required to achieve a complete colored and 25057. DOI: 10.1039/C6CP04068C
52 (8) Miller M. A.; Wainright J. S.; Savinell R. F. Iron Electrodepo-
bleached states. The reduction of viscosity of the DES seems to
53 sition in a Deep Eutectic Solvent for Flow Batteries. J. Electro-
improve the original transition times.
54 chem. Soc. 2017, 164, A796-A803. DOI: 10.1149/2.1141704jes
55
56 7
57
58
59
60 ACS Paragon Plus Environment
 ACS Sustainable Chemistry & Engineering Page 8 of 10

(9) Mondal D.; Sharma M.; Wang C.-H.; Lin Y.-C.; Huang H.-C.; (24) Cruz H.; Jordão N.; Branco L. C. Deep Eutectic Solvents
1 Saha A.; Nataraj S. K.; Prasad K. Deep eutectic solvent promoted (DES) as low-cost and electrolytes for electrochromic devices.
2 one step sustainable conversion of fresh seaweed biomass to Green Chem. 2017,19, 1653-1658. DOI: 10.1039/C7GC00347A
3 functionalized graphene as a potential electrocatalyst. Green (25) Monk P. M. S.; Mortimer R. J.; Rosseinsky D. R.; Electro-
Chem., 2016, 18, 2819-2826. DOI: 10.1039/C5GC03106K chromism: Fundamentals and Applications, VCH, Weinheim,
4
(10) Bhatt J.; Mondal D.; Bhojani G.; Chatterjee S.; Prasad K. Germany 1995.
5 Preparation of bio-deep eutectic solvent triggered cephalopod (26) Monk P. M. S.; Mortimer R. J.; Rosseinsky D. R.; Electro-
6 shaped silver chloride-DNA hybrid material having antibacterial chromism and Electrochromic Devices, Cambridge University
7 and bactericidal activity. Mater. Sci. Eng. C 2015, 56, 125-131. Press, Cambridge, UK 2007.
8 DOI: 10.1016/j.msec.2015.06.007 (27) Niklasson G. A.; Granqvist C. G. Electrochromics for smart
9 (11) Mukesh C.; Gupta R.; Srivastava D. N.; Nataraj S. K.; Prasad windows: thin films of tungsten oxide and nickel oxide, and de-
K. Preparation of a natural deep eutectic solvent mediated self- vices based on these. J. Mater. Chem. 2007, 17, 127-156. DOI:
10
polymerized highly flexible transparent gel having super capaci- 10.1039/B612174H
11 tive behaviour. RSC Adv. 2016, 6, 28586-28592. DOI: (28) Mortimer R. J.; Dyer A. L.; Reynolds J. R. Electrochromic
12 10.1039/C6RA03309A organic and polymeric materials for display applications. Displays
13 (12) Chakrabarti M. H.; Mjalli F. S.; AlNashef I. M.; Hashim M. 2006, 27, 2- 18. DOI: 10.1016/j.displa.2005.03.003
14 A.; Hussain M. A.; Bahadori L.; Low C. T. J. Prospects of apply- (29) Wang X. J.; Lau W. M.; Wong K. Y. Display device with
15 ing ionic liquids and deep eutectic solvents for renewable energy dual emissive and reflective modes. Appl. Phys. Lett. 2005, 87
16 storage by means of redox flow batteries. Renew. Sustainable (113502)-1-3. DOI:10.1063/1.2043249
Energy Rev. 2014, 30, 254-270. DOI: 10.1016/j.rser.2013.10.004 (30) Rosseinsky D. R.; Mortimer R. J. Electrochromic Systems
17 (13) Mamajanov I.; Engelhart A. E.; Bean H. D.; Hud N. V. DNA and the Prospects for Devices. Adv. Mater. 2001, 13, 783- 793.
18 and RNA in anhydrous media: duplex, triplex, and G-quadruplex DOI:10.1002/1521-4095(200106)
19 secondary structures in a deep eutectic solvent. Angew. Chem. (31) Lyman N. R.; Agrawal A. in: Large Area Chromogenics:
20 2010, 49, 6310-6314. DOI: 10.1002/ange.201001561 Materials and devices for Transmittance Control, ed. C. M. Lam-
21 (14) Wagle D. V.; Zhao H.; Baker G. A. Deep Eutectic Solvents: pert; C. G. Granqvist, SPIE Optical Engineering Press, Belling-
22 Sustainable Media for Nanoscale and Functional Materials. Acc. ham, Washington, USA 1990, 46
Chem. Res. 2014, 47, 2299-2308. DOI: 10.1021/ar5000488 (32) Ma C.; Taya M.; Xu C. Smart sunglasses based on electro-
23 (15) Gu C. D.; Tu J. P. Thermochromic behavior of chloro- chromic polymers. Polym. Eng. Sci. 2008, 48, 2224-2228.
24 nickel(II) in deep eutectic solvents and their application in ther- DOI:10.1002/pen.21169
25 mochromic composite films. RSC Adv. 2011, 1, 1220-1227. DOI: (33) Dyer A. L.; Grenier C. R. G.; Reynolds J. R. A Poly(3,4-
26 10.1039/C1RA00345C alkylenedioxythiophene) Electrochromic Variable Optical Atten-
27 (16) Gu C. D.; Tu J. P. One-Step Fabrication of Nanostructured uator with Near-Infrared Reflectivity Tuned Independently of the
28 Ni Film with Lotus Effect from Deep Eutectic Solvent. Langmuir Visible Region. Adv. Funct. Mater. 2007, 17, 1480-1486. DOI:
2011, 27, 10132-10140. DOI: 10.1021/la200778a 10.1002/adfm.200601145
29
(17) Ge X.; Gu C. D.; Lu Y.; Wang X. L.; Tu J. P. A versatile (34) Pozo-Gonzalo C.; Mecerreyes D.; Pomposo J. A.; Sal-
30 protocol for the ionothermal synthesis of nanostructured nickel samendi M.; Marcilla R.; Grande H.; Vergaz, R.; Barrios D.;
31 compounds as energy storage materials from a choline chloride- Sanchez-Pena J. All-plastic electrochromic devices based on
32 based ionic liquid. J. Mater. Chem. A 2013, 1, 13454-13461. DOI: PEDOT as switchable optical attenuator in the near IR. Sol. Ener-
33 10.1039/C3TA13303F gy Mater. Sol. Cells 2008, 92, 101. DOI:
34 (18) Mondal D.; Sharma M.; Mukesh C.; Gupta V.; Prasad K. 10.1016/j.solmat.2007.03.031
Improved solubility of DNA in recyclable and reusable bio-based (35) Gomes L.; Marques A.; Branco A.; Araujo J.; Simoes M.;
35
deep eutectic solvents with long-term structural and chemical Cardoso S.; Silva F.; Henriques I.; Laia C. A. T.; Costa C. IZO
36 stability. Chem. Commun. 2013, 49, 9606. DOI: deposition by RF and DC sputtering on paper and application on
37 10.1039/C3CC45849K flexible electrochromic devices. Displays 2013, 34, 326-333.
38 (19) Mukesh C.; Prasad K. Formation of Multiple Structural DOI: 10.1016/j.displa.2013.06.004
39 Formats of DNA in a Bio-Deep Eutectic Solvent. Macromol. (36) Granqvist C. G., Handbook of Inorganic Electrochromic
40 Chem. Phys. 2015, 216, 1061-1066. DOI: Materials, Elsevier, Amsterdam, Holland 1995.
41 10.1002/macp.201500009 (37) Higgins S. J., Conjugated polymers incorporating pendant
(20) Tang B.; Zhang H.; Row K. H. Application of deep eutectic functional groups-synthesis and characterisation. Chem. Soc. Rev.
42 solvents in the extraction and separation of target compounds 1997, 26, 247-257. DOI: 10.1039/CS9972600247
43 from various samples. J. Sep. Science 2015, 38, 1053-1064. DOI: (38) B. Scrosati, Application of Electroactive Polymers, Chapman
44 10.1002/jssc.201401347 and Hall, London, UK 1993.
45 (21) Das A. K.; Sharma M.; Mondal D.; Prasad K. Deep eutectic (39) Mortimer R. J. Electrochromic Materials. Annual Rev. Mater.
46 solvents as efficient solvent system for the extraction of κ- Res. 2011, 41, 241-268. DOI: 10.1146/annurev-matsci-062910-
47 carrageenan from Kappaphycus alvarezii. Carbohydr Polym. 100344
2016, 136, 930-935. DOI: 10.1016/j.carbpol.2015.09.114 (40) Somani P. R., Radhakrishnan S. Electrochromic materials
48
(22) Kholiya F.; Bhatt N.; Rathod M. R.; Meena R. Fundamental and devices: present and future. Mater. Chem. Phys. 2003, 77,
49 studies on the feasibility of deep eutectic solvents for the selective 117-133. DOI: 10.1016/S0254-0584(01)00575-2
50 partition of glaucarubinone present in the roots of Simarouba (41) Skotheim T. A.; Elsenbaumer R. L.; Reynolds J. R. Hand-
51 glauca. J. Sep. Science 2015, 38, 3170-3175. DOI: book of Conducting polymers, 2nd ed., Marcel Dekker, New York
52 10.1002/jssc.201500470 1998.
53 (23) Sharma M.; Mukesh C.; Mondala D.; Prasad K., Dissolution (42) Rowley N.M.; Mortimer R. J., New electrochromic materials
of α-chitin in deep eutectic solvents. RSC Adv. 2013, 3, 18149- Sci. Prog. 2002, 85, 243-262. DOI:
54
18155. DOI: 10.1039/C3RA43404D 10.3184/003685002783238816
55
56 8
57
58
59
60 ACS Paragon Plus Environment
Page 9 of 10 ACS Sustainable Chemistry & Engineering

(43) Jordão N.; Cruz H.; Branco A.; Pina F.; Branco L. C. (54) Sangoro J. R.; Iacob C.; Serghei A.; Friedrich C.; Kremer F.
1 Electrochromic Devices Based on Disubstituted Oxo- Universal scaling of charge transport in glass-forming ionic liq-
2 Bipyridinium Ionic Liquids. ChemPlusChem. 2015, 80, 202-208. uids. Phys. Chem. Chem. Phys. 2009, 11, 913-916. DOI:
3 DOI: 10.1002/cplu.201402232 10.1039/B816106B
(44) Du H.; Qian X.; The effects of acetate anion on cellulose (55) Mirtaheri P.; Grimnes S.; Martinsen Ø. G. Electrode polari-
4
dissolution and reaction in imidazolium ionic liquids. Carbohydr zation impedance in weak NaCl aqueous solutions. IEEE Transac-
5 Res. 2011, 346, 1985–1990. DOI: 10.1016/j.carres.2011.05.022 tions on Biomedical Engineering 2005, 52, 2093-2099. DOI:
6 (45) Cruz H.; Fanselow M.; Holbrey J. D.; Seddon K. R. Deter- 10.1109/TBME.2005.857639
7 mining relative rates of cellulose dissolution in ionic liquids (56) Ohno, H., Yoshizawa, M. and Mizumo, T. Ionic Conductivi-
8 through in situ viscosity measurement. Chem. Commun. 2012,48, ty, in Electrochemical Aspects of Ionic Liquids, John Wiley &
9 5620-5622. DOI: 10.1039/C2CC31487H Sons, Inc., Hoboken, NJ, USA, 2005, Chapter 6.
(46) Oh H. J.; Freeman B. D.; McGrath J. E.; Lee C. H.; Paul D. (57) Cruz H.; Gallardo I.; Guirado G. Understanding specific
10
R. Thermal analysis of disulfonated poly(arylene ether sulfone) effects on the standard potential shifts of electrogenerated species
11 plasticized with poly(ethylene glycol) for membrane formation. in 1-butyl-3-methylimidazolium ionic liquids. Electrochim. Acta
12 Polymer 2014, 55, 235-247. DOI: 10.1016/j.polymer.2013.11.041 2008, 53, 5968-5976. DOI: 10.1016/j.electacta.2008.03.062
13 (47) Boisset A.; Jacquemin J.; Anouti M. Physical properties of a (57) Bird C. L.; Kuhn A. T. Electrochemistry of the viologens.
14 new Deep Eutectic Solvent based on lithium Chem. Soc. Rev. 1981, 10, 49-82. DOI: 10.1039/CS9811000049
15 bis[(trifluoromethyl)sulfonyl]imide and N-methylacetamide as (58) R. Vergaz, D. Barrios, J-M Sánchez-Pena, C. Pozo-Gonzalo,
16 superionic suitable electrolyte for lithium ion batteries and electric M. Salsamendi, Relating cyclic voltammetry and impedance
double layer capacitors. Electrochim. Acta 2013, 102, 120-126. analysis in a viologen electrochromic device, Sol. Energ. Mat.
17 DOI: 10.1016/j.electacta.2013.03.150 Sol. Cells 2009, 93, 2125-2132. DOI:
18 (48) Baokou X.; Anouti M. Physical Properties of a New Deep 10.1016/j.solmat.2009.08.009
19 Eutectic Solvent Based on a Sulfonium Ionic Liquid as a Suitable (58) R. Vergaz, D. Barrios, J-M Sánchez-Pena, C. Pozo-Gonzalo,
20 Electrolyte for Electric Double-Layer Capacitors. J. Phys. Chem. M. Salsamendi, Sol. Energ. Mat. Sol. Cells 2009, 93, 2125-2132.
21 C 2015, 119, 970-979. DOI: 10.1021/jp5110455 (59) R. Nakajima, Y. Yamada, T. Komatsu, K. Murashiro, T. Saji,
22 (49) Boisset A.; Menne S.; Jacquemin J.; Balduccib A.; Anouti M. K. Hoshino, Electrochromic properties of
Deep eutectic solvents based on N-methylacetamide and a lithium ITO nanoparticles/viologen composite film electrodes, RSC Adv.,
23 salt as suitable electrolytes for lithium-ion batteries. Phys. Chem. 2012, 2, 4377-4381. DOI: 10.1039/C2RA01090A
24 Chem. Phys. 2013, 15, 20054-20063. DOI: 10.1039/C3CP53406E (60) L. Xiao, G. G. Wildgoose, R. G. Compton, Investigating the
25 (50) Kremer F.; Rozanski S. A. The Dielectric Properties of Sem- voltammetric reduction of methylviologen at gold and carbon
26 iconducting Disordered Materials. In Broadband Dielectric Spec- based electrodematerials. Evidence for a surface
27 troscopy; F. Kremer, A. Schonhals, Eds.; Springer-Verlag: Berlin, bound adsorptionmechanism leading to electrode ‘protection’
28 Germany 2003; Chapter 12. using multi-walled carbon nanotubes, New J. Chem., 2008, 32,
(51) Sangoro J. R.; Iacob C.; Naumov S.; Valiullin R.; Rexhausen 1628-1633. DOI:10.1039/B804842H
29
H.; Hunger J.; Buchner R.; Strehmel V.; Kärger J.; Kremer F. (61) M. Rozman, J. Cerar, M. Lukšič, M. Uršič, A. Mourtzikou,
30 Diffusion in ionic liquids: the interplay between molecular struc- H. Spreizer, I. Škofic, E. Stathatos, Electrochromic properties of
31 ture and dynamics. Soft Matter 2011, 7, 1678-1681. DOI: thin nanocrystalline TiO2films coated electrodes with adsorbed
32 10.1039/C0SM01404D Co(II) or Fe(II) 2,2′-bipyridine complexes, Electrochim. Acta
33 (52) Carvalho T.; Augusto V.; Brás A. R.; Lourenço N. M. T.; 2017, 238, 278-287. DOI: 10.1016/j.electacta.2017.04.030
34 Afonso C. A. M.; Barreiros S.; Correia N. T.; Vidinha P.; Cabrita (62) R. Nakajima, Y. Yamada, T. Komatsu, K. Murashiro, T. Saji,
E. J.; Dias C. J.; Dionísio M.; Roling B. Understanding the Ion K. Hoshino, Electrochromic properties of
35
Jelly Conductivity Mechanism. J. Phys. Chem. B 2012, 116, ITO nanoparticles/viologen composite film electrodes. RSC Adv.,
36 2664-2676. DOI: 10.1021/jp2108768 2012,2, 4377-4381. DOI:10.1039/C2RA01090A
37 (53) Carvalho T.; Augusto V.; Rocha Â.; Lourenço N. M. T.; (63) Jordão N.; Cruz H.; Branco A.; Pinheiro C.; Pina F.; Branco
38 Correia N. T.; Barreiros S.; Vidinha P.; Cabrita E. J.; Dionísio M. L. C. Switchable electrochromic devices based on disubstituted
39 Ion Jelly Conductive Properties Using Dicyanamide-Based Ionic bipyridinium derivatives. RSC Adv., 2015, 5, 27867-27873. DOI:
40 Liquids. J. Phys. Chem. B 2014, 118, 9445-9459. DOI: 10.1039/c5ra02368h
41 10.1021/jp502870q
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56 9
57
58
59
60 ACS Paragon Plus Environment
 ACS Sustainable Chemistry & Engineering Page 10 of 10

1
2
3
4 For table of contents use only
5
6
7
8 Deep Eutectic Solvents (DES) as suitable electrolytes were developed and successfully applied as reversible electrochromic devices (ECD)
9 incorporating bipyridinium derivatives.
10
11
12
13
14
15
16
17
18
19
20
0V/-2V
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56 10
57
58
59
60 ACS Paragon Plus Environment